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DOI 10.1007/s11144-014-0790-3
Received: 9 June 2014 / Accepted: 23 September 2014 / Published online: 1 October 2014
Akademiai Kiado, Budapest, Hungary 2014
Abstract The present work aims to study the effects of the activation method on the
performance of base metal catalysts for toluene hydrogenation in liquid phase. For
this, catalysts of Fe, Co and Ni supported on c-Al2O3 were prepared by wet
impregnation from chlorinated precursors and reduced by formaldehyde. The pre-
pared catalysts were activated ex situ at 773 K or in situ at 523 K both under H2 and
characterized by N2 physisorption, SEM ? EDX, TEM, XPS and TPR techniques.
Catalytic tests were conducted in a slurry Parr reactor at 373 K under H2 pressure of
5 MPa. The results indicate the formation of metal hydroxides during the catalysts
preparation, which are not reduced by the formaldehyde. The ex situ activation seems
able to reduce both hydroxides of Fe and Ni, but there is no evidence of reduction in
the case of Co hydroxide. Co and Ni catalysts present higher activities when not
activated, whereas the in situ activation increases the activity of the Fe catalyst.
Introduction
R. Landers
Laboratory of Surface Physics, Department of Applied Physics, Gleb Wataghin Institute of
Physics, University of Campinas, Campinas, SP CEP 13083-859, Brazil
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hydrogenation reactions [1, 2], base metals are also of great interest mainly due to their
lower cost [14]. In addition, base metals such as Ni have presented reasonable resistance
to sulfur poisoning, which is very important in hydrodearomatization processes [1].
Among the base metals employed in hydrogenation reactions, Ni is the dominant
on an industrial scale and also in the research literature [28]. Co-based catalysts
have been employed in numerous studies of hydrogenation reactions [9, 10],
particularly in FischerTropsch reactions, given the intrinsic ability of Co to
hydrogenate dissociated carbon species and promote chain growth [11]. In turn, Fe
catalysts are less employed in hydrogenation studies [12].
Some authors have reported the enhancement of base metal catalytic perfor-
mances by the addition of a noble metal. The hydrogenation of aromatic compounds
in the presence of PtNi [13, 14], PtCo [13], PdNi [15] and Ru-base metals (such
as Fe, Co, Ni) [16] was assessed by previous works. In general, the results indicate
an improvement on both activity and selectivity of these catalysts with the addition
of the noble metals.
Several materials, such as SiO2, Al2O3 and zeolites, may be used as support for
base metal catalysts [3, 9, 10, 17] and the nature of the support may affect the
properties of the active phase. The metal interacts with the support and this
interaction has influence on both the dispersion and reducibility of the metal species
[3]. Due to its high surface area and thermal stability, c-Al2O3 has been widely used
in chemical processes, notably in association with Ni. Therefore, Ni/Al2O3 catalysts
are among the most employed on petrochemical and fine chemical synthesis [4].
Different factors may have influence on the hydrogenation performance of nickel
catalysts, especially with respect to the dispersion and reducibility of the metal.
These two properties are usually contradictory and are difficult to improve
simultaneously, hence a balance of them tend to optimize the active surface area of
Ni/Al2O3 catalysts [4].
Catalysts destined to aromatics hydrogenation may be prepared by many methods,
such as solgel [3], co-precipitation [4], incipient [1821] and wet impregnation [10,
2226]. According to Savva et al. [3], the solgel method ensures a better compromise
between the dispersion of nickel phase and its interaction with the support surface than
co-precipitation and incipient impregnation. However, Ni loadings higher than
15 wt% were not achieved by the solgel method, as the gelation was difficult and the
initially formed gel, if any, was not stable.
The impregnation methods are the most commonly employed, mainly due to the
simplicity of the procedures [27]. In a recent review, Maki-Arvela and Murzin [28]
stated that usually the metal dispersions are lower in catalysts prepared by incipient
impregnation than with wet impregnation. Bu et al. [23] and Suppino et al. [26]
demonstrated that wet impregnation leads to the formation of smaller metal particles
in comparison with incipient impregnation for supported Ru catalysts. The activity
of these solids on the partial hydrogenation of benzene were also superior, as well as
its selectivity to cyclohexene [23, 26].
It is important to emphasize that very few studies regarding the preparation of
base metal catalysts by wet impregnation are found in the literature [1, 10], while
this method is widely employed to prepare noble metal catalysts [22, 23, 26]
destined to hydrogenation of aromatics.
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Experimental
Catalysts preparations
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The specific surface area of the solids was determined through N2 physisorption
(BET method). A sample of 1.00 g of each solid was previously dried at 473 K
under vacuum and the physisorption was conducted at 77 K in a Tristar
Micromeritics ASAP 2010 instrument.
Scanning electron microscopy coupled with spectrometric X-ray analysis
(SEM ? EDX) was used with the principal aim of evaluating semi-quantitatively
the chemical composition of the catalysts. The analyses were conducted in a LEO
440i Leica instrument. Before insertion in the SEM, all samples were covered with a
fine layer of gold atoms using a 3 mA current for 180 s in order to obtain a gold film
thickness of 92 A .
TEM analyses were carried out on a Libra 120 Zeiss microscope with Cantega
2 k/Olympus CCD camera and iTEM data acquisition platform. The samples were
gently grinded and then dispersed in water. The dispersion was placed on ultrasound
for 10 min and then left to rest for another 10 min. A drop of the solution was
placed on a 300 mesh cupper grid coated with parlodium and carbon. The grids were
dried at ambient temperature and examined at 80 kV using the energy filter at zero
loss, 25, 30 or 50 eV. The energy positions 25 and 50 eV correspond to the first and
second plasmon.
X-ray photoelectron spectroscopy (XPS) analyses were conducted in order to
study the chemical composition on the surface of the catalysts. A spherical analyzer
VSWHA-100 with aluminum anode (Al Ka, hv = 1,486.6 eV) was used. The
pressure during the analyses was lower than 2 9 10-6 Pa. To correct bonding
energies, the line Al 2p with bonding energy of 74.0 eV was used as reference.
The formation of active phases in the catalysts was studied through temperature
programmed reduction (TPR). A Micromeritics Auto Chem 2910 instrument was
used to obtain the TPR profiles. In these analyses, a sample of 50 mg of each solid
was heated at 10 K/min from 298 to 1,073 K under 50 mL/min flow of a 10 % H2 in
N2 mixture.
Catalytic tests
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As seen in Table 1, there is an increase of the specific surface areas of the catalysts
in comparison to the support (97 m2/g). This effect is considered to be related to the
formation of hydroxide species of the metals by the addition of NaOH during the
wet impregnation procedure [25], according to Eq. 1, exemplified by NiCl2.
2NaOH NiCl2 ! NiOH2 2NaCl 1
Al2O3 97 44 56
Fe/Al2O3 109 42 54 0.0 4.2
Co/Al2O3 99 37 57 0.2 5.5
Ni/Al2O3 116 41 55 0.0 4.1
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Fig. 1 TEM images: a Ni/Al2O3 and b Fe/Al2O3, both reduced only by formaldehyde; c Fe/Al2O3
activated ex situ under H2 flow and d Fe/Al2O3 activated in situ under H2 pressure
The elementary chemical composition of the solids, obtained through EDX analysis,
is also presented in Table 1.
Although this method is considered semi-quantitative, the results indicate that the
metal load on all catalysts are very close to the nominal amount (5 wt%). As stated
before, the impregnation pH has direct influence on the metal fixation. With this
result, one can infer that the chosen pH value of 10 led to a proper fixation of all
base metals in this study.
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It can also be seen in Table 1 that residual chlorine was only detected on the Co/
Al2O3 catalyst. This result suggests that not all CoCl2 have been converted to
Co(OH)2 during the preparation. In turn, the amount of chlorine is rather small,
around 10 % of the nominal quantity present on the precursor.
The XPS technique allowed the evaluation of the effect of subsequent H2
reduction on the elimination of residual chlorine. The atomic ratios obtained from
this analysis are shown in Table 2 in which the catalysts reduced only with
formaldehyde present no abbreviation, whereas the E abbreviation indicates that the
solid was submitted to a subsequent ex situ reduction. In turn, the I abbreviation
indicates that the solid was reduced in situ, besides its previous reduction with
formaldehyde.
Comparing the results of Table 2 and those obtained via EDX (Table 1), one can
observe that the XPS analysis reveals the presence of chlorine (Cl/Metal ratio) on
catalysts reduced by formaldehyde, in which the EDX analysis indicate the total
absence of this compound. Such differences might be due to a lower penetration of
XPS on the solids, which allows a better resolution of the surface where the active
metals and chlorine are probably concentrated.
Even though chlorine is detected, the Cl/Metal ratios indicate that the wet
impregnation method leads to an efficient elimination of most of the chlorine,
probably due to hydroxide formation. Indeed, whilst the theoretical Cl/Metal ratio
for Ni and Co precursors is 2.0 and for Fe is 3.0, a maximum of 0.10 Cl per metal
atom is observed. It is noteworthy that the subsequent reduction ex situ with H2 flow
decreases even more the amount of chlorine on the catalysts, especially on Fe/
Al2O3-E. This solid presents ten times less chlorine than the one reduced only by
formaldehyde (Fe/Al2O3).
The analysis of the binding energies of the metals was conducted with the XPS
technique and is also presented in Table 2. With these results, the probable species
present on each catalyst were identified based on XPS pattern data.
It is worth mentioning the possible presence of base metal hydroxide on the
surface of every catalyst reduced by formaldehyde. The existence of hydroxides is
consistent with the addition of NaOH with the purpose of adjusting the
impregnation pH (Eq. 1). Additionally, one can observe that the effects of the
activation treatments are, in general, strongly influenced by the nature of the metal.
The binding energy obtained for the iron catalyst (710 eV) suggest that, given a
0.5 eV range, Fe(OH)3 (709.5 eV) is not reduced with the addition of formaldehyde
(Fe/Al2O3 catalyst). As a matter of fact, the same binding energy may also indicate
the presence of FeCl3 (709.9 eV), according to the energy patterns. Indeed, as
previously discussed, chlorine was found on the surface of this solid. However, its
amount suggests that only a small quantity of the Fe may be found in the chloride
form. In turn, the catalyst submitted to ex situ H2 reduction presented a completely
different binding energy for the Fe species (706.8 eV), in this case related to its
metallic form. Therefore, the results suggest that only under high temperature and
H2 flow one can obtain Fe0. The mild conditions of liquid phase reduction with
formaldehyde are not suitable for this purpose.
Cobalt presented the very same binding energy, independent of the activation
method, and probably related to Co(OH)2. This result indicates that, despite of the
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Table 2 Mean particle diameter of the metal (dp); XPS analysis on chlorine and surface metal species; H2 consumption and peak temperature on the TPR profiles of the
studied catalysts
Catalyst TEM analysis XPS analysis TPR analysis
a b
dp (nm) r (nm) Atomic ratio Cl/Metal B. E. (eV) Probable surface species T (K) H2 consumption (lmolH2 /mgmetal)
r standard deviation of the particles diameters, T temperature, n.a. sample not submitted to this analysis
a
B. E. binding energies for the metals Fe 2p3/2, Co 2p3/2, Ni 2p3/2
b
Binding energies patterns obtained from www.lasurface.com
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formation of cobalt hydroxide, the reduction of this specie may be difficult, since
not even with the elevated temperature (773 K) of ex situ treatment Co0 was
formed. The Co binding energy identified in these catalysts (781.5 eV) also
indicates that the chlorine observed via EDX and XPS may be adsorbed on the
support, in opposition of CoCl2 (782.9 eV).
The binding energy obtained for the Ni/Al2O3 catalyst (856.1 eV) suggests that
the metal species found on this solid may be Ni(OH)2 (856 eV). Hence, the addition
of formaldehyde does not lead to the formation of Ni0. According to the results,
nickel hydroxide is reduced when the solid is submitted to ex situ H2 reduction,
since the binding energy found in this case (855.2 eV) is related to NiO (855.3 eV).
The nickel oxide may be evidence that the metal was reduced and suffered an
oxidation when exposed to atmospheric air during its manipulation.
Particle size
The Fe, Co and Ni/Al2O3 catalysts were submitted to TEM analysis with the
purpose of studying the effects of the activation methods on the particle size of the
metals. The results are shown in Table 2.
It is important to emphasize that under the conditions employed in this analysis,
one could not differentiate the particles in elementary state from those in chloride,
hydroxide or oxide forms. As seen via the XPS technique, the base metals might not
be completely reduced and therefore the particle diameter measured with TEM
cannot be directly related to metallic particles or metallic dispersion.
The reduction treatment led to an increase in Fe particles compared to the
catalyst reduced only with formaldehyde (Figs. 1b1d). The ex situ reduction, for
instance, led to the formation of Fe particles almost twice the size of the ones in Fe/
Al2O3 catalyst. The standard deviation of the diameters is higher for the solid
reduced ex situ, suggesting a heterogeneous distribution of the particles. This result
may be due to a coalescence of the metal particles, as suggested by Pattabiraman
et al. [29]. Despite the high Tamman temperature of Fe (1,043 K), the ex situ
reduction was conducted at a temperature, which could favor the mobility of iron
particles. The in situ treatment, conducted at lower temperature also led to an
increase on Fe particles diameters, but it was slighter than on the solid activated ex
situ.
It is possible that the mean particle diameter is also related to the metal species
on each catalyst surface. Therefore, the increase on the metal particle size could be
due to the reduction of Fe(OH)3 to Fe0. This result suggests that it is very difficult to
obtain metallic Fe particles without sacrificing some of its dispersion, which is in
agreement with previous findings reported in literature [4].
Similarly, for Co catalysts, an increase in the particle size was obtained
with ex situ reduction. The standard deviation of the particle sizes suggest a more
heterogeneous distribution, in comparison with the solid reduced only by
formaldehyde. The Co(OH)2 species was found on both Co/Al2O3 and Co/Al2O3-
E catalysts, which could reinforce the coalescence hypothesis.
Ni catalyst reduced with H2 was not submitted to TEM analysis. The solid
reduced only with formaldehyde (Ni/Al2O3) presented Ni species with both
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spherical and lamellar form (Fig. 1a), indicating a different morphology for
Ni(OH)2, in comparison to the Fe and Co. The mean particle diameter of Ni was
calculated with the few nearly spherical particles found in the analysis and the
standard deviation shows a narrow distribution of the Ni particles sizes.
Table 2 shows the H2 consumption (per peak and total) as well as the temperatures
of the peaks in TPR profiles for the Fe/Al2O3, Co/Al2O3 and Ni/Al2O3 catalysts
reduced by formaldehyde and activated with H2 ex situ (E abbreviation) and in situ
(I abbreviation).
The presence of two peaks on the Fe/Al2O3 catalyst is consistent with the FeCl3
and Fe(OH)3 species identified with XPS. Since the H2 consumption for this catalyst
was 15 lmol of H2/mgFe and the theoretical consumption for the complete reduction
of the metal precursor (FeCl3) is 27 lmol of H2/mgFe, the TPR analysis suggests
that a small part of the metal may have been reduced with the addition of the
formaldehyde, although the XPS technique did not reveal the presence of Fe0.
The catalyst submitted to a subsequent reduction with H2 in situ (Fe/Al2O3-I)
presents similar behavior in comparison with the catalyst reduced only with
formaldehyde, both in temperature peaks and H2 consumption (ca. 13 2 lmol of
H2/mgFe). In addition, the H2 consumption at higher temperature suggests that the
reduction of FeCl3 requires more drastic treatments to be achieved. Indeed, in the
TPR analysis of Fe/Al2O3-E, one can observe a single peak at a much lower
temperature, which is consistent with XPS results that revealed the presence of Fe0
on this solid. The lower H2 consumption of this solid (7.0 lmol of H2/mgFe) may be
related to a partial oxidation of the Fe specie due to the exposure of the catalyst to
atmospheric air during its manipulation.
The in situ reduction had little influence on the formation of the active phase for
Co catalysts. Comparing the TPR profiles of Co catalysts in Fig. 2 and the H2
consumption in Table 2, the resemblance of the profiles of Co/Al2O3 and Co/Al2O3-
I catalysts is remarkable. Both of them presented two peaks, which may be related
to the interaction of Co with the support surface, as suggested by Jacobs et al. [35].
The reduction peaks of these solids are practically at the same temperature and
present close H2 consumptions (ca. 8.8 2 lmol of H2/mgCo), which are lower
than the stoichiometric value for the complete reduction of CoCl2 (17 lmol of H2/
mgCo). This result suggests that the addition of formaldehyde may have led to a
slight reduction of the metal, although the energy signature of metallic Co was not
identified with the XPS analysis.
Although a single peak was observed for the Co/Al2O3-E solid, the H2
consumption (8.0 lmol of H2/mgCo) is close to the other Co catalysts, suggesting
that the ex situ treatment could not completely reduce the Co(OH)2 present on this
solid. Nevertheless, evidence suggests that the subsequent ex situ treatment may
contribute by decreasing the temperature required for this reduction, as seen on the
TPR profile of Co/Al2O3-E and in Table 2.
In contrast to what was obtained on TPR profiles for Fe and Co catalysts, Ni/
Al2O3 presented a single peak, independent of the activation method. However, the
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(a)
H2 consumption (a.u.)
(b)
(c)
Fig. 2 TPR profiles of Co/Al2O3 catalysts: a reduced only by formaldehyde, b activated ex situ under H2
flow and c activated in situ under H2 pressure
In order to evaluate the effects of the activation method on the performance of the
Fe, Co and Ni catalysts, these solids were tested in toluene hydrogenation. Table 3
presents the values of initial reaction rate (r0) and the conversion of toluene after
360 min of reaction (X).
From the analysis of Table 3, one may observe that the subsequent activation
treatments led to an increase in the activity of Fe catalysts, which may be related to
the species of Fe found on the surfaces of these solids. On the Fe/Al2O3
catalyst, reduced only by formaldehyde, the XPS analysis indicated the presence of
FeCl3, which may hinder the adsorption of the reagents, thereby decreasing the
catalytic activity. In contrast, on the Fe/Al2O3-E solid the XPS and TPR analyses
suggest that most of the Fe was in metallic form. It is probable that the existence of
Fe0 in the catalyst reduced ex situ increases the number of active sites, and
consequently the activity of this solid. In turn, the Fe/Al2O3-I catalyst presented a
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slightly higher initial activity, in comparison to the solid reduced ex situ. These
results indicate that the activation of Fe/Al2O3 with H2 and elevated temperature is
paramount to obtain more active solids. Moreover, the in situ treatment had little
effect on the Fe particle size, whereas the ex situ activation led to larger particles of
this metal.
Regarding the active forms of the metals, Taimoor and Pitault [36] have
presented a kinetic study of the gas phase hydrogenation of toluene with Pt
catalysts, in which they propose that both sites metallic and cationic (metalsupport
interaction) have an important role in this reaction. According to the authors, H2
would be adsorbed over the metallic sites, whereas toluene would be adsorbed over
cationic sites. Moreover, in a previous study, Mazzieri et al. [37] also considered
that the ratio between metallic and cationic Ru sites have influence on the selectivity
and activity of catalysts employed on hydrogenation of aromatics. In the present
work, catalytic activity has been observed with solids in which metallic species
could not be detected (Fe/Al2O3, for instance) as well as with solids that are almost
completely reduced (Fe/Al2O3-E). Therefore, the authors agree with Taimoor and
Pitault [36] and Mazzieri et al. [37], in the sense that both sites M0 and Md? are the
active forms of the metals in this study.
The conversion of toluene after 360 min followed the same behavior as the
activity, indicating that the Fe catalysts submitted to subsequent activation
treatments, especially in situ, led to more active and stable solids, not susceptible
to deactivation.
Co solids showed different catalytic behaviors depending on the reduction
treatment, as seen in Fig. 3. The subsequent reduction of Co catalysts with H2 led to
an initial activity comparable to Fe/Al2O3 (Table 3) and much lower in comparison
to the Co/Al2O3, solid reduced only by formaldehyde. As seen in the TPR analyses,
the reduction of Co species tends to be difficult even with higher temperatures
treatments (such as ex situ). In addition, an increase on the Co particle size was
observed with the reduction under H2 flow, which could be related to the lower
activity of this solid.
The higher activity among Co catalysts was observed for the solid reduced only
by formaldehyde. The performance of this solid is probably related to the intrinsic
catalytic properties of Co [11], associated to effects induced by the wet
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4,0
Co/Al2O3
3,5 Co/Al2O3-E
Co/Al2O3-I
2,5
2,0
1,5
1,0
0,5
0,0
0 50 100 150 200 250 300 350 400
Reaction time (min)
Fig. 3 Influence of the activation method on the performance of cobalt catalysts: reduced only by
formaldehyde (Co/Al2O3), activated ex situ under H2 flow (Co/Al2O3-E) and activated in situ under H2
pressure (Co/Al2O3-I). Reaction conditions 300 mg of the catalyst; 25 mL of toluene, 30 mL of distilled
water and 5 mL of n-heptane; reaction temperature 373 K, pressure 5 MPa of H2, stirring rate 1,000 rpm
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possible that the Ni hydroxide is more easily activated on reaction conditions, than
the oxidized specie, which could lead to the formation of the active phase on the
beginning of the reaction.
Additionally, as previously discussed for Co, the toluene conversion after
360 min for the Ni/Al2O3 catalyst is lower than what was obtained for Ni/Al2O3-E.
Although the deactivation of the Ni/Al2O3 catalyst is not as strong as the Co/Al2O3,
in both cases the activity loss may be due to an increase of toluene adsorption over
these metals, according to the competitive adsorption model (H2 versus toluene)
proposed by Taimoor and Pitault [36].
Finally, it is noteworthy that despite the presence of water, no intermediate
reaction product, such as methylcyclohexene, was identified in any of the catalytic
tests conducted in this study. Therefore it can be inferred that the studied base
metals catalysts, regardless of the metal nature or activation method, are not
selective for partial hydrogenation products.
Conclusions
The present work studied the effects of the activation method on the performance of
base metal catalysts supported on c-Al2O3 for toluene hydrogenation in liquid
phase.
During the catalyst preparation by wet impregnation from chlorinated precursors,
metal hydroxides are formed, which are not reduced by the formaldehyde.
An ex situ activation, conducted at 773 K under H2 flow, seems able to reduce
both hydroxides of Fe and Ni, but there is no evidence of reduction in the case of Co
hydroxide.
Co and Ni catalysts present higher activities when not activated, whereas an
in situ activation at 573 K under H2 increases the activity of the Fe catalyst.
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