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Catalysis Today 265 (2016) 2735

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

FischerTropsch synthesis on the Al2 O3 -modied ordered


mesoporous Co3 O4 with an enhanced catalytic activity and stability
Chang-Il Ahn, Jong Wook Bae
School of Chemical Engineering, Sungkyunkwan University (SKKU), Suwon, Gyeonggi-do 440-746, Republic of Korea

a r t i c l e

i n f o

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.

to their well-developed regular mesopore structures with a higher


surface area [2,3] through well-known nano-casting methods for
some applications of battery technologies and oxidation catalytic
reactions and so on [5,6]. However, the direct applications of the
transition metal oxides for some catalytic reactions have been limited due to their structure instability under H2 -rich conditions [7,8].
The phase transformation from metal oxides to metallic species can
cause a severe aggregation and a structural collapse of the reducible
mesoporous transition metal oxide frameworks resulted in accelerating catalyst deactivation. As far as we know, these deactivation
mechanisms may be main reasons for the small research reports
concerning practical applications of mesoporous transition metal
oxides for the FTS reaction till now.
In the present study, we investigated two possible methodologies to suppress the structural collapses of the mesoporous Co3 O4
even under the reductive CO hydrogenation conditions by introducing an irreducible aluminum oxide in the mesoporous surfaces
[10] or by preparing mixed binary metal oxides of CoAlOx in the
main frameworks of Co3 O4 to elucidate the roles of aluminum
oxide on the surfaces or mainframes of mesoporous Co3 O4 . These
modications of the mesoporous Co3 O4 with irreducible Al2 O3
species showed a stable activity by maintaining regular mesoporous structures during the FTS reaction. The improved catalytic
activity and structural stability of the mesoporous Co3 O4 were

28

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

explained through surface characterizations such as TEM and XPS


analyses by verifying the positive roles of Al2 O3 species for the
robust structural maintenances even under reductive FTS conditions.
2. Experimental
2.1. Synthesis of the ordered mesoporous KIT-6 and Co3 O4
The ordered three-dimensional mesoporous KIT-6 was synthesized by a nano-casting method using a structure-directing
agent with silica source in aqueous solution [9]. For more detail,
amphiphilic triblock copolymer of EO20 PO70 EO20 (Pluronic P123,
Aldrich) was used as the structure-directing agent and tetraethylorthosilicate (TEOS, Alfa Aesar) was used as the silicon precursor.
P123 copolymer was rstly fully dissolved in deionized water,
and then diluted 37 wt% aqueous HCl solution was mixed with
n-butanol at 35 C by stirring 1 h followed by a subsequent addition of TEOS under a vigorous stirring for 24 h. The above aqueous
mixtures were placed in an autoclave and heated for 24 at 100 C
without stirring under hydrothermal condition. The obtained white
precipitant powder was further dried at 100 C after ltering and
several washing steps using deionized water. The as-prepared powders were dried again at 100 C, and subsequently calcined under
air at 550 C for 6 h.
The ordered mesoporous Co3 O4 was prepared using the above
KIT-6 material as a hard template referring to the previous research
[6]. To remove adsorbed impurities and water, as-prepared KIT6 powder was additionally placed in a drying oven at 100 C for
1 h. The cobalt nitrate hexahydrate (Co(NO3 )2 6H2 O) precursor of
around 9.5 g was dissolved in deionized water and mixed with the
KIT-6. After cobalt precursor solution was sufciently impregnated
into the pores of the KIT-6, the cobalt precursor solution containing KIT-6 powder was further dried at 80 C overnight. The dried
violet-colored powder was calcined in air at 550 C for 3 h with
a heating rate of 1 C/min. To remove the hard template, KIT-6
from the complexes of Co3 O4 and KIT-6, it was rinsed with 2 M
NaOH solution and washed several times using deionized water
and acetone. The hard template-free mesoporous Co3 O4 was dried
at room temperature, and denoted as meso-Co3 O4 which contains
73% cobalt metal. In order to compare the catalytic activity, the
precipitated Co3 O4 was also synthesized by general precipitation
method using a same cobalt precursor and a precipitant of sodium
carbonate (Na2 CO3 ) according to our previous report [8], and asprepared Co3 O4 catalyst is denoted as bulk-Co3 O4 which contains
73% cobalt metal.
2.2. Synthesis of Al2 O3 pillared and incorporated mesoporous
Co3 O4 catalysts
For preparing an irreducible Al2 O3 pillared meso-Co3 O4 catalyst
through an incipient wetness impregnation method with 5 wt%Al
based on a total weight of Co3 O4 , aluminum nitrate precursor
(Al(NO3 )3 9H2 O) was dissolved in deionized water and mixed with
the dried meso-Co3 O4 black powder to ll up the mesopores partially with Al2 O3 pillar. The well-mixed meso-Co3 O4 solution with
Al precursor was dried at 80 C for 12 h and subsequently calcined
at 550 C for 3 h at a heating rate of 1 C/min, and the Al2 O3 pillared
meso-Co3 O4 was denoted as Al/meso-Co3 O4 which contains 70%
cobalt metal.
In addition, Al2 O3 incorporated mesoporous Co3 O4 catalyst was
also synthesized through coimpregnation of Al and Co precursors by an incipient wetness impregnation method using cobalt
nitrate hexahydrate (Co(NO3 )2 6H2 O) of around 9.5 g and aluminum nitrate precursor at the molar ratios of mixed metal oxide

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

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

calculated to compare the surface composition changes before and


after FTS reaction. Transmission electron microscopy (TEM) analysis was also carried out to verify the changes of the local surface
morphologies on the fresh and used mesoporous Co3 O4 catalysts
using TECNAI G2 operated at an accelerating voltage of 200 kV.
Catalytic activity test of the as-prepared mesoporous Co3 O4
catalysts were carried out in a stainless steel xed-bed tubular
reactor having an outer diameter of 12.7 mm using 100 mg of
the catalyst after mixing with 1.0 g of gamma-Al2 O3 as a diluent
with the a granule size of 60100 m. Prior to the FTS reaction, the mesoporous Co3 O4 catalysts were reduced in situ at
400 C under a ow of 5%H2 balanced with N2 for 12 h. After
the reduction, the reactor temperature was cooled down to room
temperature and the reactant of syngas having a feed gas composition of H2 /N2 /CO = 62.84/5.60/31.56 was introduced. The FTS
reaction was performed for around 2060 h under the following
reaction conditions; T = 230 and 240 C, P = 2.0 MPa, and weight
hourly space velocity (WHSV) = 24000 L (mixed gas)/(kgcat h). The
efuent products from the reactor were analyzed by using an online
gas chromatograph (YoungLin Acme 6500, GC) equipped with GSGASPRO capillary column connected to ame ionization detector
(FID) for the analysis of hydrocarbons, and Carboxen 1000 packed
column connected to TCD for the analysis of CO, CO2 , CH4 and H2 . CO
conversion was calculated using the variations of CO moles before
and after FTS reaction corrected by using the area changes of internal standard gas and the product distributions were also calculated
based on the total carbon balances. In addition, 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 results of FTS reaction at around
20 h on stream.

3. Results and discussion


3.1. Physicochemical properties of the Al-modied mesoporous
Co3 O4
The surface area, pore volume and average pore diameter of the
mesoporous Co3 O4 catalysts with their pore size distributions were
measured by N2 sorption method, and the results are summarized
in Table 1 and Fig. 1. As shown in Fig. 1, the presence of the mesopore structures was clearly observed with a type IV isotherm and
H1 hysteresis on the mesoporous Co3 O4 catalysts. In addition, the
hysteresis pattern on the comparative bulk-Co3 O4 suggests a typical non-porous material structure. The sharp peak intensities with
a pore size around 4 nm were observed on the Al-modied mesoporous Co3 O4 catalysts such as the meso-Co3 O4 , Al/meso-Co3 O4 ,
and Al/meso-CoAlOx , however the bulk-Co3 O4 showed a broad pore
size distribution between 10 and 100 nm in pore size as shown
in an inset of Fig. 1. The broad pore size distribution on the bulkCo3 O4 seems to be attributed to the inter-particular pores of Co3 O4
nanoparticles by showing a lower surface area of 32 m2 /g and larger
pore diameter of 20.3 nm. The surface areas of the mesoporous
Co3 O4 catalysts were signicantly decreased after Al modication
from 104 m2 /g on the meso-Co3 O4 by showing a bimodal pore
size distribution to 98 m2 /g on the Al/meso-Co3 O4 and 47 m2 /g on
the Al/meso-CoAl0.25 Ox by showing an unimodal size distribution
with a sharp peak intensity at around 4 nm in size. The observation strongly suggests that Al2 O3 pillar was highly dispersed on the
inner surfaces of the meso-Co3 O4 and the meso-CoAlOx without
signicant aggregation of Al2 O3 pillar or a possible structural collapse during the preparation steps [8,10,11]. The pore volume and
average pore diameter were also observed with a similar trend by
showing the respective values of 0.070.19 cm3 /g and 4.76.1 nm
except for the bulk-Co3 O4 as summarized in Table 1. The slightly

29

Fig. 1. N2 adsorptiondesorption patterns and pore size distributions of the fresh


mesoporous Co3 O4 catalysts.

increased average pore diameter of 6.1 nm on the Al/meos-Co3 O4


from that of 5.0 nm on the meos-Co3 O4 can be possibly attributed
to the formation of inter-particular pores originated from the partially collapsed Co3 O4 and Al2 O3 pillar at around 50 nm (an inset
of Fig. 1). Interestingly, the ordered mesoporous structures were
well developed on the Al/meso-CoAl0.25 Ox and Al/meso-CoAl0.13 Ox ,
which seems to have a positive effect for a superior catalytic activity and stability through a facile transport of heavy hydrocarbons
formed during FTS reaction [10].
Wide angel powder XRD patterns of the fresh mesoporous
Co3 O4 catalysts are displayed in Fig. 2(A), and the calculated average particle sizes of Co3 O4 were also summarized in Table 1. The
spinel structures of Co3 O4 crystalline phases were clearly observed
at the 2 values of 19.0, 31.2, 38.5, 44.8, 59.3 and 65.2 , which can be
corresponding to the characteristic crystalline Co3 O4 diffractions
of (1 1 1), (2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0) planes [12]. The
particle sizes of Co3 O4 were further calculated by DebyeScherrer
equation using the most intense characteristic diffraction peak at
2 = 36.8 . The particle sizes of the mesoporous Co3 O4 catalysts
even after Al modication were found to be around 15.916.9 nm,
which could be a grain size of main framework of cobalt oxides,
except for the bulk-Co3 O4 with a particle size of 27.9 nm. The particle sizes of metallic cobalt were calculated by using the equation
of d(Co0 ) = 0.75 d(Co3 O4 ) [13], and the calculated particle sizes of
metallic cobalt were found to be above 12 nm on all the mesoporous
Co3 O4 catalysts, which has been generally known to be a trivial
effect to the intrinsic activity for the FTS reaction due to its character of structure insensitivity above 8 nm in size [4]. Therefore, the
different intrinsic catalytic activity of the turnover frequency (TOF)
on the mesoporous Co3 O4 catalysts seems to be mainly attributed
to the other characteristics such as the mesoporosity with its stability and the mass transport of products of heavy hydrocarbons
and so on. Even though the spinel structure of the cobalt aluminate
of CoAl2 O4 was not clearly observed by the XRD analysis due to an
identical diffraction peak position with Co3 O4 [14,15], a possible
formation of cobalt aluminate on the Al/meso-Co3 O4 , Al/mesoCoAl0.25 Ox and Al/meso-CoAl0.13 Ox seems to be a main reason for
an enhanced structural stability and activity by forming a particle
size of around 16 nm, which corresponds to a main frameworks
granule size of Co3 O4 . As shown in Fig. 2(B), the characteristic 2D

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C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

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

IAl /ICo b (103 )

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.

hexagonal ordered mesostructures assigned to planes of (1 0 0),


(1 1 0), and (2 0 0) reections [16,17] were clearly observed on the
ordered mesoporous Co3 O4 before and after Al modication. The
peak intensity of (1 0 0) plane was observed much larger on the Alincorporated meso-Co3 O4 such as on the Al/meso-CoAl0.25 Ox , and
it suggests the facile formation of well-ordered mesoporous structures on the mesoporous mixed oxides which is in line with the
results of N2 sorption analysis.
3.2. Reducibility and structural stability of the Al-modied
mesoporous Co3 O4
The reduction patterns of Co3 O4 crystallites are known to follow two-step reductions such as Co3 O4 CoO Co0 . From TPR
analysis of the mesoporous Co3 O4 catalysts as shown in Fig. 3, the
stepwise reductions with two distinctive reduction peaks can be
assigned as the rst reduction of Co3 O4 to CoO at around 300 C
and the second reduction of CoO to metallic cobalt above 400 C
[18,19]. In the case of the unmodied Co3 O4 , two H2 absorption
peaks of Co3 O4 were clearly observed at much lower temperatures
of 303 and 374 C on the bulk-Co3 O4 , and at the temperatures of
280 C and 493 C on the meso-Co3 O4 , which are also responsible for the typical two step reductions of Co3 O4 . Interestingly, a
higher reduction temperature shift of the second peak on the mesoCo3 O4 can be possibly attributed to the suppressed H2 transport

Fig. 3. TPR proles of the fresh mesoporous Co3 O4 catalysts.

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

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.

rate by the trapped water generated during the reduction step in


the mesopores of the meso-Co3 O4 [2,8,20]. On the Al/meso-Co3 O4 ,
two characteristic reduction peaks appeared at 371 and 446 C with
a medium reduction temperature of 402 C, which are also in line
with the typical stepwise reduction steps of Co3 O4 , and a shoulder
peak at 402 C may be originated from the aggregated cobalt particles during the synthesis steps through partial structural collapses
[8,10]. The shifts of reduction peaks to higher temperatures on the
Al/meso-Co3 O4 compared to the meso-Co3 O4 were attributed to
the dispersed Al2 O3 pillar on the inner framework surfaces of the
mesoporous Co3 O4 by forming a strong metal-support interaction.
In addition, a reduction peak at 724 C on the Al/meso-Co3 O4 seems
to be originated from a possible formation of spinel structural cobalt
aluminate [4]. Generally, it has been known that irreducible metal
oxides such as Al2 O3 , SiO2 and TiO2 can lead to the formation of
strong metal-support interactions on the supported metal catalysts
[4,21]. Even though these phenomena can show negative effects
in terms of catalytic activity due to the difcult reduction behavior of the strongly interacted cobalt particles on the supports, the
enhanced structural stability can be originated from a strongly
interacted Al2 O3 pillar on the meso-Co3 O4 and meso-CoAlOx even
under H2 -rich reaction conditions.
The reduction patterns on the Al2 O3 incorporated Al/mesoCoAlOx were similar with the Al/meso-Co3 O4 by shifting to lower
temperatures, especially on the Al/meso-CoAl0.25 Ox . The two step
reductions of Co3 O4 particles were observed at around 330 and
490 C, and the medium temperature of 383 C on the Al/mesoCoAl0.13 Ox seems to be originated from the aggregated cobalt
particles through a partial structural collapses [8,10]. Interestingly, the higher temperature reduction peaks at a respective
654 and 611 C on the Al/meso-CoAl0.13 Ox and Al/meso-CoAl0.25 Ox
can generate a strong interaction between Co3 O4 and impregnated (or incorporated) Al2 O3 species. This can be benecial for
an enhanced structural stability of the mesoporous Co3 O4 catalysts
by forming spinel CoAl2 O4 phases possibly. The reduction degrees
of Co3 O4 particles were found to be lower on the Al-modied mesoporous Co3 O4 catalysts with the values of 44.0, 50.4, and 50.3% on
the respective Al/meso-Co3 O4 , Al/meso-CoAl0.13 Ox and Al/mesoCoAl0.25 Ox compared to the meso-Co3 O4 with a value of 62.9%,

which strongly suggests the formation of new strong interactions


between Co3 O4 and Al2 O3 particles. In addition, the observed lower
reduction temperatures on the Al/meso-CoAl0.25 Ox than that of the
Al/meso-CoAl0.13 Ox seems to be attributed to smaller total amounts
of Al2 O3 content n in the mesoporous Co3 O4 main frameworks.
To further verify the structural stability after Al modication on
the mesoporous Co3 O4 catalysts, TEM analyses were carried out on
the as-prepared catalysts as shown in Fig. 4 with magnied inset
gures. The bulk-Co3 O4 showed the bundles of spheres with the
particle sizes of 2030 nm, and the ordered mesopore structures
on the meso-Co3 O4 were clearly observed with an average pore
diameter around 5 nm. In addition, the observed different particle sizes of Co3 O4 on the Al-modied meso-Co3 O4 between XRD
and TEM analysis seems to be mainly attributed to a formation
of larger cobalt clusters in the frameworks of mesoporous Co3 O4
which could be the aggregates of the separate Co3 O4 grains mainly
measured by XRD analysis. The regularity of the mesoporous structures on the meso-Co3 O4 seems to be responsible for the observed
higher specic surface area of metallic cobalt compared to that of
the bulk-Co3 O4 . In addition, the typical ordered mesoporous structures with a pore diameter of 68 nm were clearly observed on the
Al/meso-Co3 O4 which was also sustained even after the addition of
Al2 O3 pillaring material. This observation suggests that the Al2 O3
pillar is well dispersed inside the mesopores of the meso-Co3 O4 . It
also suggests that Al2 O3 particles can be strongly interacted with
the mesoporous Co3 O4 surfaces by forming a strong metal-support
interaction (conrmed by TPR), which can play an important role in
stabilizing the mesopore structures of Co3 O4 under the reductive
FTS conditions. In addition, TEM images of the fresh Al/mesoCoAl0.25 Ox also support that the mesoporous frameworks of Co-Al
mixed oxides originated from vacant pores of the KIT-6 mesopores
are well developed with similar pore sizes of the Al/meso-Co3 O4 .
H2 chemisorption analysis was carried out on the mesoporous
Co3 O4 catalysts to verify the active metallic surface area of cobalt
species, and the results are summarized in Table 1. The larger metallic cobalt surface areas of 22.8 and 31.0 m2 /gCo were observed on
the meso-Co3 O4 and the Al/meso-Co3 O4 , respectively, compared
to that of bulk-Co3 O4 with a value of 12.1 m2 /gCo . However, with
an incorporation of Al2 O3 particles on the Al/meso-CoAl0.13 Ox and

32

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

Fig. 5. Catalytic activities on the mesoporous Co3 O4 catalysts with time on stream
(h).

Al/meso-CoAl0.25 Ox mixed oxides, the metallic cobalt surface areas


were decreased to 8.4 and 10.9 m2 /gCo due to a smaller content
of cobalt species. In addition, from our previous study [10], the
decreased metallic surface area after the reduction treatment was
mainly attributed to the partial structure collapses of the mesoCo3 O4 . Although the Al2 O3 modied meso-Co3 O4 has a smaller
metallic surface area than that of the meso-Co3 O4 due to the
well-developed mesoporous structures, the structural collapse of
the ordered mesoporous structures without Al modication can
increase the structural instability during the reduction step through
a intrinsic volume contraction from Co3 O4 to metallic cobalt, which
resulted in showing a lower catalytic activity and stability. The
observed higher metallic cobalt surface area of the Al-modied
meso-Co3 O4 suggests that the ordered mesoporous structures are
well preserved through a higher dispersion of the Al2 O3 pillar inside
the pores of the meso-Co3 O4 and meso-CoAlOx . Generally, it has
been also known that the irreducible metal oxide having a lower
melting point and smaller particle size can have a higher mobility
on the surfaces at a much lower meting temperature of metal oxides
during thermal treatment [21,22]. Based on the above phenomena,
a pillaring oxide of Al2 O3 can be evenly dispersed on the inside
of the meso-Co3 O4 or meso-CoAlOx surfaces which are veried
by the variations of specic surface areas after the Al impregnation. The higher metallic cobalt surface area of the Al/meso-Co3 O4
suggests the formation of the stronger interaction between the surfaces of mesoporous Co3 O4 with thermally stable Al2 O3 particles
under a higher temperature reductive condition. In addition, with
the increase of the amount of Al2 O3 in the main frameworks of
the meso-CoAlOx , the amount of active metallic cobalt sites can be
diminished by showing a lower metallic cobalt surface area around
8.410.9 m2 /gCo compared to the Al/meso-Co3 O4 .
3.3. Activity and stability of the Al modied meso-Co3 O4 under
reductive conditions
The catalytic activities on the mesoporous Co3 O4 catalysts were
carried out at T = 230 and 240 C, P = 2.0 MPa, and WHSV = 24000 L
(mixed gas)/(kgcat h). As shown in Fig. 5 with the summarized
results in Table 2, the superior catalytic activity at 230 C was
observed on the meso-Co3 O4 compared to the bulk-Co3 O4 by showing CO conversions of 6.1 and 11.7% with a similar trend of reaction
rates at steady-state, which can be induced from regular mesoporous structures and suppressed parafn wax deposition on the
active cobalt sites resulted in the enhancement of mass transport of
the heavier hydrocarbons formed as reported in our previous work

[8]. The TOFs (dened as number of reacted CO molecules/(surface


cobalt atom s)) were found to be similar values of 0.055 and
0.035 s1 on the bulk-Co3 O4 and the meso-Co3 O4 because of the
structure insensitive characters of the cobalt nanoparticles above
8 nm in size [4,23,24]. A higher CH4 and a lower C5 + selectivity on
the meso-Co3 O4 (i.e., 6.9% for CH4 and 81.8% for C5 +) compared
to those on the bulk-Co3 O4 (i.e., 3.1% for CH4 and 94.0% for C5 +)
were attributed to the presence of the partially reduced cobalt
particles with a higher mesoporosity on the meso-Co3 O4 due to
a lower intrinsic activity for the secondary reactions of light olens
to the heavy hydrocarbons [4,23,2527]. Based on our previous
work [20], the catalyst deactivation was mainly originated form
the structural collapses of the meso-Co3 O4 and the wax encapsulation and lamentous carbon formation on the bulk-Co3 O4 surfaces
veried by the characterizations of FT-IR, Raman and TEM analyses.
In addition, the possible catalyst deactivation by the deposition of
heavy wax components in the mesopores of meso-Co3 O4 cannot
be overlooked [4], however, a collapse of regular mesopore structures seems to be more dominant deactivation mechanism of the
meso-Co3 O4 .
As shown in Fig. 6(A) and (B), the particle sizes of cobalt after
the FTS reaction were increased up to 50100 nm on the used
meso-Co3 O4 with the complete structural collapse of mesoporous
Co3 O4 , and the particle size of cobalt on the used bulk-Co3 O4
was more signicantly increased from 30 nm to above 100 nm
[8,10]. The morphologies of deposited carbons were signicantly
different by showing an encapsulation of the aggregated cobalt
particles with amorphous carbons on the bulk-Co3 O4 which can
disrupt the transport of reactants to the active cobalt sites, and a
growth of lamentous whisker carbons on the meso-Co3 O4 which
is likely to form on the surfaces of metallic crystallites having a
weak metal-support interaction with a small cobalt particle size
[28,29].
To stabilize the ordered mesoporous Co3 O4 structures with
lower carbon depositions, the modication with irreducible metal
oxide of Al2 O3 was further applied to the meso-Co3 O4 by pillaring Al2 O3 into the mesopores or by preparing mixed-metal oxide
frameworks such as CoAlOx . As shown in Fig. 5 and summarized
in Table 2, a signicant increase of activity and stability on the
Al/meso-Co3 O4 was observed at T = 230 C with CO conversion
above 83% during 40 h on stream without a signicant deactivation.
The reaction rate and TOF were also dramatically increased on the
Al/meso-Co3 O4 with values of 82.8 [reacted CO mol/(gcat s)] and
0.153 [reacted CO molecules/(surface cobalt atom s)] compared to
the unmodied meso-Co3 O4 . A slight increase of CH4 selectivity of
11.6% and decrease of C5 + selectivity of 77.3% on the Al/meso-Co3 O4
can be attributed to the formation of the strongly interacted Al2 O3
pillaring oxide with the surfaces of meso-Co3 O4 which also resulted
in forming a largely oxidized electronic states of cobalt particles
by decreasing the adsorption properties of H2 and increasing CH4
selectivity possibly due to a known relatively fast formation rate of
light hydrocarbons [4,10,3032]. However, the strong interactions
between the metallic cobalt surfaces of the meso-Co3 O4 frameworks and the Al2 O3 pillar can stabilize the mesopore structures
even under FTS reaction condition by maintaining stable catalytic
activity. As shown in Fig. 6(C) with the magnied inset TEM image,
the ordered mesoporous structures with a pore size of around 6 nm
on the used Al/meso-Co3 O4 were well maintained after the FTS
reaction for 40 h with local aggregations of the mesoporous Co3 O4
and without lamentous carbon formations. The structural stability
on the Al/meso-Co3 O4 was improved because of an even distribution of the thermal stable Al2 O3 pillar inside the meso-Co3 O4
pores, which resulted in showing a higher catalytic activity and
stability. Since the collapses of the mesopore structures of the
Al/meso-Co3 O4 were also insignicant under H2 reduction pretreatment as conrmed by our previous study through N2 sorption

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

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

Reaction duration (h)

20
20
20
40
20
60
20
60

Activitya

Product distribution (C-mol%)

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].

and TEM analysis [10], the highly ordered mesoporous structures of


the Al/meso-Co3 O4 seems to be maintained through the formation
of the strong interaction between the reducible cobalt particles and
the irreducible Al2 O3 pillaring metal oxide.
To further improve a structural stability of mesoporous metal
oxide catalysts, the Al2 O3 incorporated mixed metal oxides of
the Al/meso-CoAl0.13 Ox and Al/meso-CoAl0.25 Ox were prepared
by nano-casting method and the representative catalytic activities are summarized in Table 2 with the activity with time on
stream at T = 240 C in Fig. 5. A higher catalytic activity and stability without signicant deactivation (i.e., CO conversion of 93.9%
at 20 h and 91.3% after 60 h on stream) were observed on the
Al/meso-CoAl0.13 Ox , and the activity was slightly decreased with
an increase of Al2 O3 content in the mixed metal oxide structures
such as the Al/meso-CoAl0.25 Ox (i.e., Co conversion of 95.8% at
20 h and 85.9% after 60 h on stream). The reaction rates and TOFs
were also found to be higher on the Al/meso-CoAl0.13 Ox with the
values of 88.2 [reacted CO mol/(gcat s)] and 0.406 [reacted CO
molecules/(surface cobalt atom s)] with a lower CH4 selectivity
of 8.3% and a higher C5 + selectivity of 85.6% than those on the
Al/meso-CoAl0.25 Ox . These higher catalytic activity and stability can
be mainly attributed to the stable maintenance of the mesoporous
frameworks by using Al2 O3 modier through the formation of the

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

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

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

C.-I. Ahn, J.W. Bae / Catalysis Today 265 (2016) 2735

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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