i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

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Light olefins synthesis from CO2 hydrogenation

over mixed FeeCoeK supported on micro-
mesoporous carbon catalysts

Thongthai Witoon a,b,*, Thanapha Numpilai a,b,c, Khanin Nueangnoraj d,

Chin Kui Cheng e, Metta Chareonpanich a,b, Jumras Limtrakul f
a
Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of
Engineering, Kasetsart University, Bangkok, 10900, Thailand
b
Center for Advanced Studies in Nanotechnology for Chemical, Food and Agricultural Industries, KU Institute for
Advanced Studies, Kasetsart University, Bangkok, 10900, Thailand
c
Department of Environmental Science, Faculty of Science and Technology, Thammasat University, Pathumthani,
12120, Thailand
d
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology (SIIT),
Thammasat University, Thailand
e
Center for Catalysis and Separation (CeCaS), Department of Chemical Engineering, College of Engineering, Khalifa
University, P.O. Box 127788, Abu Dhabi, United Arab Emirates
f
Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi
Institute of Science and Technology, Rayong, 21210, Thailand

highlights graphical abstract

FeeCoeK loaded on microporous

and micro-mesoporous carbon
supports.

Micropores confined particle sizes
of metal oxides and level of
aggregates.

Mesopores allowed aggregates of
metal oxides providing an inti-
mate contact of particles.

FeeCoeK supported on micropo-
rous carbon produced a high frac-
tion of CH4.

FeeCoeK supported on micro-
mesoporous carbon provided a
high light olefins yield.

article info abstract

Article history: Recycling CO2 into light olefins is a promising approach to reduce CO2 emissions. To pro-
Received 8 August 2021 mote this technology, an efficient catalyst with high activity and selectivity towards light

* Corresponding author. Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty
of Engineering, Kasetsart University, Bangkok, 10900, Thailand.
E-mail address: fengttwi@ku.ac.th (T. Witoon).
https://doi.org/10.1016/j.ijhydene.2021.10.265
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
42186 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

Received in revised form olefins is imperative. In this work, a series of FeeCoeK supported on micro-mesoporous
7 October 2021 carbon (MMC) and microporous carbon (MC) with different metal loading contents (20
Accepted 31 October 2021 e80 wt%) were prepared for CO2 hydrogenation to light olefins. Impregnating mixed metal
Available online 21 November 2021 oxides on both MMC and MC reduced particle sizes and enhanced their dispersion and
reducibility, yielding a higher CO2 conversion compared to the unsupported FeeCoeK
Keywords: catalyst. The metal oxides were highly dispersed inside the micropores of MC support,
CO2 hydrogenation achieving the highest CO2 conversion. However, the high dispersion of metal oxides inside
Light olefins micropores led to the formation of isolated particles with a low interfacial contact with
Fe-based catalysts each other, resulting in a low light olefins selectivity. The MMC support provided a lower
Micro-mesoporous carbon degree of metal dispersion, creating more interfacial contact area, promoting the selec-
Microporous carbon tivity towards olefins. Overall, the 60 wt% FeeCoeK supported on MMC catalyst exhibited
the highest light olefins yield of 10.8% at 400  C and 20 bar and excellent stability.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

operating these reactions in tandem needs to be carried out at

Introduction
Human activities like combustion of fossil fuels have contin-
uously increased CO2 levels in the atmosphere which irre-
versibly affects the climate change. As a consequence,
mitigation of CO2 emissions is an urgent necessity. Various
approaches, comprising CO2 capture, storage and utilization
have been employed to curtail the CO2 concentrations [1e3].
Among them, utilizing CO2 as a carbon source for producing
high-value chemicals with large market share and growth,
especially light olefins (i.e., ethylene, propylene and butylene)
has received much attention [4e9]. Light olefins, generally
produced by the petroleum-derived naphtha cracking process
and ethane/propane dehydrogenation [10e12], are important
platform molecules in the production of polymers, synthetic
fibers, packaging, construction materials, and so on. With the
dwindling supply of fossil fuels resources and the rapidly
growing demands for light olefins, converting CO2 to light
olefins becomes more and more attractive.
The conversion of CO2 to light olefins can take place
through two different paths: (1) CO2 hydrogenation to meth-
anol (MeOH)/dimethyl ether (DME) over In2O3-based, ZnOx-
ZrO2 and spinel oxide (i.e., ZnGa2O4 and ZnAl2O4) catalysts
followed by its conversion into light olefins over acid sites of
zeolites [13e16], and (2) CO2 transformation to CO by a reverse
water gas shift (RWGS) reaction and subsequent CO conver-
sion to light olefins via FischereTropsch (FT) synthesis
[17e19]. Despite the satisfied selectivity towards light olefins
in hydrocarbon products (>70%), the former route suffers from
the poor performance in term of productivity (light olefins
yield <10%) due to thermodynamic limitation of CO2-to-MeOH
reaction. In the latter approach, beyond 10% light olefins yield
can be achieved as a high overall CO2 conversion associated
with the thermodynamically favored RWGS reaction, making
it more attractive for industrial-scale applications [6,20,21].
However, this process is restricted by low selectivity towards
light olefins (<50%) regardless of diverse mixture of hydro-
carbons products, requiring an efficient catalyst for highly
selective transformation of CO2 and H2 to desired light olefins.
Fe- and Co-based catalysts can function efficiently for both
RWGS and FT synthesis reactions in the latter route. However,
high reaction temperature (300e350  C) for achieving a high
CO to be converted into hydrocarbons. Fe-based catalysts are
more favored because they offer short-chain hydrocarbons as
main products unlike the Co-based catalysts, yielding mainly
CH4 [22,23]. The activity and selectivity of light olefins pro-
nouncedly enhanced by alkali promoters (i.e., Li, Na, K and Cs)
as well as secondary metals (i.e., Cu, Co, Mn and Zn)
[17,24e28], which was attributed to the modifying adsorption-
desorption properties of CO2 and H2 on the catalyst surface.
The alkali promoters are responsible for donating electrons to
active Fe atoms, strengthening the interaction between
adsorbed H and the surface of Fe, suppressing the hydroge-
nation activity and thus bringing about more light olefins
formation. Meanwhile, it enhances strong basic sites which
contribute to the increase in the CO2 adsorption. The sec-
ondary metals can manipulate the products distribution by
neither accreting nor restraining the chain-growth reaction,
which contributes to boosting the light olefins productivity.
Furthermore, confinement of Fe nanoparticles into porous
matrices also potentially brings benefits for the catalytic per-
formance [29,30]. Compared to the oxide materials, a moder-
ate metalsupport interaction between carbonaceous
substrates and Fe nanoparticles is more beneficial to the
reduction of Fe species, boosting active phase generation and
thus resulting in a higher catalytic performance [31e33].
Carbon materials in the form of activated carbon (AC),
carbon nanotubes (CNTs), carbon nanofibres (CNFs), gra-
phene oxide and metal organic frameworks (MOFs) are
extensively used for active metals dispersion due to their
high accessible surface areas, multitudinous pore structure,
ultrahigh porosity and tunable functionalities [18,34e41]. In
addition, a superior heat-transfer property of carbon mate-
rials is useful for a highly exothermic reaction, alleviating a
hot spot in the catalyst bed [35]. In comparison to those
carbon materials, AC which can be prepared from residual
biomass and waste materials is more attractive from both
economics and sustainability perspective. Regarding the
large-scale manufacturing, the production of advanced car-
bon materials like graphene and CNTs is restricted by their
high cost relevant to low mass production of high-quality
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9
materials, long time consumption and multiple processing
steps [42e44]. The production cost of graphene, graphene
oxide and CNTs are in the ranges of $50e10,000/kg, while AC
has relatively low price ($3e8/kg) [44]. Besides, a high envi-
ronmental impact of a graphene-based device production
which provided two-times higher global warming potential
(GWP) than an activated carbon-based supercapacitor [45],
makes AC more environmentally friendly and potentially
applicable for widespread applications, including catalytic
system. The Fe-based catalysts supported on AC have been
previously investigated in hydrocarbons, including light
olefins synthesis from syngas conversion (CO þ H2),
achieving high olefins selectivity of 39.4% and 30% over
FeeMneK/AC [40] and FeeCueMn/AC [41] catalysts, respec-
tively. However, applying AC as an effective support for Fe-
based catalyst in light olefins synthesis from CO2 hydroge-
nation has not yet been implemented. Moreover, there are no
reports regarding the influence of coexisting pore sizes
ranging from micropores to mesopores in the structure of
AC. Herein, a series of FeeCoeK oxide supported on AC
materials with different metal loading contents were pre-
pared. The effects of pore structures including bimodal
micro-mesoporous carbon (MMC) and unimodal micropo-
rous carbon (MC) on the physicochemical properties of
mixed FeeCoeK oxides supported catalysts as well as their
catalytic performance in CO2 hydrogenation to light olefins
were investigated.
Experimental
Catalyst preparation
The carbon materials with different pore characteristics,
including micro-mesoporous carbon (MMC) and microporous
carbon (MC) were purchased from Sigma-Aldrich, Singapore.
A series of FeeCoeK oxide supported on carbon materials
were prepared by two-step wetness impregnation method.
Briefly, the carbon support was first impregnated with desired
amount of KNO3 solution in order to avoid a block of metal
active sites by K deposition. The mixture was stirred at 60  C
for 4 h and then dried at 100  C for 24 h. Subsequently, the
KNO3/carbon was further impregnated with mixed solution
containing Fe(NO3)3$9H2O and Co(NO3)2$6H2O. The molar ratio
of Fe:Co:K was 1:0.2:0.5. The sample was eventually dried
overnight at 100  C and calcined in a flow of N2 at 400 for 4 h.
The resulting catalysts were labeled as xFe-Co-K/yMMC and
xFe-Co-K/yMC, in which x and y represented weight percent
of FeeCoeK and carbon in the total weight of catalysts,
respectively. The unsupported FeeCoeK catalyst was also
employed for purpose of comparison. In Brief, Fe(NO3)3$9H2O,
Co(NO3)2$6H2O and KNO3 were dissolved in 5 mL of deionized
water. The mixture was stirred at 60  C for 4 h, followed by
dried at 100  C for 24 h, and eventually calcined in a flow of N2
at 400 for 4 h.
Catalyst characterization
The physical properties, including surface area, pore volume
and pore diameter of calcined samples as well as carbon
42187
supports were examined by N2 physisorption at 196  C
(Micromeritics 3 Flex) after outgassing at 200  C under vacuum
for 24 h.
Transmission electron microscope (TEM) images were
attained on a JEOL JEM-2010 microscope operated at 200 kV.
Powder X-ray diffraction (XRD) patterns of the calcined,
reduced and spent FeeCoeK supported on carbon materials
were recorded with a Bruker D8 Advance Phaser diffrac-
tometer using Cu-Ka radiation (l ¼ 1.5406
A). The 2q was
scanned from 25 to 70 with a step of 0.05 . The Fe crystallite
size of the reduced catalysts were calculated using the
Scherrer Equation [46].
Thermogravimetric (TG) analysis experiment was con-
ducted on a Mettler-Toledo TGA/DSC 3þ analyzer by heating a
sample from 30 to 400  C at a heating rate of 10  C min1 in a
flow of N2 (75 mL min1).
H2 temperature-programmed reduction (H2-TPR) was per-
formed with a Micromeritics AutoChem II 2920 apparatus. The
as-prepared catalyst (0.1 g) was mounted in a U-type quartz
tube and heated from room temperature to 150  C with a
ramping rate of 10  C min1 under Ar flow (50 mL min1) for
30 min. Then, the temperature was lowered to 50  C and gas
flow was switched to 10% H2/Ar. The response to TCD for the
H2 consumption was monitored continuously upon rising
temperature from 50  C to 900  C with a heating rate of 10  C
min1.
Temperature-programmed desorption of CO2 (CO2-TPD)
and H2 (H2-TPD) measurements were carried on the same
apparatus as that in TPR analysis. 0.1 g sample was firstly
reduced in situ with 10% H2/Ar (50 mL min1) at 400  C for 5 h,
and then cooled to 50  C under Ar flow (50 mL min1). After-
ward, 10% CO2/He or 10% H2/Ar flow was passed over the
catalyst bed for 1 h, followed by flushing with Ar for at least
30 min to eliminate the physisorbed species until the baseline
was restored. The desorption curve was acquired by rising
temperature from 50  C to 600  C under Ar flow at a heating
rate of 10  C min1.
Catalytic activity test
The catalytic CO2 hydrogenation over prepared FeeCoeK
oxide supported on carbon materials were executed in a fixed-
bed reactor. Prior to the reaction, 1 g of catalyst mixed with 3 g
of SiO2 sand was loaded in the stainless-steel tube and
reduced in H2 flowing at 400  C for 5 h under. After cooling to
300  C, the feed stream was switched to H2/CO2/N2 (3/1/1)
mixed gas with total flow rate of 75 mL min1, and the reaction
temperature and pressure were raised to 320  C and 20 bar.
The effluent gases were collected every hour for 4 h and then
the reaction temperature increased to 340  C with a heating of
2  C min1. The method was repeated for the reaction tem-
perature of 340  C, 350  C, 360  C, 380  C and 400  C. The outlet
gas compositions were analyzed by two gas chromatographs
(GC). CO2, CO, H2 and N2 were measured by GC-14B (Shimadzu)
with a thermal conductivity detector (TCD) and a Shin Carbon
ST column. While, GC-8A (Shimadzu) connected with a flame
ionization detector (FID) and Porapak Q column was employed
for separating C1eC4 hydrocarbons, and C5eC18 hydrocarbons
were analyzed with an OV-1 column. The CO2 conversion,
selectivities to CO and hydrocarbon, hydrocarbon
42188 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

distribution, olefins to paraffins ratio and light olefins yield 1.1 nm and 34 nm, respectively (Fig. 1b). Unlike the isotherm of
were calculated on a molar carbon basis according to the MMC, the isotherm of MC was a type I (Fig. 1c) which was
equations (1)e(7): indicative of micropores. The MC displayed a narrow pore size
distribution in the range of 1e3 nm (Fig. 1d). The unsupported
nproducts  100
CO2 conversion ð%Þ ¼ (1) FeeCoeK exhibited type II isotherm, representative of non-
nproducts þ moles CO2;out
porous and macroporous materials (Fig. 1a). The pore size
distribution of the unsupported FeeCoeK was 20e100 nm
X
n
nproducts ¼ moles COout þ i  moles of hydrocarboni ; i created by aggregates of metal oxides particles that give rise to
i¼1 pores. The isotherm of FeeCoeK oxides loaded onto MMC
¼ atomic number of carbon displayed between that of MMC and unsupported FeeCoeK
(2) (Fig. 1a), and the volume of gas adsorbed significantly
decreased at P/P0 < 0.1 and 0.5 < P/P0 < 0.99, indicating that
moles COout  100 particles of metal oxides were placed on a portion of micro-
Selectivity of CO ð%Þ ¼ (3) pores and mesopores (Fig. 1b). Loading mixed FeeCoeK oxides
nproducts
onto MC (40FeeCoeK/60MC) led to a significant reduction of
volume of gas adsorbed at P/P0 < 0.1, indicating the deposition

P
n
i  moles of hydrocarboni  100
i¼1
Selectivity of hydrocarbon ð%Þ ¼ (4)
nproducts

of metal oxides inside the micropores. Further increasing

i moles of hydrocarboni 100
Hydrocarbon distributioni ð%Þ¼
Pn
i moles of hydrocarboni
i¼1
(5)
Olefins to paraffins ratio ¼
2 x moles of C2 H4 þ 3 x moles of C3 H6 þ 4 x moles of C4 H8
2 x moles of C2 H6 þ 3 x moles of C3 H8 þ 4 x moles of C4 H10
(6)
metal content to 60 wt% (60FeeCoeK/40MC) increased the
volume of gas adsorbed at P/P0 of 0.99, suggesting the gener-
ation of macropores. The results demonstrated that micro-
pores of MC support were filled at 60 wt% metal loading, and
part of the remaining metal oxides was aggregated them-
selves outside micropores. The BET surface area, pore volume
and average pore diameter of MMC, MC and all catalysts are
given in Table 1.
Transmission electron microscope (TEM) and scanning
electron microscope (SEM) were performed to capture the
structure of FeeCoeK oxide supported on carbons materials;

2 x moles of C2 H4 þ 3 x moles of C3 H6 þ 4 x moles of C4 H8

Yield of light olefins ð%Þ ¼ x 100 (7)
nproducts þ moles CO2;out

the results are shown in Figs. 2 and 3, respectively. TEM image

Results and discussion
Catalyst characterization
Fig. 1 shows N2 sorption isotherm and pore size distribution of
micro-mesoporous carbon (MMC), microporous carbon (MC),
unsupported FeeCoeK, and FeeCoeK oxide supported on
MMC and MC with different metal loading contents. As shown
in Fig. 1a, the isotherm of MMC was a composite type I and IV
with H3 hysteresis loop, a characteristic of micro-mesoporous
materials consisting of slit-shaped pores. The pore size dis-
tribution of MMC ranged 1e2 nm and 2e100 nm centered at
of the unsupported FeeCoeK showed an aggregation of par-
ticles with their size larger than 10 nm (Fig. 2a). However, its
morphology (Fig. 3a) was inhomogeneous as the K-rich phase
confirmed by EDX analysis (Fig. S1) was present. Impregnating
40 wt% FeeCoeK onto MMC (Fig. 2b) enhanced the distribution
of metal oxides and reduced their particle sizes. Nevertheless,
an aggregation of particles on the external surface of carbon
material was also observed (Fig. 3b). In comparison to the
MMC support, the distribution of metal oxides (40 wt%) over
the microporous carbon (Fig. 2c) was even better and the
particle sizes of metal oxides were smaller attributed to the
regulation of particle sizes by the micropores (1e3 nm) of MC.
In addition, there was a tiny portion of particles existed on the
external surface of microporous carbon (Fig. 3c). Increasing
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9 42189

Fig. 1 e N2 sorption isotherm (a and b) and pore size distribution (c and d) of micro-mesoporous carbon (MMC), microporous
carbon (MC), calcined unsupported FeeCoeK oxide catalyst, and calcined FeeCoeK oxide supported on carbons materials
(MMC and MC) with different metal loading contents.

the metal loading content to 60 wt% (Fig. 2d) led to the for-
mation of larger particle sizes aggregated outside the pores.
SEM images clearly revealed that number of particles gathered
on the outside of carbon materials steadily increased with
increasing metal loading contents (Fig. 3def).
Fig. 4 shows the XRD patterns of unsupported FeeCoeK
sample and FeeCoeK supported on carbon materials (MMC
and MC) with different metal loading contents. The XRD
pattern of the unsupported FeeCoeK displayed the presence
of mixed phases of metal oxides, including rhombohedral
KNO3 (PDF 01-078-7937), orthorhombic KNO3 (PDF 00-001-
0493), Fe2O3 (PDF 01-071-5088), and Co3O4 (PDF 00-042-1467).
The diffraction lines representative of Fe2O3, Co3O4, and KNO3
phases were no longer detectable, and Fe3O4 (PDF 01-076-0955)
phase appeared instead for all FeeCoeK supported on carbon
materials. In addition, CoO (PDF 01-089-2803) phase was also
visible for the catalysts with low metal loading contents
(20FeeCoeK/80MMC and 40FeeCoeK/60MC). The results
suggested that the carbon materials facilitated the reduction
of metal oxides during the calcination stage. Nevertheless, the
diffraction line of Fe3O4 at 35.5 of all FeeCoeK supported on
carbon materials became broader as the carbon contents
42190 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

decreased, especially for 80FeeCoeK/20MMC (e). Note that the

Table 1 e BET surface area, pore volume, average pore
broad diffraction line overlapped with a diffraction line of
diameter and metals composition determined by SEM-
EDX of MMC, MC and FeeCoeK supported on MMC and Fe2O3 (35.7 ). The results suggested that Fe2O3 might coexist
MC with different metal loadings. with Fe3O4 for the samples with lower carbon contents.
Fig. 5 displays the TG analysis of MMC, unsupported
Catalysts BET surface Pore Average
area volume pore FeeCoeK, and FeeCoeK supported on carbon materials (MMC
and MC) with different metal loading contents. The TG profile
(m2g1) (cm3g1) diameter
(nm) of MMC showed one step of weight loss at 30e100  C due to the
desorption of adsorbed moisture. The weight of MMC
Micro-mesoporous 782 0.84 4.2
remained unchanged at temperatures higher than 100  C,
carbon (MMC)
Microporous carbon (MC) 1757 0.95 2.2
indicating its high thermal stability. Note that the TG profile of
FeeCoeK 5.5 0.03 23.6 MC was similar to that of MMC. The unsupported FeeCoeK
20FeeCoeK/80MMC 496 0.50 4.2 exhibited two steps of weight loss at 30e100  C and 200e400  C
40FeeCoeK/60MMC 275 0.31 4.5 corresponded to the evaporation of water molecules (2.2%)
60FeeCoeK/40MMC 109 0.18 6.5 and the decomposition of iron and cobalt nitrates precursors
80FeeCoeK/20MMC 36 0.11 11.6
(15.42%), respectively. All FeeCoeK supported on carbon ma-
40FeeCoeK/60MC 438 0.27 2.3
terials also presented two steps of weight loss. The weight loss
60FeeCoeK/40MC 45 0.07 6.4
in the second step was 7.96%, 12.88%, 16.8%, 19.32%, 11.79%,

Fig. 2 e TEM images of unsupported FeeCoeK oxide catalyst (a) and FeeCoeK oxide supported on carbons materials (MMC
and MC) with different metal loading contents: 40FeeCoeK/60MMC (b), 40FeeCoeK/60MC (c) and 60FeeCoeK/40MC (d).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9 42191

Fig. 3 e SEM images of unsupported FeeCoeK oxide catalyst (a) and FeeCoeK oxide supported on carbons materials (MMC
and MC) with different metal loading contents: 40FeeCoeK/60MMC (b), 40FeeCoeK/60MC (c), 60FeeCoeK/40MMC (d),
60FeeCoeK/40MC (e) and 80FeeCoeK/20MMC (f).

and 16.05% for 20FeeCoeK/80MMC, 40FeeCoeK/60MMC,
60FeeCoeK/40MMC, 80FeeCoeK/20MMC, 40FeeCoeK/60MC,
and 60FeeCoeK/40MC, respectively. Based on the decompo-
sition of iron and cobalt nitrates precursors for the 100 wt%
FeeCoeK catalyst, the weight loss in the second step was
theoretically proportional to 3.08%, 6.17%, 9.25%, and 12.34%
for 20 wt%, 40 wt%, 60 wt%, and 80 wt% metal loading,
respectively. The larger weight loss in the second step of all
FeeCoeK supported on carbon materials was attributed to
losses of oxygen atoms of Fe2O3 and Co3O4 phases and carbon
atoms of carbon materials caused by the interaction of those
metal oxides with carbon to produce CO and CO2 (Fig. 5c). The
results were in good agreement with the XRD analysis (Fig. 4).
SEM-EDS was used to determine the metals composition of
different catalysts; the results are listed in Table 2. The molar
ratio of Fe:Co:K of all catalysts was closed to the starting
metals composition (Fe:Co:K ¼ 1:0.2:0.5), while the carbon
content of all catalysts was slightly lower than their starting
values. In addition, the amount of Fe, Co and K for
80FeeCoeK/20MMC was greater than those of unsupported
FeeCoeK (100 wt% FeeCoeK), confirming the removal of ox-
ygen atoms of Fe2O3 and Co3O4 phases.
The reduction behavior of metal oxides in different cata-
lysts was investigated by H2-TPR (Fig. 6). The unsupported
42192 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9
Fig. 4 e XRD patterns of calcined unsupported FeeCoeK
oxide catalyst (a) and calcined FeeCoeK oxide supported
on carbons materials (MMC and MC) with different metal
loading contents: 20FeeCoeK/80MMC (b), 40FeeCoeK/
60MMC (c), 60FeeCoeK/40MMC (d), 80FeeCoeK/20MMC (e),
40FeeCoeK/60MC (f) and 60FeeCoeK/40MC (g).
Fig. 5 e TG profile (a) and its derivative (b) of micro-mesoporous carbon (MMC), unsupported FeeCoeK oxide catalyst and
FeeCoeK oxide supported on carbon materials (MMC and MC) with different metal loading contents and schematic diagram
representative of metal oxides reduction assisted by carbon materials (c).
FeeCoeK (a) showed H2 consumption at three temperature
ranges (a, b and g) centered at 350  C, 540  C and 830  C
assigned to a reduction of Fe2O3 to Fe3O4 and Co3O4 to CoO [26],
a transformation of Fe3O4 to FeO to metallic Fe, and CoO to
metallic Co, and a reduction of isolated FexOy particles
without the interaction with Co particles, respectively.
Impregnating FeeCoeK oxides onto the carbon supports (c-g)
remarkably altered the H2-TPR profiles as the broad peak at g
region disappeared, indicating an intimate contact of oxidic Fe
and Co. Nevertheless, a shoulder peak at g region of 20 wt%
metal oxides loaded on carbon material (b) was visible, sug-
gesting a lower contact of oxidic Fe and Co particles due to a
very high dispersion of each metal oxides particle. The
amount of H2 consumption for each temperature range was
reported in Table 3. The FeeCoeK oxide supported on carbon
materials exhibited a significant lower H2 consumption at a
region compared to the unsupported FeeCoeK because the
initial phase of Fe and Co species of all FeeCoeK oxide sup-
ported on carbon materials was mainly reduced to Fe3O4 and
CoO, respectively.
The phases of catalysts subsequent to the reduction stage
were examined with XRD (Fig. 7). All catalysts showed the
presence of Fe3O4 (PDF 01-076-0955) and metallic Fe (PDF 00-
006-0696) phases. However, Fe2O3 (PDF 01-071-5088) still
remained in the unsupported FeeCoeK corresponded to the
H2-TPR analysis (Fig. 6). The metallic Fe crystallite size was
calculated using the line width of Fe (110) reflection (44.7 )
with the Scherrer Equation (Table 3). The unsupported
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9 42193

Table 2 e Metals composition determined by SEM-EDS of Table 3 e H2 consumption of unsupported FeeCoeK and
calcined unsupported FeeCoeK and all FeeCoeK FeeCoeK oxide supported on carbon materials
supported on carbon materials. determined from the area under H2-TPR curve calibrated
Catalysts Element (wt%) Molar ratio by an injection of known H2 volume.
of Fe:Co:K Catalysts H2 consumption Fe
Fe Co K C O
(mmol g1) crystallite
FeeCoeK 36.3 8.7 12.6 e 42.4 1:0.23:0.50 size (nm)
А b g Total
20FeeCoeK/80MMC 9.5 1.9 2.8 71.4 14.4 1:0.19:0.43
40FeeCoeK/60MMC 17.7 2.8 4.4 56.5 18.6 1:0.19:0.44 FeeCoeK 369.5 277.5 198.1 845.1 41.4
60FeeCoeK/40MMC 20.8 4.9 7.0 36.7 30.6 1:0.22:0.48 20FeeCoeK/80MMC 44.2 127.1 31.8 213.1 22.4
80FeeCoeK/20MMC 37.1 8.8 12.8 17.8 23.5 1:0.22:0.49 40FeeCoeK/60MMC 43.9 203.7 247.6 31.9
40FeeCoeK/60MC 15.7 2.5 4.0 54.7 23.1 1:0.19:0.47 60FeeCoeK/40MMC 43.0 329.8 372.8 34.9
60FeeCoeK/40MC 24.9 5.4 8.6 30.6 30.5 1:0.20:0.49 80FeeCoeK/20MMC 72.8 479.3 552.1 40.4
40FeeCoeK/60MC 62.2 214.9 277.1 30.6
60FeeCoeK/40MC 49.5 317.7 367.2 40.2

Fig. 7 e XRD patterns of reduced FeeCoeK oxide catalyst (a)

Fig. 6 e H2-TPR profile of unsupported FeeCoeK oxide
catalyst (a) and FeeCoeK oxide supported on carbon
materials (MMC and MC) with different metal loading
contents: 20FeeCoeK/80MMC (b), 40FeeCoeK/60MMC (c),
60FeeCoeK/40MMC (d), 80FeeCoeK/20MMC (e),
40FeeCoeK/60MC (f) and 60FeeCoeK/40MC (g).
FeeCoeK exhibited the largest Fe crystallite size of 41.4 nm.
The Fe crystallite size reduced to 22.4 nm for 20 wt% metal
oxide loading (20FeeCoeK/80MMC) and gradually increased
with increasing metal loading contents.
The interaction of reactant gases with the catalyst surface
was examined with H2-TPD and CO2-TPD; the results are
displayed in Fig. 8a,b, respectively. The H2-TPR profile of un-
supported FeeCoeK showed three notable peaks at 120  C,
211  C, and 291  C assigned to the desorption of H2 from
metallic Fe, Fe3O4, and Fe2O3, respectively. A small broad
and reduced FeeCoeK oxide supported on carbons
materials (MMC and MC) with different metal loading
contents: 20FeeCoeK/80MMC (b), 40FeeCoeK/60MMC (c),
60FeeCoeK/40MMC (d), 80FeeCoeK/20MMC (e),
40FeeCoeK/60MC (f) and 60FeeCoeK/40MC (g).
desorption peak at 474  C was visible attributed to the
desorption of H2 from FexOy interacted with K2O [24]. In
comparison to the unsupported FeeCoeK, adding 20 wt%
metal oxides onto MMC (20FeeCoeK/80MMC) led to a signifi-
cant increase of H2 desorbed at 120  C due to the higher
fraction of metallic Fe with its smaller particle sizes.
Increasing metal oxides loading to 40 wt% (40FeeCoeK/
60MMC) developed the strong adsorption of H2 ranging from
300 to 600  C attributed to a higher interfacial contact of FexOy
and K2O particles. The strong adsorption of H2 became more
pronounced when the metal oxides loading increased up to
60 wt% (60FeeCoeK/40MMC). Further increase of metal oxides
loading to 80 wt% (80FeeCoeK/20MMC) decreased the weak
adsorption of H2. The FeeCoeK supported on MC (40FeeCoeK/
42194 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

Fig. 8 e H2-TPD (A) and CO2-TPD (B) profiles of reduced FeeCoeK oxide catalyst (a) and reduced FeeCoeK oxide supported on
carbons materials (MMC and MC) with different metal loading contents: 20FeeCoeK/80MMC (b), 40FeeCoeK/60MMC (c),
60FeeCoeK/40MMC (d), 80FeeCoeK/20MMC (e), 40FeeCoeK/60MC (f) and 60FeeCoeK/40MC (g).

The CO2-TPD profile of unsupported FeeCoeK showed one

prominent desorption peak, and a broad desorption peak
ranging from 150 to 600  C. Both desorption peaks of the
FeeCoeK supported on MMC and MC became more pro-
nounced. The development of the low-temperature desorp-
tion peak was associated with the higher dispersion of metals
on the supports, providing a greater number of exposed sur-
face area for CO2 adsorption. The larger desorption peak at
higher temperature was attributed to the interfacial contact of
K2O particles with Fe and Co particles, favoring the stronger
interaction of CO2 with the catalyst surface due to a donation
of electrons from K to FexOy and CoxOy. In comparison to the
FeeCoeK supported on MC, the FeeCoeK supported on MMC
exhibited a higher CO2 adsorption compared to the FeeCoeK
supported on MC, especially at 40 wt% metal loading content
(40FeeCoeK/60MMC and 40FeeCoeK/60MC). This was
because the limitation of metal oxides growth inside the mi-
cropores of MC reduced the interfacial contact of particles as
indicated by the N2 sorption (Fig. 1) and TEM (Fig. 2) analyses.

Catalytic activity test

Fig. 9 e CO2 conversion as a function of reaction
temperatures of different catalysts.
60MC and 60FeeCoeK/40MC) possessed a higher weak H2
adsorption compared to the FeeCoeK supported on MMC at
the identical metal loading content.
Fig. 9 shows total CO2 conversion at different reaction tem-
peratures of all catalysts. The total CO2 conversion of all cat-
alysts progressively increased with ascending reaction
temperature from 320 to 400  C. The reaction of CO2 and H2 to
produce hydrocarbon proceeded via two consecutive
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9
Fig. 10 e CO (a) and hydrocarbon (b) selectivity as a function of reaction temperatures of different catalysts.
reactions involving reverse water gas shift reaction (reaction
1) and Fischer-Tropsch synthesis reaction (reaction 2) as
follows:
CO2 þ H2 4 CO þ H2O (reaction 1)
nCO þ 2nH2 4 (eCH2e)n þ nH2O (reaction 2)
The reverse water gas shift was an endothermic reaction
for which its equilibrium CO2 conversion increased with
increasing reaction temperatures. In addition, the rate of re-
action also increased with rising temperatures. Consequently,
the increased reaction temperature assuredly offered a high
CO2 conversion. In contrast to the reverse water gas shift re-
action, Fischer-Tropsch synthesis was an exothermic reac-
tion, and thus the equilibrium CO conversion (reaction 2)
decreased with rising reaction temperatures. Although the
reaction rate of Fischer-Tropsch synthesis was more favored
at higher temperatures, the CO conversion was limited by the
thermodynamics equilibrium. Therefore, the higher CO2
conversion at higher temperatures indicates that both re-
actions are in a kinetic regime. The unsupported FeeCoeK
catalyst gave the total CO2 conversion of 18.7%, 22.8%, 25%,
27.9%, 32.2%, and 37% at 320  C, 340  C, 350  C, 360  C, 380  C
and 400  C, respectively. Comparing the identical tempera-
ture, all FeeCoeK supported on MMC and MC catalysts ach-
ieved a higher CO2 conversion, except the CO2 conversion at
400  C of 20FeeCoeK/80MMC due to the lower metal loading
content.
Fig. 10 shows the selectivities of CO (Fig. 10a) and hydro-
carbon (Fig. 10b) of all catalysts. The unsupported FeeCoeK
catalyst gave CO selectivity of 69%, 62%, and 54.6% at 320  C,
340  C, and 350  C, respectively. All FeeCoeK supported on
MMC and MC catalysts provided a lower CO selectivity at
those operating temperatures because the unsupported
FeeCoeK catalyst contained the unreduced Fe2O3 species
42195
(Fig. 7) which was inactive for CO hydrogenation to hydro-
carbon. However, a sudden decrease in CO selectivity of the
unsupported FeeCoeK catalyst was visible at temperature
>350  C, and its CO selectivity at 380  C was lower than all
FeeCoeK supported on MMC and MC catalysts, except that of
40FeeCoeK/60MC. The result indicated that the rate of CO
conversion (reaction 2) of the unsupported FeeCoeK catalyst
was improved at high temperatures which might be attributed
to a change of catalyst phases. The CO selectivities of 60 wt%
metal loading on MMC (60FeeCOeK/40MMC) MC and
(60FeeCoeK/40MC) were similar. However, the significant
difference in CO selectivity for different carbon supports was
visible at 40 wt% metal loading. The 40 wt% FeeCoeK sup-
ported on MC catalyst showed a much lower CO selectivity
attributed to the highest number of active sites for CO con-
version to hydrocarbon.
Fig. 11 displays the CH4 (Fig. 11a) and C5þ (Fig. 11b) distri-
bution, C2eC4 olefin to C2eC4 paraffin ratio (Fig. 11c), and light
(C2eC4) olefin yield (Fig. 11d) of different catalysts. The
FeeCoeK supported on MC catalysts showed the highest CH4
distribution followed by the unsupported FeeCoeK and the
FeeCoeK supported on MMC catalysts. The reverse trend was
attained for the C5þ distribution and C2eC4 olefin to C2eC4
paraffin ratio. Numpilai et al. [24] reported that the intimate
contact of FexOy species with K entailed an electron transfer
from K to FexOy species. The higher electron density over
FexOy species strengthened the adsorption of CO2 and H2,
improving the CeC chain growth and retarding the hydroge-
nation ability of the catalysts, resulting in the formation of
longer chain hydrocarbon and higher olefin to paraffin ratio,
respectively. Based on the N2-sorption (Fig. 1) and TEM (Fig. 2)
analyses, 40 wt% metal oxides supported on MC distributed
solely in micropores, restraining the intimate contact of K
with FexOy species. The high distribution of isolated FexOy
particles (Fig. 2c) provided the larger number of active sites for
weak H2 adsorption (Fig. 8), promoting the hydrogenation
42196 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9

Fig. 11 e CH4 (a) and C5þ (b) distribution, C2eC4 olefin to C2eC4 paraffin ratio (c) and light olefins yield (d) as a function of
reaction temperatures of different catalysts.

ability of the catalyst, favoring the formation of CH4 and
paraffin products. Increasing metal oxides loading to 60 wt%
allowed the aggregates of metal oxides outside the micro-
pores, rising a fraction of longer chain hydrocarbon and O/P
ratio. The MMC support contained mesopores, giving a suffi-
cient space for the intimate contact of K and FexOy species. As
a result, the FeeCoeK supported on MMC achieved a superior
performance in terms of olefin formation. Fig. 11d depicts that
the light olefins yield of both MMC and MC series increased
with increasing metal loading content up to 60 wt%. Further
increase of metal loading to 80 wt% (80FeeCoeK/20MMC)
significantly reduced the amount of H2 adsorbed (Fig. 8a)
associated with the formation of larger metal particle sizes.
The maximum light olefins yield (10.8%) was attained over the
60FeeCoeK/40MMC catalyst at 400  C and 20 bar. Note that the
60FeeCoeK/40MMC catalyst exhibited an increased C5þ dis-
tribution (Fig. 11b) accompanied by a decreased olefins to
paraffins ratio (Fig. 11c) when the reaction temperature
increased from 350 to 360  C. This might be attributed to a
slight increase of reaction pressure in the system. In fact, we
try to keep the constant reaction pressure at 20 bar. However,
the reaction pressure could be fluctuated in the range of
19e22 bar.
Fig. 12 shows the XRD patterns of all spent catalysts after
12 h of a time-on-stream experiment at 400  C. The XRD
pattern of all spent catalysts showed diffraction lines of Fe3O4
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9
Fig. 12 e XRD patterns of spent FeeCoeK oxide catalyst (a)
and spent FeeCoeK oxide supported on carbons materials
(MMC and MC) with different metal loading contents:
20FeeCoeK/80MMC (b), 40FeeCoeK/60MMC (c),
60FeeCoeK/40MMC (d), 80FeeCoeK/20MMC (e),
40FeeCoeK/60MC (f) and 60FeeCoeK/40MC (g).
Fig. 13 e CO2 conversion, olefins to paraffins ratio, and light
olefins yield as a function of time-on-stream of
60FeeCoeK/40MMC. Reaction conditions: T ¼ 400  C,
P ¼ 20 bar, H2:CO2:N2 ¼ 3:1:1, and total flow rate of
75 mL min¡1.
42197
(PDF 01-076-0955), Fe (PDF 00-006-0696), Fe5C2 (PDF 01-080-
4102), and Fe3C (PDF 00-035-0772) phases. The diffraction line
of Fe2O3 which was apparent in the reduced FeeKeCo catalyst
(Fig. 7) was invisible, indicating that the Fe2O3 phase in the
reduced FeeKeCo catalyst was transformed into more active
Fe phases during the reaction with CO, CO2 and H2 gases. This
is the reason why the CO selectivity of the unsupported
FeeCoeK catalyst suddenly decreased at temperature >350  C
(Fig. 10a). Comparing between the series of MMC and MC
catalysts, the FeeCoeK supported on MC catalysts exhibited
predominant diffraction lines of Fe3O4 phase with poor
diffraction lines of Fe5C2 phase. This affirms an abundant
isolated FexOy particles in the FeeCoeK supported on MC
catalysts because the intimate contact of K and FexOy particles
can stabilize the Fe5C2 phase. Fig. 13 shows the stability test of
the best 60FeeCoeK/40MMC catalyst. The CO2 conversion,
olefins to paraffins ratio, and light olefins yield of the
60FeeCoeK/40MMC catalyst were almost constant during the
50 h time-on-stream experiment, indicating its excellent
stability.
Conclusions
The present study elucidated the effect of carbon supports,
including micro-mesoporous carbon (MMC) and microporous
carbon (MC), on the structure of FeeCoeK catalysts and their
catalytic performance in CO2 hydrogenation to light olefins.
The impregnation of FeeCoeK onto both MMC and MC
reduced particle sizes and thereby improved their dispersion
and reducibility. As a result, all FeeCoeK supported on MMC
and MC catalysts (except 20FeeCoeK/80MMC) achieved a
higher CO2 conversion than the unsupported FeeCoeK even
the metal loading contents for all catalysts were lower. The
FeeCoeK supported on MC (40FeeCoeK/60MC) was the most
active catalyst because the metal particles are well-dispersed
within micropores. However, the main product of the
40FeeCoeK/60MC was methane because the high dispersion
of metal particles lessened the interfacial contact of Fe and K
particles, which was an indispensable determinant for the
formation of long-chain hydrocarbon and olefin products. In
contrast to the MC support, the MMC support allowed aggre-
gates of metal oxides inside mesopores, providing the larger
interfacial contact of Fe and K particles, favoring the selective
formation of olefin products. With the optimum metal
loading, the 60FeeCoeK/40MMC achieved superior perfor-
mance in terms of light olefins yield (10.8%) with excellent
stability.
Credit authorship contribution statement
Thongthai Witoon: Investigation, Conceptualization, Meth-
odology, Writing-Original draft preparation, Writing-
Reviewing and Editing. Thanapha Numpilai: Investigation,
Validation, Writing-Original draft preparation, Writing-
42198 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 1 8 5 e4 2 1 9 9
Reviewing and Editing. Khanin Nueangnoraj: Writing-
Reviewing and Editing. Chin Kui Cheng: Visualization,
Writing-Reviewing and Editing. Metta Chareonpanich:
Writing-Reviewing and Editing. Jumras Limtrakul:
Supervision.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This research was supported in part by the National Research
Council of Thailand (N41A640081 and N42A640324 for T.W.
and M.C.), the Kasetsart University Research and Develop-
ment Institute (KURDI) through its program of Development of
Advance Researcher Competence System for Competitiveness
in Agriculture and Food, and the Thailand Science Research
and Innovation through its program of fundamental fund
(FF(KU)21.65).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.10.265.
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