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Catalysis Today
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a r t i c l e
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Article history:
Received 26 June 2015
Received in revised form 19 August 2015
Accepted 10 September 2015
Keywords:
FischerTropsch synthesis
Ordered mesoporous Co3 O4
Al2 O3 modication
Structural stability
Deactivation
a b s t r a c t
Ordered mesoporous Co3 O4 metal oxide synthesized by nano-casting method using a hard template of
KIT-6 was subsequently modied with Al component to increase catalytic activity and structural stabilities even under H2 -rich FischerTropsch synthesis (FTS) conditions. While using a highly ordered
mesoporous Co3 O4 for FTS reaction, a signicant structural change by forming larger cobalt aggregates
and encapsulated cokes accelerated a catalyst deactivation. By introducing an irreducible Al species on
the inner surfaces or in the main frameworks of mesoporous Co3 O4 , the ordered mesoporous structures
of Co3 O4 were successfully maintained even after FTS reaction. These modications of the mesoporous
Co3 O4 structures were carried out by adding a pillaring material of aluminum oxide or by preparing
mesoporous mixed binary metal oxides with the partial formation of a spinel CoAl2 O4 phase, and a
higher structural stability and activity were observed due to the suppressed collapses of the mesopore
structures of Co3 O4 . The improved stability of the Co3 O4 mesopores seems to be related with a lower
mobility of an irreducible Al2 O3 pillar by strongly interacting with the inner surfaces of the mesoporous
Co3 O4 or by enhancing the interactions of Co3 O4 with Al2 O3 in a main framework of mixed binary metal
oxides.
2015 Elsevier B.V. All rights reserved.
1. Introduction
FischerTropsch synthesis (FTS) reaction has been well known
to be an efcient chemical conversion process using the synthesis gases, which can be synthesized from the reforming of natural
gas or coal (or biomass) gasication, to produce some clean fuels
or petrochemicals [13]. The cobalt-based FTS catalysts have the
advantages such as a higher yield for linear hydrocarbons at a lower
operating temperature with a suppressed water gas shift activity
compared to the iron-based FTS catalysts [4]. The supported FTS
catalysts can be prepared by supporting cobalt nanoparticles on
the highly porous irreducible metal oxides with a high dispersion
of them, however, signicant aggregations of the cobalt nanoparticles with the reoxidation to form an inactive cobalt species and
the possible deposition of heavy waxes (or coke precursors) during
the FTS reaction haven been known for the main reasons for catalyst deactivations [4]. To overcome these general disadvantages
of supported catalysts, ordered mesoporous supports such as the
ordered mesoporous silica, carbons or transition metal oxides have
been widely investigated in the eld of heterogeneous catalysis due
Corresponding author.
E-mail address: nejw@skku.edu (J.W. Bae).
http://dx.doi.org/10.1016/j.cattod.2015.09.047
0920-5861/ 2015 Elsevier B.V. All rights reserved.
28
of Co:Al = 1:0.125 and 1:0.25 in aqueous slurry of mesopores of KIT6. The sample was placed in a drying oven at 100 C for 1 h and the
impregnated cobalt and aluminum precursors on the KIT-6 were
dried at 80 C overnight and followed by drying and calcination in
a mufe furnace at 550 C for 3 h at a heating rate of 1 C/min. To
remove the hard template of KIT-6, the sample was rinsed with 2 M
NaOH aqueous solution and washed several times using deionized
water and acetone. The as-prepared mesoporous mixed oxides is
denoted as meso-CoAlOx . The template-free catalyst was dried at
room temperature, and an irreducible Al2 O3 was further pillared
into the meso-CoAlOx with 5 wt%Al based on the total weight of the
meso-CoAlOx . After impregnation of Al precursor, the well-mixed
meso-CoAlOx was further dried at 80 C for 12 h and calcined at
550 C for 3 h with a heating rate of 1 C/min, and the Al2 O3 pillared
mesoporous CoAlOx were nally denoted as Al/meso-CoAl0.13 Ox
which contains 62% cobalt metal and Al/meso-CoAl0.25 Ox , respectively.
2.3. Catalytic characterizations and activity tests
Wide angle powder X-ray diffraction (XRD) patterns of the fresh
mesoporous Co3 O4 catalysts were recorded using a Rigaku D/MAX2200V diffractometer operated at 40 kV and 40 mA with a Cu-K
radiation and a scanning rate of 5 /min. The Co3 O4 particle sizes on
the fresh mesoporous Co3 O4 catalysts were also calculated using
DebyeScherrer equation with the values of a full width at half maximum (FWHM) obtained from the most intense diffraction peak of
Co3 O4 at 2 = 36.8 . In addition, small angle X-ray scattering (SAXA)
analysis was also carried out using Anton Paar instrument operated
at 60 kV and 58 mA with Cu-K radiation of 0.15406 nm in a range of
0.44.5 to verify the formation of ordered mesoporous structures.
The surface area, pore volume and average pore diameter on the fresh mesoporous Co3 O4 catalysts were analyzed
by N2 adsorptiondesorption method operating at 196 C
using Micromeritics ASAP 2020 instrument with the help of
BrunauerEmmettTeller (BET) method. The pore size distribution
of the mesoporous Co3 O4 catalysts was also calculated using BJH
(BarrettJoynerHalenda) method from the desorption branch of
N2 isotherms. In addition, the surface area of metallic cobalt species
was measured by H2 chemisorption at 100 C using Micromeritics
ASAP 2000 instrument. Prior to the analysis, a calcined 0.5 g of catalyst was pretreated in situ at 400 C for 12 h under a ow of 5 vol%H2
balanced with N2 , and the surface area of metallic cobalt species
was calculated with an assumption of H/Co stoichiometry of 1.0.
Temperature-programmed reduction (TPR) analysis was performed to verify the reduction behaviors of the fresh mesoporous
Co3 O4 catalysts using BETCAT instrument equipped with thermal
conductivity detector (TCD). Prior to the analysis, the sample was
pretreated under He ow at 350 C for 2 h to remove adsorbed water
and contaminants, followed by cooling to 50 C. After pretreatment,
the reducing gas of 5%H2 balanced with He was introduced to the
sample at a heating rate of 10 C/min from 100 to 900 C. The efuent gases were passed into a molecular sieve trap to remove water
produced, and then the reduction patterns of the sample were
obtained using TCD. Furthermore, the degree of reduction on the
mesoporous Co3 O4 catalysts were calculated using the TPR data
with a percentage of the amount of H2 consumption below 450 C
divided by that of total consumed H2 in full temperature regions.
The surface composition and binding energy (BE) of Co2p3/2 and
Al2p on the fresh and used mesoporous Co3 O4 catalysts were determined by X-ray photoelectron spectroscopy (XPS; ESCALAB MK-II)
analysis with Al K source (1486.6 eV) in a vacuum level at around
107 Pa. The obtained BEs were further corrected by considering a
reference BE of C1s at 284.4 eV. The intensity ratio of the Al and
Co species denoted as IAl /ICo which was dened as the integrated
area of the Al metal species divided by that of cobalt species, was
29
30
Table 1
Characteristics of the Al-modied ordered mesoporous Co3 O4 catalysts.
Catalysts
BET
Bulk-Co3 O4 c
Meso-Co3 O4 c
Al/meso-Co3 O4 c
Al/meso-CoAl0.13 Ox
Al/meso-CoAl0.25 Ox
XRD
H2 -Chem.
TPR
XPS
Surface
area
(m2 /g)
Pore
volume
(cm3 /g)
Pore
diameter
(nm)
Particle
size of
Co3 O4 (nm)
Surface area
of cobalt
(m2 /gCo )
Degree of
reduction
(%)a
BE (eV) of
Co2p3/2
BE (eV) of Al2p
Fresh/used
Fresh/used
Fresh/used
32
104
98
68
47
0.22
0.19
0.21
0.10
0.07
20.3
5.0
6.1
4.7
5.5
27.9
15.5
16.9
15.9
16.4
12.1
22.8
31.0
8.4
10.9
98.2
62.9
44.0
50.4
50.3
780.2/780.0
780.5/780.3
781.0/780.9
778.8/778.7
/
75.8/75.0
74.4/74.2
74.2/73.8
/
1.28/1.14
2.12/2.15
4.36/4.31
a
The degrees of reduction of catalysts were calculated using TPR data with an amount of H2 consumption below 450 C divided by total H2 consumption in the full
temperature ranges.
b
The values of the intensity ratio of IAl /ICo were calculated using the integrated area of each peak by correcting the area using the atomic sensitivity factors (ASF) with the
values of SCo = 4.5 and SAl = 0.11.
c
The characterization results of the bulk-Co3 O4 , meso-Co3 O4 and Al/meso-Co3 O4 was partly reported in our previous works [8,10].
Fig. 2. (A) Wide-angle XRD patterns and (B) small angle X-ray scattering (SAXS) patterns of the fresh mesoporous Co3 O4 catalysts.
31
Fig. 4. TEM images of the fresh (A) bulk-Co3 O4 , (B) meso-Co3 O4 , (C) Al/meso-Co3 O4 , (D) Al/meso-CoAl0.25 Ox catalysts.
32
Fig. 5. Catalytic activities on the mesoporous Co3 O4 catalysts with time on stream
(h).
33
Table 2
Catalytic performances on the Al-modied ordered mesoporous Co3 O4 catalysts.
Catalysts
Bulk-Co3 O4
Meso-Co3 O4
Al/mesoCo3 O4 c
Al/mesoCoAl0.13 Ox
Al/mesoCoAl0.25 Ox
Reaction Temp. ( C)
230
230
230
240
240
20
20
20
40
20
60
20
60
Activitya
CO conv. (C-mol%)
Rateb
TOFb
C1 /C2 C4 /C5 +
Olens in C2 C4 (%)
6.1
11.7
88.2
83.6
93.9
91.3
95.8
85.9
5.8
10.9
82.8
0.055
0.035
0.153
88.2
0.406
90.0
0.234
3.1/2.9/94.0
6.9/11.3/81.8
11.6/11.1/77.3
9.7/11.9/78.4
8.3/6.1/85.6
6.4/5.4/88.2
13.4/7.5/79.1
12.1/8.8/79.1
43.4
61.1
11.6
16.5
7.5
16.5
4.2
25.2
a
The FTS reaction was carried out at the following conditions; T = 230 and 240 C, P = 2.0 MPa, WHSV = 24000 L/(kgcat h), and a feed gas composition of
H2 /N2 /CO = 62.84/5.60/31.56.
b
The reaction rate was dened as the reacted CO mol/(gcat s) and the TOF was dened as the reacted CO molecules/(surface cobalt atom s), where the rate and TOF were
calculated using the reaction date at around 20 h on stream.
c
The results of the Al/meso-Co3 O4 was reported in our previous work [10].
strongly interacted Al2 O3 and a possible formation of the inactive CoAl2 O4 species on the Al/meso-Co3 O4 and Al/meso-CoAlOx .
As shown in Fig. 6(D) with the magnied inset TEM image, there
were no large differences in the ordered mesoporous structures
between the fresh and used Al/meso-CoAl0.25 Ox , which strongly
suggests that the structural collapse can be successfully suppressed
by using the Al2 O3 modier to the mesoporous Co3 O4 structures through pillaring method of irreducible Al2 O3 or preparing
mixed metal oxide structures of meso-CoAlOx . In addition, the
increased C5 + selectivity with an increase of reaction time on all
the Al-modied mesoporous Co3 O4 can be attributed to the surface
changes through the reconstruction and aggregation of cobalt particles or the carbon depositions and so on [4,18,25,32]. The decreased
olen selectivity on the Al-modied meso-Co3 O4 compared to the
meso-Co3 O4 seems to be attributed to the higher oxidation states
of cobalt particles or the increased surface acidity [4,16] due to the
formation of the strong new interactions of Al2 O3 species with the
outer surfaces or the frameworks of the mesoporous Co3 O4 . It was
also supported from the measured isoparafn percentage based
on the total parafn in the range of C2 C4 hydrocarbons with the
values of 3.73, 3.59, 2.29, 1.97 and 0% on the Al/meso-CoAl0.25 Ox ,
Al/meso-CoAl0.13 Ox , Al/meso-Co3 O4 , meso-Co3 O4 and bulk-Co3 O4 ,
respectively.
Fig. 6. TEM images of the used (A) bulk-Co3 O4 , (B) meso-Co3 O4 , (C) Al/meso-Co3 O4 , (D) Al/meso-CoAl0.25 Ox catalysts.
34
Fig. 7. XPS spectra of Co2p on the mesoporous (A) fresh and (B) used Co3 O4 catalysts.
To further verify the possible reasons for the enhanced structural stability after the Al2 O3 modication on the mesoporous
Co3 O4 , XPS analysis was also carried out on the fresh and used
FTS catalysts and the results are summarized Table 1 with the
XPS peaks of Co2p in Fig. 7. The values of BEs on the fresh mesoporous Co3 O4 were found to be in the ranges of 778.8781.0 eV
and 778.7780.9 eV on the used mesoporous Co3 O4 . In general,
the core level BEs of Co2p3/2 on the supported Co3 O4 catalysts
have been reported to slightly increase compared to those of pure
Co3 O4 nanoparticles due to the strong metal-support interaction
due to different surface properties of the supports such as acidity or hydrophilicity and so on [33,34]. Therefore, the observed
slight increases of BEs after Al2 O3 modication on the mesoporous
Co3 O4 compared to the pure meso-Co3 O4 may suggest the formation a new strong interactions between the Al2 O3 pillar (or the
mixed metal oxides of CoAlOx ) and the mesoporous Co3 O4 surfaces. Due to the possible superposition of Co2p3/2 peak assigned
to the cobalt oxides with various oxidation states such as Co3 O4 ,
CoO and CoAl2 O4 with the reference metallic cobalt BE of 780.0 eV
[35,36], the formation of spinel cobalt aluminate species cannot be
overlooked due to a observed new reduction peak at a higher reduction temperature above 600 C from TPR results after the Al2 O3
modication on the meso-Co3 O4 . In addition, a main aluminum
phase seems to be the stable gamma-Al2 O3 from the observed BEs
of Al at around 75 eV on the fresh and used mesoporous Co3 O4
catalysts without signicant variations. The modication with a
thermally stable Al2 O3 on the Al/meso-Co3 O4 and Al/CoAlOx may
be related with an enhanced stability of mesopore structures by
partially forming CoAl2 O4 spinel structures in the interfaces of
Al2 O3 and Co3 O4 particles possibly. This hypothesis was supported
by comparing the intensity ratio of Co2p3/2 peak with that of Al2p
peak on the fresh and used catalysts as summarized in Table 1.
The calculated values of IAl /ICo were found to be 1.28, 2.12 and
4.36 on the fresh Al/meso-Co3 O4 , Al/meso-CoAl0.13 Ox and Al/mesoCoAl0.25 Ox respectively, and the observed higher ratios of IAl /ICo on
the fresh Al/meso-CoAlOx were attributed to a higher content of
Al2 O3 species. In addition, a small shoulder peak intensity at around
785.0 eV on the fresh Al/meso-CoAlOx and Al/meso-Co3 O4 can be
assigned to a shake-up process of a high spin Co2+ species, which
can be correlated with the formation of non-reducible inactive
cobalt aluminate species as well [37]. Therefore, the XPS spectra
of the Al2 O3 -modied mesoporous Co3 O4 catalysts after FTS reaction further revealed that the shake-up process of the high spin Co2+
increased due to the additionally generated spinel cobalt aluminate
species during FTS reaction possibly, which can be mainly responsible for the structural stability with a lower deactivation rate on
the Al/meso-Co3 O4 and Al/meso-CoAlOx . Interestingly, the calculated values of IAl /ICo were found to be 1.14, 2.15 and 4.31 on the
used Al/meso-Co3 O4 , Al/meso-CoAl0.13 Ox and Al/meso-CoAl0.25 Ox ,
respectively without signicant variations compared to those of
the fresh catalysts. These observations also support that the Al2 O3
species as a pillaring material or as a mixed metal oxide formation seems to be thermally stable even under the FTS reaction by
not being segregated and by forming strong interactions with the
mesoporous Co3 O4 surfaces and the framework structures of the
Al/meso-Co3 O4 and Al/meso-CoAlOx sufciently.
In summary, the irreducible Al2 O3 modication of the mesoporous Co3 O4 catalysts through the pillaring method or the
formation of mixed metal oxide of mesoporous CoAlOx can successfully enhance the catalytic activity and stability by maintaining
stable ordered mesopore structures even under the reductive FTS
reaction conditions at a higher space velocity with a simultaneous
suppression of coke or wax deposition on the active cobalt metal
surfaces. The newly formed strong interactions between Co3 O4 and
Al2 O3 particles by partially forming spinel structure of the inactive
CoAl2 O4 species were the main reasons for the enhanced structural stability of the mesopores of Al-modied Co3 O4 . The improved
structural stability of mesoporous Co3 O4 was attributed to the
lower mobility and thermal stability of the irreducible Al2 O3 pillar by strongly interacting with the inner surfaces of the ordered
mesoporous Co3 O4 which were well veried by the surface characterizations such as TEM, XPS and TPR analysis.
4. Conclusions
The FTS activity of the mesoporous Co3 O4 synthesized through
a well-known nano-casting method using the mesoporous KIT-6 as
a hard template was investigated. The mesoporous structures and
the enhanced structural stability of the mesopores after the modication with an irreducible and thermally stable metal oxide of
Al2 O3 showed an enhanced catalytic activity with less coke or wax
deposition on the active sites. These improved activity and structural stability were mainly attributed to a lower mobility of the
Al2 O3 modier by strongly interacting with cobalt particles on the
surfaces of the mesoporous Co3 O4 or in the main frameworks of the
mixed metal oxide of CoAlOx . The formation of an inactive CoAl2 O4
spinel structure on the Al/meso-Co3 O4 and Al/meso-CoAlOx seems
to be responsible for maintaining the stable ordered mesoporous
structures even under the reductive FTS reaction conditions. The
irreducible Al2 O3 modication of the mesoporous structures of
Co3 O4 by pillaring Al2 O3 on the surfaces of active cobalt particles or
by forming mixed metal oxide of mesoporous CoAlOx can be further
applied for the FTS reaction working at a higher space velocity with
a lower coke or wax deposition on the active cobalt metal surfaces
due to its ordered mesoporosity and structural stability.
Acknowledgments
This work was also supported by the R&D Center for Valuable
Recycling (Global-Top R&D Program) of the Ministry of Environment with a project number of GT-14-C-01-038-0. The authors
acknowledge the nancial support from the National Research
Foundation of Korea (NRF) grant funded by the Korea government
(NRF-2014R1A1A2A16055557). This work was supported by the
National Research Council of Science and Technology (NST) through
Degree and Research Center (DRC) Program (2014). This work was
also supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) under Energy Efciency and Resources
Programs with Project numbers of 20142010102790.
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