Catalysis Today 198 (2012) 116124

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Catalysis Today
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Effects of metal loading and support for supported cobalt catalyst

Taraknath Das, Goutam Deo
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

a r t i c l e

i n f o

Article history:
Received 14 February 2012
Received in revised form 4 April 2012
Accepted 6 April 2012
Available online 1 June 2012
Keywords:
Support effect
Cobalt loading
Hydrogenation reaction
DRIFT

a b s t r a c t
Several series of supported cobalt catalysts were synthesized with different loadings and supports.
These catalysts were studied by in situ diffuse reectance Fourier transformed infrared (DRIFT) spectroscopy during the CO2 hydrogenation reaction. The catalysts were also characterized by Ultraviolet
visible near-infrared (UVvisNIR) spectroscopy and X-ray diffraction (XRD). The nature of interaction
between cobalt and the support was determined by calcining the catalysts at elevated temperature and
observing changes, if any, by UVvisNIR spectroscopy. The reduced catalysts did not possess cobalt oxide
phases or cobalt-support compounds, except for the niobia supported cobalt catalyst, where cobalt niobate was readily formed. During reaction adsorbed CO and formate species were observed. The intensity
and presence of the adsorbed species was dependent on the specic supported cobalt catalyst. The highest activity was observed for high loadings of cobalt supported on ceria followed by magnesia, alumina,
zirconia, silica, titaina and niobia. At low loadings, however, ceria supported cobalt catalyst possessed a
lower activity. Thus, the choice of the supports and the loading of the active metal are important while
designing the supported cobalt catalysts.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Supported cobalt catalysts are used for various chemical reactions such as FischerTropsch synthesis (FTS), CO2 hydrogenation,
steam reforming of ethanol and methane, hydrogen production,
CO preferential oxidation, soot conversion, and hydrodesulfurization [110]. Various supports have been used to prepare the cobalt
based catalysts, such as SiO2 , Al2 O3 , MgO, TiO2 , Nb2 O5 , CeO2 , and
ZrO2 [6,1115]. Previous studies reveal that during preparation of
some of these supported cobalt catalysts, cobalt-aluminate, cobaltsilicate, cobalt-niobate, cobalt-titanate, and cobalt-magnesia solid
solutions were formed. The formation of these cobalt-support compounds may be detrimental to the catalytic activity of the cobalt
metal since they are hard to reduce [1,7,8,1217]. Consequently, the
formation of cobalt metal during reduction depends on the nature
and interaction of specic support with the cobalt metal. Furthermore, these interactions of cobalt with the support may also depend
on the metal loading.
Supported cobalt catalysts have been studied by various characterization techniques. Some of the techniques considered to
study supported cobalt catalysts are: Raman spectroscopy [1],
Fourier transform infrared (FTIR) spectroscopy [2,1726], XRD
[1,10,20,23,27,28], UVvisNIR spectroscopy [10,12,2730], and Xray photoelectron spectroscopy (XPS) [1,7,8,1217,23].

Corresponding author. Tel.: +91 512 2597881; fax: +91 512 2590104.
E-mail address: goutam@iitk.ac.in (G. Deo).
0920-5861/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2012.04.028

In the present study several series of supported cobalt catalysts

were synthesized to observe the effect of support and loading. The
supports considered were: silica (SiO2 ), alumina (Al2 O3 ), magnesia (MgO), titania (TiO2 ), niobia (Nb2 O5 ), ceria (CeO2 ), and zirconia
(ZrO2 ). The supports and supported catalysts were characterized
by XRD, UVvisNIR, and DRIFT spectroscopy obtained during the
CO2 hydrogenation reaction. The simultaneous collection of conversion and yield data with the corresponding in situ IR spectra
were obtained. The surface areas of the supports and supported catalysts were also determined. Based on the combined information
from the above characterization and reactivity studies, the effect of
the support and loading was proposed.
2. Experimental
2.1. Material synthesis
Several series of cobalt catalysts containing 520 wt % cobalt
on various supports were synthesized by the incipient wetness
impregnation method. The cobalt precursor was cobalt (II) nitrate
hexa hydrate (Merck, 98%) and the supports were silica (SiO2 ),
alumina (Al2 O3 ), magnesia (MgO), titania (TiO2 ), niobia (Nb2 O5 ),
zirconia (ZrO2 ), and ceria (CeO2 ). Of these supports, MgO and ZrO2
were synthesized using available precursors and the remaining
supports were obtained from commercially sources. The details of
the supports are tabulated in Table 1. The MgO and ZrO2 supports
were prepared by taking stoichiometric amounts of double distilled
water and adding magnesium nitrate hexa hydrate or zirconium

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

Support

Chemical formula

Commercial name/precursor

Silica
Alumina
Magnesia
Titaina
Niobia
Ceria
Zirconia

SiO2
Al2 O3
MgO
TiO2
Nb2 O5
CeO2
ZrO2

AEROSIL-200
Sasol
Magnesium nitrate hexa hydrate (Merck)
Degussa-P25
CBMM, AD-1599
Alfa Aesar
Zirconium prop oxide (SigmaAldrich)

propoxide, respectively. These solutions were continuously stirred

at room temperature and then step wise calcined at various temperatures and nally calcined at 773 K for 6 h. The commercially
available supports were also calcined at 773 K for 6 h. After forming the supports, incipient wetness amounts of the cobalt precursor
solution was added drop wise to a measured amount of support
and the two were thoroughly mixed. The impregnated support
was then kept overnight in a desiccator. These dried samples were
further dried in an oven at 383 K for 6 h and stepwise calcined at
various temperatures and nally at 773 K for 6 h. Prior to the reaction studies the calcined samples were reduced as specied below.
The series of samples were denoted as xCoSi, xCoAl, xCoMg, xCoTi,
xCoNb, xCoCe, and xCoZr, where x = 5, 10, 15, or 20, and is the wt.% of
cobalt in the sample containing the support: silica (Si), alumina (Al),
magnesia (Mg), titaina (Ti), niobia (Nb), ceria (Ce), and zirconia (Zr).
2.2. Characterization studies
Surface areas of the supports and supported cobalt catalysts
were determined by nitrogen adsorption using the single point
BET equation. To measure the surface area, 3050 mg of the samples were taken and degassed at 423 K before the measurement. A
30% N2 He gas mixture was used for physisorption and a SMART
SORB 92/93 BET Surface area analyzer was used for surface area
measurements.
An UVvisNIR spectrophotometer (Cary 5000) equipped with a
diffuse reectance accessory (Harrick Scientic) was used to study
the calcined and reduced catalysts. The effect of calcination temperature was also studied by UVvisNIR spectroscopy. The spectra
were collected under ambient conditions using BaSO4 as the reference.
X-ray diffraction patterns of all the samples were obtained in
the range of 3060 with a scanning range of 3 min1 on an XPert

Powder Diffractometer using Cu K irradiation ( = 1.541841 A).

The metal particle sizes were calculated using the XPert High Score
Plus software available with the equipment.
2.3. Simultaneous DRIFT and reactivity studies of the CO2
hydrogenation reaction
The DRIFT spectra were recorded on a BRUKER TENSOR 27 FTIR
spectrometer attached with a Praying Mantis, diffuse reectance
accessory and a high temperature reaction chamber equipped with
ZnSe windows. A measured amount of powder sample was loaded
to completely ll the sample cup of the high temperature reaction chamber to obtain the DRIFT spectra. The reaction chamber
was heated by an automatic temperature controller module. All
the spectra were collected at a resolution rate of 4 cm1 . Additional
details about the set up can be found elsewhere [17].
The CO2 hydrogenation reaction studies over the supports and
supported cobalt catalysts were carried out in the DRIFT set up
described above. Prior to reaction the samples were reduced at
823 K for 4 h in a xed bed reactor in a stream of hydrogen (H2 ) owing at 50 ml/min. The externally reduced samples was loaded into
the reaction chamber and again reduced at 823 K for 1 h. After in situ

reduction the temperature of the reaction chamber was decreased

to the reaction temperature, which was kept constant at 533 K. The
total ow rate of H2 and CO2 was maintained at 52 ml/min with a
H2 to CO2 molar ratio of 25:1 and passed through the catalyst bed
in a down ow mode. The individual ow rates were maintained by
separate mass ow controllers (Bronkhorst). The FTIR spectra were
recorded against a background of the same sample reduced in H2 .
Gas samples were collected in a gas sampling chamber connected to the exit of the reaction cell. Samples from the sampling
chamber were injected into a gas chromatograph (GC) (AIMIL)
equipped with a methanizer and a ame ionization detector. A 3 m
carbosphere column was used in the GC for separation of CO, CO2
and methane. Blank experiments were also conducted under identical reaction conditions with the ow of reactants, H2 and CO2 ,
to ensure no contribution of homogeneous reaction in the reactor
occurred under the present conditions.
3. Results and discussion
3.1. Surface area analysis
The surface areas of the supports and supported catalysts were
measured and changes in each series were analyzed. The alumina
and silica supports had a surface of about 190 m2 /g, the titania
and ceria supports had a surface area of about 50 m2 /g, the niobia and zirconia supports had a surface area of about 38 m2 /g and
the magnesia support had a surface area of 18 m2 /g. The surface
area of the supported catalysts were normalized with the surface
area of the support and presented together in Fig. 1, except for the
xCoMg series of catalysts. From Fig. 1 it was observed that the surface area of the supported catalysts decrease with the addition of
cobalt. Specically, the xCoZr series of catalysts show the maximum decrease in surface area and the xCoNb series of catalysts
show the minimum change in surface area. The decrease in surface
area by addition of cobalt is attributed to the blocking of micropores of the support [7,17]. For the xCoMg series of catalysts the
surface area signicantly increases with cobalt loading, which has
been attributed to the change in crystallinity of magnesia. It has
been suggested that this change in crystallinity of magnesia creates
additional micropores and the surface area increases [15].
3.2. UVvisNIR spectra analysis
The silica support and silica supported cobalt catalysts containing 520 wt.% cobalt and calcined at 773 K were studied by
1.0

Normalized surface area

Table 1
Details of the supports/precursor used for making the supported cobalt catalysts.

117

0.9

Nb
Si

0.8

Al
Ce

0.7

Ti
0.6

Zr

0.5

Support

10

15

20

Wt % of Cobalt in support

Fig. 1. Normalized surface areas for the supported cobalt catalysts, except xCoMg.

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

1510

1360

1210

700

Abs ( a.u. )

400

1510

1320

Abs ( a.u. )

1210

700

400

118

e
d
c
b

c
b
a

a
600

800

1000

1200

1400

1600

1800

2000

200

400

600

800

1000

1200

1400

1600

1800

2000

Wavelength ( nm )

Wavelength ( nm )

1315

1210

580

730

400

UVvisNIR spectroscopy and the spectra are shown in Fig. 2. The

calcined xCoSi catalysts revealed the presence of octahedral Co3+
and tetrahedral Co2+ ions as in Co3 O4 [17]. For the xCoAl, catalysts
similar spectra were observed and have been previously reported
[17]. The titania, ceria and zirconia supported cobalt catalysts also
revealed similar spectra for the cobalt species and are not shown
for brevity. The xCoMg series of catalysts revealed relatively weaker
intensity bands at 400, 700, 1210, 1360 and 1510 nm as shown in
Fig. 3. The weaker intensity of these bands may be due to the partial formation of cobalt magnesia solid solutions, which have been
reported previously [15,17]. The UVvis NIR spectra of the xCoNb
series of catalysts were, however, different as shown in Fig. 4. For
the 5CoNb catalyst, bands were observed at 580 and 1315 nm. For
higher cobalt loadings on the niobia support, bands corresponding
to Co3 O4 were observed in addition to the band at 580 nm. This band
at 580 nm observed for the xCoNb catalysts were also present when
these samples were reduced at 823 K, which suggests that this band
is due to the formation of a non-reducible tetrahedral Co+2 species
in cobalt niobate. The bands observed in the UVvisNIR spectra of
the support and supported cobalt catalysts calcined at 773 K were
compiled and shown in Table 2.
It is often possible for cobalt to form compounds with the supports and these compounds may have an adverse effect on the
catalytic activity. To investigate the possibility of compound formation, the supported catalysts containing 15 wt.% cobalt were
calcined at increasing temperatures and nally at 1173 K. The
UVvisNIR spectra for the 15CoSi, 15CoCe and 15CoZr samples calcined at 773 and 1173 K were similar and revealed the presence of
Co3 O4 species only. These spectra suggest that cobalt does not readily form compounds with these supports. In contrast, the spectra of

Fig. 3. UVvisNIR spectra obtained under ambient conditions of (a) MgO, (b)
5CoMg, (c) 10CoMg, (d) 15CoMg, and (e) 20CoMg catalysts calcined at 773 K.

Abs ( a.u. )

Fig. 2. UVvisNIR spectra obtained under ambient conditions of (a) SiO2 , (b) 5CoSi
(c) 10CoSi (d) 15CoSi (e) 20CoSi catalysts calcined at 773 K.

1515

400

1315

200

e
d
c
b
a

200

400

600

800

1000

1200

1400

1600

1800

2000

Wavelength ( nm)
Fig. 4. UVvisNIR spectra obtained under ambient conditions of (a) Nb2 O5 , (b)
5CoNb, (c) 10CoNb, (d) 15CoNb, and (e) 20CoNb catalysts calcined at 773 K.

the 15CoAl, 15CoMg, 15CoTi and 15CoNb samples calcined at 773

and 1173 K were signicantly different. For these samples, there is
a strong tendency of compound formation between cobalt and the
support. Furthermore, the compound formation was observed to
start from 923 to 973 K. The formation of CoOMgO solid solutions,
CoAl2 O4 and CoTiO3 and CoNb2 O6 compounds have been previously suggested [1217]. The prominent bands in the UVvisNIR

Table 2
UVvisNIR spectra of the support and supported cobalt catalysts calcined at 773 K and 1173 K; assignment of cobalt ions on various supports.
Sample

UVvisNIR bands (nm)

Calcined at 773 K

Co3 O4 /SiO2
Co3 O4 /Al2 O3
Co3 O4 /MgO
Co3 O4 /TiO2
Co3 O4 /Nb2 O5
Co3 O4 /CeO2
Co3 O4 /ZrO2

Calcined at 1173 K
3+

2+

2+

Support

Co (Oh)

Co (Td)

Co (Oh)

Co3+ (Oh)

Co2+ (Td)

Co2+ (Oh)

320
300
270, 348
230

400, 715
400, 700
400, 720
450, 720
400, 737
480, 732
413, 728

1210, 1320, 1510

1210, 1320, 1516
1220,1375, 1520
1210, 1325, 1520
1210, 1330, 1515
1210, 1315, 1520
1210, 1321, 1520

580, 1315

440, 780
790

545, 580, 630, 1230, 1380, 1516

360, 533, 600, 1560

290, 524, 1200

320, 525, 580, 1567

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

119

Co
CoNb2O6
Nb2O5

Intensity ( a.u. )

e
d
c
b
a

30

35

40

45

50

55

60

Fig. 5. XRD patterns of (a) Nb2 O5 , (b) 5CoNb, (c) 10CoNb, (d) 15CoNb, and (e) 20CoNb
reduced at 823 K.

spectra of the samples calcined at 1173 K are also included in

Table 2, for quick reference.
The UVvisNIR spectra of the reduced supported catalysts, previously calcined at 773 K were also obtained and, with the exception
of xCoNb, the remaining catalysts did not show any features. The
absence of any features in the UVvisNIR spectra suggests that
these catalysts do not possess cobalt-support compounds and complete reduction of the cobalt oxide phases occurs.
3.3. X-ray diffraction studies
The XRD patterns of the supports and supported cobalt catalysts
were obtained for the samples in the calcined and reduced state.
The XRD patterns of the supported catalysts containing 15 wt.%
cobalt and calcined at 773 K revealed the presence of Co3 O4 , except
for 15CoMg and 15CoNb catalysts. The XRD patterns of 15CoMg and
15CoNb catalysts were dominated by features due to the MgO and
CoNb2 O6 . The UVvisNIR spectra, however, revealed the presence
of Co3 O4 in these two samples as well.
The XRD patterns of all the reduced supported catalysts did not
possessed features due to Co3 O4 or CoO suggesting that complete
reduction of the oxide phase oxide phase has occurred, except for
the xCoNb catalysts, which are discussed below. The XRD patterns
for the xCoAl catalysts have been previously reported by us [17]. The
cobalt metal feature at a 2 value of 44.16 was used to determine
the metal crystallite size. The cobalt crystallite size increased from
about 8 nm for 5CoAl, to about 12 nm for 10CoAl, to about 15 nm for
15CoAl, to about 17 nm for 20CoAl. For the xCoSi reduced catalysts,
the cobalt metal crystallite also increased with increasing cobalt
loading and the crystallite sizes were similar to the xCoAl catalysts
for the 5 and 10 wt.% samples and slightly larger than the xCoAl
catalysts for the 15 and 20 wt.% samples. The XRD patterns for the
xCoMg catalysts were dominated by the support and the presence
of cobalt metal could not be conrmed. For the xCoTi catalysts, the
cobalt metal features were distinct from 10 wt.% cobalt loading and
higher. The crystallite sizes were larger than those observed for the
xCoSi and xCoAl catalysts. For the 5CoTi catalysts, the XRD feature
for cobalt metal was weak.
The XRD patterns for the xCoNb catalysts revealed the formation
of CoNb2 O6 as shown in Fig. 5. A trace amount of cobalt metal was
observed for the 20CoNb sample. These observations are consistent
with the UVvisNIR studies, where a band at 580 nm was observed
to persist after reduction, indicative of a bulk cobalt niobate compound that was not reduced at 823 K. For the xCoCe catalysts, cobalt

Fig. 6. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and 1 atm.
Pressure over the supports (a) SiO2 , (b) 5CoSi, (c) 10CoSi, (d) 15CoSi, and (e) 20CoSi.
Amount of catalyst = 30 mg, temperature = 533 K, total ow rate = 52 ml/min, H2 :CO2
molar ratio = 25:1. (B) Corresponding reactivity data of the CO2 hydrogenation reaction carried out over the catalysts given in Fig. 6A.

metal crystallites were only observed for the 20CoCe sample, which
was unexpected since the UVvisNIR spectra revealed the presence of Co3 O4 in the calcined sample, similar to the xCoSi, xCoAl,
xCoTi and xCoZr samples. The Co3 O4 features in the UVvisNIR
spectra persisted in the xCoCe samples calcined at 1173 K. It appears
that the interaction of cobalt with ceria is different from the interaction of cobalt with the other supports.
3.4. Simultaneous DRIFT and reactivity studies of the CO2
hydrogenation reaction
The simultaneous DRIFT and reactivity studies of the supports
and supported cobalt catalysts during the carbon dioxide hydrogenation reactions were considered. In all the DRIFT spectra and
FTIR band due to gas phase CO2 were observed at 2345 cm1 .
The simultaneous reactivity data were also obtained and analyzed
below.
3.4.1. Effect of support and cobalt loading
3.4.1.1. The SiO2 support and supported catalysts. The CO2 hydrogenation reaction was studied over the silica support and silica
supported 520 wt.% cobalt catalysts in the DRIFT set up described
above and the spectra are shown in Fig. 6A. The corresponding CO2
conversions and methane yields are shown in Fig. 6B. Fig. 6A reveals
that for the reduced 5CoSi catalyst, an FTIR band at 2003 cm1 was
only observed. This band at 2003 cm1 is due to adsorbed CO on

120

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

Fig. 7. (A) In situ DRIFT spectra during CO2 hydrogenation reaction over (a) Al2 O3 ,
(b) 5CoAl, (c) 10CoAl, (d) 15CoAl, and (e) 20CoAl. Reaction were carried out at
temperature 533 K. Amount of catalyst = 60 mg, temperature = 533 K, total ow
rate = 52 ml/min, H2 :CO2 molar ratio = 25:1. (B) Corresponding reactivity data of the
CO2 hydrogenation reaction carried out over the catalysts given in Fig. 7A.

cobalt metal [2,17]. With an increase in cobalt metal loading over

the silica support the intensity of the adsorbed CO band gradually
increases.
Fig. 6B reveals that the CO2 conversions and methane yields
gradually increases with cobalt loading. Characterization studies
reveal that the interaction of cobalt with the silica support is relatively weak since no compound formation occurs even at 1173 K,
and the metal crystallite size increases with cobalt loading. The
cobalt metal sites adsorb CO, which is also a product of the reaction. The increase in intensity of the adsorbed CO band indicates an
increase in the number of surface cobalt sites. With an increase in
loading the metal crystallite size and the number of surface cobalt
sites increase. The larger number of surface active sites formed with
increasing cobalt loading were able to convert more CO2 .
3.4.1.2. The Al2 O3 support and supported catalysts. The CO2 hydrogenation reaction was studied over the alumina support and
alumina supported 520 wt.% cobalt catalysts by the DRIFT set up
described above and the spectra are shown in Fig. 7A. The corresponding CO2 conversions and methane yields are shown in Fig. 7B.
Fig. 7A reveals the presence of bicarbonate bands at 1225, 1434 and
1652 cm1 , which are associated with the alumina support [17]. For
the 5CoAl catalysts, distinct FTIR bands at 1372, 1392, 1600, 1998,
and 2905 cm1 were observed. The bands at 1638 and 1998 cm1
were due to adsorbed H2 O and CO, respectively [17]. The remaining

Fig. 8. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and
1 atm. Pressure over the supports (a) MgO, (b) 5CoMg, (c) 10CoMg (d) 15CoMg,
and (e) 20CoMg. Amount of catalyst = 40 mg, temperature = 533 K, total ow
rate = 52 ml/min, H2 :CO2 molar ratio = 25:1. (B) Corresponding reactivity data of the
CO2 hydrogenation reaction carried out over the catalysts given in Fig. 8B.

bands at 1372, 1392, 1600, and 2905 cm1 , were due to adsorbed
formate [2]. With an increase in cobalt metal loading the intensity
of the CO and formate bands gradually decrease.
With an increase in cobalt loading, Fig. 7B reveals that the conversion of CO2 and product methane yield gradually increases,
similar to the xCoSi catalysts. Characterization studies suggest that:
(i) unlike xCoSi catalysts a stronger interaction exists between
cobalt and alumina since cobalt aluminate was formed at 1173 K,
(ii) cobalt aluminate was absent for the reduced xCoAl catalysts,
which were previously calcined at 773 K, and (iii) the metal crystallite size gradually increases with loading for the reduced xCoAl
catalysts previously calcined at 773 K. Adsorbed CO was clearly
observed for the 5CoAl sample and was weak or absent for the
higher loading samples. Instead formate species was observed for
the xCoAl catalysts. The formation of formate species depends on
the metal support interface for which the precursor appears to be
adsorbed carbonate species [17]. Water is a product of the reaction
and its appearance in the IR spectra appears to be related to the
adsorption ability of the support.
3.4.1.3. The MgO support and supported cobalt catalysts. The effect
of cobalt loading on magnesia during the CO2 hydrogenation reaction was also studied by the DRIFT set up described above and the
IR spectra are shown in Fig. 8A. The corresponding CO2 conversions and methane yields are shown in Fig. 8B. Fig. 8A reveals that

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

121

the xCoMg catalysts possess IR bands that are distinct from those
observed over the MgO support. For the reduced 5CoMg catalyst,
IR bands at 1272, 1339, 1372, 1521, 1600, 1672, 1993, 2734 and
2835 cm1 were observed. The band at 1993 cm1 corresponds to
adsorbed CO. The adsorbed CO band appears to initially increase
and then remains relatively constant with cobalt loading. The bands
at 1339, 1372, 1600, 2734 and 2835 cm1 are due to adsorbed
formate species [24]. The band intensities of the formate species
appear to decrease with cobalt loading. The bands of the formate
species were more intense and at the same position as the xCoAl
catalysts. In addition to these species, relatively weaker bands at
1272 and 1673 cm1 appear to be due to the formation of stronglybound chemisorbed formic acid [25,31] or bi-dentate carbonate of
CO2 [32]. A band at 1520 cm1 was also observed during reaction,
which appears to be due to a uni-dentate carbonate species [17].
With an increase in cobalt loading the conversion of CO2 gradually increases up to 15 wt.% and above this loading the conversion
decreases. Characterization studies of the xCoMg catalysts revealed
the possibility of cobalt forming solid solutions with the magnesia
support, especially at high temperatures. The presence of surface
cobalt metal species in these xCoMg catalysts, though not detected
by XRD, was clearly indicated by the presence of the adsorbed CO
and formate species during the CO2 hydrogenation reaction. The
possibility of a part of cobalt metal being present as a solid solution
in the magnesia support cannot be discounted [6].
3.4.1.4. The TiO2 support and supported cobalt catalysts. The CO2
hydrogenation reaction was studied over the titania support and
titania supported 520 wt.% cobalt catalysts using the DRIFT set
up described above and the IR spectra are shown in Fig. 9A. The
corresponding CO2 conversions and methane yields are shown in
Fig. 9B. Fig. 9A reveals IR bands at 1363, 1387, 1565, and 2865 cm1
due to the formate species for the 5CoTi catalyst [21,33]. A trace
of adsorbed CO was also detected with a relatively weak band at
1996 cm1 . The formate bands were shifted to lower wavenumbers
when compared to the xCoAl and xCoMg catalysts. With increasing
cobalt loading the formate band intensity gradually decreases.
From Fig. 9B it is observed that with increasing cobalt loading
the CO2 conversion increases up to 15 wt.% cobalt and above this
loading the conversion slightly decreases. Characterization studies
reveal that: (i) a strong interaction exists between cobalt and titania
since cobalt titanate was formed at 1173 K, (ii) cobalt titanate was
absent for the reduced xCoTi catalysts, which were previously calcined at 773 K, and (iii) the metal crystallite size gradually increases
with loading for the reduced xCoTi catalysts and were signicantly
larger in size than those observed for the xCoSi and xCoAl catalysts.
The relatively weak CO band intensity makes it difcult to provide
any insights into the changes in intensity of this band as a function
of loading.
3.4.1.5. The Nb2 O5 support and supported catalysts. The CO2 hydrogenation reaction was studied over the niobia support and niobia
supported cobalt catalysts containing 520 wt.% cobalt and the
spectra are shown in Fig. 10A. The corresponding CO2 conversions
and methane yields are shown in Fig. 10B. The DRIFT spectra
shown in Fig. 10A reveal weak bands at 1372, 1576 and 1638 cm1 .
The CO2 conversions and methane yields shown in Fig. 10B were
low and similar for all the xCoNb catalysts. The presence of small
amounts of surface cobalt was suggested by the slight increase in
methane yields and CO2 conversions. The UVvisNIR and XRD
results revealed that cobalt interacts strongly with the niobia
support to form CoNb2 O6 . There was, however, no indication of
this compound formation from the surface areas of the xCoNb
samples presented previously. Furthermore, it appears that the
reduction of the Co3 O4 species present in the calcined xCoNb
samples result in the formation of additional CoNb2 O6 , expect

Fig. 9. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and 1 atm.
Pressure over the supports (a) TiO2 , (b) 5CoTi, (c) 10CoTi, (d) 15CoTi, and (e) 20CoTi.
Amount of catalyst = 60 mg, temperature = 533 K, total ow rate = 52 ml/min,
H2 :CO2 molar ratio = 25:1. (B) Corresponding reactivity data of the CO2 hydrogenation reaction carried out over the catalysts given in Fig. 9A.

for the 20CoNb catalyst, where small amounts of cobalt metal

was observed. The cobalt niobate species are difcult to reduce
at 823 K. Thus, the available cobalt metal is small and the CO2
conversion is low for the niobia supported cobalt catalysts.
3.4.1.6. The CeO2 support and supported catalysts. The CO2 hydrogenation reaction was studied over the ceria support and the xCoCe
catalysts and the results are shown in Fig. 11A and B. The FTIR
spectra in Fig. 11B reveal that adsorbed CO2 is present on the
ceria support during the CO2 hydrogenation reaction. For the xCoCe
catalysts, additional IR bands at 1294, 1368 and 1590 cm1 were
observed, which correspond to the adsorbed formate species. The
intensity of the formate bands appear to decrease with increasing
cobalt loading. Furthermore, the bands of the formate species are
shifted compared to the xCoAl and xCoMg catalysts. A weak band at
1998 cm1 was also observed for the higher cobalt loadings, which
is assigned to the adsorbed CO species and suggests the presence
of surface cobalt metal.
The reaction data in Fig. 11B reveals that the CO2 conversions
and methane yields were low and relatively constant for the 5CoCe
and 10CoCe catalysts and signicantly increase for the 15CoCe and
20CoCe catalysts. The nature of increase in CO2 conversions and
methane yields is different when compared to the xCoSi and xCoAl
catalysts. The characterization studies reveal that the Co3 O4 species
present in the calcined xCoCe catalysts were absent in the reduced

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T. Das, G. Deo / Catalysis Today 198 (2012) 116124

Fig. 10. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and
1 atm. Pressure over the supports (a) Nb2 O5 , (b) 5CoNb, (c) 10CoNb, (d) 15CoNb,
and e) 20CoNb. Amount of catalyst = 65 mg, temperature = 533 K, total ow
rate = 52 ml/min, H2 :CO2 molar ratio = 25:1. (B) Corresponding reactivity data of the
CO2 hydrogenation reaction carried out over the catalysts given in Fig. 10A.

catalysts. Furthermore, small XRD features of cobalt metal were

observed only for the 20CoCe catalyst. Correlating the information
provided by the characterization and reactivity studies it appears
that at low cobalt loading, e.g. for the 5CoCe and 10CoCe catalysts,
most of the cobalt metal is not available for reaction and the reactivity is low. At higher cobalt loadings, e.g. for the 15CoCe and 20CoCe
catalysts, the cobalt metal is highly dispersed and available for
the reaction. Consequently, the CO2 conversion and methane yield
increase signicantly. The reasons for the unavailability of cobalt
metal at low loadings are currently not well understood and may
be associated with the possibility of cobalt metal forming a solid
solution with the ceria support. Previous studies dealing with ceria
supported cobalt catalyst do indeed indicate a complex behavior
[34] and additional studies are required to understand this system
better.
3.4.1.7. The ZrO2 support and supported cobalt catalysts. The CO2
hydrogenation reaction was studied over the zirconia support and
xCoZr catalysts using the DRIFT set up described above and the
spectra are shown in Fig. 12A. The corresponding CO2 conversions
and methane yields are shown in Fig. 12B. Fig. 12A reveals IR bands
at 1333, 1535 and 1633 cm1 due to adsorbed CO2 species on the
zirconia support. In the presence of cobalt, IR bands were observed
at 1358, 1383, 1582 and 2870 (weak) cm1 , which were assigned
to the formate species [35]. An additional band due to adsorbed CO

Fig. 11. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and
1 atm. Pressure over the supports (a) CeO2 , (b) 5CoCe, (c) 10CoCe, (d) 15CoCe,
and (e) 20CoCe. Amount of catalyst = 60 mg, temperature = 533 K, total ow
rate = 52 ml/min, H2 :CO2 molar ratio = 25:1. (B) Corresponding reactivity data of the
CO2 hydrogenation reaction carried out over the catalysts given in Fig. 11A.

at 1998 cm1 was also observed. The formate bands were shifted
from those observed over the xCoAl and xCoMg catalysts and their
intensities decrease with an increase in cobalt loading, similar to
the xCoAl catalysts. The intensity of the adsorbed CO band also
decreases with an increase in cobalt loading similar to the xCoAl
catalyst.
With an increase in cobalt loading the data in Fig. 12B reveals
that the conversion of CO2 and methane yield gradually increases.
Characterization studies suggest that cobalt-zirconia compounds
are not formed at elevated calcination temperatures and the metal
crystallite size increases with an increase in cobalt loading. Considering the information available from characterization and reactivity
studies, the behavior of the xCoZr catalysts appears to be similar to
the xCoAl catalysts with an additional advantage of not forming a
cobalt-zirconia compound at elevated calcinations temperatures.
The behavior of the different supported cobalt catalyst depends
specically on the type of the support. It is evident from the
above that niobia is not suitable for synthesizing supported cobalt
catalysts since cobalt-niobate compound formation readily occurs.
With the exception of xCoNb, the in situ DRIFT spectra obtained for
the different supported cobalt catalysts reveal varying amounts of
adsorbed CO and formate species depending on the specic series
of catalyst. The variation of intensity of the two adsorbed species
with cobalt loading is, however, different. The adsorbed CO band

T. Das, G. Deo / Catalysis Today 198 (2012) 116124

123

Fig. 13. Comparison of reactivity data of the CO2 hydrogenation reaction carried
out with 30 mg of the supported catalysts containing 15 wt.% cobalt.

Fig. 12. (A) In situ DRIFT spectra of CO2 hydrogenation reaction at 533 K and 1 atm.
Pressure over the supports (a) ZrO2 , (b) 5CoZr, (c) 10CoZr, (d) 15CoZr, and (e) 20CoZr.
Amount of catalyst = 70 mg, temperature = 533 K, total ow rate = 52 ml/min, H2 :CO2
molar ratio = 25:1. (B) Corresponding reactivity data of the CO2 hydrogenation reaction carried out over the catalysts given in Fig. 12A.

intensity increases with the cobalt loading for the xCoSi catalysts.
For the xCoAl and xCoZr catalysts the adsorbed CO band intensity
decreases with an increase in cobalt loading. Not much could
be said about the variation of adsorbed CO band intensity for
the xCoMg, xCoTi and xCoCe catalysts. The adsorbed formate
species were observed in all supported cobalt catalysts during the
CO2 hydrogenation reaction, except for the xCoSi catalysts. The
intensity of the formate bands, when present, appear to decrease
with cobalt loading for the xCoAl, xCoMg, xCoTi, xCoCe and xCoZr
catalysts. Furthermore, the band positions of the formate species
depended on the oxide support suggesting the importance of the
metalsupport interface.
The DIRFT studies during CO2 hydrogenation discussed above
and shown in Figs. 612 were conducted using different amounts
for each series of supported catalyst. To compare the CO2 conversions and methane yields for the supported cobalt catalyst
containing 15 and 20 wt.% Co, studies were conducted using the
same amount of each catalyst and the reactivity data is shown in
Fig. 13. The effect of specic support is clearly observed in the
comparison shown in Fig. 13. The 15CoCe catalyst possesses the
highest CO2 conversion and methane yield. The variations in CO2
conversion and methane yield follow the trend:
15CoCe > 15CoMg 15CoAl > 15CoZr
15CoTi > 15CoSi > 15CoNb

Amongst these catalysts the xCoNb readily form bulk compounds and possesses poor catalytic activity. For the rest of the
catalysts, the cobalt metal crystallite size followed the inverse
trend, except for the 15CoTi catalyst. Similar variations in the
methane yields were observed for the supported cobalt catalysts
containing 20 wt.% cobalt. The variations of methane yield for
supported catalysts containing 10 wt.% cobalt were, however, different. The 10CoCe catalyst possessed low conversion and methane
yield. Thus, the cobalt loading is also and important factor to
consider.
One of the important factors that the oxide supports provide is
the ability of dispersing the cobalt metal. The ability of the support
to disperse cobalt results in a smaller metal crystallite size and a
high activity. The XRD features of the 15CoCe and 15CoMg catalyst
did not reveal the presence of cobalt metal suggesting the high dispersion of the cobalt metal; 15CoAl revealed the presence of cobalt
metal crystallites of about 17 nm; 15CoZr revealed the presence
of cobalt metal crystallites of about 19 nm; 15CoTi revealed the
presence of cobalt metal crystallites of about 34 nm; and 15CoSi
revealed the presence of cobalt metal crystallites of about 21 nm.
Thus, the metal crystallite size is inversely related to the conversion for the supported catalysts containing high cobalt loadings,
except for titania supported cobalt catalysts. For the titania supported cobalt catalysts other factors may affect the CO2 conversion
and methane yield. There are some suggestions that indicate the
role of other factors inuencing the catalytic activity of titania supported cobalt catalysts [36].
4. Conclusion
Series of silica, alumina, magnesia, titania, niobia, zirconia, and
ceria supported cobalt catalysts were synthesized, characterized
and tested for the CO2 hydrogenation reaction to understand the
effect of loading and support. The surface area of the catalysts
decreased with increasing cobalt loading, except for the magnesia
supported cobalt catalyst. For magnesia supported cobalt catalysts,
however, the surface area signicantly increases. Characterization
of the catalysts revealed that the presence of Co3 O4 in the calcined
samples. At high calcination temperatures, however, formation of
compounds was observed for the alumina, magnesia, titania and
niobia supported catalysts. For niobia supported cobalt catalysts,
compound formation also occurred at lower calcination temperatures. Complete disappearance of the cobalt oxide phase when
the supported catalysts were reduced at 823 K and the presence of
cobalt metal were conrmed in the catalysts.

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T. Das, G. Deo / Catalysis Today 198 (2012) 116124

The CO2 hydrogenation reaction was a function of the oxide

support and cobalt loading. Adsorbed CO and/or formate species
were detected for the supported cobalt catalysts under reaction
conditions. The presence and intensity of the adsorbed species
was dependent on the specic series of supported catalysts. The
intensity of the adsorbed CO band was observed to increase with
metal loading for the silica supported cobalt catalysts, whereas the
intensity decreases for the alumina and zirconia supported cobalt
catalysts. The variation of the intensity of the adsorbed CO band was
difcult to ascertain for the magnesia, titania and ceria supported
cobalt catalysts. Adsorbed formate species were not observed for
the series of silica and niobia supported catalysts, which appears
to be related to the ability of CO2 adsorption on the oxide support.
Previously we have suggested that the formate species is formed
on the metalsupport interface [17]. Thus, if the support is unable
to adsorb CO2 , the formate species is not formed, as in the case of
xCoSi and xCoNb catalyst. Furthermore, the position of the formate
bands in the supported cobalt catalysts depends on the specic
support, which re-iterates the importance of the metalsupport
interface towards the formation of the formate species. The variation of the formate band intensities appear to change with loading
for the xCoAl, xCoMg, xCoTi, xCoCe and xCoZr catalysts. In all of these
catalysts the formate band intensities appear to decrease with an
increase in cobalt loading. Comparing the results from CO2 conversion and the formate band intensities it is evident that the two are
not correlated.
On a constant mass basis, CO2 conversions of the ceria
supported catalysts were the best for the catalysts containing 15 and 20 wt.% cobalt. The CO2 conversions and methane
yields continuously increased with cobalt loading for the silica, alumina, zirconia and ceria supported catalysts, whereas
the conversion reached a maximum for the magnesia and
titania supported cobalt catalysts. For the high cobalt loading catalysts, the CO2 conversion and methane yield followed
the trend: xCoCe > xCoMg CoAl > xCoZr xCoTi > xCoSi > xCoNb,
where x = 15 or 20. This trend in CO2 conversions and methane
yields appears to be inversely related to the cobalt metal crystallite size, except for the xCoCe and xCoMg catalysts, where
the cobalt metal crystallite size could not be determined,
and the xCoTi catalysts where the crystallite size was relatively large. For lower loadings, however, the CO2 conversion
and methane yields were different and followed the trend:
10CoMg > 10CoAl 10CoZr 10CoSi 10CoTi > 10CoCe > 10CoNb.
The reasons for the unusually behavior of the ceria supported
cobalt catalysts, which showed high conversions and yields at high
ceria loadings and extremely low conversions and yields at low
loadings, is currently not known and requires further analysis.
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