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Jingkang Zhu, Qiuming Gao, Zhi Chen, Preparation of mesoporous copper cerium bimetal oxides with high performance
for
catalytic oxidation of carbon monoxide, Applied Catalysis B: Environmental, Volume 81, Issues 34, 24 June 2008, Pages
236-243, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2007.12.017.
(http://www.sciencedirect.com/science/article/pii/S0926337307004791)
Abstract: A series of mesoporous copper cerium bimetal oxides with different copper contents were replicated from the
KIT-6 silica using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxides were characterized by
XRD, TEM, nitrogen sorption at 77 K and XPS. Catalytic oxidation of CO as a standard reaction was used to test their
activities. The optimized performance was achieved for the catalyst CuCeO2-20 with 20 mol% copper contents and half CO
conversion was reached at 350 K with a space velocity of 260,000 mL h1 gcat1. No obvious deactivation was observed for
over 10 h on stream at 373 K.
Keywords: Copper cerium bimetal oxide; Mesoporous; KIT-6 silica; Nanocasting; CO oxidation
F. Eigenmann, M. Maciejewski, A. Baiker, Selective reduction of NO by NH3 over manganesecerium mixed oxides: Relation
between adsorption, redox and catalytic behavior, Applied Catalysis B: Environmental, Volume 62, Issues 34, 22 February
2006, Pages 311-318, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2005.08.005.
Abstract: Manganesecerium mixed oxide catalysts with different molar ratio Mn/(Mn + Ce) (0, 0.25, 0.50, 0.75, 1) were
prepared by citric acid method and investigated concerning their adsorption behavior, redox properties and behavior in the
selective catalytic reduction of NOx by NH3. The studies based on pulse thermal analysis combined with mass spectroscopy
and FT-IR spectroscopy uncovered a clear correlation between the dependence of these properties and the mixed oxide
composition. Highest activity to nitrogen formation was found for catalysts with a molar ratio Mn/(Mn + Ce) of 0.25,
whereas the activity was much lower for the pure constituent oxides. Measurements of adsorption uptake of reactants,
NOx (NO, NO2) and NH3, and reducibility showed similar dependence on the mixed oxide composition indicating a clear
correlation of these properties with catalytic activity. The adsorption studies indicated that NOx and NH3 are adsorbed on
separate sites. Consecutive adsorption measurements of the reactants showed similar uptakes as separate measurements
indicating that there was no interference between adsorbed reactants. Mechanistic investigations by changing the
sequence of admittance of reactants (NOx, NH3) indicated that at 100150 C nitrogen formation follows an EleyRideal
type mechanism, where adsorbed ammonia reacts with NOx in the gas phase, whereas adsorbed NOx showed no significant
reactivity under conditions used.
Keywords: Manganesecerium mixed oxides; NO; NO2 and NH3 adsorption; Redox behavior; Selective catalytic reduction of
NOx by NH3; Pulse thermal analysis combined with mass spectroscopy and Fourier transform infrared spectroscopy
Sylvain Keav, Alejandra Espinosa de los Monteros, Jacques Barbier Jr., Daniel Duprez, Wet Air Oxidation of phenol over Pt
and Ru catalysts supported on cerium-based oxides: Resistance to fouling and kinetic modelling, Applied Catalysis B:
Environmental, Volumes 150151, 5 May 2014, Pages 402-410, ISSN 0926-3373,
https://doi.org/10.1016/j.apcatb.2013.12.028.
(http://www.sciencedirect.com/science/article/pii/S092633731300773X)
Abstract: Abstract
Ceria and doped ceria supported Pt and Ru catalysts were tested at 160 C in the Catalytic Wet Air Oxidation (CWAO) of
phenol. Catalysts were compared in terms of activity, selectivity and resistance towards fouling. The respective influences
of metal phase and support were studied. Under the selected operating conditions, 100% phenol conversion could be
reached. Contrary to what was expected, improved Oxygen Storage Capacities (OSC) accelerated the accumulation of
adsorbed species on the catalyst surface, therefore limiting the catalytic performance. By contrast, high metal dispersions
enhanced both the elimination of aqueous organic compounds and the degradation of heavy molecules involved in the
catalyst fouling. The progressive decrease in activity induced by carbonaceous deposits could be kinetically modelled using
a simple reaction scheme.
Keywords: CWAO; Phenol; Noble metal; OSC; Deactivation
B. Renard, J. Barbier Jr., D. Duprez, S. Durcu, Catalytic wet air oxidation of stearic acid on cerium oxide supported noble
metal catalysts, Applied Catalysis B: Environmental, Volume 55, Issue 1, 10 January 2005, Pages 1-10, ISSN 0926-3373,
Abstract: Catalytic wet air oxidation (CWAO) of stearic acid was carried out in a batch reactor over noble metals (Ru, Pd, Pt,
Ir) catalysts supported on ceria. The influence of reaction conditions such as temperature, oxygen pressure and stearic acid
concentration were investigated. The reaction occurs via a complex mechanism. The molecule of stearic acid can be
oxidized by successive carboxydecarboxylation (RnCOOH + O2 Rn1COOH +CO2) yielding essentially CO2 (route A). It
may also be oxidized after CC bond rupture within the alkyl chain, which gives rise to significant amounts of acetic acid
besides CO2 (route B). Pt/CeO2 is a very active catalyst in the conversion of stearic acid and extremely selective to carbon
dioxide (route A), while the mechanism via CC bond splitting is much more marked on Ru/CeO2. The catalyst
characterization indicates that both noble metal and CeO2 particles remain stable during the reaction.
Keywords: Catalytic Wet Air Oxidation; Stearic acid; Acetic acid; Fatty acids; Ruthenium; Platinum; Cerium oxide
Jan Petryk, Ewa Koakowska, Cobalt oxide catalysts for ammonia oxidation activated with cerium and lanthanum, Applied
Catalysis B: Environmental, Volume 24, Issue 2, 17 January 2000, Pages 121-128, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(99)00099-5.
Abstract: The effect of cerium and lanthanum oxides in cobalt oxide catalysts for both activity and selectivity in ammonia
oxidation was studied. The molar ratios of Ce/Co and La/Co in the catalysts were 0.02. All the catalysts were characterized
by XRD. The activity was measured in a fixed bed reactor at a temperature range of 720820C. Cerium oxide proved to be a
more efficient promoter than lanthanum oxide, both being advantageous. The selectivity of ammonia oxidation to NO over
Ce-containing sample was even as high as 97.7% and the selectivity to N2O was as low as 0.5%.
Keywords: Ammonia oxidation; Cobalt catalyst; Cerium; Lanthanum; Activity; Selectivity; Nitrous oxide
Adrin M.T Silva, Rita R.N Marques, Rosa M Quinta-Ferreira, Catalysts based in cerium oxide for wet oxidation of acrylic acid
in the prevention of environmental risks, Applied Catalysis B: Environmental, Volume 47, Issue 4, 20 February 2004, Pages
Abstract: Acrylic acid is a refractory compound for the non-catalytic wet oxidation (WO) process and can seriously damage
the environment when released in industrial effluents. Oxidation of acrylic acid by catalytic wet oxidation (CWO) was
studied in slurry conditions in a high-pressure batch reactor at 200 C and 15 bar of oxygen partial pressure. Several solid
cerium-based catalysts prepared in our laboratory were used (Ag/Ce, Co/Ce, Mn/Ce, CeO, MnO) and evaluated in terms of
activity, selectivity and stability. Mn/Ce shows the higher activity in 2 h with 97.7% reduction of total organic carbon (TOC)
followed by: MnO(95.5%)>Ag/Ce(85.0%)>Co/Ce(65.1%)>CeO(61.2%). Attempts were also carried out to analyze
the influence of different Mn/Ce molar ratios. High percentages of Mn lead to practically total organic carbon concentration
(TOC) abatements while low ratios lead to the formation of non-oxidizable compounds. Acrylic acid was readily degraded by
all the catalysts pointing out the high importance of using a catalytic process. pH was an indicator of the reaction pathway
and acetic acid was found as the major reaction intermediate compound; however it is completely oxidized after 2 h with
exception for Co/Ce, CeO and MnO. Carbon adsorption and leaching of metals were poorly found for Mn/Ce indicating high
stability. The catalyst microstructure after the reaction was analyzed and formation of whiskers of -MnO2 (or less probably
MnOOH) were observed at the catalyst surface. Therefore, Mn/Ce revealed to be a promising catalyst for the treatment of
effluents containing acrylic acid; nevertheless, its commercialization depends on further research.
Keywords: Environment; Pollution; Acrylic acid effluents; Wet oxidation; Catalysts; Manganese; Cerium
M. Abecassis-Wolfovich, R. Jothiramalingam, M.V. Landau, M. Herskowitz, B. Viswanathan, T.K. Varadarajan, Cerium

incorporated ordered manganese oxide OMS-2 materials: Improved catalysts for wet oxidation of phenol compounds,
Applied Catalysis B: Environmental, Volume 59, Issues 12, 8 July 2005, Pages 91-98, ISSN 0926-3373,
Abstract: Cryptomelane type manganese oxide OMS-2 material was synthesized by redox reaction between potassium
permanganate and manganese sulphate in acidic medium under reflux or hydrothermal crystallization conditions. Ce was
added by ion-exchange, impregnation or directly at crystallization stage. The chemical composition, structure, texture,
morphology and thermal stability of the materials were measured by EDX spectroscopy, XRD, N2-adsorption, SEM and TGA.
Results of the catalytic wet oxidation of phenol at 100 C indicate best performance of the well-crystallized octahedral
molecular sieve with cryptomelane structure where all the accessible potassium ions were exchanged for cerium cations.
OMS-2 materials containing pure CeO2 phase and excess of active oxygen species had lower stability, activity and capacity
for oxidative reactive adsorption of phenol. Implementation of Ce-exchanged crystalline OMS-2 catalyst improves the
wastewater treatment capacity by a factor of 1.52 and 3 compared with co-precipitated MnCe-oxide and activated
carbon, respectively.
Keywords: MnCe-oxide catalyst; Cryptomelane; Phenol; Wet oxidation
Baithy Mallesham, Putla Sudarsanam, Bellala Venkat Shiva Reddy, Benjaram M. Reddy, Development of cerium promoted
coppermagnesium catalysts for biomass valorization: Selective hydrogenolysis of bioglycerol, Applied Catalysis B:
Environmental, Volume 181, February 2016, Pages 47-57, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2015.07.037.
Abstract: Abstract
The selective hydrogenolysis of bioglycerol to 1,2-propanediol was investigated over a series of Ce-promoted Cu/Mg
catalysts, namely, Cu/Mg (1/9), Cu/Ce/Mg (1/1/5), Cu/Ce/Mg (1/3/5), and Cu/Ce/Mg (1/5/5) prepared by a coprecipitation
method. The physicochemical properties of the synthesized catalysts were analyzed by XRD, Raman, BET, BJH, XPS, NH3-
and CO2-TPD, and H2-TPR techniques. The XRD and BET surface area results indicated that addition of Ce to Cu/Mg sample
remarkably inhibits the crystal growth of CuO and improves the specific surface area. More number of oxygen vacancy
defects were found in the Cu/Ce3/Mg sample, as evidenced from Raman studies. The reducible nature of the Cu/Mg sample
was significantly enhanced after the Ce-incorporation. The NH3- and CO2-TPD results show that the acidbase properties of
the Ce-promoted Cu/Mg samples are highly dependent on the Ce-loading. Among the synthesized samples, the Cu/Ce3/Mg
sample exhibited higher concentration and superior strength of acidic sites. The achieved activity order of various catalysts
for glycerol hydrogenolysis is Cu/Mg < Cu/Ce1/Mg < Cu/Ce3/Mg < Cu/Ce5/Mg. The high surface area, higher
concentration of acid sites, abundant oxygen vacancies, and remarkable reducibility are found to be the key factors for the
observed superior performance of the Cu/Ce3/Mg catalyst. Notably, the Cu/Ce3/Mg catalyst could be used multiple times
for glycerol hydrogenolysis without considerable loss of activity.
Keywords: Bioglycerol; Hydrogenolysis; 1,2-Propanediol; Ce-promoted Cu/Mg catalyst; Characterization studies
L Xu, G Guo, D Uy, A.E ONeill, W.H Weber, M.J Rokosz, R.W McCabe, Cerium phosphate in automotive exhaust catalyst
poisoning, Applied Catalysis B: Environmental, Volume 50, Issue 2, 30 June 2004, Pages 113-125, ISSN 0926-3373,
Abstract: Conditions leading to cerium phosphate poisoning of both model and fully formulated automotive exhaust
catalysts have been investigated. Temperatures above 700 C favor the formation of cerium orthophosphate (CePO4) as do
rich engine operating conditions (i.e. excess fuel). No apparent differences were observed in the type or amount of cerium
phosphate produced by impregnating ceria with Pt, Pd, or Rh. Cerium phosphate is produced both by reaction of ceria with
gaseous H3PO4 (P2O5), and by reaction of ceria with other phosphorus compounds deposited on the catalyst (e.g.
aluminum and zinc phosphates). These results provide the first direct evidence of a decrease in oxygen storage capacity
associated with the irreversible conversion of CeO2 to CePO4, thus identifying CePO4 formation as a high-temperature
mode of catalyst deactivation.
Keywords: Cerium phosphate; Ceria; Monazite; Oxygen storage (OSC); Automotive catalyst; Poisoning
Suresh Maddila, Venkata D.B.C. Dasireddy, Ekemena O. Oseghe, Sreekanth B. Jonnalagadda, Ozone initiated dechlorination
and degradation of trichlorophenol using CeZr loaded metal oxides as catalysts, Applied Catalysis B: Environmental,
Volumes 142143, OctoberNovember 2013, Pages 129-141, ISSN 0926-3373,
Abstract: Abstract
Oxidative dechlorination and degradation of trichlorophenol (TCP) in aqueous system initiated by ozone and catalyzed by
varied loadings of ceriumzirconium oxide on metal oxides supports namely; Al2O3, SiO2 and TiO2 was investigated.
Catalyst materials were synthesized and characterized by using various surface characterization techniques including XRD,
BET, TPD, ICP, SEM, TEM and FT-IR. XRD showed that ceriumzirconia exists as three different phases on the surface of the
catalysts. SEM and SEMEDX indicated that ceriumzirconia oxide is well dispersed on the surface of the TiO2 with
compared to Al2O3 and SiO2 supports. TEM showed that particle size of CeZr is in the range of 4080 nm. Catalyst testing
was done as function of reaction time and pH in a semi batch reactor. The oxidation products formed in the reaction were
characterized by IR, 1H NMR and LCMS mass spectral data. Dihydroxyfumaric acid (DHFA) and oxalic acid (OA) were the
main oxidation products. The product distribution was dependent on the acidic character of the catalysts. Among the
catalysts tested, 2.5% CeZr/SiO2 showed good activity with 100% conversion in 4 h while others needed 5 h.
Keywords: Trichlorophenol; Ozone; CeriumZirconium oxide; Titania; Dihydroxyfumaric acid
Alessandra F. Lucrdio, Gregory Jerkiewicz, Elisabete M. Assaf, Cobalt catalysts promoted with cerium and lanthanum
applied to partial oxidation of methane reactions, Applied Catalysis B: Environmental, Volume 84, Issues 12, 25 October
Abstract: Catalysts of Co/Mg/Al promoted with Ce and La were tested in the catalytic partial oxidation of methane (POM)
reaction. The addition of promoters was made by anion-exchange. X-ray diffraction (XRD) confirmed the formation of
hydrotalcite phase for precursors. The mixed oxides were characterized as a mixture of Co3O4, periclase (Co, Al)MgO
and/or spinel structure (Mg, Co)Al2O4. In the catalytic POM reaction over the promoted catalysts, a reduction in the carbon
formation rate was found.
Keywords: Hydrotalcite; Cobalt; Promoter; Methane partial oxidation
Toms Garca, Benjamn Solsona, Stuart H. Taylor, Naphthalene total oxidation over metal oxide catalysts, Applied Catalysis
B: Environmental, Volume 66, Issues 12, 20 June 2006, Pages 92-99, ISSN 0926-3373,
Abstract: Metal oxide catalysts (CoOx, MnOx, CuO, ZnO, Fe2O3, CeO2, TiO2, Al2O3 and CuZnO) prepared by a precipitation
method have been characterised and tested for the total oxidation of naphthalene. The most effective catalyst for
naphthalene oxidation was CeO2 prepared by a homogeneous precipitation method with urea. Moreover, the cerium oxide
catalyst showed stable conversion with 100% selectivity to CO2 with time-on-stream at very low temperatures, 175 C. The
total oxidation of propane was also probed using the same range of catalysts and no correlation between naphthalene and
alkane oxidation was apparent, indicating that different mechanisms are involved. It was observed that whilst redox
properties were the main factor controlling propane total oxidation, the surface area and the strength of the bond between
adsorbed molecules and catalyst surface were also important parameters affecting naphthalene catalytic combustion.
Keywords: VOCs; PAHs; Catalytic oxidation; Metal oxides; Cerium oxide
S. Nousir, S. Keav, J. Barbier Jr., M. Bensitel, R. Brahmi, D. Duprez, Deactivation phenomena during catalytic wet air
oxidation (CWAO) of phenol over platinum catalysts supported on ceria and ceriazirconia mixed oxides, Applied Catalysis
B: Environmental, Volume 84, Issues 34, 1 December 2008, Pages 723-731, ISSN 0926-3373,
Abstract: Catalytic wet air oxidation (CWAO) of aqueous solution of phenol was carried out with pure oxygen at 160 C in a
stirred batch reactor on platinum supported oxide catalysts (Pt/CeO2c calcined at 650 and 800 C and Pt/CexZr1 xO2 with
x = 0.90, 0.75 and 0.50). The catalysts were characterized before (BET, FT-IR spectroscopy, hydrogen chemisorptions,
oxygen storage capacity (OSC)) and after reaction (TPO, elementary analysis, GCMS and DTATGA). The results
demonstrate a poisoning of the catalysts during CWAO reaction due to the formation of different forms of carbon deposit
on the materials: carbonates and polymeric carbon species. This poisoning phenomenon is limited by the introduction of
50% of zirconium into ceria lattice for the catalysts presenting the lowest surface area. Polymeric deposits play a major role
in the catalyst deactivation.
Keywords: Catalytic wet air oxidation; Phenol; Platinum; Cerium; Zirconium; Deactivation; Oxygen storage capacity; Carbon
deposit; Carbonates
Wei Liu, Adel F. Sarofim, Maria Flytzani-Stephanopoulos, Reduction of sulfur dioxide by carbon monoxide to elemental
sulfur over composite oxide catalysts, Applied Catalysis B: Environmental, Volume 4, Issues 23, 13 September 1994, Pages
167-186, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(94)00019-0.
(http://www.sciencedirect.com/science/article/pii/0926337394000190)
Abstract: The catalyst activity of fluorite-type oxide, such as ceria and zirconia, for the reduction of sulfur dioxide by carbon
monoxide to elemental sulfur can be significantly promoted by active transition metals, such as copper. More than 95%
elemental sulfur yield, corresponding to almost complete sulfur dioxide conversion, was obtained over a Cu-Ce-O oxide
catalyst with a feed gas of stoichiometric composition ([CO]/[SO2]=2) at temperatures above 450C. This type of mixed
metal oxide catalyst has stable activity and is resistant to water and carbon dioxide poisoning. XPS analysis found copper in
the Cu-Ce-O oxide in a reduced oxidation state (Cu1+, Cu0). The stable fluorite-type structure, regarded as the backbone
structure of the catalyst, existed in both the fresh and the spent catalyst. The high activity resulted from the strong
interaction of transition metal and fluorite oxide.
Keywords: Copper-cerium oxide; Elemental sulfur production; Fluorite oxide; Reduction; Sulfur dioxide
Yang Guo, Shuzhong Wang, Thomas Yeh, Phillip E. Savage, Catalytic gasification of indole in supercritical water, Applied
Catalysis B: Environmental, Volumes 166167, May 2015, Pages 202-210, ISSN 0926-3373,
Abstract: Abstract
We tested Ru/C, Pt/C, Pd/C, Pt/Al2O3, Pd/Al2O3, activated carbon, and NiRu/CeO2 catalysts for the gasification of indole
in supercritical water. All of the materials enhanced the gasification of this nitrogen-containing compound, but the
bimetallic catalyst, NiRu/CeO2, showed the highest activity for producing CO and CH4 and for converting indole. We
focused on this catalyst in more detail. The catalyst loading in the reactor has no effect on the H2 yield, but both CH4 and
CO2 yields decrease with decreased loading. Water density has no statistically significant effect on the yield of gas products,
but operating above the critical pressure of water is a prerequisite for the NiRu composite catalyst to reach a high
conversion of indole. The catalyst surface area and pore volume decrease from 5.91 m2 g1 and 0.0169 cm3 g1 to 2.86 m2
g1 and 0.0137 cm3 g1, respectively, after an SCWG reaction time of 180 min. NiO species were detected in both fresh
and used catalysts and may be due to oxidation of the reduced Ni metal during sample preparation for XPS analysis, and/or
a strong interaction between metal and support possibly leading to the formation of cationic Ni species. These results point
to potential benefits of using this bimetallic catalyst for SCWG of streams with recalcitrant N-containing compounds.
Keywords: Supercritical water gasification; Bimetallic catalyst, Nickel; Ruthenium; Cerium oxide.
F. Bimbela, J. brego, R. Puerta, L. Garca, J. Arauzo, Catalytic steam reforming of the aqueous fraction of bio-oil using Ni-
Ce/Mg-Al catalysts, Applied Catalysis B: Environmental, Volume 209, 15 July 2017, Pages 346-357, ISSN 0926-3373,
Abstract: Abstract
The performance of different Ni/Mg-Al catalysts modified with Ce was evaluated in the catalytic steam reforming of
aqueous fractions of bio-oil from biomass pyrolysis. The effects of several preparation methods for incorporating Ce as a
modifier (co-precipitation, impregnation and direct thermal decomposition of the salt precursors), the Ce content (05
wt.%) and the feed streams (three different aqueous fractions from bio-oil) on the catalyst performance were examined,
and it was found that the stability and activity of the catalysts were significantly influenced by all these factors. In general,
the addition of Ce to a reference Ni/Mg-Al catalyst improved the overall carbon conversion to gas and the yield to H2 as
well as enhancing the catalyst stability in the steam reforming of aqueous fractions of bio-oils. The best preparation method
was impregnation and the optimal Ce content was found to be 0.5 wt.%. Much higher initial carbon conversion to gas and
initial H2 yields was obtained using bio-oils derived from pine than those derived from poplar. A very low coke formation,
103 mg C/(g of catalyst g of organics in the aqueous fraction reacted), was achieved using the optimized catalyst, 0.5 wt.%
Ce prepared by impregnation.
Keywords: Bio-oil; Steam reforming; Nickel; Cerium; Hydrogen
Hailong Li, Chang-Yu Wu, Ying Li, Junying Zhang, Superior activity of MnOx-CeO2/TiO2 catalyst for catalytic oxidation of
elemental mercury at low flue gas temperatures, Applied Catalysis B: Environmental, Volumes 111112, 12 January 2012,
Pages 381-388, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2011.10.021.
Abstract: TiO2 supported Mn-Ce mixed oxides (Mn-Ce/Ti) synthesized by an ultrasound-assisted impregnation method
were employed to oxidize elemental mercury (Hg0) at low temperatures in simulated low-rank (sub-bituminous and lignite)
coal combustion flue gas and corresponding selective catalytic reduction (SCR) flue gas. The catalysts were characterized by
BET surface area analysis, X-ray diffraction (XRD) measurement and X-ray photoelectron spectroscopy (XPS) analysis. The
combination of MnOx and CeO2 resulted in significant synergy for Hg0 oxidation. The Mn-Ce/Ti catalyst was highly active
for Hg0 oxidation at low temperatures (150250 C) under both simulated flue gas and SCR flue gas. The dominance of
Mn4+ and the presence of Ce3+ on the Mn-Ce/Ti catalyst were responsible for its excellent catalytic performance. Hg0
oxidation on the Mn-Ce/Ti catalyst likely followed the LangmuirHinshelwood mechanism, where reactive species on
catalyst surface react with adjacently adsorbed Hg0 to form Hg2+. NH3 consumed the surface oxygen and limited the
adsorption of Hg0, hence inhibiting Hg0 oxidation over Mn-Ce/Ti catalyst. However, once NH3 was cut off, the inhibited
mercury oxidation activity could be completely recovered in the presence of O2. This study revealed the possibility of
simultaneously oxidizing Hg0 and reducing NOx at low flue gas temperatures. Such knowledge is of fundamental
importance in developing effective and economical mercury and NOx control technologies for coal-fired power plants.
Keywords: Mercury; Manganese oxide; Cerium oxide; Catalyst; Coal combustion
Jian Liu, Zhen Zhao, Jiqiu Wang, Chunming Xu, Aijun Duan, Guiyuan Jiang, Qing Yang, The highly active catalysts of
nanometric CeO2-supported cobalt oxides for soot combustion, Applied Catalysis B: Environmental, Volume 84, Issues 12,
25 October 2008, Pages 185-195, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2008.03.017.
Abstract: Nanometric CeO2-supported cobalt oxide materials with variable Co/Ce atomic ratios were prepared by the
method of ultrasonic-assisted incipient-wetness impregnation. The catalytic behaviors of a series of CoOx/nmCeO2
catalysts have been studied for soot combustion. XRD, XPS, Raman, UVvis DRS and FT-IR spectroscopy characterization
results indicated that CoO or cobaltcerium solid solutions were formed in the samples with the low Co loading amount,
while Co3O4 was formed in the samples with high Co loading amount. CoOx/nmCeO2 catalysts can further promote soot
combustion in contrast to nanometric CeO2. This improvement is related to the increase in the redox properties of the
catalysts brought about by loading cobalt oxide on nanometric CeO2. The TPR experiment results under hydrogen
atmosphere indicated that the presence of Co decreases the reduction temperature of catalyst from 555 C (nanometric
CeO2) to 286 C (Co20/nmCeO2). On the other hand, attributing to nanoparticle effect and NO2 formation, Com/nmCeO2
oxide catalysts prepared in this study have very high activity for soot combustion. The best catalytic activity was obtained
over Co20/nmCeO2 catalyst that T10, T50, T90 were 286 C, 368 C, 418 C, respectively, and S C O 2 m was 98.8%.
Compared with the blank case (i.e., without catalyst) for soot combustion, T50 decreased by more than 200 C and S C O 2
m increased by 40% point. And this catalytic activity for the combustion of soot particle is as good as supported Pt catalysts,
which is the best catalyst system so far reported for soot combustion under loose contact conditions. This temperature of
soot combustion can ensure immediate activation of the catalyst on the filter under the conditions of diesel engine
emissions.
Keywords: Nanometric CeO2-supported cobalt oxides; Catalysts; Soot combustion; Ceria; Cobalt
Mara Ariela Peralta, Mara Soledad Zanuttini, Carlos Alberto Querini, Activity and stability of BaKCo/CeO2 catalysts for
diesel soot oxidation, Applied Catalysis B: Environmental, Volume 110, 2 November 2011, Pages 90-98, ISSN 0926-3373,
Abstract: The activity and stability of Ba,K,Co/CeO2 catalyst in the diesel soot oxidation reaction are studied. Different
modes of preparation are analyzed, varying both the cobalt precursor and its order of impregnation. In order to study the
stability in a diesel exhaust atmosphere, the catalysts were pretreated in streams of CO2, H2O, NO and SO2. The fresh and
the treated catalysts were characterized by FTIR and XRD techniques. The catalytic activity was measured by TPO of soot
catalyst mixtures. The tight contact was used to analyze the intrinsic activity. It was found that the activity was higher for
the catalysts prepared using Co(NO3)2 compared with the catalysts prepared using Co(AcO)2. This is because in the former,
KNO3 is present on the catalyst, being this compound very active for this reaction. The thermal stability is lower for the
catalyst prepared with Co(NO3)2. This catalyst displays a higher K lost when treated at high temperature. When K is present
as K2CO3, as is the case of the catalysts prepared with Co(AcO)2, the thermal stability is higher since K2CO3 is less volatile
than KNO3. All the catalysts are stable in the presence of mixtures of (CO2 + H2O + NO + O2) having a composition similar
to a real diesel exhaust. Under these conditions, the K mantains its original chemical state, either carbonate or nitrate,
depending on the precursor used in the catalyst preparation. In presence of SO2, all the catalysts deactivate due to K2SO4
formation, which is not active for soot combustion. However, the sensitivity to SO2 depends on the precursors used to
prepare the catalyst. The Ba,K,Co/CeO2 catalyst prepared impregnating Co(NO3)2 on the Ba,K/CeO2 catalyst has a higher
resistance to the deactivation by SO2, since the following reaction occurs: Ba ( NO 3 ) 2 + K 2 SO 4 BaSO 4 + KNO 3 ,
which implies that active KNO3 will dissapear slower from the catalytic surface, thus maintaining the activity. TPO
experiments of the catalyst in loose contact with soot were also carried out. The Ba,K,Co/CeO2 catalyst prepared
impregnating Co(NO3)2 on the Ba,K/CeO2 catalyst showed the higher activity in loose contact mode.
Keywords: Diesel soot; Cobalt; Potassium; Barium; Cerium oxide; Catalyst stability
Bahaa M. Abu-Zied, Wilhelm Schwieger, Andr Unger, Nitrous oxide decomposition over transition metal exchanged ZSM-5
zeolites prepared by the solid-state ion-exchange method, Applied Catalysis B: Environmental, Volume 84, Issues 12, 25
October 2008, Pages 277-288, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2008.04.004.
Abstract: This paper studied nitrous oxide decomposition over a series of transition metal exchanged ZSM-5 zeolites
prepared by solid-state ion-exchange method. Crystallographic structure of the catalysts has been investigated with the aid
of XRD analysis. The texture of the prepared catalysts was investigated using nitrogen sorption. FTIR measurements
applying pyridine as a probe molecule have been carried out in order to investigate the nature of the acid sites of the
different catalysts. In situ electrical conductivity measurements were carried out in order to relate the activity of this series
of catalysts to their electrical conductivity variation in the presence of N2O. The obtained results revealed that the N2O
decomposition activity is related to the relative conductivity decrease upon the admission of N2O over metal exchanged
ZSM-5 zeolites. Further studies have been performed over Co-, Cu- and Fe-ZSM-5 catalysts since they showed the highest
activity patterns among all the tested catalysts. Such studies included the effect of changing Si/Al ratio, the exchange level,
the calcination temperature and the milling time.
Keywords: Nitrous oxide; Solid-state ion-exchange; Co-ZSM-5; Cu-ZSM-5; Fe-ZSM-5
Shinji Iwamoto, Ryosuke Takahashi, Masashi Inoue, Direct decomposition of nitric oxide over Ba catalysts supported on
CeO2-based mixed oxides, Applied Catalysis B: Environmental, Volume 70, Issues 14, 31 January 2007, Pages 146-150, ISSN
0926-3373, https://doi.org/10.1016/j.apcatb.2006.01.016.
Abstract: The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was
examined in the absence and presence of O2. Among the Ba catalysts supported on single-component metal oxides,
Ba/Co3O4 and Ba/CeO2 showed high NO decomposition activities, while Ba/Al2O3, Ba/SiO2, and Ba/TiO2 exhibited quite
low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found
that the activities were significantly enhanced using CeMn mixed oxides as support materials. XRD results indicated the
formation of CeO2MnOx solid solutions with the cubic fluorite structure. O2-TPD of the CeO2MnOx solid solutions
showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO2MnOx solid
solutions were larger than those of pure CeO2 and Mn2O3. These effects caused by the addition of Mn are responsible for
the enhanced activities of the Ba catalysts supported on CeMn mixed oxides.
Keywords: NO decomposition; Barium catalyst; CeMn oxide; Solid solution
Wei Li, Shun Zhao, Bin Qi, Yang Du, Xiaohong Wang, Mingxin Huo, Fast catalytic degradation of organic dye with air and
MoO3:Ce nanofibers under room condition, Applied Catalysis B: Environmental, Volume 92, Issues 34, 9 November 2009,
Abstract: One-dimensional Ce doped MoO3 nanofibers with different Ce doping amount have been synthesized by a
combination method of solgel process and electrospinning technique. X-ray diffraction (XRD), X-ray photoelectron
spectrum (XPS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) were used to
characterize the resulting samples. These fibers are interesting for a number of catalytic applications. The best catalytic
activity was obtained over 11.86 wt.% CeO2-doped MoO3 with 98% degradation effect of 0.3 g L1 Safranin-T by air under
room condition towards complete degradation products such as HCO3 and NO3 within 20 min. The leaching test showed
that this MoO3:Ce nanofiber catalyst has an excellent stability and can be used as a rapid heterogeneous catalyst for about
ten times by simply treatment.
Keywords: Catalytic wet air oxidation; Molybdenum oxide; Cerium oxide; Degradation of dye; Nanofibers
Iljeong Heo, Jin Woo Choung, Pyung Soon Kim, In-Sik Nam, Young Il Song, Chi Bum In, Gwon Koo Yeo, The alteration of the
performance of field-aged Pd-based TWCs towards CO and C3H6 oxidation, Applied Catalysis B: Environmental, Volume 92,
Issues 12, 19 October 2009, Pages 114-125, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2009.07.016.
Abstract: The deactivation of a three-way catalyst (TWC) included in warm-up catalytic converters (WCC) employed in
passenger vehicles has been examined with respect to the catalyst field mileage by drivers. By a sweep test (ST) under the
A/F oscillation of 1 Hz simulating the actual operation of a gasoline engine, the gradual deactivation of CO oxidation activity
under rich condition over the Pd TWCs customer-aged was clearly observed with respect to the catalyst mileage, while the
oxidation activity of C3H6 had been hardly altered. No proportional dependence of the deactivation of the CO and C3H6
oxidation activity on the catalyst mileage, however, was determined by both a steady-state sweep test (st-ST) and a light-off
test (LOT) without A/F perturbation, although the initial deactivation of both reactions by both test modes was apparent.
The sintering of noble metal (NM) itself might not be the only cause for the deactivation of TWC with respect to the catalyst
aging mileage. The gradual alteration of the oxygen storage capacity (OSC) of TWC, mainly due to the degradation of the
oxygen storage components and the weakness of the Pd-Ce interaction, is also the cause for TWC deactivation, particularly
for the CO oxidation reaction under rich condition. No deactivation of the oxidation reaction of C3H6 by ST, regardless of
the catalyst mileages is likely due to the strong oxidative capability of Pd toward hydrocarbons.
Keywords: TWC; Catalyst deactivation; Cerium-zirconium mixed oxide; OSC; Pd-Ce interaction; Pd sintering; Poisoning
Carlos A. Franchini, Wladimir Aranzaez, Andra M. Duarte de Farias, Gina Pecchi, Marco A. Fraga, Ce-substituted LaNiO3
mixed oxides as catalyst precursors for glycerol steam reforming, Applied Catalysis B: Environmental, Volume 147, 5 April
Abstract: Abstract
Mixed oxides of general formula La1xCexNiO3 were prepared by self-combustion method and taken as precursors of Ni-
supported catalysts for an experimental investigation of steam reforming of glycerol. The mixed oxide precursors and the
corresponding derived fresh catalysts were characterized by XRD, TPR and TEM while the used catalysts were investigated
by FE-SEM, TEM and TPO/TGA-MS. All catalysts were investigated on glycerol steam reforming with special focus on the
resistance to deactivation. The precursors led to active catalysts, producing hydrogen-rich gas stream. Deactivation was
seen to occur irrespective of catalyst composition. Substitution of 50% La by Ce provided more deactivation-resistant
catalyst, allowing only minor amount of more reactive carbon deposits. It was suggested to be associated with the
formation of CeO2La2O3 solid solutions, as evidenced by XRD, which would act as an oxygen buffer and therefore
facilitate the removal of carbon deposits onto the catalyst surface.
Keywords: Hydrogen production; Nickel catalyst; Deactivation; Carbon deposition
David R. Sellick, Asuncin Aranda, Tomas Garca, Jos M. Lpez, Benjamn Solsona, Ana M. Mastral, David J. Morgan, Albert
F. Carley, Stuart H. Taylor, Influence of the preparation method on the activity of ceria zirconia mixed oxides for
naphthalene total oxidation, Applied Catalysis B: Environmental, Volumes 132133, 27 March 2013, Pages 98-106, ISSN
Abstract: Cerium/zirconium mixed oxides, with different Ce/Zr ratios, have been synthesised by a co-precipitation method
using two different precipitating agents (sodium carbonate and urea) and tested for the total oxidation of naphthalene.
Catalysts were characterised by N2 adsorption, XRD, Raman, TPR, XPS and DRIFTS. Ceria prepared by carbonate
precipitation had low activity and this is likely to be related to the high concentration of residual surface carbonate that
covers catalytic sites and inhibits reaction. For carbonate precipitation, increasing the Zr content to 1% resulted in a
significant increase of activity, which is related to the decrease of surface carbonate. Increasing the Zr content up to 50%
resulted in catalysts more active than ceria, but activity decreased as Zr content increased. This was in spite of increasing
the number of oxygen vacancies, and this effect has been related to the decrease in the number of surface hydroxyl groups,
which favours naphthalene adsorption. Ceria prepared by urea precipitation was markedly more active than that produced
by carbonate precipitation. The urea-derived catalyst with 1% Zr is marginally more active than pure ceria, whilst for higher
Zr contents activity was marginally lower. Two factors can account for these observations; they are the increase of oxygen
vacancies contributing positively to activity and the opposing negative effect of decreasing the number of surface hydroxyl
groups when the zirconium content increases.
Keywords: VOCs; Catalytic oxidation; Ceria; Zirconia; Naphthalene; PAHs
Lenka Matjov, Pavel Topka, Ludk Kalua, Satu Pitkaho, Satu Ojala, Jana Galov, Riitta L. Keiski, Total oxidation of
dichloromethane and ethanol over ceriazirconia mixed oxide supported platinum and gold catalysts, Applied Catalysis B:
Environmental, Volumes 142143, OctoberNovember 2013, Pages 54-64, ISSN 0926-3373,
Abstract: Abstract
Ce0.5Zr0.5O2 prepared by solgel method was used as a support for platinum and gold catalysts that were tested in total
oxidation of dichloromethane and ethanol. It was shown that the deposition of platinum and gold on Ce0.5Zr0.5O2 support
enhanced the reducibility of surface ceria. This phenomenon was more pronounced for platinum catalysts. Introduction of
both noble metals led to the decrease of catalysts acidity. In total oxidation of dichloromethane, the noble metal catalysts
showed lower catalytic performance compared to parent Ce0.5Zr0.5O2, due to lower amount of acid sites that act as
chemisorption sites for chlorinated compounds. On the other hand, platinum catalysts exhibited significantly enhanced
selectivity to CO2 in comparison with the Ce0.5Zr0.5O2 support. In total oxidation of ethanol, the deposition of platinum on
Ce0.5Zr0.5O2 resulted in a significant increase in catalytic performance, while the introduction of gold had only a minor
effect. Moreover, the positive effect of higher noble metal loading on catalytic performance was more pronounced for Pt
catalysts. For all investigated catalysts, the temperature of the H2-TPR peak corresponding to the reduction of surface ceria
correlated with their catalytic performance. The influence of Pt loading on the mechanism of ethanol oxidation was
revealed. Based on the concentration profiles of individual by-products/products detected by on-line FTIR analysis, the
possible pathways of their formation were suggested. Both noble metal catalysts exhibited higher selectivity to CO2 than
the pristine Ce0.5Zr0.5O2.
Keywords: Gold; Platinum; Ceria; Zirconia; VOC oxidation
Laura del Ro, Gregorio Marbn, Stainless steel wire mesh-supported potassium-doped cobalt oxide catalysts for the
catalytic decomposition of nitrous oxide, Applied Catalysis B: Environmental, Volume 126, 25 September 2012, Pages 39-46,
ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2012.06.022.
Abstract: Abstract
Structured catalysts consisting of potassium-doped cobalt oxide supported on stainless steel wire mesh were tested for the
decomposition of N2O under dry and wet conditions. The cobalt oxide catalysts were prepared by the ammonia-
evaporation-induced method. Of the several doping procedures tested, dropwise impregnation with potassium carbonate
solutions provided the best catalytic results at lower K/Co molar ratios. Kinetic analysis of a potassium-doped catalyst
yielded a reaction order on the N2O partial pressure slightly below unity (0.87). The activation energy values and the
natural logarithms of the pre-exponentials factors for the different catalysts followed the classical compensation effect. This
effect may be the result of a combination of competing reactions on different groups of active centers. Thus, cobalt ions
affected by potassium display a low activation energy (40 kJ/mol), whereas cobalt atoms unaffected by potassium display
a higher activation energy equal to that of the undoped catalysts (106 kJ/mol). The catalytic activity of the catalysts in
N2O decomposition increases with the amount of reducible Co3+ ions, although there does not appear to be a direct
relation between the amount of Co3+ ions and the textural and crystal properties of the catalysts. The addition of water
produces some inhibition of the N2O decomposition reaction on K-doped catalysts, although catalytic activity is completely
restored when the water is removed from the reaction stream. The catalysts prepared in this work were found to be among
the most active, selective and stable catalysts reported in the literature.
Keywords: Co3O4; N2O decomposition; Stainless steel mesh; Potassium
Kamolwan Rintramee, Karin Fttinger, Gnther Rupprechter, Jatuporn Wittayakun, Ethanol adsorption and oxidation on
bimetallic catalysts containing platinum and base metal oxide supported on MCM-41, Applied Catalysis B: Environmental,
Volumes 115116, 5 April 2012, Pages 225-235, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2011.11.050.
Abstract: Ethanol pollutant either emitted from ethanol-fueled vehicles at low temperature or released from industries as
volatile organic compound (VOC) could be removed by catalytic oxidation. This work investigated adsorption of ethanol on
bimetallic catalysts containing Pt with loading of 0.5 wt% and Co, Cu, or Mn with loading of 15 wt% supported on RH-MCM-
41 by temperature programmed desorption (ethanol-TPD) and thermogravimetric analysis (ethanol-TGA). Evolution of
gases from the ethanol-TPD indicated the role of oxides as potential oxygen supplier in ethanol oxidation. On the
monometallic catalyst containing oxides of Co, Cu, and Mn on MCM-41, the oxide of Co was the better oxygen supplier than
that of the others to react with the adsorbed ethanol to produce CO2. Furthermore, the bimetallic 0.5Pt15Co/RH-MCM-41
with cobalt in the form of Co3O4, showed the highest ethanol adsorption and CO2 desorption. Consequently, ethanol
oxidation was studied on the bimetallic 0.5Pt15Co/RH-MCM-41 by in situ infrared spectroscopy in which intermediates
and reaction pathways were proposed when ethanol and oxygen were flowed through the cell at various temperatures.
Results from the ethanol oxidation in a fixed bed flow reactor showed that the bimetallic catalyst gave lower ethanol
conversion than monometallic Pt but seemed to be more stable than the monometallic Pt catalyst.
Keywords: Ethanol adsorption; Ethanol oxidation; Bimetallic catalyst; MCM-41; Platinum; Cobalt
Stanko Hoevar, Ura Opara Kraovec, Boris Orel, Antonino S Aric, Hasuck Kim, CWO of phenol on two differently prepared
CuOCeO2 catalysts, Applied Catalysis B: Environmental, Volume 28, Issue 2, 6 November 2000, Pages 113-125, ISSN 0926-
3373, https://doi.org/10.1016/S0926-3373(00)00167-3.
Abstract: The activity and selectivity of the Ce1xCuxO2 catalysts prepared by co-precipitation and by solgel methods
were studied in the catalytic wet oxidation (CWO) of phenol at 432 K and at 7.3 bar oxygen partial pressure in a semibatch
CST reactor. Both types of catalysts are very stable under hydrothermal reaction conditions at low pH values. It has been
found that activity and selectivity increase with the dispersion of copper oxide phase on the cerium oxide. While the Cu
content was equal in both types of catalysts, the samples prepared by solgel technique are up to four times more active
and about 25% more selective toward CO2 formation than the samples prepared by co-precipitation at given reaction
conditions. The heterogeneously initiated radical mechanism results in autocatalytic type kinetics. The activity and
selectivity depend on the initial concentration of heterogeneously catalytically formed radicals in each subsequent
oxidation step. Between these steps the radicals react further on in liquid phase.
Keywords: Cerium oxide; Copper oxide; Co-precipitation; Solgel; XRD; XPS; Phenol; Catalytic wet oxidation
Lyubov A Isupova, Galina M Alikina, Olga I Snegurenko, Vladislav A Sadykov, Sergei V Tsybulya, Monolith honeycomb mixed
oxide catalysts for methane oxidation, Applied Catalysis B: Environmental, Volume 21, Issue 3, 5 July 1999, Pages 171-181,
ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(99)00024-7.
Abstract: Low cost and active monolith catalysts for methane oxidation were developed. The preparation procedure
includes the mechanochemical activation of mixed LaCe rare-earth oxides and transition metal oxides, followed by their
annealing, kneading with the binder, extrusion of plastic pastes, drying and calcination. For disordered oxide composites
with the perovskite- or fluorite-like structures intermixed with alumina, their specific catalytic activity in the methane
oxidation weakly depends upon the nature of transition metal cations (Mn, Ni, Fe, Co). In the temperature range of the
methane + air mixture ignition (500C), the performance of optimized monolithic catalysts is mainly determined by their
specific surface area controlled by the binder composition and preparation procedure.
Keywords: Methane; Oxidation; Kinetics; Mixed oxide; Monolith; Preparation
T.A. Zepeda, A. Martinez-Hernndez, R. Guil-Lpez, B. Pawelec, Preferential CO oxidation in excess of hydrogen over
Au/HMS catalysts modified by Ce, Fe and Ti oxides, Applied Catalysis B: Environmental, Volume 100, Issues 34, 20 October
Abstract: The effect of the modification of HMS (hexagonal mesoporous silica) support with Fe3+, Ce4+ or Ti4+ ions on the
physico-chemical and catalytic properties of mesoporous Au/HMS catalyst was evaluated in the preferential oxidation
(PROX) of CO, in hydrogen-rich stream (50 vol.% H2) and in the total CO oxidation (TOX) reaction. The bare supports were
prepared via neutral S0I0 templating route, employing one pot synthesis, whereas the supported gold catalysts were
prepared by the depositionprecipitation method. The reduced and spent Au catalysts have been studied by different
techniques such as N2 physisorption, oxygen storage capacity (OSC), XRD, HRTEM, hydrogen chemisorption (by TPD-H2),
DRS UVvis, Mssbauer and XPS spectroscopic techniques. Among the catalysts studied, Au/HMSFe recorded the highest
activity and stability for total CO oxidation. The XPS and DRS UVvis data suggest that the active-sites configuration of this
catalyst during this reaction could be small gold particles and ionic gold species stabilized by the support. The Au/HMSFe
catalyst was also able to oxidize CO selectively in a hydrogen-rich gas mixture (PROX reaction) at a relevant temperature to
hydrogen fuel cell applications (T50 = 83 C). Additionally, the Au/HMSFe sample recorded the lowest hydrogen oxidation
(undesired reaction) during the CO-PROX reaction in excess hydrogen. From the catalyst activitystructure correlation, the
main factors influencing the superior catalytic behaviour of this sample in the CO-PROX reaction are (i) its largest Au species
surface exposure, as determined by XPS for the spent catalysts; (ii) the largest population of small Au particles, as
determined by HRTEM for the freshly reduced samples; (iii) the large oxygen and hydrogen storage capacities, and (iv) the
lowest deactivation by the formation of surface coke species, as determined by coke burning followed by TGA technique.
Keywords: CO oxidation; CO preferential oxidation; Mesoporous silica; HMSCe; HMSFe; HMSTi; Au catalysts
Tianli Zhu, Andreas Dreher, Maria Flytzani-Stephanopoulos, Direct reduction of SO2 to elemental sulfur by methane over
ceria-based catalysts, Applied Catalysis B: Environmental, Volume 21, Issue 2, 7 June 1999, Pages 103-120, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(99)00016-8.
Abstract: The catalytic reduction of SO2 to elemental sulfur by methane was studied over ceria-based catalysts. Both La-
doped and undoped ceria were found to catalyze the SO2 reduction by CH4 in the temperature range of 550750C at
atmospheric pressure and with feed gases containing a molar ratio of CH4/SO2 = 0.53. At temperatures below 550C, the
catalyst surface is capped by SO2. The reaction light-off coincides with the threshold temperature for sulfate
decomposition. Various SO2/CH4/H2O gas mixtures were used to study the catalyst activity and selectivity to elemental
sulfur. The incorporation of nickel and copper improves the wet activity of Ce(La)Ox catalysts. Also, the addition of a low
amount (5 at.%) of copper or nickel into La-doped ceria, Ce(La)Ox, had a markedly different effect on the catalyst selectivity
under fuel-rich conditions. The CuCe(La)Ox catalyst has higher selectivity to elemental sulfur and complete oxidation
products (H2O, CO2), while NiCe(La)Ox favors the formation of H2S and partial oxidation products (CO). The catalyst
activity/selectivity studies were complemented by SO2 uptake experiments and by reduction of the as-prepared and pre-
sulfated catalysts in methane, both isothermally and in the TPR mode. The initial rate of reduction of pre-sulfated catalysts
with methane is similar for Ce(La)Ox, CuCe(La)Ox and NiCe(La)Ox in the temperature range of 500-700C. Activation of
methane on these surfaces requires partial sulfate decomposition.
Keywords: Elemental sulfur recovery; Catalytic sulfur dioxide reduction; Methane-TPR; Copper and cerium oxide; Nickel and
cerium oxide; SO2 uptake
S. Parres-Esclapez, M.J. Illn-Gmez, C. Salinas-Martnez de Lecea, A. Bueno-Lpez, On the importance of the catalyst redox
properties in the N2O decomposition over alumina and ceria supported Rh, Pd and Pt, Applied Catalysis B: Environmental,
Volume 96, Issues 34, 7 June 2010, Pages 370-378, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2010.02.034.
Abstract: Rh, Pd and Pt have been supported on -Al2O3, pure CeO2 and La- or Pr-doped CeO2, and these catalysts have
been tested for N2O decomposition. The effect of CO and O2 in the feed has been studied. The characterisation techniques
used were Raman spectroscopy, XRD, N2 adsorption at 196 C, H2-TPR and TEM. The catalytic activity for N2O
decomposition of the noble metals follows the trend Rh > Pd > Pt, and the support affects significantly the activity.
For CeO2-containing catalyst, a relationship between N2O decomposition capacity and H2 reduction of ceria has been
found, the easier is the reduction the higher is the catalytic activity. The rate-limiting step of the N2O decomposition
mechanism over noble metal/ceria catalysts seems to be the reduction of the catalytic active sites. For Rh catalysts, ceria
supports are involved actively in the decomposition of N2O, and all the ceria-based supports improve the catalytic activity
of Rh with regard to -Al2O3 due to the redox properties of ceria. The Pd catalysts with pure and doped ceria support
showed similar activity, this being higher than that of Pd/-Al2O3. Pt/CeO2 is the most active catalyst among those of Pt,
but ceria doping by La or Pr has a negative effect on the activity. The most active catalyst among those prepared in this
study is Rh/CeO2(Pr).
Keywords: N2O decomposition; Noble metal catalyst; Ceria support; Ceriumpraseodymium; Ceriumlanthanum
A.E Palomares, J.M Lpez-Nieto, F.J Lzaro, A Lpez, A Corma, Reactivity in the removal of SO2 and NOx on Co/Mg/Al mixed
oxides derived from hydrotalcites, Applied Catalysis B: Environmental, Volume 20, Issue 4, 5 April 1999, Pages 257-266, ISSN
0926-3373, https://doi.org/10.1016/S0926-3373(98)00121-0.
Abstract: Metal containing hydrotalcites, where metal oxides present redox properties and hydrotalcite shows a basic
character, appear to be new important environmental catalysts for the removal of SOx and NOx. Redox and basic properties
of a mixed Co/Mg/Al oxide derived from hydrotalcites are tuned in order to achieve the optimal catalytic behavior required.
This sample has been characterized showing that cobalt is present in two forms, as isolated and well dispersed
paramagnetic ions, and as very small Co-containing particles (in the nanometric range), with an internal antiferromagnetic
ordering at low temperature. The redox properties of cobalt allow the reduction of NO with propane at high temperatures
and in presence of oxygen. The reduced cobalt species are proposed as the active sites. Nevertheless, for the removal of
SO2 and contrary to the case of Cu/Mg/Al samples, the addition of an oxidant as cerium oxide on Co/Mg/Al is necessary in
order to oxidize SO2 to SO3. In this case, similar results than those obtained with previously reported catalyst, i.e. cerium or
coppercerium hydrotalcite, are obtained. These results indicate that this catalyst could be an adequate material for the
simultaneous removal of SO2 and NOx in a FCC unit.
Keywords: Hydrotalcites; Reactivity; SOx; NOx
W.E.J. van Kooten, B. Liang, H.C. Krijnsen, O.L. Oudshoorn, H.P.A. Calis, C.M. van den Bleek, Ce-ZSM-5 catalysts for the
selective catalytic reduction of NOx in stationary diesel exhaust gas, Applied Catalysis B: Environmental, Volume 21, Issue 3,
5 July 1999, Pages 203-213, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(99)00023-5.
Abstract: This paper describes the preparation of Ce-ZSM-5 SCR catalysts for stationary diesel engine applications, such as
marine diesels, and the performance of these catalysts with ammonia as a reducing agent in both simulated and real diesel
exhaust gas. Catalysts prepared by ion exchange in aqueous solution, show an increasing NOx conversion with increasing
cerium ion-exchange level at all temperatures tested (NOx conversion > 80% in the temperature range 350500C at a
gas hourly space velocity (GHSV) of 40.000 h1 with simulated diesel exhaust). Ce-ZSM-5 does not convert nitric oxide or
ammonia into the greenhouse gas nitrous oxide. Moreover, Ce-ZSM-5 does not exhibit ammonia slip up to ammonia/nitric
oxide feed ratios of 1.4, the excess ammonia being converted to nitrogen. Ce-ZSM-5 extrudates with 50 wt.% alumina
binder do not show ammonia slip up to ammonia/nitric oxide feed ratios of at least 1.1. With diesel exhaust gases of a
three-cylinder, 10 kW diesel engine, Ce-ZSM-5 can reach about 70% NOx conversion at 500C at a GHSV of 50.000 h1.
Deactivation of the catalysts in real diesel exhaust occurs mainly in the first 60 h of operation resulting in stable catalysts
which show about 40% NOx conversion at 450C, at a GHSV of 32.000 h1. The preparation of Ce-ZSM-5 via solid-state ion
exchange results in a remarkably active catalyst.
Keywords: ZSM-5; Cerium; SCR; NOx removal; Ammonia; Diesel; Deactivation; Solid-state ion exchange
Davide Ferri, Lucio Forni, Methane combustion on some perovskite-like mixed oxides, Applied Catalysis B: Environmental,
Volume 16, Issue 2, 27 March 1998, Pages 119-126, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(97)00065-9.
Abstract: Some perovskite-like mixed oxides of general formula La1xAxBO3 were prepared by the amorphous citrate
method and tested for methane combustion within the 300600C temperature range. Substitution at A-site with a bivalent
(Eu, Sr) or tetravalent (Ce) metal cation led to a decrease or increase of catalytic activity, respectively. La0.9Ce0.1CoO3
proved to be the most active catalyst, showing complete conversion at 500C. The nature of the metal cation introduced
modifies the oxidation state of cobalt, which leads to the formation of cationic or anionic vacancies. TPD-MS analysis
confirmed that the catalytic activity is related to the oxygen storage properties of the catalyst. The substitution at B-site
(B=Fe, Co, Ni) allowed to find interesting correlations between catalytic activity and the temperature Tmax of maximum
oxygen desorption rate.
Keywords: Perovskite as catalyst; Methane combustion; Oxygen mobility
Russell S. Drago, Krzysztof Jurczyk, David J. Singh, Vaneica Young, Low-temperature deep oxidation of hydrocarbons by
metal oxides supported on carbonaceous materials, Applied Catalysis B: Environmental, Volume 6, Issue 2, 1 July 1995,
Pages 155-168, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(95)00009-7.
Abstract: First row transition metal oxides supported on carbonaceous materials are shown to be effective in the low
temperature deep oxidation of hexane, butane and toluene to carbon dioxide and water. The oxides of manganese, cobalt,
copper and zinc were supported on several different types of carbon, out of which it was found that manganese and cobalt
oxide supported on Ambersorb 572 were most durable. In addition, Ambersorb 563 and Ambersorb 572 were thermally
stable under the reaction conditions. Mechanistic studies in cobalt oxide/Ambersorb 572 indicate a synergism between
the metal oxide and carbonaceous material. A catalytic cycle has been described, involving a CoII/CoIII couple, and the
stabilizing effect of the support on the reduced form of the metal oxide.
Keywords: Hydrocarbon oxidation; Carbon support; Deep oxidation; Ambersorb; Hydrocarbons
Jerry C. Summers, Stphane Van Houtte, Dimitrios Psaras, Simultaneous control of particulate and NOx emissions from
diesel engines, Applied Catalysis B: Environmental, Volume 10, Issues 13, 14 September 1996, Pages 139-156, ISSN 0926-
3373, https://doi.org/10.1016/0926-3373(96)00028-8.
Abstract: In view of increased concerns regarding the effects of diesel engine particulate and NOx emissions on human
health and the environment, legislators are currently reviewing and proposing legislation targeting the reduction of these
pollutants. The reported serious health risks of particulate matter on the respiratory system and its carcinogenic effects,
along with the known contributions of NOx in acid rain and ground ozone formation, demand that the enacted legislation
reflect in severity the health and environmental threats. As a consequence, diesel engine manufacturers and users are
under increasing pressure to greatly reduce the engine's exhaust emissions.
A system which is currently being proposed for the simultaneous control of diesel particulate matter and NOx emissions
involves the use of a cerium fuel-borne catalyst/filter/EGR system. This paper describes the principles of operation of
Rhone-Poulenc's cerium fuel-borne catalyst and the factors that govern its use.
Keywords: Emissions control; Diesel engine; NOx; Particulate matter; Particulate filter; Cerium; Fuel additives; Particulate
filter regeneration
W.E.J van Kooten, H.C Krijnsen, C.M van den Bleek, H.P.A Calis, Deactivation of zeolite catalysts used for NOx removal,
Applied Catalysis B: Environmental, Volume 25, Issues 23, 6 March 2000, Pages 125-135, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(99)00125-3.
Abstract: The deactivation of Ce-zeolite deNOx catalysts has been studied. Catalysts were aged in exhaust gases of a diesel
engine and a natural gas engine. The deactivation in real exhaust gas has been compared to deactivation in simulated
exhaust gas. Ammonia and urea were used as reducing agent. Deactivated catalysts were characterized with amongst
others XPS, XRF and DRIFT. Zeolite deNOx catalysts show different types of deactivation apart from hydrothermal
dealumination. Deactivation may occur at low and at higher temperatures. Several depositions were found on the catalysts:
coke, CxHy, S, Zn, P, N and Ca. Coke, CxHy and N containing species can be removed by heating under oxygen rich (deNOx)
conditions resulting in (partial) recovery of the catalyst activity. The type of lubricating oil used in the internal combustion
engine might be an important factor in the deactivation of the deNOx catalyst.
Keywords: Deactivation; NOx reduction; ZSM-5; Cerium; XPS
L.M. Martnez T, M. Araque, J.C. Vargas, A.C. Roger, Effect of Ce/Zr ratio in CeZr-CoRh catalysts on the hydrogen production
by glycerol steam reforming, Applied Catalysis B: Environmental, Volumes 132133, 27 March 2013, Pages 499-510, ISSN
Abstract: The H2 production by glycerol steam reforming has been studied using fluorite-type mixed oxides of CZCoRh. The
effect of the Ce/Zr ratio on the catalytic properties and its influence on the catalytic behavior are discussed. The catalysts
were characterized before and after catalytic test by XRD, Raman spectroscopy, BET surface area, HRTEM, H2-TPR and TPD-
TPO. The results show that an increase of the cerium amount enhances both the stability and the selectivity toward H2 and
CO2. This is related to the improvement of the reducibility and re-oxidation properties, oxygen storage capacity and metal
support interaction. The activity results demonstrate that selective H2 production is related to the capacity of the catalysts
to activate H2O under reaction conditions. This step ensures the steam reforming of the by-products to H2. The progressive
loss of this capacity reduces the H2 production, decreasing the steam reforming ability and the glycerol decomposition
becomes predominant. In this last case the production of CO, CH4 and C2H4 is promoted along with the formation of
condensable products as hydroxyacetone, acetaldehyde and acrolein.
Keywords: Glycerol; Hydrogen production; Steam reforming; Mixed oxides; Rhodium catalysts; Cobalt catalysts; Glycerol
decomposition
I. Atribak, B. Azambre, A. Bueno Lpez, A. Garca-Garca, Effect of NOx adsorption/desorption over ceria-zirconia catalysts
on the catalytic combustion of model soot, Applied Catalysis B: Environmental, Volume 92, Issues 12, 19 October 2009,
Abstract: CeO2, ZrO2 and CexZr1xO2 mixed oxides with different Ce/Zr ratios were prepared by (co-)precipitation and 500
C-calcination, and were characterized by Raman spectroscopy, XRD and N2 adsorption at 196 C. The catalytic activity of
these materials for soot oxidation by NOx/O2 has been correlated with the catalytic activity for NO2 production, and the
surface processes occurring upon NO + O2 interaction with the different catalysts have been studied by in situ DRIFTS and
NOx adsorption and further He-TPD. The catalytic activity for soot combustion of cerium-containing catalysts depends on
the NO2 production capacity, and a linear relationship between the temperature of maximum NO2 production and the
temperature of half soot conversion has been obtained. In a first step, surface nitrites are formed upon catalysts interaction
with NO + O2, for all the catalysts. These nitrites are progressively converted to nitrates, and NO2 is yielded after these
adsorption/oxidation/desorption processes. For CexZr1xO2 mixed oxides, the catalytic activity for NO2 production
depends on the cerium content, the higher the better, rather than on the BET area of the catalyst. The whole results
demonstrate that the production of NO2 in the range of temperatures relevant to soot oxidation not only depends on the
NO/nitrites oxidation capacity of the catalyst used but also probably on the adsorption strength of the nitrates under NO
oxidation conditions. The thermostability of the nitrates adsorbed on zirconium sites is higher than that of nitrates
adsorbed on cerium sites.
Keywords: Catalyzed soot oxidation; Ceria; Ceria-zirconia mixed oxides; Soot; NOx; Diesel; DRIFTS
Saminda Dharmarathna, Cecil K. Kingondu, Lakshitha Pahalagedara, Chung-Hao Kuo, Yashan Zhang, Steven L. Suib,
Manganese octahedral molecular sieve (OMS-2) catalysts for selective aerobic oxidation of thiols to disulfides, Applied
Catalysis B: Environmental, Volume 147, 5 April 2014, Pages 124-131, ISSN 0926-3373,
Abstract: Abstract
Selective aerobic oxidation of thiols to disulfides without any over oxidized products is studied using cryptomelane type
manganese oxides (K-OMS-2) with a tunnel structure as catalysts. Using K-OMS-2 prepared by different synthetic
procedures, complete conversion was obtained under air atmosphere without generating any overoxidized products. K-
OMS-2 prepared by solvent free method (K-OMS-2SF) with the highest surface area (155 1 m2/g) gave complete
conversion, while materials prepared using hydrothermal method (K-OMS-2HY) with the lowest surface area (44 1 m2/g)
gave only 18% conversion at room temperature. Selective poisoning of the acid sites suggests that Lewis acid sites are the
dominating active site during the reaction. Effects of surface area of the catalyst, solvent polarity, substrate effect, catalyst
recyclability and temperature were studied. The catalyst could be recovered in the active form after the reaction without
significant structural changes. The characterization of the catalyst using XRD, SEM, TGA, BET, TEM, and FT-IR are reported.
The process developed is environmentally benign and is indeed heterogeneous.
Keywords: Self-assembly; Catalysis; Manganese oxide molecular sieve; Nanorods; Microstructure
N. Guilhaume, B. Bassou, G. Bergeret, D. Bianchi, F. Bosselet, A. Desmartin-Chomel, B. Jouguet, C. Mirodatos, In situ

investigation of Diesel soot combustion over an AgMnOx catalyst, Applied Catalysis B: Environmental, Volumes 119120, 30
May 2012, Pages 287-296, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2012.03.009.
Abstract: An AgMnOx catalyst (3.5 wt.% Ag) incorporating silver ions in a Mn2O3 phase exhibits high performances for soot
oxidation below 300 C. Its structural and redox properties have been investigated under reaction conditions using in situ
XRD and DTA-TGA measurements. The catalyst appears unmodified during soot combustion experiments under oxygen, but
in the absence of oxygen the soot is stoichiometrically oxidised by lattice oxygen leading to catalyst bulk reduction
according to the steps Mn2O3 Mn3O4 MnO.
The isotopic reaction product composition (C16O2, C18O16O, C16O2, C16O and C18O) obtained during soot combustion
experiments under 18O2 reveals that the reaction follows a redox mechanism, in which the transfer of lattice oxygen from
the catalyst to the soot is responsible for the soot ignition at low temperature.
Keywords: Diesel soot; Soot combustion; Mechanism; AgMn mixed oxide; In-situ XRD; Oxygen isotopic exchange
Won-Jong Hong, Mao Ueda, Shinji Iwamoto, Saburo Hosokawa, Kenji Wada, Hiroyoshi Kanai, Hiroshi Deguchi, Masashi
Inoue, Effect of Fe content on physical properties of BaOCeOxFeOy catalysts for direct NO decomposition, Applied
Catalysis B: Environmental, Volume 106, Issues 12, 21 July 2011, Pages 142-148, ISSN 0926-3373,
Abstract: The physical properties of the Ba-loaded CeFe mixed oxide catalysts, which exhibited high activity for NO
decomposition to N2, were investigated. The optimum Fe/(Ce + Fe) molar ratio was 0.02. The X-ray absorption near edge
structure, electron spin resonance, and diffuse reflectance UVvis spectra indicated that the optimum catalyst had the
highest proportion of isolated tetrahedral Fe3+ ions in all the Fe species. Raman spectra suggested that incorporation of
Fe3+ in the fluorite structure of CeO2 caused an increase in the concentration of oxygen vacancies, which play an important
role in the NO decomposition activity of the catalysts. Temperature-programmed desorption (TPD) of O2 showed that the
addition of the Fe component to BaO/CeO2 enhanced O2 uptakes and facilitated oxygen desorption. NO-TPD profiles
showed that NO desorption was associated with the desorption of O2, indicating that these two species are formed by
decomposition of surface nitrate species.
Keywords: CeFe mixed oxide; Oxygen vacancy; O2-TPD; NO-TPD; NO decomposition
Dimitrios Delimaris, Theophilos Ioannides, VOC oxidation over MnOxCeO2 catalysts prepared by a combustion method,
Applied Catalysis B: Environmental, Volume 84, Issues 12, 25 October 2008, Pages 303-312, ISSN 0926-3373,
Abstract: MnOxCeO2 catalysts were prepared by a urea combustion method and their performance in the oxidation of
ethanol, ethyl acetate and toluene was evaluated. XRD, XPS, H2-TPR and N2 physisorption were employed in catalyst
characterization. Mn2+ and Mn3+ ions are present in the catalysts. In ceria-rich materials, crystalline manganese oxide
phases are absent and Mn ions are homogeneously distributed between the bulk and the surface suggesting incorporation
of Mn ions in ceria structure. In Mn-rich materials, segregation of a Mn3O4 phase takes place. The mixed oxides get
reduced by H2 at lower temperatures than the corresponding single oxides and Mn ions promote reduction of ceria. The
surface area of MnOxCeO2 catalysts is larger than the one of single oxides prepared with the same method. The larger
surface area of MnOxCeO2 catalysts counterbalances their smaller specific activity allowing complete conversion of the
examined VOCs at lower temperatures compared to the single oxides.
Keywords: VOC; Oxidation; Ethanol; Ethyl acetate; Toluene; Ceria; Manganese oxide; Compensation effect
K. Krishna, A. Bueno-Lpez, M. Makkee, J.A. Moulijn, Potential rare-earth modified CeO2 catalysts for soot oxidation: Part
III. Effect of dopant loading and calcination temperature on catalytic activity with O2 and NO + O2, Applied Catalysis B:
Environmental, Volume 75, Issues 34, 26 September 2007, Pages 210-220, ISSN 0926-3373,
Abstract: CeO2 and CeReOx_y catalysts are prepared by the calcination at different temperatures (y = 5001000 C) and
having a different composition (Re = La3+ or Pr3+/4+, 090 wt.%). The catalysts are characterised by XRD, H2-TPR, Raman,
and BET surface area. The soot oxidation is studied with O2 and NO + O2 in the tight and loose contact conditions,
respectively. CeO2 sinters between 800900 C due to a grain growth, leading to an increased crystallite size and a
decreased BET surface area. La3+ or Pr3+/4+ hinders the grain growth of CeO2 and, thereby, improving the surface catalytic
properties. Using O2 as an oxidant, an improved soot oxidation is observed over CeLaOx_y and CePrOx_y in the whole
dopant weight loading and calcination temperature range studied, compared with CeO2. Using NO + O2, the soot
conversion decreased over CeLaOx_y catalysts calcined below 800 C compared with the soot oxidation over CeO2_y.
CePrOx_y, on the other hand, showed a superior soot oxidation activity in the whole composition and calcination
temperature range using NO + O2. The improvement in the soot oxidation activity over the various catalysts with O2 can be
explained based on an improvement in the external surface area. The superior soot oxidation activity of CePrOx_y with NO
+ O2 is explained by the changes in the redox properties of the catalyst as well as surface area. CePrOx_y, having 50 wt.% of
dopant, is found to be the best catalyst due to synergism between cerium and praseodymium compared to pure
components. NO into NO2 oxidation activity, that determines soot oxidation activity, is improved over all CePrOx catalysts.
Keywords: Catalytic diesel soot oxidation; Rare earth oxide; Mixed oxides; O2; NO2
Zhicheng Tang, Gongxuan Lu, Synthesis and characterization of high performance Pt-(PrxCeyOz)/C catalysts for methanol
electrooxidation, Applied Catalysis B: Environmental, Volume 79, Issue 1, 21 February 2008, Pages 1-7, ISSN 0926-3373,
Abstract: In this paper, PrxCeyOz (x/y = 3/1, 1/1, 1/3) modified Pt/C catalysts were prepared by wet precipitation and
reduction method. The catalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and
energy dispersive X-ray analysis (EDX). TEM showed that Pt nanoparticles were uniformly dispersed on the surface of
carbon support with an average particle size of 4.05.0 nm in the Pt-(PrxCeyOz)/C catalysts. XRD showed that all the Pt-
(PrxCeyOz)/C catalysts displayed the typical character of Pt face centered cubic (fcc) phase. XRD and EDX analysis indicated
that the rare earth oxides exist in an amorphous form. The Pt-(PrxCeyOz)/C electrocatalysts were compared with the Pt/C,
Pt3-(PrOx)1/C and Pt3-(CeOx)1/C catalysts in terms of electrochemical activity and stability for methanol electrooxidation
using cyclic voltammetry (CV) and chronoamperometry (CA) in 0.5 M H2SO4 + 0.5 M CH3OH solutions. The CO-tolerance
experiment was measured in the CO-saturated 0.5 M H2SO4 solutions. The results showed that the Pt-(Pr1Ce1Oz)/C
catalyst had the highest catalytic activity, the best stability and CO-tolerance, which could be used as a suitable
electrocatalyst for direct methanol fuel cell.
Keywords: Methanol electrooxidation; Direct methanol fuel cell; Rare earth oxides; Electrocatalyst; Electrocatalytic reaction
S. Nassos, E. Elm Svensson, M. Boutonnet, S.G. Jrs, The influence of Ni load and support material on catalysts for the
selective catalytic oxidation of ammonia in gasified biomass, Applied Catalysis B: Environmental, Volume 74, Issues 12, 18
June 2007, Pages 92-102, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2007.01.015.
Abstract: The effect of nickel (Ni) load (0, 5 and 10 wt.%) and support material (Ce0.9La0.1O2, Ce0.9Zr0.1O2 and -Al2O3),
together the amount of oxygen ( = 0.25 and = 0.5) and gas hourly space velocity (50 000, 100 000 and 150 000 h1) were
investigated for the selective catalytic oxidation of ammonia in gasified biomass. The mixed metal oxide support materials
were prepared by microemulsion, whereas the alumina was a commercial product. Ni was added to the different supports
by incipient wetness. All the obtained catalysts were characterised by BET and XRD analysis. Cordierite monoliths coated
with 20 wt.% catalytic material were tested in a tubular quartz reactor. For simulating the gasified biomass fuel, 500 ppm of
NH3 was added to the fuel. Water was also present during the activity tests, which were carried out between 500 and 750
C.
The results from the activity tests at = 0.25 and gas hourly space velocity of 100 000 h1 indicated that the 10 wt.% Ni on
Ce0.9La0.1O2 was the best catalyst obtaining 65 and 97% N2 yield at 500 and 750 C, respectively. By increasing to 0.5
and decreasing the gas hourly space velocity, the N2 yield improved considerably at low temperature level (500 C).
Moreover, NOx emissions maintained at low levels depending on the experimental conditions. Constant conversion and
negligible carbon deposition were also two other important observations from the mixed metal oxide supported catalysts.
On the contrary, all the alumina-based catalysts displayed the lowest performance.
Keywords: Selective catalytic oxidation; Biomass; Microemulsion; Mixed metal oxides; Nitrogen yield; Lambda; Gas hourly
space velocity
Dong-Ha Lim, Weon-Doo Lee, Dong-Hyeok Choi, Ho-In Lee, Effect of ceria nanoparticles into the Pt/C catalyst as cathode
material on the electrocatalytic activity and durability for low-temperature fuel cell, Applied Catalysis B: Environmental,
Volume 94, Issues 12, 1 February 2010, Pages 85-96, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2009.10.024.
Abstract: An effective method is developed for preparing highly dispersed CeO2 nanoparticles on a Pt/C catalyst
synthesized by a continuous two-step process as a cathode material in low-temperature fuel cell. The XRD patterns of the
20Pt10CeO2/C catalyst reveal that both crystalline Pt and CeO2 phases coexist. The HR-TEM images show that Pt and
CeO2 nanoparticles have average particle sizes of approximately 3.4 nm and 4.2 nm, respectively, with quite a narrow
distribution between 3 nm and 5 nm. Based on the analysis of the polarization curves for the ORR, the optimum proportion
of CeO2 into the 20Pt/C catalyst is 10 wt%. In the ORR and single cell tests, the 20Pt10CeO2/C catalyst shows higher
performance than the commercial 20Pt/C catalyst, owing to the oxygen storage capacity of CeO2 and its ability to exchange
oxygen rapidly with oxygen in the buffer. In the accelerated stability tests, the 20Pt10CeO2/C catalyst has a better
durability compared to the commercial 20Pt/C catalyst due to the existence of CeO2, which prevents the agglomeration
and dissolution of Pt nanoparticles on the carbon support, extending the life of the catalyst.
Keywords: Continuous two-step process; Nano-sized metal oxide; PtCeO2/C electrocatalyst; Oxygen reduction reaction;
Accelerated durability; Low-temperature fuel cell
Gregorio Marbn, Antonio B. Fuertes, Highly active and selective CuOx/CeO2 catalyst prepared by a single-step citrate
method for preferential oxidation of carbon monoxide, Applied Catalysis B: Environmental, Volume 57, Issue 1, 15 April
Abstract: This work describes a novel citrate procedure to prepare highly active and selective copper oxideceria catalysts
for the preferential oxidation of CO in the presence of hydrogen. At the conditions studied, the prepared catalysts are very
active and selective at temperatures around 160 C, even though suffer from slow deactivation during reaction, which is
ascribed to the progressive loss of active sites by copper oxide reduction. In spite of this, the catalytic activity of these
catalysts is comparable to or higher than that of the most active catalysts reported in literature. Cobalt and manganese
oxide-based catalysts prepared by the same procedure present a much lower catalytic activity than that of the copper
oxide-based catalyst. The catalysts are formed by small arrangements of ceria crystals (240 crystals per particle) of
nanometric size (410 nm), partially covered by XRD amorphous clusters of copper oxide. The presence of copper oxide
reduces the normal growing of the ceria crystals during calcination and induces the agglomeration of such crystals. Raman
spectroscopy was used to study the catalytic activity-related structural characteristics of the catalysts. Only ceria-related
peaks were detected in the Raman spectra. The parameters of the main peak (at 450464 cm1) were found to depend
on the crystal size and on the extent of copper oxide covering of the ceria surface. On the other hand, the relation existing
between the area of the second peak (at 585598 cm1) and the amount of oxygen vacancies permitted to analyse their
effect on the activity of the catalysts prepared at different conditions.
Keywords: Fuel cell; Preferential CO oxidation; Ceria; Copper oxide; Citrate; Raman; XRD
K. Krishna, A. Bueno-Lpez, M. Makkee, J.A. Moulijn, Potential rare earth modified CeO2 catalysts for soot oxidation: I.
Characterisation and catalytic activity with O2, Applied Catalysis B: Environmental, Volume 75, Issues 34, 26 September
Abstract: Ceria (CeO2) and rare-earth modified ceria (CeReOx with Re = La, Pr, Sm, Y) catalysts are prepared by nitrate
precursor calcination and are characterised by BET surface area, XRD, H2-TPR, and Raman spectroscopy. Potential of the
catalysts in the soot oxidation is evaluated in TGA with a feed gas containing O2. Seven hundred degree Celsius calcination
leads to a decrease in the surface area of the rare-earth modified CeO2 compared with CeO2. However, an increase in the
meso/macro pore volume, an important parameter for the soot oxidation with O2, is observed. Rare-earth ion doping led to
the stabilisation of the CeO2 surface area when calcined at 1000 C. XRD, H2-TPR, and Raman characterisation show a solid
solution formation in most of the mixed oxide catalysts. Surface segregation of dopant and even separate phases, in
CeSmOx and CeYOx catalysts, are, however, observed. CePrOx and CeLaOx catalysts show superior soot oxidation activity
(100% soot oxidation below 550 C) compared with CeSmOx, CeYOx, and CeO2. The improved soot oxidation activity of
rare-earth doped CeO2 catalysts with O2 can be correlated with the increased meso/micro pore volume and stabilisation of
external surface area. The segregation of the phases and the enrichment of the catalyst surface with unreducible dopant
decrease the intrinsic soot oxidation activity of the potential CeO2 catalytic sites. Doping CeO2 with a reducible ion such as
Pr4+/3+ shows an increase in the soot oxidation. However, the ease of catalyst reduction and the bulk oxygen-storage
capacity is not a critical parameter in the determination of the soot oxidation activity. During the soot oxidation with O2,
the function of the catalyst is to increase the active oxygen transfer to the soot surface, but it does not change the rate-
determining step, as evident from the unchanged apparent activation energy (around 150 kJ mol1), for the catalysed and
un-catalysed soot oxidation. Spill over of oxygen on the soot surface and its subsequent adsorption at the active carbon
sites is an important intermediate step in the soot oxidation mechanism.
Keywords: Diesel soot; Oxidation; Rare earth oxide; Mixed oxides
J P rez-Ram rez, F Kapteijn, K Schffel, J.A Moulijn, Formation and control of N2O in nitric acid production: Where do we
stand today?, Applied Catalysis B: Environmental, Volume 44, Issue 2, 20 August 2003, Pages 117-151, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(03)00026-2.
Abstract: Nitric acid production represents the largest source of N2O in the chemical industry, with a global annual emission
of 400 kt N2O. The high impact of N2O on the environment as greenhouse gas and stratospheric ozone depletor, and the
ongoing agreements and prospective regulations calls for the development of efficient and economical systems for N2O
mitigation, but no mature commercial technology is yet available. In this review, the current state-of-the-art for N2O
control in the nitric acid manufacture is presented. The formation of N2O and the process are analyzed and several options
for reducing its emissions are discussed, depending on the position in the process. Primary abatement options deals with
modifications in the ammonia oxidation catalyst, secondary abatement with options between the ammonia converter and
the absorber, tertiary abatement with options in the tail-gas upstream of the expander, and quaternary abatement with
options in the tail-gas downstream of the expander. The abatement technologies are evaluated based on the technical
advantages and disadvantages, and cost efficiency.
Keywords: Nitrous oxide; Laughing gas; N2O; Nitric acid production; Abatement; Technology; Catalyst; Environment;
Greenhouse gas; Ozone layer; In-process-gas; Tail-gas
Deborah L Mowery, Michael S Graboski, Tim R Ohno, Robert L McCormick, Deactivation of PdOAl2O3 oxidation catalyst in
lean-burn natural gas engine exhaust: aged catalyst characterization and studies of poisoning by H2O and SO2, Applied
Catalysis B: Environmental, Volume 21, Issue 3, 5 July 1999, Pages 157-169, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(99)00017-X.
Abstract: A palladium oxide on alumina oxidation catalyst was employed to remove combustible pollutants from the
exhaust of a spark-ignited, lean-burn natural gas engine. Rapid deactivation was seen for the oxidation of methane and
ethane. Characterization results are consistent with sulfur as the primary source of catalyst activity loss. In microreactor
studies, deactivation of the engine aged catalysts was only apparent if water was present in the feed stream. In dry feed
gas, the activity of fresh and engine aged samples was the same. SO2 in dry gas was shown to cause both inhibition and
deactivation for methane oxidation. This deactivation is partly reversible at 733 K and completely reversible at 793 K. Water
inhibits the rate of methane oxidation and causes some permanent activity loss. Activity studies at 733 and 793 K indicate
that activity loss is greater when both water and SO2 are present. Sulfur oxide groups on the surface increase both the
amount of water sorbed and the water desorption temperature in TPD experiments. It is proposed that water and SO2
compete for adsorption sites on the alumina surface. Enhanced activity loss in the presence of both poisons is attributed to
enhanced water inhibition and spillover of sorbed SO2 and SO3 species from alumina to the PdO surface.
Keywords: Methane oxidation; Engine exhaust; Catalyst poisoning; Palladium; Sulfur oxide; Water
Patrick Glin, Michel Primet, Complete oxidation of methane at low temperature over noble metal based catalysts: a
review, Applied Catalysis B: Environmental, Volume 39, Issue 1, 8 November 2002, Pages 1-37, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(02)00076-0.
Abstract: This review examines recent developments in the complete oxidation of methane at low temperature over noble
metal based catalysts in patents and open literature. The abatement of natural gas vehicle (NGV) methane emissions is
taken as one example among possible applications. The review develops current ideas about the properties of palladium
and platinum catalysts supported on silica and alumina supports in the complete oxidation of methane under oxidising
conditions, focusing on low-temperature reaction conditions. The influence of residual chloride ions on the catalytic
activity, the kinetic aspects of the oxidation of methane over these catalysts, the nature of the active sites, the influence of
metal particle size and reaction products on the activity, the observed changes in catalytic activity with reaction time and
the effect of sulphur containing compounds are examined. The latest studies concerned with improved palladium and
platinum supported catalysts which would exhibit enhanced and stable catalytic activity at low temperature in the presence
of water and sulphur containing compounds are reported. Possible routes for preparing catalysts able to meet future
regulations concerning methane emissions from lean-burn NGV vehicles are discussed.
Keywords: Methane oxidation; Noble metals; Catalytic combustion; Low temperature; Lean-burn NGV; Natural gas;
Emission abatement; Platinum; Palladium; Catalyst poisoning; Water inhibition; Poisoning by sulphur and chlorine
containing compounds; Kinetic studies; Silica; Alumina; Zirconia; Tin dioxide; Ceria; Ceria-zirconia solid solution; Zeolite;
Aluminophosphate; Mixed oxide supports; Oxide additives; Bimetallic catalysts
H. Mahzoul, J.F. Brilhac, P. Gilot, Experimental and mechanistic study of NOx adsorption over NOx trap catalysts, Applied
Catalysis B: Environmental, Volume 20, Issue 1, 4 January 1999, Pages 47-55, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(98)00093-9.
Abstract: The storage capacity of NOx trap catalysts is affected by the gas composition. The capacity increases when the
oxygen content goes from 0% to 3%. Above 3%, no effect is exhibited. The presence of NO2 enhances the storage capacity.
Storage is significant even if no oxygen is present in the gas phase and even in the absence of platinum. Two kinds of sites
for NO, NO2 and O2 adsorption seem to operate. Platinum sites close to BaO crystallites (sites 1) are responsible for nitrate
formation. The other platinum sites allow the catalyst to behave as an oxidation catalyst. A mechanism based on NO, NO2
and O2 adsorption and reaction over type 1 sites is able to qualitatively explain the experimental results. The rate of nitrate
formation depends on the gas composition while the rate of nitrate decomposition increases with the amount of nitrate
formed. This explains the effect of gas composition on the storage capacity obtained at steady-state, when formation and
decomposition rates are the same.
Keywords: NOx storage catalysts; Lean-burn; Mechanism; NOx adsorption; Platinum; Barium oxide
Akira Obuchi, Isamu Kaneko, Junko Oi, Akihiko Ohi, Atsushi Ogata, Gratian R. Bamwenda, Satoshi Kushiyama, A practical
scale evaluation of catalysts for the selective reduction of NOx with organic substances using a diesel exhaust, Applied
Catalysis B: Environmental, Volume 15, Issues 12, 15 January 1998, Pages 37-47, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(97)00035-0.
Abstract: Several promising catalysts for the selective reduction of NOx with organic compounds were made into large scale
samples (cylindrical, = 118 mm, length = 50 mm), either as washcoated honeycomb monoliths (400 cell/in2) or as packings
of pellets with a diameter of 23 mm. These samples were tested under diesel exhaust gas conditions with the SV = 16 400
h1, in the temperature range from 200 to 460C. When propylene was used as a reducing agent, Pt/Al2O3, Pt-ZSM-5 and
Au/Al2O3 + Mn2O3 showed high catalytic activities in the low temperature range from 200 to 250C. Cu-ZSM-5 (propylene
as a reductant), Co/Al2O3 (methanol) and Ag/Al2O3 (ethanol) showed high activities at temperatures >350C. Except for
the manifestation of differences in the activity among catalysts, the general behaviors of these catalysts, such as the active
temperature range, selectivity to N2O and emission of non-reacted or or incompletely oxidized reductants, were similar to
that shown when model gas mixture systems were used.
Keywords: Diesel exhaust; Nitrogen oxide
A. Fritz, V. Pitchon, The current state of research on automotive lean NOx catalysis, Applied Catalysis B: Environmental,
Volume 13, Issue 1, September 1997, Pages 1-25, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(96)00102-6.
Abstract: A predominant challenge to both industrial and academic research institutions is the selective reduction of NOx
during lean exhaust conditions. Despite a proliferation of publications, papers and reviews, a large number of catalysts fall
short of a credible and consistent diesel application. Herein are reviewed systems designed specifically with the goal of
assisting researchers in their assessment of catalytic performance. By way of conclusion, three principal types of catalysts
active for HC-SCR are discussed.
Keywords: Lean NOx; Decomposition; Reduction; Zeolites; Noble metals; Oxides
Teuvo Maunula, Juha Ahola, Tapio Salmi, Heikki Haario, Matti Hrknen, Marjo Luoma, Veikko J. Pohjola, Investigation of
CO oxidation and NO reduction on three-way monolith catalysts with transient response techniques, Applied Catalysis B:
Environmental, Volume 12, Issue 4, 25 July 1997, Pages 287-308, ISSN 0926-3373, https://doi.org/10.1016/S0926-
3373(96)00084-7.
Abstract: The kinetics of CO oxidation and NO reduction reactions over alumina and alumina-ceria supported Pt, Rh and
bimetallic Pt/Rh catalysts coated on metallic monoliths were investigated using the step response technique at atmospheric
pressure and at temperatures 30350C. The feed step change experiments from an inert flow to a flow of a reagent (O2,
CO, NO and H2) showed that the ceria promoted catalysts had higher adsorption capacities, higher reaction rates and
promoting effects by preventing the inhibitory effects of reactants, than the alumina supported noble metal catalysts. The
effect of ceria was explained with adsorbate spillover from the noble metal sites to ceria. The step change experiments
CO/O2 and O2/CO also revealed the enhancing effect of ceria. The step change experiments NO/H2 and H2/NO gave
nitrogen as a main reduction product and N2O as a by-product. Preadsorption of NO on the catalyst surface decreased the
catalyst activity in the reduction of NO with H2. The CO oxidation transients were modeled with a mechanism which
consistent of CO and O2 adsorption and a surface reaction step. The NO reduction experiments with H2 revealed the role of
N2O as a surface intermediate in the formation of N2. The formation of NN bonding was assumed to take place prior to,
partly prior to or totally following to the NO bond breakage. High NO coverage favors N2O formation. Pt was shown to be
more efficient than Rh for NO reduction by H2.
Keywords: Carbon monoxide oxidation; Nitric oxide reduction; Three-way catalysts; Platinum; Rhodium
John P.A. Neeft, Michiel Makkee, Jacob A. Moulijn, Catalysts for the oxidation of soot from diesel exhaust gases. I. An
exploratory study, Applied Catalysis B: Environmental, Volume 8, Issue 1, 29 February 1996, Pages 57-78, ISSN 0926-3373,
https://doi.org/10.1016/0926-3373(95)00057-7.
Abstract: A large number of candidate soot oxidation catalysts were screened on their catalytic activity with a model soot. It
was found that the intensity of contact between soot and catalyst is one of the major parameters that determine the soot
oxidation rate. Two types of contact were studied; many catalysts increase the rate of soot oxidation considerably when the
contact is intimate (tight), whereas under conditions of poor (loose) contact only some catalysts accelerate this oxidation
reaction. It is tentatively suggested that (i) mobility of the catalyst is a major parameter determining the loose contact
activity of catalysts and (ii) this mobility correlates with the melting point or the partial pressure of the catalyst.
Keywords: Soot; Oxidation; Metal oxide catalysts; Alkali metal catalysts; Copper; Silver
D. Panayotov, M. Khristova, M. Velikova, Interactions NOCO and O2NOCO on CuCo2O4/-Al2O3 and on -Al2O3- and
CuCo2O4/-Al2O3-supported Pt, Rh and PtRh catalysts, a transient response study, Applied Catalysis B: Environmental,
Volume 9, Issues 14, 2 September 1996, Pages 107-132, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(96)90076-4.
Abstract: The interactions NOCO and O2NOCO have been studied onCuCo2O4-Al2O3 and on -Al2O3- and
CuCo2O4-Al2O3-supported Pt, Rh and PtRh catalysts. The deposition of noble metals (Pt, Rh and PtRh) on CuCo2O4-
Al2O3 instead of -Al2O3 is beneficial in: lowering the temperature at which maximum N2O is formed and decreasing the
maximum N2O concentration attained; lowering the onset temperature of NO to N2 reduction, and increasing the N2
selectivity; preserving the activity towards NO to N2 reduction on a higher level following the concentration step NO +
COO2+ NO + CO and changing the conditions from stoichiometric to oxidizing (50% excess of oxidants). The reason for this
behaviour of the CuCo2O4-Al2O3-based noble metal catalysts is the formation (reversible) of a reduced surface layer on
the CuCo2O4 supported spinel under the conditions of a stoichiometric NO + CO mixture.
Keywords: Nitric oxide; Carbon monoxide; Oxygen; Interaction; Reduction; Carbon-monoxide; Copper; Cobalt; Oxide spinel;
Platinum; Rhodium; Transient response technique
L. Forni, C. Oliva, F.P. Vatti, M.A. Kandala, A.M. Ezerets, A.V. Vishniakov, LaCeCo perovskites as catalysts for exhaust gas
depollution, Applied Catalysis B: Environmental, Volume 7, Issues 34, 18 January 1996, Pages 269-284, ISSN 0926-3373,
https://doi.org/10.1016/0926-3373(95)00039-9.
Abstract: A series of La1 xCexCoO3 + perovskite-type catalysts, with x ranging from 0 to 0.20, showed to be quite active
for reduction of NO by CO (reaction 1) and for oxidation of CO by air oxygen (reaction 2) at temperatures ranging from 373
to 723 K. Analysis by X-ray diffraction, electron probe microanalysis, temperature-programmed desorption-temperature-
programmed reaction and electron paramagnetic resonance, coupled with catalytic activity data, showed that the active
sites on these catalysts are very likely localised onto Co ions, which coordinate O2 ions as intermediates for reaction 2, the
latter taking place essentially through a suprafacial mechanism. For reaction 1, taking place through both a suprafacial and
an intrafacial mechanism, the Co-based sites play also an additional role, favouring the electron transfer from site to site
and so enhancing the transfer of oxygen species from surface to bulk and vice versa. Ce ions seem to act only as a stabiliser
of O2 ions, helping in keeping them at the catalyst surface.
Keywords: LaCeCo perovskites; Nitric oxide reduction by CO; Carbon monoxide oxidation by air oxygen; Exhaust gas
depollution
I. Jimnez-Morales, F. Vila, R. Mariscal, A. Jimnez-Lpez, Hydrogenolysis of glycerol to obtain 1,2-propanediol on Ce-

promoted Ni/SBA-15 catalysts, Applied Catalysis B: Environmental, Volumes 117118, 18 May 2012, Pages 253-259, ISSN
Abstract: Metallic Ni (10 wt.%) supported on SBA-15 silica and promoted with cerium loading ranged between 2.5 and 10
wt.%, reduced at 723 K during 1 h, were used as catalysts in the hydrogenolysis of a glycerol aqueous solution (80 wt.%) at
473 K and 2.4 MPa of H2 pressure. Whereas pure Ni catalyst mainly produces volatile products by CC hydrogenolysis
reaction, the promoted cerium catalysts lead to the formation of 1,2-propanediol (1,2-PDO) as majority product. After 8 h
of reaction the catalyst with 10 wt.% of Ni and 7.5 wt.% of Ce gives the maximum glycerol conversion and selectivity to 1,2-
PDO, with yield of this substance of 24.2%/g of catalyst. The presence of cerium species is essential to produce 1,2-PDO.
The effect of cerium oxide is to act as strong acid sites (TPD-NH3), improve the metallic Ni dispersion (XRD, H2
chemisorption and XPS) and to make more difficult their reduction (TPR). The stronger acidity suggests that the formation
of acetol takes place easier in these catalysts and subsequently this intermediate is reduced by activated hydrogen from the
nearby Ni metallic sites.
Keywords: Glycerol; Hydrogenolysis; SBA-15; Acid catalysts; Metallic nickel; Ceria
Jiandong Bi, Min Liu, Chunsan Song, Xiangsheng Wang, Xinwen Guo, C2C4 light olefins from bioethanol catalyzed by Ce-
modified nanocrystalline HZSM-5 zeolite catalysts, Applied Catalysis B: Environmental, Volume 107, Issues 12, 31 August
Abstract: Conversion of bioethanol into bulk chemicals besides ethylene is a promising process in which the stability of
catalyst and the selectivity of products are important. In this study, a series of Ce-modified nanocrystalline HZSM-5 catalysts
were prepared and their catalytic performance in the conversion of bioethanol into C2C4 light olefins was investigated in a
fixed-bed reactor at 400 C under atmospheric pressure. The results show that the stability of catalyst and the distribution
of products depend strongly on the content of cerium and the calcination temperature; both cerium content and
calcination temperature affect not only the acid properties of the tested catalyst samples but also the composition of
cerium species (Ce3+/Ce4+) as revealed by XPS. Among the tested catalyst samples, the catalyst with 5 wt% cerium loading
and 520 C calcination temperature exhibits the best stability and selectivity to C3C4 light olefins.
Keywords: Bioethanol; Transformation; Light olefins; Ce-modified; Nanocrystalline HZSM-5
Javier Santiago-Morales, Ana Agera, Mara del Mar Gmez, Amadeo R. Fernndez-Alba, Jaime Gimnez, Santiago Esplugas,
Roberto Rosal, Transformation products and reaction kinetics in simulated solar light photocatalytic degradation of
propranolol using Ce-doped TiO2, Applied Catalysis B: Environmental, Volume 129, 17 January 2013, Pages 13-29, ISSN
Abstract: The visible light photocatalytic degradation of propranolol was studied using cerium doped titanium dioxide, a
catalyst that showed an increased light absorption in the visible region. The experiments were carried out in ultrapure
water and in a biologically treated wastewater from the secondary effluent of a treatment plant spiked with propranolol.
The best results were obtained for a cerium loading of 0.5 wt.% and a bulk catalyst concentration of 0.14 g/L, with which
propranolol became essentially depleted after 1.5 h of irradiation. The extent of mineralization reached 17.4% after 6 h on
stream under the same conditions. Both oxidation on catalyst holes and reaction with hydroxyl radicals contribute to
propranolol depletion, but for the reaction conditions tested in this study, the first mechanism predominated and
accounted for 60% of the propranolol rate constant. The runs performed in wastewater matrix led to a very low
photocatalytic rate compared with pure water, which was attributed to the presence of radical scavengers and competing
substances. Over thirty reaction intermediates were detected by means of exact mass measurements performed by liquid
chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-ESI-QTOFMS/MS) based on the
characteristic fragmentation of oxidation by-products. Their relative abundance was also assessed in catalytic and non-
catalytic runs. The most abundant transformation products could be attributed to the cleavage of the ether bond of
propranolol. Other compounds detected derived from the addition of hydroxyl groups to the aromatic nuclei or to the ring-
opening attack of hydroxyl radicals on the naphthol moiety. Finally, the toxicity of oxidized mixtures was determined using
the green algae Pseudokirchneriella subcapitata and the bioluminescent marine bacterium Vibrio fischeri. Although the
toxicity of treated mixtures tended to decrease as propranolol was depleted, mixtures treated in pure water may lead to
the accumulation of toxic transformation products.
Keywords: Propranolol; Solar photocatalysis; Transformation products; Liquid chromatography; Mass spectrometry
Magdalena Bosomoiu, Grigore Bozga, Daniela Berger, Cristian Matei, Studies on combustion catalytic activity of some pure
and doped lanthanum cobaltites, Applied Catalysis B: Environmental, Volume 84, Issues 34, 1 December 2008, Pages 758-
765, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2008.06.008.
Abstract: The aim of this work is to compare the catalytic activity of some pure and doped lanthanum cobaltites, prepared
by solution combustion technique, with a Pt/Al2O3 commercial catalyst. As test reaction we used the combustion of lean
methane mixtures. The experimental data evidenced a significantly better catalytic activity of a cerium-doped lanthanum
cobaltite, prepared by using -alanine as fuel. The combustion data, for the lean methane mixtures we tested, are well
fitted by a first-order kinetic expression. The calculated activation energy values are in good agreement with the published
data.
Keywords: Catalysis; Combustion; Kinetics; Packed bed; Parameter identification; Perovskites
Juliana M. Jacob, Patricia G. Corradini, Ermete Antolini, Nathalia Abe Santos, Joelma Perez, Electro-oxidation of ethanol on
ternary PtSnCe/C catalysts, Applied Catalysis B: Environmental, Volume 165, April 2015, Pages 176-184, ISSN 0926-3373,
Abstract: Abstract
Ternary PtSnCe/C catalysts were prepared by a modified formic acid method, and their activity for the ethanol oxidation
reaction (EOR) was compared to that of PtSn/C, PtCe/C and Pt/C catalysts. No bulk alloy formation was detected by XRD
analysis. XPS measurements indicated no segregation on the catalyst surface and the presence of Sn(0) and SnOx, Ce2O3
and CeO2 oxides. The onset potential for CH3CH2OH oxidation on PtSn/C and PtSnCe/C (60:20:20) catalysts, which have
the highest Sn content on the surface, was lower than that of PtSnCe/C (70:20:10) and (50:20:30), PtCe/C and Pt/C
catalysts. This work highlights the dependence on the potential of the effect of cerium in PtSnCe/C catalysts on the EOR
activity and on the reaction mechanism. By derivative voltammograms, different reaction pathways at different potentials,
involving Sn (at ca. 0.44 V vs. RHE), Sn + Ce (at ca. 0.55 V vs. RHE) and Ce (at ca. 0.67 V vs. RHE) were inferred. The PtSn
Ce/C catalysts were less tolerant to poisoning by ethanol oxidation intermediate species than Pt/C and PtSn/C, but more
stable than PtCe/C catalysts. DEFC tests at 90 C indicated that a higher Sn surface content is more effective for ethanol
oxidation than the addition of Ce to PtSn/C.
Keywords: Ternary catalysts; PtSnCe/C; Fuel cell; Ethanol oxidation
Magorzata Adamowska, S bastien Muller, Patrick Da Costa, Andrzej Krzton, Philippe Burg, Correlation between the surface
properties and deNOx activity of ceria-zirconia catalysts, Applied Catalysis B: Environmental, Volume 74, Issues 34, 31 July
Abstract: The catalytic activities of ceria-zirconia mixed oxides CexZr1xO2 (x = 0.17, 0.42, 0.62 and 0.8) are determined by
isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that
all supports are active in deNOx reaction in the presence of the previous hydrocarbons. However, their catalytic activity
varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NOx consumption. This activity
was correlated with physicochemical properties determined by a linear solvation energy relationship (LSER) approach.
Moreover, a mechanism of HC assisted reduction of NO is proposed on ceria-zirconia supported catalysts. This mechanism
is divided in three catalytic cycles involving: (i) the oxidation of NO into NO2, (ii) the reaction of NO2 and the hydrocarbons
leading to RNOx species and CxHyOz, and finally (iii) the decomposition of NO assisted by these latter CxHyOz species.
Keywords: deNOx; Coal; Ceria-zirconia; LSER; Mechanism
Haiyan Chen, Abdelhamid Sayari, Alain Adnot, a al Larachi, Compositionactivity effects of MnCeO composites on
phenol catalytic wet oxidation, Applied Catalysis B: Environmental, Volume 32, Issue 3, 1 August 2001, Pages 195-204, ISSN
0926-3373, https://doi.org/10.1016/S0926-3373(01)00136-9.
Abstract: MnCeO composite catalysts have been widely used in sub- and supercritical catalytic wet oxidation of toxic
organics contained in aqueous streams. In order to investigate their compositionactivity relationship, 11 samples with
Ce/(Mn+Ce) atomic bulk ratios ranging from 0 to 100% were prepared by co-precipitation. Phenol was selected as a model
pollutant and the catalytic oxidation was carried out in a batch slurry reactor using oxygen as the oxidizing agent under mild
reaction conditions. The results showed that the catalytic activity was greatly influenced by the catalyst composition. The
catalyst with Mn/Ce ratio=6/4 was found to be the most active in reducing both phenol concentration and total organic
carbon (TOC). All catalysts were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD),
temperature programmed reduction (TPR) and nitrogen adsorption techniques. Systematic shifts in binding energy,
diffraction angle, and reduction temperature were observed in the XPS, XRD and TPR spectra, respectively. XPS and XRD
data revealed the occurrence of significant interactions between Mn and Ce oxides, resulting in the evolution of textural,
structural and oxidation state with composition. TPR analysis showed that the interaction between Mn and Ce greatly
improved the oxygen storage capacity of manganese and cerium oxides as well as oxygen mobility on the surface of
catalyst. Catalytic active sites have been ascribed to manganese oxide species exhibiting higher oxidation state.
Furthermore, XPS revealed that the most active catalyst, i.e. Mn/Ce 6/4, exhibits an electron-rich surface which may be very
important in the activation of adsorbed oxygen.
Keywords: MnCe composite catalyst; Heterogeneous wet oxidation; Phenolic wastewater; Detoxification
Juan A.C. Ruiz, Marco A. Fraga, Heloise O. Pastore, Methane combustion over Pd supported on MCM-41, Applied Catalysis
B: Environmental, Volume 76, Issues 12, 30 October 2007, Pages 115-122, ISSN 0926-3373,
Abstract: This work aimed at studying the feasibility of using mesoporous molecular sieves (MCM-41) as supports for
palladium-based catalysts for methane combustion. The effects brought about by the chemical composition as well as by
the presence of cerium and lanthanum were investigated. The MCM-41 structures were found to be thermally stable under
air: the MCM-41 is stable until 1273 K while the [Al]-MCM-41 resists up to 1173 K. Silicate-based catalysts are more active
than the aluminosilicate-supported Pd samples; while no changes were observed on the structure of the materials during
the catalytic test, it was found that the addition of La and Ce decreased their activity. The catalytic activity was correlated
with the hydrophobic character of the supports, and with the smaller temperature of PdO reduction presented by the
catalysts.
Keywords: MCM-41; Methane combustion; PdO reducibility; Natural gas
Magorzata Adamowska, Andrzej Krzto, Mieczysawa Najbar, Jzef Camra, G rald Dj ga-Mariadassou, Patrick Da Costa,
Ceriazirconia-supported rhodium catalyst for NOx reduction from coal combustion flue gases, Applied Catalysis B:
Environmental, Volume 90, Issues 34, 17 August 2009, Pages 535-544, ISSN 0926-3373,
Abstract: The catalytic activities of ceriazirconia mixed oxides CexZr1xO2 (x = 0.17, 0.62 and 0.8) rhodium catalysts were
determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion.
Results show that all supports are active in deNOx reaction in the presence of the mentioned gas mixture. However, their
catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NOx
consumption. The effect of rhodium on Ce0.62Zr0.38O2 considerably improves the catalytic activity during the deNOx
process assisted by hydrocarbons. The rhodium addition decreases by about 34 C the temperature of NOx consumption,
which goes up to 57%. A mechanism of hydrocarbon (HC) assisted reduction of NO is proposed on ceriazirconia-supported
rhodium catalysts. This mechanism is divided in three catalytic cycles involving (i) the oxidation of NO into NO2, (ii) the
reaction of NO2 and the hydrocarbons leading to RNOx species and CxHyOz, and finally (iii) the decomposition of NO
assisted by these latter CxHyOz species.
Keywords: Lean deNOx of coal; Ceriazirconia; Rhodium; Mechanism
P. Marecot, A. Fakche, L. Pirault, C. Geron, G. Mabilon, M. Prigent, J. Barbier, Effect of the preparation procedure on the
properties of three-way automotive platinumrhodium/ aluminaceria catalysts, Applied Catalysis B: Environmental,
Volume 5, Issues 12, 31 December 1994, Pages 43-55, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(94)00039-5.
Abstract: The properties of three-way automotive Pt Rh/Al2O3 CeO2 catalysts prepared either by coimpregnation of the
two noble metals (CI catalysts) or by a newly devised technique of successive impregnations with an intermediate reducing
treatment (SI catalysts) were investigated for the oxidation of a propanepropene mixture under lean conditions and for
the CO + NO reaction. After high-temperature aging, bimetallic CI catalysts are far less active than SI catalysts for propane
oxidation. On the other hand, they show comparable activities for propene oxidation and reaction CO + NO. The
characterization of bimetallic catalysts by TPR and FT-IR experiments suggests that the coimpregnation leads to an intimate
interaction between platinum and rhodium while rhodium added by successive impregnations with a reduction step after
platinum impregnation would be selectively deposited onto cerium oxide surface in the vicinity of platinum particles,
avoiding the formation of Pt/Rh alloy.
Keywords: Catalyst preparation (coimpregnation/successive impregnation); Exhaust; Platinumrhodium; Propane
oxidation; Propene oxidation
William T. Gibbons, Tracy H. Liu, Karen J. Gaskell, Gregory S. Jackson, Characterization of palladium/copper/ceria
electrospun fibers for watergas shift catalysis, Applied Catalysis B: Environmental, Volumes 160161, November 2014,
Abstract: Abstract
Nano-fibers of palladiumcopper (Pd/Cu) in ceria for watergas-shift (WGS) catalysis were prepared by electrospinning
solutions containing polyvinylpyrrolidone (PVP) and soluble salts of cerium, palladium, and copper in a water/ethanol co-
solvent. Catalyst precursors were mixed in a single pot, electrospun, and calcined to produce ceramic fibers with 88 wt%
CeO2, 2% Pd, and 10% Cu. Slowing the rate of polymer removal with controlled heating during calcining did not significantly
change fiber diameters (200 nm) but did lower the ceria crystallite to typically less than 10 nm and produce longer fibers
that formed non-woven mats with structural integrity. The resulting catalyst materials were characterized for WGS activity
by temperature-programmed and time-on-stream reactor tests. X-ray photoelectron spectroscopy, Raman spectroscopy,
and transmission electron microscopy analysis indicated that for different precursor salts, much of the Cu and Pd are
incorporated into the ceria lattice before testing. For the Pd/Cu/ceria nano-fiber catalysts, time-on-stream testing at 400 C
showed high WGS activity, that asymptotically decayed with time. Post-testing XPS and Raman spectroscopy indicated that
reduced Pd and Cu segregate to the surface during time-on-stream testing, which lowers activity. Exposure to intermittent
oxidizing environments, particularly with O2, partially reverses the metal segregation and restores catalyst activity. Adding
surfactant to the synthesis solution increases catalyst surface area without significantly improving activity or slowing its
asymptotic decay, which suggests that activity is not limited strictly by surface area, but rather by metal/ceria interactions,
for these catalysts.
Keywords: Watergas shift; Catalysis; Ceria; Palladiumcopper; Electrospinning
P. Marcot, L. Pirault, G. Mabilon, M. Prigent, J. Barbier, Influence of the redox properties of ceria on the preparation of
three-way automotive platinumrhodium/ aluminaceria catalysts, Applied Catalysis B: Environmental, Volume 5, Issues
12, 31 December 1994, Pages 57-69, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(94)00038-7.
Abstract: The redox properties of ceria were investigated by temperature-programmed reduction performed under
hydrogen and the catalysts were evaluated by determining the temperatures at which 50% conversion for propene and
propane oxidation were reached. The results obtained show that ceria plays a decisive role within the preparation of
bimetallic Pt Rh/Al2O3 CeO2 catalysts by successive impregnations (SI) when reduced capping cerium atoms (Ce3+) are
present on the parent Pt/Al2O3 CeO2 catalyst before introduction of the rhodium salt. Thus, rhodium deposition would
occur by a redox reaction between Ce3+ and Rh3+. The preparation procedure of Pt Rh/Al2O3 CeO2 catalysts by the SI
method increases the thermal stability of the metallic species under oxidizing conditions. This improvement would be the
consequence of a higher resistance to the formation of Pt Rh alloys with surface enrichment in rhodium.
Keywords: Ceria; Exhaust; Platinumrhodium; Propane oxidation; Propene oxidation; Redox properties; Temperature-
programmed reduction
Syed Tajammul Hussain, Abdelhamid Sayari, a al Larachi, Enhancing the stability of MnCeO WETOX catalysts using
potassium, Applied Catalysis B: Environmental, Volume 34, Issue 1, 31 October 2001, Pages 1-9, ISSN 0926-3373,
https://doi.org/10.1016/S0926-3373(01)00204-1.
Abstract: MnCeO composite catalysts are being widely advocated in sub- and supercritical catalytic wet oxidation
(WETOX) for the mineralization (i.e. complete conversion to CO2) of toxic organics contained in aqueous streams. Catalytic
WETOX of CHO-containing compounds over MnCeO catalysts is accompanied with undesirable heavy polymers building
upon the catalyst surface, thereby leading to severe loss in catalytic activity and mineralization selectivity. Hence, new
potassium-doped MnCeO mixed oxide catalysts (Mn/Ce atomic ratio=1) synthesized by co-precipitation/impregnation
were tested for the destruction of phenolic model wastewaters in a batch slurry reactor using oxygen and very mild
reaction conditions. Remarkable improvements in mineralization selectivity were attained upon addition of potassium.
Complete removal of the organic pollution, with mineralization selectivity exceeding 95%, was achieved within 1020 min
over fresh KMnCeO catalyst. Virtually, total elimination of organic carbon was also achieved using the same catalyst 3
times without any regeneration. Likewise, the stability to leaching of the WETOX catalytic ingredients was very high as
confirmed by analysis of the treated solutions. Characterization of fresh and used MnCeO and KMnCeO catalysts was
conducted using nitrogen adsorption, temperature-programmed reduction (TPR) and temperature-programmed oxidation
(TPO), infrared spectroscopy (FTIR), CHN elemental analysis and X-ray diffraction (XRD) techniques. These techniques
corroborated the drastic reduction in carbonaceous deposits on the catalyst surface and the significant enhancement in
stability of the K-doped catalysts. These improvements were discussed in terms of modification of the redox properties of
cerium and manganese through interactions with potassium in the doped MnCeO catalysts.
Keywords: Heterogeneous wet oxidation; Carbonaceous deposit; Deactivation; Detoxification
Pietro Palmisano, Nunzio Russo, Paolo Fino, Debora Fino, Claudio Badini, High catalytic activity of SCS-synthesized ceria
towards diesel soot combustion, Applied Catalysis B: Environmental, Volume 69, Issues 12, 1 December 2006, Pages 85-92,
Abstract: Nano-sized particles of ceria with high surface area were processed by solution combustion synthesis (SCS) and
their catalytic activity towards combustion of carbonaceous materials was compared with that obtained by simple thermal
decomposition of cerium nitrate, exhibiting the same specific surface area. These two kinds of ceria powders were tested
by DTA and temperature-programmed combustion of diesel soot and a commercial carbon.
Ceria processed by SCS was found to be more active than its counter part since it could decrease significantly both the
combustion activation energy (from 115 to 111 kcal/mol) and the TPC-plot peak temperature of diesel soot (from 466 to
405 C).
The mechanism of the catalytic reaction of combustion was investigated by TPD/R experiments. Likewise other combustion
catalysts acting as oxygen pumps, ceria can exchange limited amounts of oxygen even below 300 C, the SCS-synthesized
one showing a superior O2 release at low temperatures (450 C). Moreover, the SCS-ceria exhibited a microstructure (i.e. a
foam of nano-sized crystals) particularly suitable for maximizing the number of contact points between catalyst and carbon.
Finally, the effect of specific aging protocols (thermal treatment at 600 C for 96 h) in the presence of potentially
deactivating species present in diesel exhaust gases (SO2 and water) was also studied showing that the here proposed
material suffers from less significant ageing than Ce(NO3)3-derived ceria.
Keywords: Ceria; Solution combustion synthesis; Catalytic combustion; Soot; Diesel engine
Xanthias Karatzas, Jazaer Dawody, Ann Grant, Erik Elm Svensson, Lars J. Pettersson, Zone-coated Rh-based monolithic
catalyst for autothermal reforming of diesel, Applied Catalysis B: Environmental, Volume 101, Issues 34, 14 January 2011,
Abstract: In this work we present results of hydrogen generation from diesel via autothermal reforming (ATR) obtained with
monolithic catalysts consisting of either one or two layers of monometallic Rh and bimetallic RhPt washcoats. The Rh metal
loading of the monometallic washcoats was varied between 0.5, 1.0 and 3.0 wt%, while the weight ratio of Rh:Pt in the
bimetallic washcoats was kept constant at 1:1. Furthermore, non-doped and CeLa-doped catalysts were also tested to
detect differences in catalyst activity. The catalysts consisting of two layers of washcoats were termed zoned catalysts and
each layer was applied to some given length in the axial direction of the monolith. All catalysts were prepared by
impregnation using the incipient wetness technique with -Al2O3 as support and deposited onto 400 cpsi cordierite
monoliths. A total of eight catalysts, including both single layered and zone-coated, were tested in a bench-scale reactor
using low-sulfur diesel as fuel at operating conditions H2O/C = 2.5, O2/C = 0.49 ( = 0.33), GHSV = 17,000 h1 and P = 1 atm.
The results showed that the zoned catalyst, covered with the two washcoats Rh1.0Pt1.0Ce10La5.0/-Al2O3 and Rh3.0
Ce10La10/-Al2O3, respectively, was most active in terms of fuel conversion and hydrogen production. The zoned catalyst's
long-term performance and stability was also evaluated in a full-scale reactor using low-sulfur and FischerTropsch diesels
at operating conditions H2O/C = 2.5, O2/C = 0.49 ( = 0.33), GHSV = 10,800 h1, P = 1 atm, and at H2O/C = 2.4, O2/C = 0.39
( = 0.26), GHSV = 10,200 h1, P = 1 atm, respectively. The results showed that high fuel conversion and hydrogen
production were obtained from both fuels. In addition, partial oxidation and steam reforming reactions were identified by
closely studying the distribution of the analyzed product gas composition and the temperature measurements. Fresh and
aged samples of the catalysts were characterized by N2-BET, H2 chemisorption, XRD, H2-TPR, O2-TPO and XPS analyses.
Keywords: Autothermal reforming; Diesel; Rhodium; Zone-coated monolithic catalyst
Lae a Oliviero, Jac ues Barbier Jr., Daniel Duprez, A. Guerrero-Ruiz, B. Bachiller-Baeza, I. Rodr guez-Ramos, Catalytic wet
air oxidation of phenol and acrylic acid over Ru/C and RuCeO2/C catalysts, Applied Catalysis B: Environmental, Volume 25,
Issue 4, 20 March 2000, Pages 267-275, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(99)00141-1.
Abstract: Ru/C catalysts promoted, or not, by cerium were prepared by impregnation of an active carbon (961 m2 g1) with
chlorine-free precursors of Ru and Ce. They were characterized by chemisorption of H2 and of CO and by electron
microscopy. TEM and H2 chemisorption gives coherent results while CO chemisorption overestimates Ru dispersion. In Ru
Ce/C, Ce is in close contact with Ru and decreases Ru accessibility.
Catalytic wet air oxidation (CWAO) of phenol and of acrylic acid (160C and 20 bar of O2) was investigated over these
catalysts and their performance (activity, selectivity to intermediate compounds) compared with that of a reference
Ru/CeO2 catalyst. Carbon-supported catalysts were very active for the CWAO of phenol but not for acrylic acid. Although
high conversions were obtained, phenol was not totally mineralized after 3 h. It was shown that acrylic acid was more
strongly adsorbed than phenol. Moreover, the number of contact points between Ru particles and CeO2 crystallites
constitutes a key parameter in these reactions. A high surface area of ceria is required to insure O2 activation when the
organic molecule is strongly adsorbed.
Keywords: Wet air oxidation; Ruthenium catalysts; Phenol (catalytic oxidation in water of); Acrylic acid (catalytic oxidation
in water of)
Nelson E. Olong, Klaus Stwe, Wilhelm F. Maier, A combinatorial approach for the discovery of low temperature soot
oxidation catalysts, Applied Catalysis B: Environmental, Volume 74, Issues 12, 18 June 2007, Pages 19-25, ISSN 0926-3373,
Abstract: High-throughput syntheses using a commercial pipetting robot with the aid of the software Plattenbau as well
as a highly parallel screening technique were used in the search of low temperature soot oxidation catalysts. It has been
shown that emissivity-corrected infrared thermography which monitors the heat changes resulting from the heat of
reaction on catalyst surfaces is an efficient and fast screening technique of soot oxidation catalysts. It was found that alkali
metal mixed oxides have the potential to decrease the soot oxidation temperature to diesel exhaust realistic temperatures.
From the first generation, the oxides K3Ce97 and Cs3Co97 were found to be the most active and stable samples. Further
doping and composition spread of the CsCo catalyst resulted in even more active samples. HT-screening experiment hits
were successfully confirmed by thermogravimetric analysis.
Keywords: Diesel soot combustion; Combinatorial synthesis; High-throughput screening
Fernando Mario, Claude Descorme, Daniel Duprez, Noble metal catalysts for the preferential oxidation of carbon
monoxide in the presence of hydrogen (PROX), Applied Catalysis B: Environmental, Volume 54, Issue 1, 30 November 2004,
Abstract: Oxide-supported noble metal catalysts were tested in the preferential oxidation of carbon monoxide (PROX)
reaction in the temperature range between 50 and 300 C. Both the influence of the noble metal nature (Pt, Ir, Pd), the
support physical and chemical properties (redox, acidity, basicity) and the reaction conditions (oxygen stoichiometry) on the
catalyst activity and selectivity was evaluated. Platinum and iridium were shown to be the most active and selective
catalysts in the whole temperature range compared with palladium. Furthermore, noble metals supported over ceria-based
oxides were shown to be active and selective, especially at low temperature. Additionally, it was observed that the higher
the molar fraction in ceria in the oxide, the higher the activity and the selectivity in the PROX reaction. Ceria, with the
highest oxygen mobility at the oxide surface, was shown to be the best support. Accordingly, on simple oxides (CeO2, SiO2
Al2O3, Al2O3, SiO2, La2O3 and MgO), the induced mobility of the oxygen atoms at the surface of the support determined
elsewhere, well correlated with the basicity of the support, was shown to be one key parameter for the performances of
the catalysts in the PROX reaction. Finally, the formation of water (hydrogen oxidation) at high temperature and high
oxygen excess was shown to be responsible for the increasing activity of the catalysts in the conversion of CO to CO2 via the
water gas shift reaction (WGSR).
Keywords: Preferential oxidation of CO; PROX; hydrogen purification; Noble metals; Platinum; Iridium; Palladium;
Supported catalysts; Acidobasicity; Redox; Oxygen mobility; Fuel cells; WGSR
Chang Ryul Jung, Arunabha Kundu, Suk Woo Nam, Ho-In Lee, Selective oxidation of carbon monoxide over CuOCeO2
catalyst: Effect of hydrothermal treatment, Applied Catalysis B: Environmental, Volume 84, Issues 34, 1 December 2008,
Abstract: Copper oxideceria (CuOCeO2) catalyst for selective oxidation of carbon monoxide (CO) was prepared by co-
precipitation and hydrothermal treatment methods and evaluated for catalytic activity in a reformate gas composition
which simulated the produced gas from methanol steam reforming. By applying the condition of hydrothermal treatment,
the catalytic activity of CuOCeO2 catalyst was increased and the operating temperature window, in which the
concentration of carbon monoxide was lower than 10 ppm, was widened. From the thermogravimetric (TG) results of
hydrothermally treated catalyst precursor, CuOCeO2 catalyst did not show any improvement in physical properties such as
Brunauer Emmett Teller (BET) surface area, pore volume and average pore diameter, but the chemical stability might be
enhanced by hydrothermal treatment. By hydrothermal treatment, cuprous ion in the CuOCeO2 catalyst migrated to the
surface of catalyst resulting in increased surface concentration of copper and formation of cupric oxide on the surface of
catalyst during calcination. While increasing the calcination temperature (i.e. above 800 C), the phase separation occurred
with a part of copper and cupric oxide was formed on the surface of catalyst which was observed in X-ray diffraction (XRD)
analysis.
Keywords: CuOCeO2 catalyst; Hydrothermal treatment; CuCeO solid solution; Selective oxidation of CO; Phase
separation; Copper; Ceria
Mlanie Taillades-Jacquin, Carlo Resini, Kan-Ern Liew, Gilles Taillades, Ilenia Gabellini, David Wails, Jacques Rozire,
Deborah Jones, Effect of the nature of the support on the activity of Pt-Sn based catalysts for hydrogen production by
dehydrogenation of Ultra Low Sulfur Kerosene Jet A-1, Applied Catalysis B: Environmental, Volumes 142143, October
November 2013, Pages 112-118, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2013.02.037.
Abstract: Production of hydrogen on-board an airplane, to feed a fuel cell secondary power generation unit, is realisable by
catalytic partial dehydrogenation of kerosene. The influence of the nature support on the partial dehydrogenation of Ultra
Low Sulfur Kerosene Jet A-1 using Pt-Sn based catalysts is investigated in this work. The doping of an alumina support with
barium oxide leads to a catalyst providing a productivity of 2000 NLH2 kgcat1 h1 with H2 purity of 97 vol.%.
Keywords: Hydrogen production; Partial dehydrogenation; Ultra Low Sulfur Kerosene; Pt-Sn/Al2O3 based catalysts; Catalyst
support influence
J.R. Gonzlez-Velasco, J. Entrena, J.A. Gonzlez-Marcos, J.I. Gutirrez-Ortiz, M.A. Gutirrez-Ortiz, Preparation, activity and
durability of promoted platinum catalysts for automotive exhaust control, Applied Catalysis B: Environmental, Volume 3,
Issues 23, 1 February 1994, Pages 191-204, ISSN 0926-3373, https://doi.org/10.1016/0926-3373(93)E0030-F.
(http://www.sciencedirect.com/science/article/pii/0926337393E0030F)
Abstract: The effects of the addition of calcia, ceria and lanthana to alumina-supported platinum catalysts on the
simultaneous control of hydrocarbon, carbon monoxide and nitrogen oxide automobile emissions (three-way catalyst
behaviour) were analyzed. The activity of the prepared samples was determined with steady-state, reducing and oxidizing,
simulated feedstreams as well as with a cycled oxidizing-reducing feedstream averaged at the stoichiometric conditions
which resembled the exhaust air/fuel fluctuations in a closed-loop emission control system. Activity of the catalysts was
also analyzed after conducting accelerated thermal and chemical ageing in order to test their durability. Under normal
operating conditions of the automobile engine, Pt/Al2O3 catalysts promoted by rare-earth oxides are able to achieve high
HC, CO and NO conversions. The behaviour of the catalysts in the cold start period was determined by analysis of light-off
temperatures and a comparison was made with those corresponding to some commercial samples and others reported in
the literature. The catalysts prepared in this work showed lower light-off temperatures than those of commercial and
reported Pt/Al2O3 catalysts but these temperatures were not so low as with Pt Rh/Al2O3. In all cases, the prepared
catalysts resulted in a better resistance to accelerated ageing. Samples with ceria showed the best resistance to accelerated
ageing.
Keywords: automobile exhaust control; calcia; ceria; lanthana; platinum; promoter activity; three-way catalysts
M. Stanciulescu, G. Caravaggio, A. Dobri, J. Moir, R. Burich, J.-P. Charland, P. Bulsink, Low-temperature selective catalytic
reduction of NOx with NH3 over Mn-containing catalysts, Applied Catalysis B: Environmental, Volumes 123124, 23 July
Abstract: Mn-containing catalysts exhibit a high NOx conversion in selective catalytic reduction (SCR) with NH3. Their high
activity (80100%) covers a broad temperature range (195600 C). 100% N2 formation is reached at about 230 C for the
catalysts prepared by Mn ion-exchanged in CBV-2314, a MFI zeolite. The catalysts obtained by Mn- or Fe-exchange zeolites
are superior for N2 formation compared to those prepared by wet impregnation of Mn precursors on the -Al2O3 (80%)-
TiO2 (20%) catalyst support.
Since the Mn catalysts are active for NOx reduction in the intermediate temperature range of diesel engine exhaust mainly,
an effort was undertaken in this study to extend this temperature range by promoting Mn with Cu, Ce and Fe oxides. These
catalysts with two metals in the active phase were prepared and tested for DeNOx activity. All promoted catalysts showed
higher formation of N2 at either low or high temperatures. The Ce/MnCBV-2314 catalyst was more active and stable at high
temperatures, close to 600 C, than those containing Fe or Cu oxides. Cu/MnCBV-2314 showed high activity at low
temperature. 100% N2 formation for 2.1Mn/3.8FeCBV ranged from 220 to beyond 450 C.
Keywords: NH3SCR for NOx; Mn exchanged zeolites; Mn/(-Al2O3-TiO2); Ce/MnCBV-2314; Fe/MnCBV-2314; Cu/MnCBV-
2314; Low temperature SCR
T.M.C. Hoang, B. Geerdink, J.M. Sturm, L. Lefferts, K. Seshan, Steam reforming of acetic acid A major component in the
volatiles formed during gasification of humin, Applied Catalysis B: Environmental, Volume 163, February 2015, Pages 74-82,
Abstract: Abstract
Acetic acid and phenols are the major components of the condensable by-products in the low temperature de-volatilisation
stage of humin during gasification. Catalytic steam reforming of acetic acid using supported Ni on ceria-zirconia mixed oxide
prepared via the hydrothermal route is discussed. The influence of steam reforming temperatures, steam/carbon ratios
were studied. The catalyst showed high activity and good stability. Furthermore, activity improvement was achieved with
multiple redox cycles as relevant to recycling the catalysts. Characterisation of the fresh and used catalyst by various
techniques (e.g., LEIS, Raman spectroscopy, TPO/TPR) revealed the modification of metal-oxygen bond on the support
under the steam reforming conditions. It in turn improved the oxygen mobility of the catalyst.
Keywords: Steam reforming; Acetic acid; Humin; Nickel; Ceriazirconia
Qiang Yu, Lianjun Liu, Lihui Dong, Dan Li, Bin Liu, Fei Gao, Keqin Sun, Lin Dong, Yi Chen, Effects of Ce/Zr ratio on the
reducibility, adsorption and catalytic activity of CuO/CexZr1xO2/-Al2O3 catalysts for NO reduction by CO, Applied
Catalysis B: Environmental, Volume 96, Issues 34, 7 June 2010, Pages 350-360, ISSN 0926-3373,
Abstract: Effects of Ce/Zr ratio on the physicochemical properties of CuO/CexZr1xO2/-Al2O3 catalysts were investigated
by BET, XRD, Raman and H2-TPR. The catalytic activity and the interaction between the reactants with these catalysts were
compared by NO + CO model reaction and in situ FT-IR. The results suggested that the addition of ceriazirconia mixed
oxides significantly improved NO conversion and N2 yield due to dispersed copper species in proximity to ceriazirconia.
Especially, the ceria-rich catalysts displayed better performance in activity and reducibility than others, which would be
resulted from the strong interaction among copper, ceriazirconia and support. The IR results suggested NO reduction
activity was correlated with the presence of Cu+ carbonyl species, and the catalysts with variable Ce/Zr ratios had no
distinction at the adsorption type and rate of NO/CO at room temperature. However, on heating treatment would give
distinct difference in CO2 intensity and the wavenumber of adsorbed nitrates. Simultaneously, the stability of these N- and
C-containing intermediates contacted with alumina was influenced by the modified Ce/Zr ratio.
Keywords: CuO/CexZr1xO2/-Al2O3; NO + CO model reaction; H2-TPR; In situ FT-IR; Carbonate; Nitrate
Vijay M. Shinde, Giridhar Madras, Synthesis of nanosized Ce0.85M0.1Ru0.05O2 (M = Si, Fe) solid solution exhibiting high
CO oxidation and water gas shift activity, Applied Catalysis B: Environmental, Volumes 138139, 17 July 2013, Pages 51-61,
Abstract: Nanosized Ce0.85M0.1Ru0.05O2 (M = Si, Fe) has been synthesized using a low temperature sonication method
and characterized using XRD, TEM, XPS and H2-TPR. The potential application of both the solid solutions has been explored
as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe- in Ce0.95Ru0.05O2 greatly enhanced the
reducibility of Ce0.85M0.1Ru0.05O2 (M = Si, Fe), as indicated by the H2-TPR study. The oxygen storage capacity has been
used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice
oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 C. A bifunctional reaction mechanism
involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O2 has been
used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy
application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the
hydrogen production and a lack of methanation activity is an important finding of present study.
Keywords: Solid solution; Ceria supported catalyst; Oxygen storage capacity; CO oxidation; Redox mechanism; Water gas
shift
Petar Djinovi, Ilja Gasan Osojnik rnivec, Botjan Erjavec, Albin Pintar, Influence of active metal loading and oxygen
mobility on coke-free dry reforming of NiCo bimetallic catalysts, Applied Catalysis B: Environmental, Volume 125, 21
August 2012, Pages 259-270, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2012.05.049.
Abstract: Two different techniques (precipitation with ammonia and hydrothermal synthesis with ethylene glycol, both
followed by autoclave aging) were employed for the synthesis of CeO2ZrO2 mixed oxides on a 8020 wt.% basis. Aging
parameters, such as time and temperature, were systematically investigated in order to determine the optimal conditions
to maintain high surface area and oxygen mobility of the prepared solids. Different loadings of nickel and cobalt (3, 6, 12
and 18 wt.%) were subsequently deposited via homogeneous deposition precipitation method. Calcined bimetallic catalysts
were characterized by N2 adsorptiondesorption, XRD, H2-TPR, TPO-TGA and FE-SEM methods, and tested for activity,
selectivity and stability in the reforming of equimolar CH4CO2 gas streams. During temperature programmed methane
reforming tests, syngas with a H2/CO ratio between 0.3 and 0.79 was produced. Growth of carbon nanofilaments over the
catalyst does not lead to deactivation, but can cause reactor plugging. Two conditions are vital and must be fulfilled
simultaneously to avoid excessive carbon deposition: strong interaction between the NiCo bimetallic particles and CeZr
support, which exists only at NiCo loadings up to 6 wt.%, as well as high oxygen mobility within the highly defective CeO2
ZrO2 crystalline lattice for timely carbon oxidation.
Keywords: Methane dry reforming; Deactivation; CeO2ZrO2; Oxygen mobility; Nickel cobalt bimetallic catalysts
Martyn V. Twigg, Progress and future challenges in controlling automotive exhaust gas emissions, Applied Catalysis B:
Environmental, Volume 70, Issues 14, 31 January 2007, Pages 2-15, ISSN 0926-3373,
Abstract: By the early 1970s increased use of cars in some major cities had resulted in serious concerns about urban air
quality caused by engine exhaust gas emissions themselves, and by the more harmful species derived from them via
photochemical reactions. The three main exhaust gas pollutants are hydrocarbons (including partially oxidised organic
compounds), carbon monoxide and nitrogen oxides. Engine modifications alone were not sufficient to control them, and
catalytic systems were introduced to do this. This catalytic chemistry involves activation of small pollutant molecules that is
achieved particularly effectively over platinum group metal catalysts. Catalytic emissions control was introduced first in the
form of platinum-based oxidation catalysts that lowered hydrocarbon and carbon monoxide emissions. Reduction of
nitrogen oxides to nitrogen was initially done over a platinum/rhodium catalyst prior to oxidation, and subsequently
simultaneous conversion of all three pollutants over a single three-way catalyst to harmless products became possible
when the composition of the exhaust gas could be maintained close to the stoichiometric point. Today modern cars with
three-way catalysts can achieve almost complete removal of all three exhaust pollutants over the life of the vehicle. There
is now a high level of interest, especially in Europe, in improved fuel-efficient vehicles with reduced carbon dioxide
emissions, and lean-burn engines, particularly diesels that can provide better fuel economy. Here oxidation of
hydrocarbons and carbon monoxide is fairly straightforward, but direct reduction of NOx under lean conditions is practically
impossible. Two very different approaches are being developed for lean-NOx control; these are NOx-trapping with periodic
reductive regeneration, and selective catalytic reduction (SCR) with ammonia or hydrocarbon. Good progress has been
made in developing these technologies and they are gradually being introduced into production. Because of the nature of
the diesel engine combustion process they produce more particulate matter (PM) or soot than gasoline engines, and this
gives rise to health concerns. The exhaust temperature of heavy-duty diesels is high enough (250400 C) for nitric oxide to
be converted to nitrogen dioxide over an upstream platinum catalyst, and this smoothly oxidises retained soot in the filter.
The exhaust temperature of passenger car diesels is too low for this to take place all the time, so trapped soot is
periodically burnt in oxygen above 550 C. Here a platinum catalyst is used to oxidise higher than normal amounts of
hydrocarbon and carbon monoxide upstream of the filter to give sufficient temperature for soot combustion to take place
with oxygen. Diesel PM control is discussed in terms of a range of vehicle applications, including very recent results from
actual on-road measurements involving a mobile laboratory, and the technical challenges associated with developing ultra-
clean diesel-powered cars are discussed.
Keywords: Vehicle emissions; Autocatalysts; Three-way catalysts (TWCs); NOx-traps; Selective catalytic reduction (SCR);
Diesel particulate filters
N. Le Phuc, X. Courtois, F. Can, S. Royer, P. Marecot, D. Duprez, NOx removal efficiency and ammonia selectivity during the
NOx storage-reduction process over Pt/BaO(Fe, Mn, Ce)/Al2O3 model catalysts. Part II: Influence of Ce and MnCe addition,
Applied Catalysis B: Environmental, Volume 102, Issues 34, 22 February 2011, Pages 362-371, ISSN 0926-3373,
Abstract: It was previously demonstrated in the first part of this work that NOx storage-reduction process over
Pt/BaO/Al2O3 model catalyst is limited by the reduction step, with ammonia emission since H2 is not fully consumed. The
stored NOx reacts preferentially with the introduced H2 giving NH3, than with NH3 in order to produce N2. Mn addition
favors the NOx reduction with ammonia leading to better conversion and selectivity, but only at 400 C. In Part II, a special
attention was focused on the role of Ce and MnCe addition in regard to the NOx conversion and the ammonia emission in
the 200400 C temperature range. With ceria modified Pt/20Ba/Al catalyst, significant improvements are obtained from
300 C. In addition to the enhancement of the NOx + NH3 reaction, the ammonia selectivity is maintained at a lower level
compared with Pt/Ba(Mn)/Al catalysts, even in the case of a large H2 excess. It is attributed to the ammonia oxidation into
N2 via the available oxygen at the catalyst surface. A synergetic effect is observed between Mn and Ce when they are
added simultaneously in Pt/Ba/Al catalyst.
Keywords: NOx storage; NOx reduction; Ammonia; Barium; Lean/rich cycles; Manganese; Ceria
L.F. Liotta, A. Longo, A. Macaluso, A. Martorana, G. Pantaleo, A.M. Venezia, G. Deganello, Influence of the SMSI effect on
the catalytic activity of a Pt(1%)/Ce0.6Zr0.4O2 catalyst: SAXS, XRD, XPS and TPR investigations, Applied Catalysis B:
Environmental, Volume 48, Issue 2, 18 March 2004, Pages 133-149, ISSN 0926-3373,
Abstract: The steady-state activity of NO reduction by C3H6, in lean conditions, was studied on a Pt(1%)/Ce0.6Zr0.4O2
catalyst, in a plug-flow reactor, in the temperature range 100500 C. The influence of reductive pre-treatments on the
catalytic performance at low temperature (250 C) was investigated. Enhancement of the activity was found for the catalyst
pre-treated in hydrogen at 350 C as compared to the sample pre-treated in H2 at 800 and 1050 C. Moreover, transient
reactivity tests of NO reduction by hydrogen were also carried out. As previously observed, the sample reduced at 350 C
was the most active catalyst. In both types of reactions the temperature and the nature of pre-treatments had no effect on
the selectivity to N2 at the temperature of maximum NO conversion. Analyses by temperature programmed reduction
(TPR), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) supported the
occurrence of a strong metalsupport interaction (SMSI) effect between platinum and ceria and the important role of the
platinum in promoting the ceria-zirconia structural reorganization. Such type of interaction determined a decrease of the
platinum and ceria reduction temperature and a stabilization of the platinum oxide even in reducing atmosphere at high
temperature. The catalytic behavior of the Pt/ceria-zirconia catalyst was discussed in terms of the structural and electronic
modifications induced by the SMSI effect.
U. Oran, D. Uner, Mechanisms of CO oxidation reaction and effect of chlorine ions on the CO oxidation reaction over
Pt/CeO2 and Pt/CeO2/-Al2O3 catalysts, Applied Catalysis B: Environmental, Volume 54, Issue 3, 20 December 2004, Pages
Abstract: The reaction orders and activation energies of CO oxidation reaction over Pt/-Al2O3, Pt/CeO2 and Pt/CeO2/-
Al2O3 were investigated for stoichiometric gas mixtures. The effect of residual chlorine originating from catalyst precursors
on the CO oxidation activity of Pt/-Al2O3, Pt/CeO2 and Pt/CeO2/-Al2O3 was also studied. Indirect evidence was collected
indicating that platinum was selectively deposited on alumina surface when Pt/CeO2/-Al2O3 catalyst was prepared from
the physical mixture of pure oxides. The reaction orders of CO and O2 was found approximately as 2.0 and +1.0,
respectively, over the Pt/-Al2O3 catalyst, but as 1.0 and 0.0 over the Pt/CeO2 and Pt/CeO2/-Al2O3 catalysts. The
activation energy of CO oxidation reaction over Pt/-Al2O3 catalyst under stoichiometric conditions was around 120.0
kJ/mol. On the other hand, over Pt/CeO2 catalysts activation energies were measured to be around 70 kJ/mol. Surface
reaction mechanisms were postulated to explain the differences in the reaction orders and activation energies.
Keywords: CO oxidation; Platinum; Ceria; Alumina; Reaction mechanism; Chlorine poisoning
Fernando Mario, Claude Descorme, Daniel Duprez, Supported base metal catalysts for the preferential oxidation of carbon
monoxide in the presence of excess hydrogen (PROX), Applied Catalysis B: Environmental, Volume 58, Issues 34, 28 June
Abstract: Supported base metal catalysts were tested for the preferential oxidation of CO (CO PROX). The catalysts we
investigated covered a wide range of transition metals (Co, Cr, Cu, Ni, Zn) supported on oxides with very different acidic,
basic and redox properties (MgO, La2O3, SiO2Al2O3, CeO2, Ce0.63Zr0.37O2). The influence of the metal loading (Cu), the
support properties (acidity, basicity, redox, surface area) and the reaction conditions (reaction temperature, feed
composition) on the catalyst activity and selectivity was evaluated. The activity of ceria and ceriazirconia supported copper
catalysts was comparable to the performances of noble metal samples classically used for the PROX reaction. In addition,
CuCeO2 catalysts showed a practically constant and high selectivity towards CO oxidation in the temperature range of 50
150 C. Due to the strong synergetic effect between copper and ceria, only a small amount of copper (0.3 wt.%) was
necessary to get an active catalyst. The best catalytic performances were obtained for the samples containing 13 wt.%
copper. The presence of small copper particles in close interaction with the ceria support was shown to be responsible for
the enhanced activity. Except for the hydrogen oxidation, no parallel reactions (CO or CO2 methanation reactions, coking,
RWGS) could be detected over these catalysts. Classically, an increase of the oxygen excess led to an increased CO
conversion with a simultaneous loss of selectivity towards CO2. Finally, the presence of CO2 in the feed negatively affected
the catalytic activity. This effect was attributed to the adsorption of CO2 on the copper sites, probably as CO.
Keywords: Preferential oxidation of CO; PROX; Base metals; Copper; Ceria; Supported catalysts; Redox; Oxygen mobility;
Hydrogen purification; Fuel cells
C. Larese, M. Lpez Granados, F. Cabello Galisteo, R. Mariscal, J.L.G. Fierro, TWC deactivation by lead: A study of the
Rh/CeO2 system, Applied Catalysis B: Environmental, Volume 62, Issues 12, 10 January 2006, Pages 132-143, ISSN 0926-
3373, https://doi.org/10.1016/j.apcatb.2005.06.008.
Abstract: The effect of the incorporation of low amounts of Pb to a Rh/CeO2 catalyst on the typical reactions involved in
Three Way Catalysts converters was investigated. The catalytic tests showed no deactivation for CO oxidation and NO
reduction whereas for propylene oxidation the deactivation was evident and more intense with the increasing of Pb
concentration. The interpretation of this behaviour is discussed on the basis of HREM combined with XEDS analysis, TPR
and DRIFT spectroscopy of chemisorbed CO studies. The results provided clear evidence that Pb is not covering the Rh
particles neither forming a new phase with Rh nor altering the dispersion of the Rh particles. They also suggest that a mixed
oxide is formed in which lead cations are dissolved within the fluorite-like ceria structure. Thus, CeO2 support may act as
sink of Pb preventing the formation of a RhPb compound that explains why the CO oxidation and the NO reduction were
only slightly affected. However, an electronic interaction between the Rh particles and the Pb-containing CeO2 support is
evidenced by TPR and DRIFTS-CO chemisorption data: the Pb present in the Rh-CeO2 interphase as a result of the Pb
dissolution in the ceria framework is proposed to be responsible for the electronic donation to Rh metal particles. The
possibility that the electronic interaction and/or the modification of the oxygen storage capacity (OSC) of the ceria, both
caused by the Pb, bring about the deactivation in the oxidation of propylene is also discussed.
May Issa, Alain Brillard, Valrie Tschamber, Jean-Franois Brilhac, Modelling of Carbon Black oxidation in the presence of
CeO2 catalyst using a 3D representation of the solidsolid mixture, Applied Catalysis B: Environmental, Volume 181,
February 2016, Pages 228-235, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2015.07.040.
Abstract: Abstract
A model based on a 3D representation of mixtures involving Carbon Black (CB) and commercial ceria (CeO2) particles placed
in a fixed bed reactor is proposed. Catalyst particles may aggregate in different ways in the whole bed and different CB
CeO2 mass ratios are considered which range from 955 to 1090. Two types of oxidation are assigned by the model: a
catalytic oxidation under the influence of CeO2 and a non-catalytic one in the other case. The activation energies of these
oxidation processes have been determined through experiments, while their frequency factors are derived for the two
reactions using a numerical simulation. The model simulates the CB oxidation in a good way whatever the CBCeO2 mass
ratio, except for the 5050 case. The catalytic oxidation is here underestimated, as the contact between CB and CeO2 is
progressively lost.
Keywords: Soot oxidation modelling; Carbon Blackceria mixture; 3D representation of mixtures; Determination of kinetic
parameters
L. Mart ́n, J.L. Arranz, O. Prieto, R. Trujillano, M.J. Holgado, M.A. Galn, V. Rives, Simulation three-way
catalyst ageing: Analysis of two conventional catalyst, Applied Catalysis B: Environmental, Volume 44, Issue 1, 8 August
2003, Pages 41-52, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(03)00008-0.
Abstract: Two commercial automobile three-way catalysts (RENAULT) of different configuration: (I) Pt, Rh active phase
supported on ceria-promoted alumina washcoat, and (II) Pd, Rh active phase supported on zirconia-ceria-promoted alumina
washcoat on cordierite supports, have been compared fresh and aged in a conventional automobile for 100,000 km in order
to design and to adjust a catalyst ageing method suitable to imitate most relevant conditions of real tests. The
characterization techniques were N2 adsorptiondesorption isotherms, powder X-Ray diffraction, elemental chemical
analysis and activity tests. Activity tests were: (1) CO, NO and CH4 conversion versus temperature (from 120 to 500 C), and
(2) CO, NO and CH4 conversion versus the ratio between the concentrations of the oxidant and reducing species () at 500
C (normal running temperature). Gas composition was close to conventional engine exhaust composition with and without
water vapour. A strong deactivation has been observed as a consequence of thermal processes and loss of catalyst
washcoat mainly for catalyst (II). Poison concentration along the catalyst has also been shown, however, its influence on
catalyst deactivation was not as important as thermal processes were.
Keywords: Commercial automobile three-way catalysts; Characterization; Catalyst ageing method
Andr F. Rossi, Nuno Amaral-Silva, Rui C. Martins, Rosa M. Quinta-Ferreira, Heterogeneous Fenton using ceria based
catalysts: effects of the calcination temperature in the process efficiency, Applied Catalysis B: Environmental, Volumes 111
112, 12 January 2012, Pages 254-263, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2011.10.006.
Abstract: The need of more efficient solid catalysts for the heterogeneous slurry Fenton process led many investigators to
research new compounds activities. Ceria based iron catalysts have proved their good performance enhancing the removal
of organic compounds, reducing toxicity and improving biodegradability in the depuration of phenolic wastewaters. This
work evaluates the calcination temperature (300 C, 600 C and 1000 C) during the preparation of the catalystsco-
precipitation of the precursors salts, while the same previously optimized conditions were adopted (pH 3.0, 1.0 g L1 of e
CeO 70/30 as the catalyst, [H2O2] = 244 mM and 120 min of room temperature reaction) to treat a simulated wastewater
comprising 0.1 g L1 of each of the six common phenolic acids found in Olive Mills wastewaters. The three obtained solids
were characterized regarding superficial area, average pore diameter, FT-IR and XRD. Catalysts calcinated at 300 C, 600 C
and 1000 C presented superficial areas of 188, 86 and 2 m2/g, respectively, and their average pore diameter are 66, 87 and
151 , correspondingly. As showed in the XRD, the increase of the calcination temperature promotes the crystallinity of the
obtained solidhigher amount of prominent peaks, meaning that the catalysts have different states of valence for iron
(Fe2+ or Fe3+) and ceria (Ce2+ to Ce4+), what would explain their singular behaviours during the reaction. As expected, the
solids with higher superficial areas had better performances in every aspect: more COD, TOC and phenolic acids removal,
pointing the lowest calcination temperature as leading to a more efficient solid to enhance hydrogen peroxidation,
involving, however, more metal leaching. The higher the calcination temperature is, the more oxidized the solid will
become because the calcination occurs without atmospheric control and so the oxygen contained in the air will interfere on
the valence of iron ions at the solid's surface. This means that a solid calcinated at a higher temperature will have increased
Fe3+ content and, as one can find in the literature, Fe2+ is more effective than Fe3+ at hydrogen peroxidation, explaining
the better efficiency of the catalyst calcinated at the lowest temperature. Toxicological and biodegradability studies were
still performed and showed enhancement in all cases.
Keywords: Heterogeneous Fenton's process; Catalyst characterization; Environment protection; Phenolic acids; Toxicity
L. Coronel, J.F. Mnera, A.M. Tarditi, M.S. Moreno, L.M. Cornaglia, Hydrogen production by ethanol steam reforming over
Rh nanoparticles supported on lanthana/silica systems, Applied Catalysis B: Environmental, Volumes 160161, November
Abstract: Abstract
The aim of the present work was to investigate Rh nanoparticle catalysts supported on La2O3SiO2, with different contents
of La2O3, in the ethanol steam reforming reaction. The size of Rh particles was determined by both XPS, applying the Davis
model, and CO chemisorption measurements. Particle sizes between 1.2 and 3 nm were estimated with these techniques.
The catalyst with 15 wt.% of La2O3 was the most stable one under the different reaction conditions under study, i.e. 773 K
and water to ethanol molar ratios of 3 and 5. In order to explain the deactivation observed in the other catalysts, the
samples used in the reaction were characterized by XPS, TEM and in situ Raman spectroscopy. The TEM results allowed a
direct visualization of the carbon deposits that presented different degrees of catalyst coverage. The surface of the most
stable catalyst was not fully covered by carbon while the Rh/La2O3(40)SiO2 sample, which deactivated partially, exhibited
a carbon layer uniformly distributed over the surface. The oxidation of the carbon deposits was analyzed using in situ
Raman spectroscopy. Results were in agreement with those obtained by TEM microscopy. DRIFTS experiments under
reaction conditions suggested that the direct decomposition of ethoxy species would produce hydrogen, CO, and CHx
species, which could result in carbon formation.
Keywords: Ethanol steam reforming; Rh nanoparticles; Carbon deposition
, CO2 emissions from Cement manufacture have been underestimated, Applied Catalysis B: Environmental, Volume 13,
Issue 2, 14 October 1997, Pages N12-N13, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(97)90073-4.
, Chlorocarbon Destruction, Applied Catalysis B: Environmental, Volume 1, Issue 3, 29 September 1992, Pages N26-N27,
ISSN 0926-3373, https://doi.org/10.1016/0926-3373(92)80027-W.
(http://www.sciencedirect.com/science/article/pii/092633739280027W)
Asuncin Aranda, Said Agouram, Jose M. Lpez, Ana M. Mastral, David R. Sellick, Benjamn Solsona, Stuart H. Taylor, Toms
Garca, Oxygen defects: The key parameter controlling the activity and selectivity of mesoporous copper-doped ceria for the
total oxidation of naphthalene, Applied Catalysis B: Environmental, Volume 127, 30 October 2012, Pages 77-88, ISSN 0926-
3373, https://doi.org/10.1016/j.apcatb.2012.07.033.
Abstract: Mesoporous CeO2 modified by the addition of copper has shown high efficiency for the total oxidation of
naphthalene. High activity and 100% selectivity to carbon dioxide throughout the whole range of temperatures studied
were achieved for copper loadings of 3.6% and lower. The catalytic behaviour has been related to the concentration of
surface oxygen defects. A clear correlation between the concentration of surface oxygen defects (determined by XPS and
DRIFTS) and the catalytic performance has been identified. Catalytic activity increased as copper was incorporated into the
ceria up to 3.6%. In this range of copper content the copper was incorporated into the cubic fluorite lattice of CeO2 and this
was confirmed using XRD and electron diffraction studies. For copper ceria catalysts with higher copper contents the
concentration of oxygen defects decreased and an additional dispersed monoclinic CuO phase with a low intrinsic activity
was formed, thus leading to a decrease of both the activity and the selectivity to CO2.
Keywords: Catalytic oxidation; Mesoporous copper doped CeO2; Naphthalene; VOC; PAH
Dariush Shahidi, Ren Roy, Abdelkrim Azzouz, Advances in catalytic oxidation of organic pollutants Prospects for thorough
mineralization by natural clay catalysts, Applied Catalysis B: Environmental, Volumes 174175, September 2015, Pages 277-
292, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2015.02.042.
Abstract: Abstract
This review is devoted to oxidative water treatments, with emphasis on catalytic ozonation. The approach tackled herein
resides in exposing a wide variety of oxidative treatments attempts as a basis for summarizing the main findings that allow
envisaging improvements aiming towards total mineralization of organic pollutants. Comparison between specific operating
conditions for specific pollutant-catalyst-oxidizing systems is quite difficult, and is not targeted in the present work.
However, when deeply and judiciously analyzed, such a comparison allows demonstrating that, except for some works,
most of these attempts seldom took into accounts basic requirements such as the parameter interactions, the role of cation
mobility around a solid surface, if any, the multiple pollutant-catalyst-oxidizing species interactions and the significant
contribution of adsorption, etc. Otherwise, how to explain that many experiments are still conducted with unsuitable
catalysts under totally inadequate operating conditions? A better understanding of the essential requirements for a catalyst
to achieve total mineralization of any organic molecules is the main objective of this work.
The data summarized herein allow devoting a special interest to ozone, which is a powerful oxidizing agent and probably
the most easily handleable, in spite of its low solubility in water. The use of catalysts is an ultimate strategy to improve the
ozonation performance, by reducing the chemical oxygen demand (COD), even until total disappearance. However, solid
catalysts, more particularly those developing high specific surface areas, such as silicates, aluminosilicates, zeolites,
pseudozeolites, and clay minerals and derivatives are expected to display appreciable performances in ozonation. The latest
findings show strong dependency of their catalytic activity on the chemical and physical characteristics of their surface,
their concentration in the liquid media, the pH level of the reaction mixture and other parameters. The effects of these
factors will be systematically examined in this review paper. The state-of-the-art in the catalytic ozonation of organic
pollutants may be useful to understand the contribution of both surface and bulk ozonation reaction in the vicinity of the
surface of a solid catalyst, and more particularly the role of the catalytic agent and its mobility near the solid surface. A
rigorous data synthesis, made available in the present paper, allows understanding the ozone scavenging by the very
species present in water, and correlating the highest effectiveness of ozone in the presence of optimum catalyst
concentration at optimum pH. This supposes strong interactions between the main factors, which remain to be elucidated
for each type of catalyst.
The structure of this review makes emphasis on montmorillonite, which exhibits most of the required properties for
effective ozonation catalysts. These are common features of natural clay minerals and zeolites, which appear as interesting
candidates for large-scale water treatments, targeting complete mineralization of organic pollutants without generating
persistent toxins.
Keywords: Heterogeneous catalysis; Clay catalysts; Catalytic ozonation; Organic pollutants; Advanced oxidation processes
Izabela Dobrosz-Gmez, Ireneusz Kocemba, Jacek M. Rynkowski, Factors influencing structure and catalytic activity of
Au/Ce1xZrxO2 catalysts in CO oxidation, Applied Catalysis B: Environmental, Volume 88, Issues 12, 29 April 2009, Pages
Abstract: The Au/Ce1xZrxO2 (x = 0, 0.25, 0.5, 0.75, 1) catalysts were synthesized by the direct anionic exchange (DAE)
method, characterized by BET, SEMEDS, XRD, TPR-CO, HRTEM, AAS, ToF-SIMS and tested in CO oxidation. The correlations
between structural, redox and catalytic properties of Au/Ce1xZrxO2 catalysts prepared using different synthesis
procedures have been studied. The poisoning effect of residual chlorine on their catalytic performance was found. The
agglomeration of Au particles during the calcination step in the presence of residual chlorine was observed. Its removal
through the washing treatment both inhibited the sintering process and led to the increase in activity of the studied
systems. The sequence of increasing activity was followed by the sequence of increasing reducibility of the catalysts. This
shows the role of the support redox properties in the creation of the catalytic performance of supported Au nanoparticles
in CO oxidation.
Keywords: Au/Ce1xZrxO2 catalyst; Preparation procedure; Residual chlorine; Au dispersion; CO oxidation
C. Zerva, C.J. Philippopoulos, Ceria catalysts for water gas shift reaction: Influence of preparation method on their activity,
Applied Catalysis B: Environmental, Volume 67, Issues 12, 11 September 2006, Pages 105-112, ISSN 0926-3373,
Abstract: The influence of the ceria catalysts preparation method on their structure and activity in water gas shift reaction
has been studied. Ceria supports were prepared by the precipitation method from aqueous and organic solutions (e.g.
alcohols) and the impregnation method used for active metal loading. Ceria catalysts were also prepared, by the
coprecipitation method for total concentration of nitrate salts ranging from 0.006 to 0.18 mol/L. All catalysts were tested
under conditions of the water gas shift (WGS) reaction. The catalysts were characterized by BET, XRD and SEM analyses and
their activities were tested in a flow reactor in the temperature range of 150350 C with gas hourly space velocity (GHSV)
in the range of 75016,000 h1. The catalysts prepared by the coprecipitation method present the highest activity.
Keywords: Water gas shift; Ceria-based catalysts; Catalysts activity
F Delano, B Acedo, N Karpel Vel Leitner, B Legube, Relationship between the structure of Ru/CeO2 catalysts and their
activity in the catalytic ozonation of succinic acid aqueous solutions, Applied Catalysis B: Environmental, Volume 29, Issue 4,
12 February 2001, Pages 315-325, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(00)00212-5.
Abstract: Two Ru/CeO2 catalysts were used for the study of the catalytic ozonation of aqueous solutions of succinic acid
(SA). These catalysts were prepared either by impregnation (I) or by acid exchange (AE). The objectives were (1) to
determine the efficiency towards the oxidation of the organic molecule in relation to the catalysts characterization, and (2)
to examine the modifications of the structure induced by ozonation. For each catalyst, two experimental conditions of
catalyst and succinic acid concentrations were studied. The diluted conditions ([SA]0=1 mM, weightcata=0.8 g/l) were
applied for the study of the behavior of the catalysts during successive uses. The efficiency was also studied for higher initial
concentrations ([SA]0=5 mM, weightcata=3.2 g/l). Under both conditions the best efficiency was obtained with the
impregnated catalyst.
Transmission electronic microscopy analyses indicated that before ozonation of SA, ruthenium was distributed within the
whole volume of the grain of CeO2 for the AE catalyst, and included only in an external layer for the I catalyst. The size of
the particles determined by X-ray diffraction (XRD) was around 3.5 nm for Ru and in the range 1075 nm for CeO2. In most
cases, the catalytic ozonation induced Ru sintering with the formation of clusters. After four successive ozonation
experiments the AE catalyst efficiency was significantly decreased and the structure totally disorganized.
Keywords: Ozonation; Succinic acid (catalytic oxidation in water of); Ruthenium catalyst; Characterization
, Contents Continued, Applied Catalysis B: Environmental, Volume 84, Issues 34, 1 December 2008, Pages III-IV, ISSN 0926-
3373, https://doi.org/10.1016/S0926-3373(08)00354-8.
Arun Murthy, Eungje Lee, Arumugam Manthiram, Electrooxidation of methanol on highly active and stable PtSnCe/C
catalyst for direct methanol fuel cells, Applied Catalysis B: Environmental, Volumes 121122, 13 June 2012, Pages 154-161,
Abstract: Carbon supported PtSnCe and PtSn catalysts have been synthesized by a polyol reduction method and
compared for methanol oxidation reaction (MOR). X-ray photoelectron spectroscopic (XPS), X-ray diffraction (XRD), and
transmission electron microscopic (TEM) analyses reveal the beneficial effects of the Ce component in PtSnCe/C for MOR,
despite its low content. Electrochemical techniques such as COad stripping, linear scan, and derivative voltammetries along
with electrochemical impedance spectroscopy (EIS) were employed to analyze MOR on PtSnCe/C and PtSn/C from a
mechanistic point of view. Accelerated durability test (ADT) and single cell test of PtSnCe/C in comparison to a
commercial PtRu/C catalyst demonstrate the superior performance of PtSnCe/C from stability and activity points of view.
Keywords: Methanol oxidation reaction; PtSn catalyst; PtSnCe catalyst; Electrochemical stability; Direct methanol fuel
cell
Jacek Nawrocki, Barbara Kasprzyk-Hordern, The efficiency and mechanisms of catalytic ozonation, Applied Catalysis B:
Environmental, Volume 99, Issues 12, 31 August 2010, Pages 27-42, ISSN 0926-3373,
Abstract: Catalytic ozonation has recently gained significant attention as an effective process used for the removal of
organics from water. Unfortunately, despite increasing research efforts in the field of catalytic ozonation and the
introduction of new catalysts, the mechanisms of catalytic processes are still largely unknown. An understanding of the
mechanisms of catalytic ozonation is vital in order to introduce this technique in water treatment at an industrial scale.
Therefore, the main aim of this paper is to provide a short overview of catalytic processes, their recent advances and to
identify major directions taken to understand mechanisms governing catalytic processes utilised in water and wastewater
treatment. Catalytic ozonation is considered to belong to Advanced Oxidation Processes. However, the results published by
several research groups indicate that not all catalytic processes utilise the power of hydroxyl radicals.
Keywords: Catalytic ozonation; Homogeneous; Heterogeneous; Ozonation; Advanced oxidation processes; AOPs; Two-
phase ozonation
Bouchra Darif, Satu Ojala, Marja Krkkinen, Stphane Pronier, Teuvo Maunula, Rachid Brahmi, Riitta L. Keiski, Study on
sulfur deactivation of catalysts for DMDS oxidation, Applied Catalysis B: Environmental, Volume 206, 5 June 2017, Pages
Abstract: Abstract
In the present research, an industrially aged Pt/Al2O3 catalyst was used as a basis for the study on the sulfur deactivation
and the development of more resistant catalytic materials. The catalytic activities of both industrially and laboratory-aged
materials in DMDS oxidation were studied in addition to characterization by XRD, XPS, FESEM, TEM and N2 adsorption. The
industrial ageing induced a phase change from -Al2O3 towards -Al2O3, formation of aluminum sulfates and an increase in
Pt particle size as well as a change in the oxidation state of Pt to a higher state. These changes caused an increase of 30 C
in the light-off temperature for DMDS oxidation. Accelerated ageing in the presence of SO2 and H2O vapor at 400 C for 5 h
decreased the activity of the Pt/Al2O3 at the same level than for the industrially aged catalyst even though smaller sulfur
content and no sintering of -Al2O3 were observed. Pt sintering (1020 nm) in both cases was observed. The XPS results
confirmed the formation of new sulfate phases and the interaction between sulfur and the active phase as well as the
support of the catalyst undergone accelerated ageing. After the accelerated ageing of copper-based catalysts, the
0.3Pt10Cu/Al2O30.8SiO20.2 catalyst showed an interesting resistance towards sulfur deactivation, as it was expected.
Keywords: Dimethyldisulfide; Pt-Cu catalysts; Sulfur deactivation; Accelerated ageing; Industrial ageing; SVOC oxidation and
sulfur tolerance
Edwin Ntainjua Ndifor, Tomas Garcia, Benjamin Solsona, Stuart H. Taylor, Influence of preparation conditions of nano-
crystalline ceria catalysts on the total oxidation of naphthalene, a model polycyclic aromatic hydrocarbon, Applied Catalysis
B: Environmental, Volume 76, Issues 34, 15 November 2007, Pages 248-256, ISSN 0926-3373,
Abstract: Nano-crystalline ceria catalysts prepared by homogeneous precipitation with urea were tested for the total
oxidation of naphthalene, a model polycyclic aromatic hydrocarbon (PAH). Systematic variation of preparation conditions,
including calcination temperature, calcination time and aging time, resulted in differences in surface area, reducibility,
morphology and crystallite size of the CeO2 catalyst and hence differences in catalytic performance. A combination of high
surface area, small crystallite size and high oxygen defect concentration was found to favor the efficiency of the ceria
catalysts for the total oxidation of naphthalene. Optimum preparation conditions for this study included: aging time of 12 h,
calcination temperature of 500 C and a calcination time of 6 h.
Keywords: Catalytic oxidation; Ceria; Naphthalene; PAHs
, Special Issue Contents List, Applied Catalysis B: Environmental, Volume 70, Issues 14, 31 January 2007, Pages iv-vii, ISSN
0926-3373, https://doi.org/10.1016/S0926-3373(06)00506-6.
Paul Zelenka, Wolfgang Cartellieri, Peter Herzog, Worldwide diesel emission standards, current experiences and future
needs, Applied Catalysis B: Environmental, Volume 10, Issues 13, 14 September 1996, Pages 3-28, ISSN 0926-3373,
https://doi.org/10.1016/0926-3373(96)00021-5.
Abstract: The tightening of future exhaust emission limits for diesel engines and diesel vehicles require more and more
extraordinary development efforts with respect to reducing both engine-out emissions by improved combustion processes
and tailpipe emissions by new exhaust gas aftertreatment systems (EGAS). Today, the main EGAS activities in engine
application as well as in research and development concentrates on oxidation catalysts, particulate traps, and DENOX
catalysts. This paper deals with
1. a general overview on the development directions of different EGAS and typical emission reduction examples for various
diesel engine and vehicle applications;
2. the interaction between legislative emission test cycles, combustion system development and the kind of EGAS used.
Based on current development work and test results, ranking considerations with regard to the application and
development probability of EGAS are given.
Keywords: Diesel engine; Diesel exhaust gas emissions; Emission standards; Exhaust gas after treatment; Oxidation catalyst;
Particulate trap; Fuel additive; Lean-NOx catalyst
, Auto Exhaust Catalysis, Applied Catalysis B: Environmental, Volume 1, Issue 3, 29 September 1992, Pages N28-N29, ISSN
0926-3373, https://doi.org/10.1016/0926-3373(92)80029-Y.
(http://www.sciencedirect.com/science/article/pii/092633739280029Y)
B. Matas Gell, I.V. Babich, L. Lefferts, K. Seshan, Steam reforming of phenol over Ni-based catalysts A comparative study,
Applied Catalysis B: Environmental, Volume 106, Issues 34, 11 August 2011, Pages 280-286, ISSN 0926-3373,
Abstract: The influence of the support in the steam reforming of phenol at 700 C has been examined over Ni/K-La-ZrO2
and Ni/Ce-ZrO2. Both catalysts exhibited high activity and good stability in terms of phenol conversion. However, Ni/K-La-
ZrO2 showed a pronounced change in product distribution with TOS, which was related to deactivation for the watergas
shift. The high activity observed for the watergas shift over the unsupported nickel and the difference in the location of
coke between the two nickel catalysts are suggested to be the key reasons for the difference in catalyst stability. The red-ox
properties of Ce-ZrO2 are proposed to result in more oxygenated species (O and OH) than the non-red-ox K-La-ZrO2. These
oxygenated species, which are suggested to undergo back-spillover from the support to the nickel surface, could be
responsible for keeping the nickel surface clean by gasifying the carbonaceous species accumulated on nickel.
Keywords: Hydrogen; Steam reforming; Phenol; Nickel; Catalyst; Red-ox
Francisco J. Varela-Ganda, ngel Berenguer-Murcia, Dolores Lozano-Castell, Diego Cazorla-Amors, David R. Sellick, Stuart
H. Taylor, Total oxidation of naphthalene using palladium nanoparticles supported on BETA, ZSM-5, SAPO-5 and alumina
powders, Applied Catalysis B: Environmental, Volume 129, 17 January 2013, Pages 98-105, ISSN 0926-3373,
Abstract: A range of catalysts based on Pd nanoparticles supported on inorganic supports such as BETA and ZSM-5 zeolites,
a silicoaluminophosphate molecular sieve (SAPO-5) and -alumina as a standard support have been tested for the total
oxidation of naphthalene (100 ppm, total flow 50 ml/min) showing a conversion to carbon dioxide of 100% between 165
and 180 C for all the analysed catalysts. From the combined use of zeolites with PVP polymer protected Pd based
nanoparticles, enhanced properties have been found for the total abatement of naphthalene in contrast with other kinds of
catalysts. A Pd/BETA catalyst has been demonstrated to have excellent activity, with a high degree of stability, as shown by
time on line experiments maintaining 100% conversion to CO2 during the 48 h tested.
Keywords: Catalytic oxidation; Zeolite BETA; ZSM-5; Pd nanoparticles; Naphthalene
R.F.B. De Souza, A.E.A. Flausino, D.C. Rascio, R.T.S. Oliveira, E. Teixeira Neto, M.L. Calegaro, M.C. Santos, Ethanol oxidation
reaction on PtCeO2/C electrocatalysts prepared by the polymeric precursor method, Applied Catalysis B: Environmental,
Volume 91, Issues 12, 7 September 2009, Pages 516-523, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2009.06.022.
Abstract: This paper presents a study of the electrocatalysis of ethanol oxidation reactions in an acidic medium on Pt-
CeO2/C (20 wt.% of Pt-CeO2 on carbon XC-72R), prepared in different mass ratios by the polymeric precursor method. The
mass ratios between Pt and CeO2 (3:1, 2:1, 1:1, 1:2, 1:3) were confirmed by Energy Dispersive X-ray Analysis (EDAX). X-ray
diffraction (XRD) structural characterization data shows that the Pt-CeO2/C catalysts are composed of nanosized
polycrystalline non-alloyed deposits, from which reflections corresponding to the fcc (Pt) and fluorite (CeO2) structures
were clearly observed. The mean crystallite sizes calculated from XRD data revealed that, independent of the mass ratio, a
value close to 3 nm was obtained for the CeO2 particles. For Pt, the mean crystallite sizes were dependent on the ratio of
this metal in the catalysts. Low platinum ratios resulted in small crystallites, and high Pt proportions resulted in larger
crystallites. The size distributions of the catalysts particles, determined by XRD, were confirmed by Transmission Electron
Microscope (TEM) imaging. Cyclic voltammetry and chronoamperometic experiments were used to evaluate the
electrocatalytic performance of the different materials. In all cases, except Pt-CeO2/C 1:1, the Pt-CeO2/C catalysts exhibited
improved performance when compared with Pt/C. The best result was obtained for the Pt-CeO2/C 1:3 catalyst, which gave
better results than the Pt-Ru/C (Etek) catalyst.
Keywords: Ethanol oxidation reaction; Electrocatalysis; Pt nanoparticles; Ceria; Polymeric precursor method
L.F. Bobadilla, A. lvarez, M.I. Domnguez, F. Romero-Sarria, M.A. Centeno, M. Montes, J.A. Odriozola, Influence of the
shape of Ni catalysts in the glycerol steam reforming, Applied Catalysis B: Environmental, Volumes 123124, 23 July 2012,
Abstract: Biomass is an alternative to replace the use of fossil fuels. Glycerol, a byproduct in the biodiesel production, can
be used for obtaining hydrogen. The most efficient method for obtaining hydrogen from glycerol is the steam reforming
(SR). So far all the published papers report the use of conventional catalyst. In this paper, a structured catalyst has been
prepared and compared with the conventional ones (powder and spherical pellets). Results show that the structured
catalyst (monolith) is more stable as formation of coke was not observed.
Keywords: Monoliths; Conventional catalyst; Glycerol steam reforming; Coke
Di Li, Liang Zeng, Xinyu Li, Xiao Wang, Hongyan Ma, Suttichai Assabumrungrat, Jinlong Gong, Ceria-promoted Ni/SBA-15
catalysts for ethanol steam reforming with enhanced activity and resistance to deactivation, Applied Catalysis B:
Environmental, Volumes 176177, October 2015, Pages 532-541, ISSN 0926-3373,
Abstract: Abstract
This paper describes the synthesis of CeO2-promoted Ni/SBA-15 catalysts (denoted as CeNi/SBA-15) via a surfactant-
assisted iso-volumetric impregnation method and their application in ethanol steam reforming. Various techniques
including N2 adsorptiondesorption, X-ray diffraction, H2 temperature-programmed reduction, temperature-programmed
oxidation, transmission electron microscopy and thermogravimetric analysis were employed to characterize the prepared
and spent catalysts. The results showed that the incorporation of CeO2 could effectively control the particle size of Ni via
strong metal-support interaction and promote the homogeneous distribution of Ni and Ce to achieve large NiCeO2
interface. Consequently, the CeNi/SBA-15 catalysts exhibited superior activity with respect to the reference Ni/SBA-15
catalyst without ceria addition. The effect of ceria loading on the properties of the catalysts was also investigated, and the
catalyst with Ce/Ni atomic ratio of 1 was the optimized composition owing to its strong metal-support interaction and high
nickel active surface area. The ceria-promoted catalysts showed enhanced long-term stability in ethanol steam reforming.
The strong interaction between Ni and CeO2, as well as the confinement of SBA-15 support restricted the nickel particle
growth under harsh reaction conditions. Additionally, the ceria promoter contributed to suppressing coke deposition
effectively, which led to the enhanced coking-resistance as observed on CeNi/SBA-15 catalysts.
Keywords: Hydrogen; Ethanol steam reforming; Ceria; Ni sintering; Coke deposition
Gaurav Nahar, Valerie Dupont, Martyn V. Twigg, Emiliana Dvininov, Feasibility of hydrogen production from steam
reforming of biodiesel (FAME) feedstock on Ni-supported catalysts, Applied Catalysis B: Environmental, Volumes 168169,
June 2015, Pages 228-242, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2014.12.036.
Abstract: Abstract
The catalytic steam reforming of biodiesel was examined over Ni-alumina and Niceriazirconia catalysts at atmospheric
pressure. Effects of temperatures of biodiesel preheating/vaporising (190365 C) and reforming (600800 C), molar steam
to carbon ratio (S/C = 23), and residence time in the reformer, represented by the weight hourly space velocity WHSV of
around 3 were examined for 2 h. Ni supported on calcium aluminate and on ceriazirconia supports achieved steady state
hydrogen product stream within 90% of the equilibrium yields, although 4% and 1% of the carbon feed had deposited on
the catalysts, respectively, during the combined conditions of start-up and steady state. Addition of dopants to ceria
zirconia supported catalyst decreased the performance of the catalyst. Increase in S/C ratio had the expected positive
effects of higher H2 yield and lower carbon deposition.
Keywords: Biodiesel; Fuel cells; Hydrogen; Steam reforming
Xiaojiang Yao, Qiang Yu, Zeyang Ji, Yuanyuan Lv, Yuan Cao, Changjin Tang, Fei Gao, Lin Dong, Yi Chen, A comparative study
of different doped metal cations on the reduction, adsorption and activity of CuO/Ce0.67M0.33O2 (M = Zr4+, Sn4+, Ti4+)
catalysts for NO + CO reaction, Applied Catalysis B: Environmental, Volumes 130131, 7 February 2013, Pages 293-304, ISSN
Abstract: A series of ceria-based solid solutions (Ce0.67Zr0.33O2, Ce0.67Sn0.33O2, Ce0.67Ti0.33O2) were synthesized by
inverse co-precipitation, and then used as supports to prepare CuO/Ce0.67M0.33O2 (M = Zr4+, Sn4+, Ti4+) catalysts
through wetness impregnation method. The obtained samples were investigated in detail by means of XRD, LRS, N2-
physisorption, H2-TPR, XRF, XPS and in situ FT-IR techniques. The catalytic reduction of NO by CO as a model reaction was
chosen to evaluate the catalytic performance of these samples. These results suggest that: (1) the reduction of
CuO/Ce0.67Zr0.33O2 is easier than CuO/Ce0.67Sn0.33O2 and CuO/Ce0.67Ti0.33O2 catalysts, which may be attributed to
the difference in the electronegativity of dopant; (2) the reduced state Cu+ is present in CuO/Ce0.67Zr0.33O2 at ambient
temperature due to the shifting of redox e uilibrium (Cu2+ + Ce3+ Cu+ + Ce4+) to right; (3) the adsorbed NO species on
CuO/Ce0.67Zr0.33O2 are more liable to desorb/transform/decompose than those on CuO/Ce0.67Sn0.33O2 and
CuO/Ce0.67Ti0.33O2 samples. The results of catalytic performance show that Cu+/Cu0 species play a key role in NO
reduction by CO, and the activity is mainly related to the electronegativity of dopant, the reduction and adsorption
behaviors of these catalysts. Furthermore, a possible reaction mechanism (schematic diagram) is tentatively proposed to
understand this reaction.
Keywords: Ceria-based solid solution; Dopant; Electronegativity; Copper-based catalyst; NO + CO reaction
Maria Turco, Claudia Cammarano, Giovanni Bagnasco, Elisa Moretti, Loretta Storaro, Aldo Talon, Maurizio Lenarda,
Oxidative methanol steam reforming on a highly dispersed CuO/CeO2/Al2O3 catalyst prepared by a single-step method,
Applied Catalysis B: Environmental, Volume 91, Issues 12, 7 September 2009, Pages 101-107, ISSN 0926-3373,
Abstract: A Cu/CeO2/Al2O3 catalyst (6.6% Cu, 13.8% Ce) based on a structurally organized mesoporous alumina was
prepared by a new single-step solgel method starting from Al butoxide and Ce and Cu stearates. The sample was
characterized by N2 adsorption, XRD, TPR and Cu dispersion measurements and tested as catalyst for the SRM (methanol
steam reforming) and OSRM (methanol autothermal reforming) reactions. The material showed a huge surface area (360
m2 g1) and resulted to contain very dispersed CeO2 and CuO phases on a poorly crystalline alumina matrix. A highly
dispersed Cu metallic phase was obtained after a reductive treatment with H2. Catalytic tests showed that the unreduced
material was fairly active for the OSRM process, but the activity increases appreciably after the pre-reduction treatment.
The activity for the OSRM process resulted high, in terms of hydrogen production rate, if compared with data on similar
Cu/Ce/Al systems, but the activity for SRM, in the absence of oxygen was, on the other hand, very low. This behaviour was
explained either considering the occurrence of H spillover or the CeO2 assisted oxidation of Cu to Cu+.
Keywords: Oxidative methanol steam reforming; Cu/CeO2/Al2O3 catalysts; Organized mesostructured alumina; Cu
dispersion
Da-Ming Gu, Yuan-Yuan Chu, Zhen-Bo Wang, Zheng-Zhi Jiang, Ge-Ping Yin, Yang Liu, Methanol oxidation on Pt/CeO2C
electrocatalyst prepared by microwave-assisted ethylene glycol process, Applied Catalysis B: Environmental, Volume 102,
Issues 12, 1 February 2011, Pages 9-18, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2010.11.018.
Abstract: Pt/C and Pt/CeO2C catalysts with different CeO2 contents were prepared by microwave-assisted polyol process
and characterized by energy dispersive analysis of X-ray (EDAX), X-ray diffraction (XRD), elemental mapping by X-ray energy
dispersive spectroscopy (XEDS), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) in this
study. Their electrochemical activities and stabilities for methanol electrooxidation were evaluated by cyclic voltammetry,
amperometric it, electrochemical impedance spectroscopy (EIS), and continued cyclic voltammograms cycles. The results
show that the stability of the mixture support with Vulcan XC-72 carbon black and homemade CeO2 nanomaterial is
evidently enhanced in comparison with that of single carbon black, which results from anti-corrosion property of CeO2 and
the interaction between CeO2 and XC-72 carbon black. And the appropriate content CeO2 may significantly improve the
dispersion of Pt nanoparticles on surface of the mixture support. Too much content CeO2 may lead to the agglomeration of
Pt nanoparticles. The optimal weight ratio of CeO2 is 20 wt.% in Pt/CeO2C catalyst with narrower particle size distribution
and better dispersion on surface of the mixture support, which exhibits the best activity and stability for methanol
electrooxidation among all the samples. The reason for the increased activity and stability is ascribed to the promotion of
COads electrooxidation reaction kinetics by CeO2, the stability of the CeO2C mixture support in acidic media, as well as the
improvement of CeO2 for the dispersion of Pt nanoparticles. The addition of CeO2 into carbon black as a mixture support
also can improve the hydrophilicity and wettability of carbon, and this particularity was fully made use of to achieve the Pt
deposition on the contact interface of CeO2 and carbon black smoothly, avoiding the addition of other polymer conductive
electrolyte or surfactant.
Keywords: Direct methanol fuel cell; Pt/CeO2C catalyst; Microwave-assisted polyol process; Methanol electrooxidation
Shuqin Song, Kun Wang, Longlong Yan, Angeliki Brouzgou, Yueli Zhang, Yi Wang, Panagiotis Tsiakaras, Ceria promoted Pd/C
catalysts for glucose electrooxidation in alkaline media, Applied Catalysis B: Environmental, Volumes 176177, October
Abstract: Abstract
Carbon support materials are modified by CeO2 through a microwave decomposition method, and then CeO2C supported
Pd catalysts are synthesized by a pulse microwave assisted polyol method. The content of CeO2 is appropriately adjusted
and Pd/CeO2C catalysts with different Pd:CeO2 molar ratios are obtained and investigated for the reaction of glucose
electrooxidation in alkaline media.
It is found that the introduction of CeO2 onto the surface of the carbon support can significantly decrease the particle size
of Pd with respect to the Pd/C case, generating sufficient OHads at lower potentials. Accordingly, the catalytic activity of Pd
for glucose electrooxidation can be improved as a result of its high dispersion and the synergistic effect. It is also found that,
among the Pd/CeO2C catalysts, the one with Pd:CeO2 molar ratio of 3:1 exhibits the best performance for glucose
electrooxidation, 30% higher than that of Pd/C. Moreover, the optimized catalyst presents the advantages of rapid
response, high sensitivity and good tolerance to the interfering agents co-existing in the human blood with glucose.
Keywords: Glucose electrooxidation; Pd/CeO2C catalyst; Microwave assisted polyol method; Alkaline media
Fangyuan Chen, Chunfei Wu, Lisha Dong, Anthony Vassallo, Paul T. Williams, Jun Huang, Characteristics and catalytic
properties of Ni/CaAlOx catalyst for hydrogen-enriched syngas production from pyrolysis-steam reforming of biomass
sawdust, Applied Catalysis B: Environmental, Volume 183, April 2016, Pages 168-175, ISSN 0926-3373,
Abstract: Abstract
The production of hydrogen-enriched syngas from the thermo-chemical conversion of biomass was studied using Ni/CaAlOx
catalysts prepared by co-precipitation method. The effect of Ca addition with different molar ratios of Ca:Al (1:3, 1:2, 1:1,
2:1, 3:1) on the properties and catalytic behavior in relation to syngas production and the coke formation on the surface of
the catalysts were investigated. Catalysts were characterized by BET, XRD, TPR, SEM, and TEM. The SEM and TEM results
showed that rod-shaped nano-particles were highly dispersed on the surface of the catalyst. The particle size of NiO was
slightly affected with the increase of Ca content in the catalyst. It appeared that the selectivity of CO was increased and the
selectivity of CO2 was reduced with the increase of Ca addition to the catalyst. For example, CO2 concentration was
reduced from 20 to 12 vol.%, when the molar ratio of Ca/Al was increased from 1:3 to 3:1 for the Ni/CaAlOx catalyst; it is
suggested that the water gas shift reaction was inhibited and CO2 reforming reactions were promoted in the presence of
the catalyst with higher Ca content. The CO/H2 molar ratio could be manipulated by changing the Ca content in the
catalyst, while the H2 concentration remained almost constant (around 45 vol.%). Thus, using the Ni/CaAlOx catalyst
developed in this work could provide a promising route to control the syngas composition, which is an important factor for
syngas applications.
Keywords: Biomass; Pyrolysis; Co-precipitation; Calcium: Ni-catalyst
Se H. Oh, Patricia J. Mitchell, Effects of rhodium addition on methane oxidation behavior of alumina-supported noble metal
catalysts, Applied Catalysis B: Environmental, Volume 5, Issues 12, 31 December 1994, Pages 165-179, ISSN 0926-3373,
https://doi.org/10.1016/0926-3373(94)00034-4.
Abstract: Laboratory methane oxidation experiments were conducted using a series of catalyst samples prepared by
impregnating Rh-free noble metal catalysts (i.e., Pt/Pd, Pt or Pd) with various amounts of rhodium (0.0035, 0.005, and
0.014 wt.-% Rh). The addition of these small amounts of rhodium did not significantly change the temperature required for
the onset of the methane oxidation. However, variable-composition experiments conducted at a temperature characteristic
of warmed-up catalytic converters (ca. 550C) reveal that the rhodium addition tends to shift the optimum feedstream
stoichiometry (at which a maximum methane conversion occurs) toward more reducing conditions. These Rh-induced
effects on methane conversion behavior appear to be independent of how the rhodium is incorporated in the catalyst.
Keywords: Converter (catalytic); Exhaust; Methane oxidation; Rhodium
Christos Kordulis, Kyriakos Bourikas, Mantha Gousi, Eleana Kordouli, Alexis Lycourghiotis, Development of nickel based
catalysts for the transformation of natural triglycerides and related compounds into green diesel: a critical review, Applied
Catalysis B: Environmental, Volume 181, February 2016, Pages 156-196, ISSN 0926-3373,
Abstract: Abstract
The accumulation of greenhouse gases in the atmosphere resulting from the extensive use of fossil fuels and the depletion
of oil reserves due to the increasing demands for energy compel the progressive replacement of fossil fuels by renewable
energy sources among which biomass. Triglycerides-based biomass such as plant oils, animal fats, waste cooking and micro-
algal oils should be upgraded by transesterification, cracking/hydrocracking and selective deoxygenation (SDO) to provide,
respectively, biodiesel (fatty acid methyl esters), the so-called organic liquid product (mixture of hydrocarbons in the range
of gasoline, kerosene and diesel) and green diesel (hydrocarbons in the diesel range). Problems related to the production,
storage and use of the already produced biodiesel shifts the research to the second and third upgrading route. Intensive
work in the last ten years has shown that the noble metals (mainly palladium) and the NiMo, CoMo and NiW sulphide
catalysts supported on high surface area carriers, are promising concerning SDO for producing green diesel in the context of
a stand-alone process of natural triglycerides.
However, the high cost of the noble metal catalysts and the eventual S-contamination of the end product when using the
aforementioned sulfided catalysts have rise intensive parallel research in the last three years for developing low cost Ni-
based non-sulphide catalysts. The research effort in this area seems to focus on the following issues: (i) effect of supports,
nickel loading and promoters on the catalytic performance of Ni-based non-sulphide catalysts, (ii) SDO pathways over these
catalysts, (iii) effect of preparation method on their catalytic performance, (iv) comparison of nickel catalysts with other
metallic and sulphide catalysts, (v) development of nickel phosphide catalysts, (vi) development of NiMo, CoMo or NiW
non-sulphide catalysts (reduced, carbides, nitrides) and (vii) deoxygenation in low or no hydrogen containing atmosphere.
In the present article we critically review the contributions relevant to each one of the aforementioned subjects for
obtaining a synthetic picture concerning the progress pointed out so far and the future perspectives as well.
Keywords: Ni catalysts; Green diesel; Renewable diesel; Selective deoxygenation (SDO); Triglycerides; Vegetable oils; Animal
fats; Biofuels; Stand-alone process
Henrik Birgersson, Lars Eriksson, Magali Boutonnet, Sven G. Jrs, Thermal gas treatment to regenerate spent automotive
three-way exhaust gas catalysts (TWC), Applied Catalysis B: Environmental, Volume 54, Issue 3, 20 December 2004, Pages
Abstract: The effect of regeneration on the metal dispersion and catalyst activity of commercial automotive three-way
catalysts (TWC) in oxygen, hydrogen and oxy-chlorine at elevated temperatures has been investigated. In addition,
characterisation of the catalysts has been performed using XRD, TEM, TPR, CO chemisorption and BET surface area
measurements. Activity tests on monolith fragments were conducted in a micro-reactor supplied with real exhaust gases.
An increase in activity was observed with oxygen treatment on catalysts showing heavy sintering as well as a high noble
metal loading. Hydrogen proved to be an ineffective treatment procedure, whereas the addition of chlorine to the oxygen
stream resulted in an activity increase even on catalysts less sintered and with lower noble metal contents. A comparison of
the XRD and BET profiles showed no or small changes in the washcoat structure compared to fresh catalysts after successful
regeneration. The TEM, TPR and CO chemisorption measurements suggest a decrease in the size of the largest noble metal
agglomerates on the catalyst surface, as well as some Pd and RhO restructuring. The oxy-chlorine regeneration procedure is
shown to be the most efficient, both regarding the catalyst activity and the metal dispersion. An increase in the amount of
noble metal particles with a size of 2070 nm, coupled with a decrease in size of larger clusters up to 100 nm in size, was
observed for this treatment.
Keywords: Regeneration; Dispersion; Thermal gas treatment; Oxy-chlorine; TWC; Automotive catalyst
Muhammad Saeed, Mohammad Ilyas, Oxidative removal of phenol from water catalyzed by nickel hydroxide, Applied
Catalysis B: Environmental, Volume 129, 17 January 2013, Pages 247-254, ISSN 0926-3373,
Abstract: This work explores the preparation and characterization of nickel hydroxide catalyst and investigation of its
catalytic activities for oxidative degradation of phenol in aqueous medium using batch reactor. The catalyst was prepared
by reaction of sodium hypochlorite, sodium hydroxide and nickel sulfate hexahydrate in distilled water. The prepared
catalyst was characterized by surface area, particle size, FTIR, XRD, SEM, and determination of oxygen content
measurements. The prepared nickel hydroxide was used as catalyst for oxidative degradation of phenol in aqueous medium
by taking 15 mL of 0.71 M phenol solution. The catalytic performance of nickel hydroxide was explored in terms of effect of
time, temperature, partial pressure of oxygen, initial concentration of phenol, catalyst loading and effect of stirring speed
on degradation of phenol. The catalyst was separated from the reaction mixture by filtration. LangmuirHinshelwood type
of mechanism was followed in the reaction where adsorption of phenol and oxygen at the surface of catalyst was taking
place according to competitive Langmuir and Temkin adsorption isotherm, respectively.
Keywords: Phenol; Nickel hydroxide; Kinetic studies; Adsorption isotherms
Rui C. Martins, Rosa M. Quinta-Ferreira, Catalytic ozonation of phenolic acids over a MnCeO catalyst, Applied Catalysis B:
Environmental, Volume 90, Issues 12, 25 July 2009, Pages 268-277, ISSN 0926-3373,
Abstract: Catalytic ozonation of a simulated phenolic wastewater composed by six acids: syringic, vanillic, 3,4,5-
trimethoxybenzoic, veratric, protocatechuic and 4-hydroxybenzoic normally present in olive mill wastewaters was studied
over a MnCeO laboratorial catalyst under different operating conditions. A high improvement in total organic carbon
(TOC) degradation was observed even when low catalyst concentrations were used when compared with single ozonation.
The influence of the medium pH in the performance of both single and catalytic ozonation was assessed in a wide range of
pH values. An inhibitory effect in TOC removal was observed in the catalytic process performance at high pH values. The use
of radical scavengers proved that this catalytic system does not follow a free radical pathway. No differences were observed
between fresh and used catalyst structure and morphology by SEM and XRD. Nevertheless, a decrease on BET surface area
was detected. Leaching of Mn as well as carbon adsorption due to organic intermediates deposition at the catalyst surface
was analyzed for the recovered catalyst at the end of the experiments. The role of the catalyst in the catalytic ozonation
pathway was discussed being concluded that the main mechanism should be developed through surface reactions involving
both pollutants and ozone adsorption. A series of feed-batch trials was performed to test MnCeO activity along the time.
A slight decrease on TOC removal was observed from the first to the second use, remaining the catalyst performance
constant after the third run.
Keywords: Catalytic ozonation; Catalyst characterization; Environment protection; Phenolic acids; Wastewater treatment
Yongjin Luo, Yihong Xiao, Guohui Cai, Yong Zheng, Kemei Wei, Complete methanol oxidation in carbon monoxide streams
over Pd/CeO2 catalysts: Correlation between activity and properties, Applied Catalysis B: Environmental, Volumes 136137,
5 June 2013, Pages 317-324, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2013.02.020.
Abstract: Three different techniques, a hydrothermal process with impregnation, solution-combustion and common
precipitation with impregnation, were employed for the synthesis of 1.5 wt% Pd/CeO2, and the resulting catalysts were
denoted as Pd/HY, Pd/COM and Pd/PI, respectively. These catalysts have been investigated in terms of catalytic co-
oxidation of CO and methanol and characterized by means of XRD, BET, SEM, STEM-EDS, CO chemisorption, XPS, Raman,
O2-TPD, H2-TPR and CO-TPD measurements. Activity results show that a rapid catalytic oxidation of CO following the Mars-
van Krevelen-type mechanism favors the complete methanol oxidation at low temperature. Consequently, the Pd/HY
catalyst with the highest degree of defect sites connected with the mobility of activated oxygen shows the best catalytic
performance. And the generation of more defect sites demonstrated by Raman is assumed for the low crystallinity and
small crystallite size of CeO2 synthesized through a hydrothermal process while the high mobility of activated oxygen is
evidenced by O2-TPD and H2-TPR. Additionally, the outstanding catalytic performance of Pd/HY is also associated with its
high Pd dispersion and stable PdOx species as well as good redox behavior.
Keywords: Pd/CeO2; Synthetic techniques; CO; Methanol; Defect sites
Sandra S, Hugo Silva, Lcia Brando, Jos M. Sousa, Adlio Mendes, Catalysts for methanol steam reformingA review,
Applied Catalysis B: Environmental, Volume 99, Issues 12, 31 August 2010, Pages 43-57, ISSN 0926-3373,
Abstract: A large number of studies can be found in the literature regarding the production of new catalysts for methanol
steam reforming. This work summarizes the latest developments on catalysts for this application and is divided in two main
groups: copper-based and group 810 metal-based catalysts. In each section, the strategies proposed by several authors to
enhance the performance of the catalysts are described. An overall comparison between the two groups shows that
copper-based catalysts are the most active ones, while the 810 group catalysts present better results in terms of thermal
stability and long-term stability. Very promising results were reported for both groups, enhancing the value of methanol as
a hydrogen carrier for fuel cell applications.
Keywords: Catalysts; Hydrogen; Methanol steam reforming
F. Rohr, S.D. Peter, E. Lox, M. Kgel, A. Sassi, L. Juste, C. Rigaudeau, G. Belot, P. Glin, M. Primet, On the mechanism of
sulphur poisoning and regeneration of a commercial gasoline NOx-storage catalyst, Applied Catalysis B: Environmental,
Volume 56, Issue 3, 25 March 2005, Pages 201-212, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2004.09.011.
Abstract: A commercial NOx-storage catalyst for gasoline applications containing platinum, palladium and rhodium together
with Ba/CeO2/Al2O3 has been sulfated on the engine bench at 390 and 510 C with nominal exposures of 0.3 and 1.3 g
sulphur/l catalyst. Exposures of 0.3 g/l are too low to have a notable impact on the catalytic performance. At 390 C, the
sulphur is quantitatively adsorbed as opposed to 510 C. Sulphur is mainly adsorbed at the inlet side of the catalyst thereby
shielding the downstream region. Desulfation on synthetic gas bench at 700 C leads to a removal of 50% of the sulphur.
The residual sulphur is more evenly distributed along the length of the catalyst compared to the sulphur profile in the
sulfated catalyst. This leads to an improvement of the NOx-activity at the inlet side and a drop in NOx-performance at the
outlet side after desulfation. Results from SEMEDX, TPD, TPR and IR suggest that the barium component is selectively
poisoned by the sulphur while alumina and ceria are not affected significantly. The insufficient desulfation of the catalyst is
almost entirely due to the incomplete sulphur removal from the barium sites. In the desulfated state the IR and TPD-data
suggest the presence of barium carbonate species of low thermal stability together with bulk carbonate. After sulfation the
IR data indicate the presence of different sulphate species, both bulk and surface phases. Thermal ageing and sulphur
poisoning affect different parts of the operational temperature window of the NOx-storage catalyst. While thermal stress
alone mainly affects low temperature NOx-performance, sulphur poisoning mainly reduces high temperature activity. The
results of this work help to identify strategies to improve both the sulfur resistance of the catalyst and the operational
conditions for a better management of the NOx-trap system.
Keywords: NOx storage; Sulphur; Sulphur poisoning
Qinglin Zhang, Karl T. Chuang, Kinetics of wet oxidation of black liquor over a PtPdCe/alumina catalyst, Applied Catalysis
B: Environmental, Volume 17, Issue 4, 31 August 1998, Pages 321-332, ISSN 0926-3373, https://doi.org/10.1016/S0926-
3373(98)00016-2.
Abstract: The catalytic oxidation of industrial wastewater from paper and pulp mills has been investigated in a slurry reactor
at a temperature range 433463 K and at pressures from 1.5 to 2.2 MPa. Adding Ce on alumina support promotes the
catalytic activity for oxidation of black liquor. PtPdCe/alumina catalyst shows a promising activity for wet catalytic
oxidation of black liquor. The oxidation reaction over a PtPdCe catalyst is characterized by an initial fast reaction step
followed by a slow reaction step. The rate of total organic carbon (TOC) reduction was described by first-order kinetics with
respect to TOC concentration in black liquor for both initial and later reaction steps. The activation energies were
determined to be 54.53 and 50.13 kJ/mol for the initial and later oxidation steps, respectively. Comparison of the data with
the generalized kinetic model was also presented.
Keywords: Wet catalytic oxidation; Black liquor; Wastewater treatment; Kinetics; Heterogeneous catalysis; Slurry reactor
C. Milone, M. Fazio, A. Pistone, S. Galvagno, Catalytic wet air oxidation of p-coumaric acid on CeO2, platinum and gold
supported on CeO2 catalysts, Applied Catalysis B: Environmental, Volume 68, Issues 12, 26 October 2006, Pages 28-37,
Abstract: p-Coumaric acid is representative of the polyphenolic fraction typically found in olive milling waste waters
(OMWW). The catalytic wet air oxidation of p-coumaric acid has been investigated at 353 K at P = 2 MPa, using CeO2, Pt
and Au supported on CeO2 catalysts. The influence of the metal and of the preparation method of the catalysts on the
catalytic activity has been investigated.
Upon addition of Pt to CeO2, the rate of oxidation of p-coumaric acid increases whereas addition of gold do not lead to a
significant difference of the activity of CeO2. On all the catalysts investigated, the abatement of total organic carbon (TOC)
was 80% after 300 min of reaction. Catalysts containing metallic platinum are the most effective towards the
mineralization of the organic carbon to CO2 and the degree of mineralization (DM%) was higher than 50%. On CeO2 and
AuCeO2 catalysts a great contribute to the abatement of TOC is given from a significant adsorption of the organic
substrates on the solid.
Keywords: CWAO; p-Coumaric acid; Ceria; Platinum catalysts; Gold catalysts
Ulrich Hennings, Rainer Reimert, Noble metal catalysts supported on gadolinium doped ceria used for natural gas reforming
in fuel cell applications, Applied Catalysis B: Environmental, Volume 70, Issues 14, 31 January 2007, Pages 498-508, ISSN
Abstract: An attractive possibility to simplify a fuel cell system would be the use of a sulfur-tolerant reforming catalyst. In an
effort to find such a catalyst, platinum, rhodium and ruthenium catalysts supported on ceria doped with 20% gadolinium
and on pure ceria were synthesized and characterized. A temperature-programmed reduction study of the reduction
behavior of the catalysts showed that the doping of ceria with gadolinium enhances the low temperature reduction, while
the high temperature reduction is suppressed. The activity as well as the stability of the catalysts can be correlated with the
reducibility of the materials. The most stable catalyst, rhodium supported on gadolinium doped ceria, shows promising
sulfur-tolerance.
Keywords: Ceria; Gadolinium; Rhodium; Fuel cells; Reforming; Sulfur; Poisoning; Metal-decoration
, SUBJECT INDEX OF VOLUMES 52, 53 AND 54, Applied Catalysis B: Environmental, Volume 54, Issue 4, 30 December 2004,
Pages 293-304, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(04)00580-6.
Gregorio Marbn, Alba Lpez, Irene Lpez, Teresa Valds-Sols, A highly active, selective and stable copper/cobalt-
structured nanocatalyst for methanol decomposition, Applied Catalysis B: Environmental, Volume 99, Issues 12, 31 August
Abstract: A structured catalyst prepared by copper doping a support composed of mesoporous Co(OH)2/Co3O4 nanowire
arrays hydrothermally grown on a stainless steel mesh was used for the methanol decomposition reaction. When copper
doping was applied to an uncalcined cobalt-based support, followed by calcination in air, the catalytic activity of the
resulting bimetallic catalyst was observed to increase by about one order of magnitude with respect to that of the catalyst
obtained by copper doping a calcined support. This high activity, which is accompanied by a very high selectivity to CO and a
fair stability, is thought to be due to the transformation of a large proportion of the copper precursor into Cu2O of a low
crystal size during calcination. Comparison with other catalysts reported in the literature shows that the most active
catalysts prepared in this work are better than the most active, selective and stable transition metal catalysts described in
the reviewed literature.
Keywords: Methanol decomposition; Hydrogen; CO; Co3O4; Cobalt; Cu2O; Copper; Spinel; Catalytic activity; Selectivity;
Stability; Microreactor
zer Orbay, Song Gao, Brian Barbaris, Erik Rupp, A. Eduardo Sez, Robert G. Arnold, Eric A. Betterton, Catalytic
dechlorination of gas-phase perchloroethylene under mixed redox conditions, Applied Catalysis B: Environmental, Volume
79, Issue 1, 21 February 2008, Pages 43-52, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2007.09.034.
Abstract: The validity of a new method to destroy gas-phase perchloroethylene (PCE) is demonstrated at bench scale using
a fixed-bed reactor that contains a Pt/Rh catalyst. Hydrogen and oxygen were simultaneously fed to the reactor together
with PCE. The conversion efficiencies of PCE were sensitive to H2/O2 ratio and reactor temperature. When the temperature
was 400 C and H2/O2 was 2.15, PCE conversion efficiency was maintained at 90%. No catalyst deactivation was
observed for over 2 years, using only mild, convenient regeneration procedures. It is likely that PCE reduction steps precede
oxidation reactions and that the importance of oxidation lies in its elimination of intermediates that would otherwise lead
to catalyst poisoning. In practice, this catalytic dechlorination method holds potential for low-cost, large-scale field
operation.
Keywords: PCE destruction; Catalytic dechlorination; Redox conditions; Reduction; Oxidation
G.C. Koltsakis, P.A. Konstantinidis, A.M. Stamatelos, Development and application range of mathematical models for 3-way
catalytic converters, Applied Catalysis B: Environmental, Volume 12, Issues 23, 12 June 1997, Pages 161-191, ISSN 0926-
3373, https://doi.org/10.1016/S0926-3373(96)00073-2.
Abstract: The need for reliable 3-way catalytic converter modeling in the design of demanding exhaust systems for low-
emitting vehicles has been widely recognised. Although a number of related models have been presented in the literature,
the efficient performance in actual 3-way applications requires further development and validation. The major difficulties
posed in such modeling efforts arise from the complexities in the reaction schemes and the respective rate expressions for
the multitude of currently used catalytic formulations. This paper presents a two-dimensional catalytic converter model,
featuring a number of innovations regarding the catalyst transient behaviour, the reaction kinetics and the solution
procedure. The oxygen storage submodel presented is capable of accounting for the redox and temperature dependence of
the oxygen availability under transient operation. The redox sensitivity of the reaction scheme gives a clearer insight in the
lambda-window behavior of 3-way catalysts. The application range of the model and the expected accuracy levels in the
most common engineering problems are discussed. It is concluded, that although the task of predicting emissions over
random driving scenarios is quite demanding in both chemical kinetics and inlet conditions data, most optimization
applications may be sufficiently handled with existing kinetic expression information.
Keywords: Automotive emissions; Converters; Mathematical modeling; Reaction kinetics; Design optimization
R Leanza, I Rossetti, L Fabbrini, C Oliva, L Forni, Perovskite catalysts for the catalytic flameless combustion of methane:
Preparation by flame-hydrolysis and characterisation by TPDTPR-MS and EPR, Applied Catalysis B: Environmental, Volume
28, Issue 1, 18 September 2000, Pages 55-64, ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(00)00163-6.
Abstract: A new method was employed for the preparation of a set of lanthanum cobaltites of general formula
La1xMxCoO3+ with M=Ce, Eu and x=0, 0.05, 0.1, 0.2. All the samples thus prepared were nanostructured, thermally very
stable and characterised by highly crystalline perovskite-like structure and high surface area. Their activity as catalysts for
the catalytic flameless combustion (CFC) of methane was by ca. one order of magnitude higher than that of their analogues,
prepared through the usual calcination-milling (CM) procedure. Adsorption of oxygen was accompanied by formation of
paramagnetic species. Desorption of preadsorbed oxygen was dependent on the nature of the doping element and on the
value of the stoichiometric coefficient x of their formula. A correlation between the temperature of the maximal rate of
oxygen release and catalytic activity was found. The following scale of activity for the title reaction versus x values could be
set up: 0.1Ce>0.05Ce>0>0.05Eu>0.1 Eu0.2Ce. The higher activity of Ce-doped catalysts as compared to those
doped with Eu was found to be related to the strength of the bond between oxygen and Co ions.
Keywords: Perovskite-like catalysts; Flame-hydrolysis preparation method; Methane catalytic combustion; TPDTPR-MS
characterisation; EPR; Particle size effect
George W. Huber, John W. Shabaker, Steven T. Evans, James A. Dumesic, Aqueous-phase reforming of ethylene glycol over
supported Pt and Pd bimetallic catalysts, Applied Catalysis B: Environmental, Volume 62, Issues 34, 22 February 2006,
Abstract: More than 130 Pt and Pd bimetallic catalysts were screened for hydrogen production by aqueous-phase reforming
(APR) of ethylene glycol solutions using a high-throughput reactor. Promising catalysts were characterized by CO
chemisorption and tested further in a fixed bed reactor. Bimetallic PtNi, PtCo, PtFe and PdFe catalysts were significantly
more active per gram of catalyst and had higher turnover frequencies for hydrogen production ( TO F H 2 ) than
monometallic Pt and Pd catalysts. The PtNi/Al2O3 and PtCo/Al2O3 catalysts, with Pt to Co or Ni atomic ratios ranging from
1:1 to 1:9, had TO F H 2 values (based on CO chemisorption uptake) equal to 2.85.2 min1 at 483 K for APR of ethylene
glycol solutions, compared to 1.9 min1 for Pt/Al2O3 under similar reaction conditions. A Pt1 e9/Al2O3 catalyst showed TO
F H 2 values of 0.34.3 min1 at 453483 K, about three times higher than Pt/Al2O3 under identical reaction conditions. A
Pd1 e9/Al2O3 catalyst had values of TO H 2 e ual to 1.4 and 4.3 min1 at temperatures of 453 and 483 K, respectively,
and these values are 3946 times higher than Pd/Al2O3 at the same reaction conditions. Catalysts consisting of Pd
supported on high surface area Fe2O3 (Nanocat) showed the highest turnover frequencies for H2 production among those
catalysts tested, with values of TO F H 2 equal to 14.6, 39.1 and 60.1 min1 at temperatures of 453, 483 and 498 K,
respectively. These results suggest that the activity of Pt-based catalysts for APR can be increased by alloying Pt with a
metal (Ni or Co) that decreases the strengths with which CO and hydrogen interact with the surface (because these species
inhibit the reaction), thereby increasing the fraction of catalytic sites available for reaction with ethylene glycol. The activity
of Pd-based catalysts for APR can be increased by adding a water-gas shift promoter (e.g. Fe2O3).
Keywords: Aqueous phase reforming; Hydrogen production; Renewable energy; Fuel cells; Bimetallic catalysts; High
throughput
Yang Zhenming, Zhang Jinsong, Cao Xiaoming, Liu Qiang, Xu Zhijun, Zou Zhimin, Microwave enhanced exhaust conversion of
internal combustion engines, Applied Catalysis B: Environmental, Volume 34, Issue 2, 5 November 2001, Pages 129-135,
ISSN 0926-3373, https://doi.org/10.1016/S0926-3373(01)00212-0.
Abstract: The key to meeting the requirements of ever-tightening emission standards is improving the efficiency of exhaust
conversion during cold-start. In order to reach the aim, a new method using microwave-heated catalysts is proposed in this
paper. Preliminary testing results show that the three-way catalysts can be rapidly and uniformly heated using microwave-
adsorbed ceramic foams as the substrate, and sufficient purification efficiency can be achieved with microwave-heated
even under the conditions of low temperature of inlet gas, oxygen-lean, oxygen-rich and high space velocity.
Keywords: Microwave; Exhaust gas; Catalyst; Catalytic converter; Foams; Ceramic
Jin-Yong Luo, Meshari AL-Harbi, Marcus Pang, William S. Epling, Spatially resolving LNT desulfation: re-adsorption induced
by oxygen storage materials, Applied Catalysis B: Environmental, Volume 106, Issues 34, 11 August 2011, Pages 664-671,
Abstract: Spatially resolved gas concentration measurements were obtained along a commercial LNT sample, containing
both NOx storage and oxygen storage components, during exposure to different levels of sulfur and under mild desulfation
conditions. For a partially sulfated sample, with sulfur mainly deposited toward the catalyst inlet, during the desulfation
some of the sulfur species released from the front were re-adsorbed along the back part of the catalyst, leading to
redistribution of the sulfur species. For the fully sulfated sample, no re-adsorption occurred. Interestingly, for a partially
sulfated model sample, Pt/BaO/Al2O3, no re-adsorption was observed. Based on the data obtained from the model and
commercial samples, the ceria-based oxygen storage (OS) material plays a crucial role in this sulfur re-adsorption. The OS
material's main function in this process is to provide oxygen for the oxidation of the released sulfur species from the front,
so that they re-adsorb at the catalyst back. Besides this sulfur redistribution, these OS materials also influence the
desulfation products. More H2S, relative to SO2, is released from the OS-containing sample since S ultimately spent more
time within the catalyst via re-adsorption and extra reductant consumption by the OS materials. In addition, NOx re-
adsorption during regeneration was also observed, leading to a decreased NOx release at the transient from the lean to rich
phases. However, the extent of NOx re-adsorption was significantly less relative to sulfur re-adsorption under the test
conditions used.
Keywords: Lean NOx trap; Desulfation; Regeneration; Spatial resolution; Sulfur poisoning
Junichiro Kugai, Jeffrey T. Miller, Neng Guo, Chunshan Song, Role of metal components in PdCu bimetallic catalysts
supported on CeO2 for the oxygen-enhanced water gas shift, Applied Catalysis B: Environmental, Volume 105, Issues 34,
22 June 2011, Pages 306-316, ISSN 0926-3373, https://doi.org/10.1016/j.apcatb.2011.04.020.
Abstract: Catalytic hydrogen production and CO removal in a post-reforming process are critical for low-temperature fuel
cell applications. The present study aims at clarifying the role of metal components in bimetallic catalysts for oxygen-
enhanced water gas shift (OWGS), wherein a small amount of O2 is added to H2-rich reformate gas to enhance CO shift.
Among CeO2-supported bimetallic catalysts, PdCu and PtCu combinations were found to show strong synergetic
promoting effect in OWGS, which leads to much higher CO conversion and higher H2 yield than WGS at low temperature
around 250 C. Temperature programmed reduction (TPR) showed strong interaction between Pd and Cu in PdCu/CeO2 by
a single reduction peak in contrast to multiple peaks on monometallic Cu/CeO2. Extended X-ray absorption fine structure
(EXAFS) analysis revealed that such bimetallic PdCu and PtCu form alloy nanoparticles, where noble metal is mainly
surrounded by Cu atoms. Oxygen storage capacity (OSC) measurements point to higher resistance of PdCu to oxidation
indicating that Pd keeps Cu in reduced state in air pulse condition. From kinetic study, Pd in PdCu was found to promote
CO shift, rather than CO oxidation by increasing the number of active sites and by suppressing H2 activation (that is
inherent to monometallic Pd), which minimizes both the inhibition effect of H2 and the loss of H2 by oxidation in OWGS.
Transient response technique revealed that Cu in PdCu enhances desorption of strongly chemisorbed CO2 on catalyst
surface in contrast to very slow CO2 desorption from surface of monometallic Pd. Thus, the excellent OWGS activity of Pd
Cu catalyst has been attributed to the complementary roles of the two metals for enhancing CO shift, which is realized by
its alloy structure and the accompanying strong interaction between metal components.
Keywords: Oxygen-enhanced water gas shift (OWGS); Water gas shift (WGS); Pd; Cu; Metal catalyst; CeO2-supported Pd
Cu; Bimetallic catalysts

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