Catalysis Communications 67 (2015) 1620

Contents lists available at ScienceDirect

Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short communication

Optimization of unsupported CoMo catalysts for decarboxylation of

oleic acid
Jae-Oh Shim a, Dae-Woon Jeong a, Won-Jun Jang a, Kyung-Won Jeon a, Seong-Heon Kim a, Byong-Hun Jeon a,
Hyun-Seog Roh a,, Jeong-Geol Na b, You-Kwan Oh b, Sang Sup Han c, Chang Hyun Ko d,
a

Department of Environmental Engineering, Yonsei University, 1 Yonseidae-gil, Wonju, Gangwon 220-710, South Korea
Biomass and Waste Energy Laboratory, Korea Institute of Energy Research (KIER), Daejeon 305-343, South Korea
Petroleum and Gas Research Center, Korea Institute of Energy Research (KIER), Daejeon 305-343, South Korea
d
School of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, South Korea
b
c

a r t i c l e

i n f o

Article history:
Received 22 January 2015
Received in revised form 19 March 2015
Accepted 21 March 2015
Available online 27 March 2015
Keywords:
Decarboxylation
Oleic acid
Unsupported CoMo catalyst
Co/Mo ratio

a b s t r a c t
Hydrodeoxygenation (HDO) processes have been developed to remove the oxygenated compounds in lipids.
However, the HDO process consumes excess hydrogen. As opposed to the HDO process, decarboxylation does
not require hydrogen. In this study, decarboxylation of oleic acid without hydrogen was carried out over unsupported CoMo catalysts. Unsupported CoMo catalysts were prepared by a co-precipitation method. The Co/Mo
ratio was systematically varied to optimize unsupported CoMo catalyst. The catalyst properties were studied
using various characterization techniques and related to the activity results in decarboxylation.
2015 Published by Elsevier B.V.

1. Introduction
Recently, the growing threat of oil depletion and climate change has
focused attention on the world's energy consumption. In particular,
consumption of liquid transportation fuels has surged during the 20th
century, due to an increase in the number of automobiles [1]. Therefore,
alternative fuels such as biodiesel have received much attention in
recent years. Biodiesels are based on lipids derived from various biomass
resources [2]. However, biodiesel contains a large amount of oxygen
compounds [36]. High oxygen contents in biodiesel result in thermal
instability, corrosiveness, and a low heating value [46]. Therefore, the
quality of biodiesel can be improved by oxygen elimination technology.
The hydrodeoxygenation (HDO) process is commonly applied for
the elimination of oxygen in lipids derived from biodiesel. CoMoS/Al2O3 and NiMoS/-Al2O3 catalysts are commonly used for the HDO
process because hydrotreating catalysts are known to be active in the
sulde form [3,6]. However, CoMo and NiMo sulde catalysts have critical problems such as rapid deactivation by coke deposition and a need
for the addition of sulfur donor compounds (H2S) because of the low
sulfur content in the initial bio-feedstock [7]. Moreover, CoMo and
NiMo sulde catalysts require a large amount of H2 [7].
To overcome these disadvantages, catalytic decarboxylation with a
minimum consumption of hydrogen can be considered for biodiesel
Corresponding authors.
E-mail addresses: hsroh@yonsei.ac.kr (H.-S. Roh), chko@jnu.ac.kr (C.H. Ko).

http://dx.doi.org/10.1016/j.catcom.2015.03.034
1566-7367/ 2015 Published by Elsevier B.V.

upgrading process. The decarboxylation reaction removes a carboxyl

group by releasing CO2 and producing a hydrocarbon, as illustrated by
Reaction (1) [2]. Therefore, interest in non-sulde decarboxylation catalyst has grown signicantly.
Decarboxylation reaction
: RCOOHRH CO2 g; H 9:2 kJ=mol

Recently, researchers have tried to overcome the disadvantages of

CoMo and NiMo sulde catalysts. Bui et al. revealed that cobalt promoted sulde Mo catalyst is highly sensitive to support effects [8]. They
pointed out that the ZrO2 support directly inuences guaiacol conversion and deoxygenation pathways [8]. However, for Al2O3 and TiO2 supported CoMo sulde catalyst systems, unexpected reactions have been
observed. Several studies have tried to avoid any unnecessary effects
of the support. Therefore, unsupported CoMo and NiMo suldes are
used in the decarboxylation reaction [1,9]. Furthermore, Eijsbouts
et al. reported that the catalytic performance of unsupported CoMo catalysts is greatly enhanced compared to supported CoMo catalysts [10].
Thus, the rst aspect of this work is to develop unsupported CoMo
catalysts for the decarboxylation reaction of oleic acid.
The second aspect of this work is to study the effect of Co/Mo ratio on
the catalytic performance in decarboxylation. Several studies have
found that the promoter (such as Co and Ni) over Mo ratio has an impact on the catalytic performance for decarboxylation [1,9,11]. Ruinart
de Brimont et al. reported that the Ni/Mo ratio has a signicant effect

J.-O. Shim et al. / Catalysis Communications 67 (2015) 1620

2. Experimental
2.1. Catalyst preparation
CoMo catalysts were prepared by a co-precipitation method.
Stoichiometric quantities of (NH4)6Mo7O244H2O (99%, Fluka) and
Co(NO3)24H2O (98%, Aldrich) were combined in distilled water. To
this solution, 28.8% ammonium hydroxide was added at 80 C. After
aging for 4 h, they were thoroughly washed with 2 L of distilled water
to remove any impurities and air-dried for 12 h followed by drying at
110 C. The prepared catalysts were calcined at 900 C for 5 h.
2.2. Characterization
The BET surface area was measured by nitrogen adsorption at
196 C using an ASAP 2010 (Micromeritics). The XRD patterns were
recorded using a Rigaku D/MAX-IIIC diffractometer (Ni ltered CuK
radiation, 40 kV, 50 mA), and the crystallite size was estimated by
using the Scherrer equation [1217]. Temperature programmed reduction (TPR) was carried out in an Autochem 2920 (Micromeritics) using
10 vol.% H2/Ar with a heating rate of 10 C/min [1823]. Temperatureprogrammed desorption of ammonia (NH3-TPD) was carried out to
evaluate the total acidity of the catalysts using an Autochem 2920
(Micromeritics). Oxygen content was measured by elementary analysis
using a Thermo Finnigan FLASH EA-1112 Elemental Analyzer (EA). The
Co/Mo ratio of the prepared catalysts was analyzed by inductively
coupled plasma-atomic emission spectroscopy (ICP-AES) using a Thermo Scientic iCAP 6500. The analysis results are shown in Table 1.
2.3. Catalytic reaction
Decarboxylation reactions were carried out in an autoclave reactor
(100 mL) operating in batch mode. The autoclave reactor was designed
for operation up to 100 bar and 450 C. A multi-blade impeller mixed
the liquid reactant and solid catalyst. The temperature was measured
using a K-type thermocouple. In a typical batch experiment, 27.5 g of
oleic acid and 0.6785 g of catalyst (reactant/catalyst = 40/1 wt/wt)
were placed in the reactor. After oleic acid and catalyst were loaded in
the reactor, the reactor was ushed with nitrogen to remove the
remaining oxygen. Then, the reactor was heated from room temperature to 300 C at a heating rate of 4.5 C/min, and the reaction temperature was maintained for 3 h. The stirring speed was xed at 300 rpm
during the reaction. The reactor was subsequently cooled down to

Table 1
Characteristics of CoMo catalysts with various Co/Mo ratios.
Catalyst

BET S.A.
(m2/g)

Co0.1Mo0.9
Co0.2Mo0.8
Co0.5Mo0.5
Co0.8Mo0.2

1.30
1.41
4.24
2.21

a
b
c
d

CoMoO4 crystallite
sizeb (nm)

Acidity
(molNH3/gcat)

Analyzed
Co/Mo ratiod

41.8
46.2
50.6
53.2

741
1013
5870
12991

0.099:0.901
0.198:0.802
0.497:0.503
0.798:0.202

Estimated from N2 adsorption at 196 C.

Estimated from XRD.
Estimated from NH3-TPD.
Estimated from ICP-AES.

room temperature. Liquid products were collected after ltering the

solid phase catalysts. The liquid products were analyzed using a gas
chromatograph (HP 6890N) equipped with a ame ionization detector
and a capillary column (HP-5, 30 m).
3. Results and discussion
3.1. Catalyst characterization
Fig. 1 shows the XRD patterns of CoMo catalysts with various Co/Mo
ratios. According to XRD patterns, both MoO3 and CoMoO4 phases can
be detected for all the prepared catalysts [24,25]. According to the
literature, carboxylate complexes are decarboxylated at the surface of
CoMoO4 [26]. The diffractograms of CoMo catalysts show peaks corresponding to CoMoO4. The full width at half maximum (FWHM) of
CoMoO4 peak at 26.3 decreased with increasing amounts of cobalt.
The crystallite size of the CoMo catalysts was calculated from CoMoO4
peaks using the DebyeScherrer equation, and the results are listed in
Table 1. The crystallite size of CoMoO4 increased with increasing
amounts of cobalt. As a result, Co0.1Mo0.9 catalyst exhibits the smallest
crystallite size of CoMoO4, while Co0.8Mo0.2 shows the largest.
Table 1 shows the characteristics of CoMo catalysts with various
Co/Mo ratios. Among the prepared catalysts, Co0.5Mo0.5 shows the
highest BET surface area. On the contrary, Co0.1Mo0.9 shows the lowest
BET surface area. The BET surface area increased with increasing
amounts of cobalt up to 50%. However, the BET surface area was decreased with increasing amounts of cobalt greater than 50%. Generally,
unsupported catalysts have much less surface area than supported
catalysts [27].
Catalyst acidity, measured by the NH3-TPD method, is listed in
Table 1. The acidity increased with increasing cobalt oxide content. In
other words, Co0.8Mo0.2 shows the highest acidity and Co0.1Mo0.9
shows the lowest acidity. Infantes-Molina et al. reported that the existence of more Co2+ ions results in the formation of amino complexes,
which yields a high acidity [28]. The addition of cobalt oxide in
the cobaltmolybdenum oxide results in the generation of acid sites.
According to the literature, cobalt promoted molybdenum sulde
(MoS2) catalyst showed a relatively higher acidity as compared to
non-promoted MoS2 [28]. Catalyst acidity is known to be important
for deoxygenation reaction. Also, several recent studies suggested that
the acidity is a signicant factor in the deoxygenation reaction [29,30].
Fig. 2 describes H2-TPR patterns of CoMo catalysts with various
Co/Mo ratios. CoMo catalysts have three reduction peaks. The rst
peak appears in the temperature range between 250 C and 425 C.
This peak can be assigned to the reduction of Co species [31,32].
The second peak, appearing around 540 C, can be attributed to the

* CoMoO

o MoO3

*
o

* * **

**

Co0.1Mo0.9

* *

Co0.2Mo0.8

Intensity (a.u.)

on the decarboxylation selectivity [1]. Also, Wang et al. found that the
Co/Mo ratio is an important factor for catalytic activity because surface
composition changed due to variations in Co/Mo ratio [9]. In this
study, the Co/Mo ratio was systematically varied to optimize catalyst.
The effect of Co/Mo ratio on the catalytic performance has been studied
using various characterization techniques and is related to the activity
results in decarboxylation. Therefore, the nal aim of this study is to
optimize unsupported CoMo catalysts with a non-sulde nature for
decarboxylation reaction of oleic acid without hydrogen.

17

Co3O4

Co3O4

Co0.5Mo0.5
Co3O4

Co3O4

Co0.8Mo0.2

20

30

40

50

60

70

2 (degree)
Fig. 1. XRD patterns of CoMo catalysts with various Co/Mo ratios.

80

18

J.-O. Shim et al. / Catalysis Communications 67 (2015) 1620

100

588 C

Oleic acid conversion (%)

H2 consumption (a.u.)

88.1
Co0.1Mo0.9
o

574 C

Co0.2Mo0.8
o

517 C

Co0.5Mo0.5

543 C

Co0.8Mo0.2

82.7
80

67.9
61.7

60

40

20

5.2

200

400

600

800

Blank

Temperature (oC)

Co0.8Mo0.2

Co0.5Mo0.5

Co0.2Mo0.8

Fig. 3. Oleic acid conversion over CoMo catalysts with various Co/Mo ratios (reaction condition: 300 C, reactant/catalyst = 40/1, 1 atm, N2 condition).

Fig. 2. H2-TPR patterns of CoMo catalysts with various Co/Mo ratios.

reduction of CoMoO4 [31,32]. The last peak, appearing at 800 C,

corresponds to the reduction of MoO3 species, wherein the reduction
follows these steps: MoO3 MoO2 Mo [31,32]. Interestingly, the
reduction temperature of CoMoO4 species in the Co0.5Mo0.5 catalyst
was the lowest among those of the other catalysts. The addition of
Mo oxide (more than 50%) in the Co oxide matrix inhibits the reduction of the CoMo oxide species. Mo may polarize the CoO bonds,
making them more ionic, and consequently more difcult to reduce
[31]. In our previous result, reduction property is an important factor
of deoxygenation [6]. Thus, it is expected that the Co0.5Mo0.5 catalysts should have higher activity than others.
3.2. Activity tests
Scheme 1 displays the possible deoxygenation reaction pathways of
oleic acid. According to the literature, the oleic acid conversion pathways under inert conditions mainly consist of two steps [33]. In the
rst reaction step, oleic acid is decarboxylated to 8-heptadecene. In
the second step, 8-heptadecene is hydrogenated to heptadecane.
Also, oleic acid can be hydrogenated, which forms stearic acid [4].
The generation of hydrogen in inert conditions is given by the formation of di-unsaturated fatty acid for hydrogenation [33]. Additionally,
possible side reactions are cracking reactions, ketonization, polymerization, and aromatization.
Fig. 3 shows oleic acid conversion over CoMo catalysts with various
Co/Mo ratios. All catalysts exhibited higher oleic acid conversion than
the blank test. Co0.5Mo0.5 catalyst exhibited about 88% oleic acid conversion. On the contrary, other catalysts showed relatively low oleic acid

conversion. This result indicates that oleic acid conversion was strongly
dependent upon the Co/Mo ratio. Oleic acid conversion of CoMo
catalysts follows the order: Co0.5Mo0.5 N Co0.2 Mo0.8 N Co0.1 Mo0.9 N
Co0.8Mo0.2 N blank.
Fig. 4 depicts the selectivity to C17 compounds (decarboxylation
reaction products of oleic acid without hydrogen) over CoMo catalysts
with various Co/Mo ratios. Interestingly, the change in selectivity to
C17 compounds follows the same trend as the conversion of reactant.
In our previous results, the catalytic performance is related to oxygen
removal efciency [6]. To check oxygen removal efciency of CoMo
catalysts with various Co/Mo ratios, elemental analysis was carried
out. Table 2 exhibits oxygen removal efciency of CoMo catalysts with
various Co/Mo ratios. Co0.5Mo0.5 catalysts exhibited the highest oxygen
removal efciency (67.8%) among the tested catalysts. Interestingly,
even though the oleic acid conversion and C17 selectivity of Co0.8Mo0.2
are much lower than that of Co0.2Mo0.8, Co0.8Mo0.2 exhibits much higher
oxygen removal efciency than Co0.2Mo0.8 due to the strong acidity of
Co0.8Mo0.2. This result suggests that the strong acidity helps further
improve the oxygen elimination. However, Wang et al. suggests that
the excess acidity of the catalyst was responsible for the cracking,
which is in good agreement with our C17 selectivity result [34]. Therefore, excess acidity was not entirely benecial because of a decrease in
C17 selectivity.
Table 3 exhibits liquid yield of CoMo catalysts with various Co/Mo
ratios. Co0.5Mo0.5 catalyst exhibited the lowest liquid yield (34.2%)
among the prepared catalysts. It should be noted that the highest C17
selectivity of Co0.5Mo0.5 catalyst is correlated with the lowest liquid

O
OH

Oleic acid
Hydrogenation
Decarboxylation
O
OH

8-heptadecene
Hydrogenation

Heptadecane

Co0.1Mo0.9

Stearic acid
Decarboxylation

Heptadecane

Scheme 1. Reaction scheme for the decarboxylation of oleic acid to hydrocarbon.

J.-O. Shim et al. / Catalysis Communications 67 (2015) 1620

C17 selectivity (%)

30

19

Table 3
Liquid yield of CoMo catalysts with various Co/Mo ratios.

25

Catalyst

Liquid product (g)

Gaseous producta (g)

Liquid yield (%)

20

Co0.1Mo0.9
Co0.2Mo0.8
Co0.5Mo0.5
Co0.8Mo0.2

19.4
16.0
9.4
12.8

8.1
11.5
18.1
14.7

70.4
58.0
34.2
46.6

20.7
19.5
16.1

14.8

15

a
Gaseous product expressed as gram (g) is calculated by measuring initial weight of
reactant (27.5 g) minus weight of liquid product.

10

3.7

Blank

Co0.8Mo0.2

Co0.5Mo0.5

Co0.2Mo0.8

Co0.1Mo0.9

Fig. 4. C17 selectivity over CoMo catalysts with various Co/Mo ratios (reaction condition:
300 C, reactant/catalyst = 40/1, 1 atm, N2 condition).

yield. Na et al. reported that the liquid yield of the catalyst decreased
with increasing degree of decarboxylation because oxygen in oleic
acid was removed in the form of CO2 [35]. The second highest C17 selectivity was observed for the Co0.2Mo0.8 catalyst, which had a 58.0% liquid
yield. The C17 selectivity of the Co0.8Mo0.2 catalyst, which has a 46.6% liquid yield, is lower than that of the former catalyst. This is mainly due to
the fact that the cracking reaction is inuenced by the highest acidity of
the Co0.8Mo0.2 catalyst.
Earlier reports reveal that cobalt metal serves as a promoter in the
formation of the catalyst active phase, and its character is important
for catalytic activity [9]. In this study, the CoMoO4 species is formed by
cobalt promoter addition, and this is the active species in the decarboxylation reaction. However, the increase of cobalt oxide content (less
than 50%) in molybdenum resulted in a decrease in oleic acid conversion, C17 selectivity, and oxygen removal efciency. Thus, the Co/Mo
ratio inuences the catalytic performance of CoMo catalysts.
To check the carbon balance of reaction products over Co0.5Mo0.5
catalyst, all products were collected for GC analysis. However, the
exact carbon balance could not be determined due to technical limitations. A loss of gas phase products is a main reason for these technical
limitations. Thus, a carbon balance was calculated based on a quantitative analysis of the liquid phase product. The composition of reaction
products over Co0.5Mo0.5 catalyst is listed in Table 4. The amount of 8heptadecene (12.1%) is the largest among the single compositions.
This result indicates that decarboxylation is the main reaction pathway.
Moreover, the existence of heptadecane (6.1%) and stearic acid (5.2%)
even in inert conditions proved that hydrogenation occurred as in the
reaction mechanism proposed. This result is in good agreement with
the previous literature results [34]. In addition, it can be said that the
prepared catalyst in this study can be reduced even under inert
conditions. Thus, catalytic performance may be affected by the reducibility of the catalyst. Oleic acid (11.9%) is the residue which did not
react with the catalyst. Furthermore, shorter hydrocarbons (C9C16, diesel fraction, 8.6%) were formed via cracking reaction. However, we cannot determine the composition of the remaining 56.1% of compounds
Table 2
Oxygen contents of products and oxygen removal efciency.

Oleic acid (reactant)

Blank test
Co0.1Mo0.9
Co0.2Mo0.8
Co0.5Mo0.5
Co0.8Mo0.2

Oxygen contents (%)

Oxygen removal efciency (%)

11.5
10.4
6.7
5.0
3.7
4.6

9.6
41.7
56.5
67.8
60.0

because it is difcult to dene all the specic products. The other

possible other compounds are more short hydrocarbons (~C9) and oxygenate compounds (due to polymerization, ketonization, and aromatization products).
The abovementioned reaction data can be explained as follows.
Firstly, the higher activity of Co0.5Mo0.5 is mainly correlated with the
highest BET surface area. A high surface area is usually helpful to
enhance catalytic activity due to the exposure of surface active centers
to reactants. The BET surface area value of the Co0.5Mo0.5 catalyst was
about 2 to 3 times higher than the others. Thus, the increase of active
sites in Co0.5Mo0.5 catalyst results in the highest oleic acid conversion
and C17 selectivity. Secondly, reducibility of the CoMo catalyst can be
related to the decarboxylation reaction. According to the TPR results,
the CoMoO4 species of Co0.5Mo0.5 can be reduced at the lowest temperature of 512 C. It is most likely that the easier reducibility of Co0.5Mo0.5
results in the highest oleic acid conversion among the prepared CoMo
catalysts. This result is supported by the fact that heptadecane and
stearic acid species were found in the reaction products (Table 4). In
other words, CoMoO4 can be reduced through a hydrogenation step in
the reaction. Therefore, easier reducibility of CoMoO4 species probably
has a benecial effect on catalytic performance. Thirdly, the decarboxylation reaction affects the catalyst acidity. Strong acidity has a benecial
effect in elimination of oxygen. However, the presence of excess acidity
can deteriorate catalytic performance, resulting in a decrease in the oleic
acid conversion and C17 selectivity.
4. Conclusions
The catalytic performance of non-sulde unsupported CoMo catalysts depends on the Co/Mo ratio. Co0.5Mo0.5 catalyst exhibits the
highest oleic acid conversion, C17 selectivity, and oxygen removal efciency. The higher conversion, C17 selectivity, and oxygen removal efciency of this catalyst in decarboxylation reaction without hydrogen are
correlated with the highest BET surface area and easier reducibility of
CoMoO4 species. Moreover, catalyst acidity inuences the decarboxylation reaction and oxygen removal efciency. Additionally, decarboxylation is the main reaction pathway in inert condition. As a consequence,
Co0.5Mo0.5 catalyst can be a promising decarboxylation catalyst for the
biodiesel upgrading process.
Acknowledgments
This research was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by the
Ministry of Science, ICT and Future Planning (2013R1A1A1A05007370).
Table 4
Composition of collected liquid products over Co0.5Mo0.5 catalyst.
Reactant

Percentage

Products

Percentage

Oleic acid

100.0%

Total

100.0%

Oleic acid
Stearic acid
Heptadecane (C17)
8-Heptadecene (C17)
C9C16 hydrocarbons
Other compounds
Total

11.9%
5.2%
6.1%
12.1%
8.6%
56.1%
100.0%

20

J.-O. Shim et al. / Catalysis Communications 67 (2015) 1620

References
[1] M. Ruinart de Brimont, C. Dupont, A. Daudin, C. Geantet, P. Raybaud, Deoxygenation
mechanisms on Ni-promoted MoS2 bulk catalysts: a combined experimental and
theoretical study, J. Catal. 286 (2012) 153164.
[2] M. Snre, I. Kubikov, P. Mki-Arvela, K. Ernen, D.Y. Murzin, Heterogeneous catalytic deoxygenation of stearic acid for production of biodiesel, Ind. Eng. Chem. Res.
45 (2006) 57085715.
[3] Y. Wang, J. Wu, S. Wang, Hydrodeoxygenation of bio-oil over Pt-based supported
catalysts: importance of mesopores and acidity of the support to compounds with
different oxygen contents, RSC Adv. 3 (2013) 1263512640.
[4] J.G. Immer, M.J. Kelly, H.H. Lamb, Catalytic reaction pathways in liquid-phase deoxygenation of C18 free fatty acids, Appl. Catal. A Gen. 375 (2010) 134139.
[5] H.-S. Roh, I.-H. Eum, D.-W. Jeong, B.E. Yi, J.-G. Na, C.H. Ko, The effect of calcination
temperature on the performance of Ni/MgOAl2O3 catalysts for decarboxylation of
oleic acid, Catal. Today 164 (2011) 457460.
[6] J.-O. Shim, D.-W. Jeong, W.-J. Jang, K.-W. Jeon, B.-H. Jeon, S.Y. Cho, H.-S. Roh, J.-G. Na,
C.H. Ko, Y.-K. Oh, S.S. Han, Deoxygenation of oleic acid over Ce(1 x)Zr(x)O2 catalysts
in hydrogen environment, Renew. Energy 65 (2013) 3640.
[7] V.A. Yakovlev, S.A. Khromova, O.V. Sherstyuk, V.O. Dundich, D.Y. Ermakov, V.M.
Novopashina, M.Yu. Lebedev, O. Bulavchenko, V.N. Parmon, Development of new
catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel, Catal. Today 144 (2009) 362366.
[8] V.N. Bui, D. Laurenti, P. Delichre, C. Geantet, Hydrodeoxygenation of guaiacol part
II: support effect for CoMoS catalysts on HDO activity and selectivity, Appl. Catal. B
Environ. 101 (2011) 246255.
[9] W. Wang, Y. Yang, H. Luo, T. Hu, W. Liu, Amorphous CoMoB catalyst with high activity for the hydrodeoxygenation of bio-oil, Catal. Commun. 12 (2011) 436440.
[10] S. Eijsbouts, B.G. Oogjen, H.W.H. Free, M.B. Cerfontain, K.L. Riley, S.L. Soled, S. Miseo,
Process for preparing a mixed metal catalyst composition, U.S. Patent No. 6534437
(2003).
[11] P.A. Nikulshin, A.V. Mozhaev, A.A. Pimerzin, V.V. Konovalov, A.A. Pimerzin, CoMo/
Al2O3 catalysts prepared on the basis of Co2Mo10-heteropolyacid and cobalt citrate:
effect of Co/Mo ratio, Fuel 100 (2012) 2433.
[12] D.-W. Jeong, W.-J. Jang, J.-O. Shim, W.-B. Han, H.-S. Roh, U.H. Jung, W.L. Yoon, Lowtemperature watergas shift reaction over supported Cu catalysts, Renew. Energy
65 (2014) 102107.
[13] V. Subramanian, E.S. Gnanakumar, D.-W. Jeong, W.-B. Han, C.S. Gopinath, H.-S. Roh,
A rationally designed CuFe2O4mesoporous Al2O3 composite towards stable performance of high temperature watergas shift reaction, Chem. Commun. 49 (2013)
1125711259.
[14] D.-W. Jeong, W.-J. Jang, J.-O. Shim, H.-S. Roh, I.H. Son, S.J. Lee, The effect of preparation method on the catalytic performance over superior MgO-promoted NiCe0.8Zr0.2O2 catalyst for CO2 reforming of CH4, Int. J. Hydrog. Energy 38 (2013)
1364913654.
[15] D.-W. Jeong, V. Subramanian, J.-O. Shim, W.-J. Jang, Y.-C. Seo, H.-S. Roh, J.H. Gu, Y.T.
Lim, High-temperature water gas shift reaction over Fe/Al/Cu oxide based catalysts
using simulated waste-derived synthesis gas, Catal. Lett. 143 (2013) 438444.
[16] D.-W. Jeong, H.-S. Potdar, J.-O. Shim, W.-J. Jang, H.-S. Roh, H2 production from a single stage watergas shift reaction over Pt/CeO2, Pt/ZrO2, and Pt/Ce(1 x)Zr(x)O2 catalysts, Int. J. Hydrog. Energy 38 (2013) 45024507.
[17] W.-J. Jang, D.-W. Jeong, J.-O. Shim, H.-S. Roh, I.H. Son, S.J. Lee, H2 and CO production
over a stable Ni-MgOCe0.8Zr0.2O2 catalyst from CO2 reforming of CH4, Int. J. Hydrog.
Energy 38 (2013) 45084512.

[18] H.-S. Roh, I.-H. Eum, D.-W. Jeong, Low temperature steam reforming of methane
over Ni-Ce(1 x)Zr(x)O2 catalysts under severe conditions, Renew. Energy 42
(2012) 212216.
[19] H.-S. Roh, H.S. Potdar, D.-W. Jeong, K.-S. Kim, J.-O. Shim, W.-J. Jang, K.Y. Koo, W.L.
Yoon, Synthesis of highly active nano-sized (1 wt.% Pt/CeO2) catalyst for water gas
shift reaction in medium temperature application, Catal. Today 185 (2012)
113118.
[20] D.-W. Jeong, H.S. Potdar, H.-S. Roh, Comparative study on nano-sized 1 wt% Pt/
Ce0.8Zr0.2O2 and 1 wt% Pt/Ce0.2Zr0.8O2 catalysts for a single stage water gas shift reaction, Catal. Lett. 142 (2012) 439444.
[21] D.-W. Jeong, H.S. Potdar, K.-S. Kim, H.-S. Roh, The effect of sodium in activity enhancement of nano-sized Pt/CeO2 catalyst for water gas shift reaction at low temperature, Bull. Korean Chem. Soc. 32 (2011) 35573558.
[22] H.S. Potdar, D.-W. Jeong, K.-S. Kim, H.-S. Roh, Synthesis of highly active nano-sized
Pt/CeO2 catalyst via a cerium hydroxy carbonate precursor for water gas shift reaction, Catal. Lett. 141 (2011) 12681274.
[23] H.-S. Roh, D.-W. Jeong, K.-S. Kim, I.-H. Eum, K.Y. Koo, W.L. Yoon, Single stage water
gas shift reaction over supported Pt catalysts, Catal. Lett. 141 (2011) 9599.
[24] I.H. Cho, Y.C. Kang, S.B. Park, Thiophene hydrodesulfurization of unsupported Co
Mo catalysts prepared by spray-pyrolysis method, Korean Chem. Eng. Res. 35
(1997) 814818.
[25] M. Diskus, M. Balasundaram, O. Nilsen, H. Fjellvag, Inuence of precursors chemistry
on ALD growth of cobaltmolybdenum oxide lms, Dalton Trans. 41 (2012)
24392444.
[26] J. Harber, Selectivity in heterogeneous catalytic oxidation, Pure Appl. Chem. 50
(1978) 923940.
[27] K. Inamura, R. Prins, The role of Co in unsupported CoMo suldes in the
hydrodesulfurization of thiophene, J. Catal. 147 (1994) 515524.
[28] A. Infantes-Molina, J. Mrida-Robles, E. Rodrguez-Castelln, J.L.G. Fierro, A. JimnezLpez, Effect of molybdenum and tungsten on Co/MSU as hydrogenation catalysts, J.
Catal. 240 (2006) 258267.
[29] Y. Wang, Y. Fang, T. He, H. Hu, J. Wu, Hydrodeoxygenation of dibenzofuran over
noble metal supported on mesoporous zeolite, Catal. Commun. 12 (2011)
12011205.
[30] D.-Y. Hong, S.J. Miller, P.K. Agrawal, C.W. Jones, Hydrodeoxygenation and coupling
of aqueous phenolics over bifunctional zeolite-supported metal catalysts, Chem.
Commun. 46 (2010) 10381040.
[31] J.E. Herrera, L. Balzano, A. Borgna, W.E. Alvarez, D.E. Resasco, Relationship between
the structure/composition of CoMo catalysts and their ability to produce singlewalled carbon nanotubes by CO disproportionation, J. Catal. 204 (2001) 129145.
[32] B. Wang, Y. Yang, L.-J. Li, Y. Chen, Effect of different catalyst supports on the (n,m)
selective growth of single-walled carbon nanotube from CoMo catalyst, J. Mater.
Sci. 44 (2009) 32853295.
[33] M. Arend, T. Nonnen, W.F. Hoelderich, J. Fischer, J. Groos, Catalytic deoxygenation of
oleic acid in continuous gas ow for the production of diesel-like hydrocarbons,
Appl. Catal. A Gen. 399 (2011) 198204.
[34] C. Wang, Z. Tian, L. Wang, R. Xu, Q. Liu, W. Qu, H. Ma, B. Wang, One-step
hydrotreatment of vegetable oil to produce high quality diesel-range alkanes,
ChemSusChem 5 (2012) 19741983.
[35] J.-G. Na, J.K. Han, Y.-K. Oh, J.-H. Park, T.S. Jung, S.S. Han, H.C. Yoon, S.H. Chung, J.-N.
Kim, C.H. Ko, Decarboxylation of microalgal oil without hydrogen into hydrocarbon
for the production of transportation fuel, Catal. Today 185 (2012) 313317.