ARTICLES

PUBLISHED ONLINE: 12 JUNE 2017 | DOI: 10.1038/NCHEM.2794

Direct conversion of CO2 into liquid fuels with high

selectivity over a bifunctional catalyst
Peng Gao1, Shenggang Li1,2, Xianni Bu1, Shanshan Dang1,3, Ziyu Liu1, Hui Wang1, Liangshu Zhong1*,
Minghuang Qiu1, Chengguang Yang1, Jun Cai2,4, Wei Wei1,2 and Yuhan Sun1,2*

Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a
great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because
of the extreme inertness of CO2 and a high C–C coupling barrier. Here we present a bifunctional catalyst composed of
reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a
very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form
methanol, and C−C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high
octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas
shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much
better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

O
wing to the growing energy demand, dwindling fossil fuel
reserves and increasing atmospheric CO2 concentration,
renewable energy sources, such as solar, wind and biomass,
foresee increasing usage. However, the widespread utilization of
renewable energy sources is currently limited by their intermittent
and fluctuating nature. In this context, the chemical conversion of
carbon dioxide (CO2) into value-added products with the assistance
of hydrogen (H2) would represent a promising solution to the
storage of renewable energy1–3.
Thus, much attention has been paid to CO2 hydrogenation to
various C1 feedstocks (for example, methane (CH4), methanol
(CH3OH), carbon monoxide (CO) and formic acid) and considerable
progress has been achieved4–11. However, the extreme inertness of CO2
and the high kinetic barriers for the formation of C–C bonds12,13 mean
it is still a great challenge to synthesize C2+ (hydrocarbons with two or
more carbons) products directly from CO2 , such as gasoline (C5–C11
hydrocarbons), which is a very important transportation fuel widely
used around the world. CO2 is well-known to be a very stable molecule
(ΔfG o = –396 kJ mol–1), the end product of any combustion process,
either biological or chemical, along with water14,15. Another key bottle-
neck problem is the assembly of the atoms and formation of chemical
bonds to convert the relatively simple CO2 molecules into the much
more complex and energetic C5–C11 hydrocarbons. Obviously, signifi-
cant catalytic advances are required for the large-scale production of
liquid fuels directly from CO2 hydrogenation. Currently, the
Fischer–Tropsch synthesis (FTS) route using modified Fe-based
catalysts can be utilized to produce hydrocarbons directly from CO2.
However, the maximum C5–C11 hydrocarbon fraction was limited
by the Anderson–Schulz–Flory distribution to ∼48% with an undesir-
able CH4 fraction of ∼6% (refs 16,17). Furthermore, the heat of adsorp-
tion of CO2 is lower than that of CO because of the thermodynamic
stability of CO2 , which leads to a much lower coverage of CO2 over
the catalyst, and thus a low CO2 reactivity and high CH4 selectivity.
In the present work, a bifunctional catalyst that contains partially
reducible metal oxides (In2O3) and H-form Zeolite Socony Mobil-5
(HZSM-5) zeolites exhibits an excellent performance for the direct
production of gasoline-range hydrocarbons from CO2 hydrogen-
ation with a high selectivity. The C5+ selectivity in hydrocarbon dis-
tribution reached up to 78.6% with only 1% for CH4 selectivity at a
CO2 conversion of 13.1% (Fig. 1a). There was no obvious catalyst
deactivation over 150 hours, and a much better performance for
CO2 hydrogenation to C5+ hydrocarbons was observed using a
pellet catalyst with internal gas recycling. Such results thus suggest
a promising potential for its industrial application.
Results and discussions
The bifunctional catalyst consists of a metal oxide (In2O3) with a
small particle size of about 10 nm (Fig. 1b and Supplementary Figs
1 and 2) and a high specific surface area of 120 m2 g–1
(Supplementary Table 1), and a HZSM-5 zeolite with a hierarchical
micro/mesoporous structure with a mesopore diameter of 4 nm
(Fig. 1c and Supplementary Fig. 3a). The catalytic performance
and structure information of the sole In2O3 component were
investigated first. With In2O3 as the sole catalyst under the same reac-
tion conditions, CO and CH3OH were the major products. The
hydrocarbon selectivity was rather low (2.4%) and no C5+ hydrocar-
bons were detected (Fig. 1a). Density functional theory (DFT) calcu-
lations (Supplementary Fig. 4) revealed that In2O3 is reducible, which
results in a surface rich in oxygen vacancies. The oxygen vacancy on
the In2O3 surface benefits CO2 activation and hydrogenation, and
can also be generated through thermal desorption18,19. After pre-
treatment of In2O3 in argon (Ar) at 400 °C for one hour, the amount
of surface oxygen defects detected from oxygen atoms adjacent to the
defects by in situ near-ambient pressure X-ray photoelectron spec-
troscopy (NAP–XPS, O 1s at 531.7 eV (Supplementary Fig. 5a and
Supplementary Table 2)) increased to 24.8%. However, the changes
in the particle sizes calculated from in situ X-ray diffraction (XRD) pat-
terns (Supplementary Fig. 1) and specific surface areas
(Supplementary Table 1) were negligible during the pre-treatment
process. The CO2 and H2 adsorption properties of the In2O3

1
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai
201210, China. 2 School of Physical Science and Technology, ShanghaiTech University, Shanghai 201203, China. 3 University of the Chinese Academy of
Sciences, Beijing 100049, China. 4 State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information
Technology, Chinese Academy of Sciences, Shanghai 200050, China. * e-mail: zhongls@sari.ac.cn; sunyh@sari.ac.cn

NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 1

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
ARTICLES NATURE CHEMISTRY DOI: 10.1038/NCHEM.2794

a
CO2 conv. CO sel. CH3OH sel.
100 100

90 90

Conversion and selectivity (%)

Hydrocarbon distribution (%)
80 80

70 70

60 60

50 50
40
40
30
30
20
20
10
10
0
0
) ) ) ) 1) 1) -5
1/2 1/1 2/1 4/1 O3
In 2 5 (2/ (2/ ZSM
5( 5( 5( 5( -5
S M- S M- S M- S M- S M -
S M H
/HZ /HZ /HZ /HZ HZ Zr/HZ
O 3 n 2O 3 n 2O 3 n 2O 3 AI/
In 2 I I I Z n– – Al–
– n
Cu u –Z
C
b c

00
1
1 nm

10
In2O3 (222)

0
(200)

0.290 nm

5 nm 10 nm

Figure 1 | Catalytic performance over various catalysts and the morphology of the In2O3/HZSM-5 bifunctional catalyst. a, CO2 hydrogenation over various
bifunctional catalysts that contained Cu-based catalysts or In2O3 and HZSM-5 with different mass ratios, as shown in the parentheses, and the stand-alone
In2O3 catalyst (reaction conditions, 340 °C, 3.0 MPa, 9,000 ml h–1 gcat–1, H2/CO2/N2 = 73/24/3), as well as the conversion (conv.) of CH3OH over HZSM-5
(reaction conditions, 340 °C, Ar 3.0 MPa, 9,000 ml h–1 gcat–1; liquid CH3OH 0.855 ml h–1 gcat–1). Compared with Cu-based catalysts combined with HZSM-5,
the In2O3/HZSM-5 catalysts show much lower selectivities (sel.) of CO and CH4. The sole In2O3 metal oxide and HZSM-5 zeolite exhibit a typical catalytic
performance of CO2 hydrogenation into CH3OH, and CH3OH into gasoline, respectively. C5+ , red; C2–4 , blue; CH4 , grey. b, HRTEM image of In2O3 with an
exposed facet of (222) after the thermal treatment in Ar at 400 °C for 1 h. c, HRTEM image of HZSM-5 with a lattice spacing of 1.0 nm assigned to the
(200) lattice plane of the ZSM-5 crystals.

surface were investigated further by CO2 and H2 temperature-
programmed desorption (TPD), respectively. As illustrated in
Supplementary Fig. 6a, the observed peak at approximately 417 °C
originated from the desorption of CO2 that interacted strongly with
the surface. The dissociative adsorption of H2 was detected at 114 °C,
which formed atomic hydrogen on the In2O3 surface capable of
participating in hydrogenation reactions (Supplementary Fig. 6b).
The sole HZSM-5 zeolite used in the bifunctional catalyst was
also tested for CH3OH conversion and exhibited a typical catalytic
performance of CH3OH to gasoline with a complete CH3OH
conversion (100%) and a high C5+ selectivity of 71.4% (Fig. 1a)20,21.
We therefore conclude that CO2 was first hydrogenated to
CH3OH on the In2O3 surface, and CH3OH was then transformed
into hydrocarbons inside the HZSM-5. DFT calculations were
carried out to predict the catalytic cycle of CO2 hydrogenation to
CH3OH at the oxygen-vacancy site of In2O3 , and the potential
energy surface is shown in Fig. 2a,c. CO2 first chemisorbed at
the oxygen-vacancy site, and the chemisorbed CO2* species
(* represents the surface-adsorbed species) then underwent stepwise
hydrogenation to give formate (bi-HCO2*), dioxymethylene
(bi-H2CO2*), methoxy (mono-H3CO*) and finally CH3OH. The
oxygen vacancy was filled during the above process, and was regen-
erated by subsequent hydrogenation. CH3OH formed over the
surface of In2O3 passed further through the HZSM-5 zeolite,
where it was transformed into various hydrocarbons at the acidic
site of the zeolite via the hydrocarbon-pool mechanism, as shown

2 NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.2794 ARTICLES
a b

2 0.24 CnH2n
0.00 1

Cy
*+ P

2 + OH
+ CO +

c
liz
2 D
CO +

5H 3 C
D
H3 H2 3

a
5

tio
0. H
3H −0.66
2 1. Hydrocarbon pool

+ *+

n
Hydrogen
*+

HO
2 D −1.06 CH3OH transfer
−1.13
CO 2+ −1.17
3H *+ H H
+
H2
4
CO P
2
−1.65 CO + D CO + D HZSM-5
H2 H2 −1.79 H 3 2+ H3 O i-CnH2n+2 Aromatic
*+ 2 +
H
H2
O2 +D H*
HC H 2 CO + P −2.32 H2O
5
2. H3 H2
+

c d
CH4 (1%)
(2) (3)
(1) 2H2
CH3OH C2–C4 (20.4%)
CO2
H2O H2
C5+ (78.6%)
(4)

(CH2)n

In2O3 HZSM-5

Figure 2 | Molecular-level mechanism for CO2 hydrogenation into hydrocarbons. a, Energy profile from DFT calculations for CO2 hydrogenation to CH3OH
on the In2O3(110) surface (D and P stand for defective and perfect surfaces with and without the oxygen vacancy, respectively). b, Schematic of the
hydrocarbon-pool mechanism for CH3OH conversion into hydrocarbons inside HZSM-5. c, Schematic for the formation of CH3OH from CO2 at the oxygen-
vacancy site on the In2O3 catalyst surface, which involve four major steps: (1) CO2 adsorption at the oxygen-vacancy site, (2) sequential hydrogenation of
the adsorbed CO2 species to CH3OH, (3) CH3OH desorption, which leads to the surface without the oxygen vacancy, and (4) hydrogenation of the surface
to regenerate the oxygen-vacancy site. d, Schematic for hydrocarbon formation from CH3OH at the acidic site inside the pores of the HZSM-5 catalyst via
the hydrocarbon-pool mechanism.

in Fig. 2b,d22–24. Moreover, it was also found that the C5–C11 iso-
paraffins were mainly obtained from CO2 hydrogenation over the
In2O3/HZSM-5 composite catalyst, and the ratio of isoparaffins to
n-paraffins was 16.8 (Supplementary Table 3 and Supplementary
Fig. 7). This was very different from that of CO2-based FTS, in
which normal paraffins and olefins were the main products, and
nearly no isoparaffins with a high octane number were formed25–27.
CH3OH synthesis from CO2 hydrogenation is usually
accompanied by undesirable CO formation via the reverse water
gas shift (RWGS) reaction, which is further enhanced by increasing
the reaction temperature because of the endothermicity of the RWGS
reaction. According to the equilibrium calculations (Supplementary
Fig. 8), the equilibrium selectivity of CO increases significantly with
increasing temperature, and reaches 97.1% at 340 °C. When the
typical Cu–ZnO–Al2O3 industrial catalyst28 for the synthesis of
CH3OH from syngas and the highly efficient Cu–ZnO–Al2O3–
ZrO2 catalyst29 for CO2 hydrogenation to give CH3OH were
employed for this reaction instead of In2O3 , the main product was
CO with a much higher CH4 selectivity in the hydrocarbon distri-
bution under the same reaction conditions (Fig. 1a). Similar results
were found for other conventional CH3OH synthesis catalysts, such
as Cu–ZnO, Cu–ZnO–ZrO2 and Cu–ZnO–Cr2O3 combined with
various zeolites30–33. Recent DFT calculations demonstrated that
the key intermediates involved in CH3OH synthesis were more
stable on the defective In2O3 surface than those on the Cu surface,
which strongly suppressed the formation of CO (ref. 18). The
CH3OH selectivity over In2O3 can be tuned up to 100% when the
space velocity is above 16,000 h−1, even at the high reaction tempera-
ture of 300 °C, whereas much higher space velocities are required for
Cu-based catalysts19,34. Consequently, CO selectivity over In2O3
integrated with the zeolite (<45%) was much lower than that over
traditional Cu-based catalysts (>90%) at 340 °C. Furthermore,
compared with other reducible metal oxides, such as Ga2O3 ,
Fe2O3 , ZnO–Cr2O3 and ZnO–ZrO2 combined with HZSM-5, the
In2O3/HZSM-5 composite catalyst exhibited a much better perform-
ance for CO2 hydrogenation with a higher activity and a higher
selectivity to C5+ hydrocarbons (Supplementary Table 4).
The hydrocarbon selectivity and distribution were also affected
markedly by the integration manner of the active components35,36.
Using a dual-bed configuration with the HZSM-5 packed above
the In2O3 and separated by a layer of inert quartz sand (Fig. 3a),
the CH4 selectivity was very high (66.3%), whereas the selectivity
to C5+ hydrocarbons was only 26.7% and a large amount of
CH3OH (31.8%) was detected. When HZSM-5 particles were
loaded below the oxides (Fig. 3b), the formed CH3OH can be
completely converted into hydrocarbons, and the C5+ selectivity
increased to 70.4%, whereas the CH4 selectivity dropped to 4.5%.
Furthermore, by moving the two components into a closer
proximity (from Fig. 3b to Fig. 3d), the CO selectivity decreased
significantly, because of the suppression of the undesired RWGS
reaction, the C5+ selectivity enhanced and the CH4 selectivity
reduced, although the CO2 conversion only changed slightly. We
observed an even higher C5+ selectivity of 78.6% and a very low
CH4 selectivity of 1% over the composite catalyst without quartz
sand (Fig. 3d). The effect of the relative amounts of each component
of In2O3/HZSM-5 on the catalytic performance was also
investigated. With a decreasing relative amount of In2O3 , both
CO2 conversion and CO selectivity decreased. The hydrocarbon
distribution changed slightly when the oxide/zeolite mass ratio
decreased from 2:1 to 1:2, whereas the C5+ selectivity dropped and

NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 3

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
ARTICLES NATURE CHEMISTRY DOI: 10.1038/NCHEM.2794

100 100 Fig. 3d). As a result, the number of active sites for the C–C coupling
CH4 C2–C4 C5+
90 90 in the zeolite pore was significantly reduced, which leads to a severe
deactivation with very low C5+ hydrocarbon selectivity.

Conversion and selectivity (%)

80 80
Hydrocarbon distribution (%)

We also investigated the stability of the composite catalyst

70 CO sel. 70 with granule stacking (Fig. 4b). The CO2 conversion and the
60 60 CO selectivity decreased, whereas the C5+ selectivity increased
significantly during the initial 40 hours. However, the CO2
50 50
conversion and C5+ selectivity remained stable at around 12 and
40 40 80%, respectively, after a time-on-stream of 150 hours at 340 °C,
CH3OH sel.
30 30 3.0 MPa and 9,000 ml h–1 gcat–1, which suggests a promising poten-
CO2 conv.
tial for industrial applications. In situ XRD characterization revealed
20 20
that the crystal size of In2O3 increased substantially after the
10 10 exposure to the H2 and CO2 mixture at 340 °C during the initial
0 0 stage (four hours), whereas it remained almost unchanged in the
subsequent reaction period (Supplementary Fig. 1). In addition,
a b c d e the effects of pressure and the H2/CO2 ratio on the catalytic per-
Dual bed Granule stacking Mortar mixing
formance were also studied. A higher pressure and H2/CO2 ratio
can enhance CO2 conversion and decrease CO selectivity
(Supplementary Fig. 9). Moreover, a higher reaction rate with a
Quartz sand

ZSM-5
lower contact time suggested a negative effect of the generated
water (H2O) on the catalyst performance (Supplementary
In2O3 Fig. 10a). The increasing trend of CO2 conversion with decreasing
500–800 μm 0.5–1.0 μm
a 90 90
Figure 3 | Influence of the integration manner of the active components CH4 C2–C4 C5+
(In2O3/HZSM-5 mass ratio = 2:1) on catalytic behaviours under the same 80 80

Conversion and selectivity (%)

conditions. a, Dual-bed configuration with In2O3 packed below HZSM-5 and
Hydrocarbon distribution (%)

70 70
separated by a layer of quartz sand. b, HZSM-5 packed below In2O3 and
separated by quartz sand. c, Stacking of granules with the In2O3 , HZSM-5 and 60 CO sel. 60
quartz sand particle sizes of 250–380 µm. d, In2O3 and HZSM-5 particles 50 50
well mixed without quartz sand. e, In2O3 and HZSM-5 mixed with an agate
mortar. The catalytic performance is improved significantly by moving the two 40 40
components to a closer proximity, whereas the C5+ hydrocarbon selectivity 30 30
decreases remarkably with a further increase in the proximity by grinding the CO2 conv.
powder mixture of the two active components in an agate mortar. 20 20

10 10
CH3OH was detected with a selectivity of 2.5% when the weight
ratio increased from 2:1 to 4:1. In addition, an increase in the 0 0
space velocity can also greatly decrease the CO selectivity and 4,500 6,750 9,000 11,250
enhance the C5+ selectivity (Fig. 4a, 80.3% at 11,250 ml h–1 gcat–1). Space velocity (mL h–1 gcat–1)
Therefore, any measure that improves the transport of the reaction b 90 90
intermediates in the gas phase should favour the shift of the reaction
equilibrium for the selective formation of C5+ hydrocarbons. 80 C5+ 80
The sample illustrated in Fig. 3d was composed of well-mixed

Conversion and selectivity (%)

70 70
Hydrocarbon distribution (%)

micrometre-sized In2O3 and HZSM-5 particles (Supplementary

Fig. 3b). We tried to shorten the distance between the two 60 60
components further by grinding a powder mixture of them both CO sel.
50 50
in an agate mortar to investigate the effect of their intimate
contact (Fig. 3e). For the sample obtained from this integration 40 40
manner, the much smaller In2O3 particles (around 10 nm) were C2–C4
30 30
in much closer contact with the HZSM-5 particles of 500–800 nm
in size (Supplementary Fig. 2c–f ). However, CO2 was converted 20 CO2 conv. 20
mainly into CH4 (94.3% in hydrocarbon distribution) with a
rather low CO2 conversion (8%). In addition, the C5+ hydrocarbon 10 10
CH4
selectivity was only 4.2% and the CH3OH selectivity reached 51.9%, 0 0
which suggests a significant deactivation of HZSM-5. The very close 0 20 40 60 80 100 120 140 160
contact between In2O3 and the zeolite appeared to weaken the Reaction time (h)
synergistic effect. A similar phenomenon was also observed by
de Jong and co-workers, who reported that the closest proximity Figure 4 | Catalytic performance of the composite catalyst presented in
of bifunctional active sites was detrimental to the selective hydrocrack- Fig. 3d. a, CO2 conversion, CO selectivity and hydrocarbon distribution at
ing of hydrocarbons37. Similar textural and structural properties, as different space velocities. CO selectivity decreases and C5+ selectivity
well as surface acidity, were observed for the spent samples pre- increases significantly with increasing space velocities. b, Stability of the
sented in Fig. 3d,e, which indicates that the integration manner composite catalyst with granule stacking at 9,000 ml h–1 gcat–1. Both CO2
has no significant effect on these properties (Supplementary conversion and product selectivity remain stable after the initial 40 h of
Fig. 3). However, the number of strongly acidic sites of the spent reaction. Reaction conditions, 340 °C, 3.0 MPa, H2/CO2/N2 = 73/24/3 and
catalyst presented in Fig. 3e decreased markedly (Supplementary In2O3/HZSM-5 mass ratio = 2:1.

4 NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.2794
a 90
C5+
80
Hydrocarbon distribution (%)
70 CO sel.
60
50
40
CO2 conv.
30
20
10 CH4
0 0
0 1 2 3
Recycle ratio
b
30
25 C5+ yield
CO2 conversion (%)
20
15
CO2 conv.
10
5 allic phase in the absence of CO2 at 340 °C (Supplementary Fig. 6d),
0 0.0
0 20 40 60 80 100
CO/(CO + CO2) (%)
Figure 5 | Catalytic performance with tail-gas recycling and as a function
of CO concentration in the feed. a, Catalytic results over a technical
catalyst composed of In2O3 and HZSM-5 pellets (size in cylindrical shape of
Φ3.0 × 3.5 mm, In2O3/HZSM-5 mass ratio = 1:2) with internal gas recycling
as functions of the recycle ratio. The recycle ratio represents the flow rate of
the recycled tail gas over that of the original feed gas. With increasing
recycle ratio, the catalytic performance becomes much better over the
well-mixed In2O3 and HZSM-5 pellet catalyst under industrially relevant
conditions. b, CO2 conversion and yield of C5+ hydrocarbons over a
In2O3/HZSM-5 composite catalyst (particle size, 250–380 µm) as a
function of CO concentration in the feed at H2/(CO2 + CO)/N2 = 73/24/3.
The CO concentration in the feed gas will grow with increasing recycle ratio,
and therefore CO was added into the feed gas to investigate the effect of
CO on the performance without internal gas recycling. The C5+ yield
increases substantially with an increasing CO/(CO2 + CO) ratio. Reaction
conditions, 340 °C, 3.0 MPa, space velocity of the original feed gas
9,000 ml h–1 gcat–1 and In2O3/HZSM-5 mass ratio = 1:2.
space velocity should lead to an increase in the H2O partial pressure
across the catalyst bed, which would oxidize In2O3 vacancies (e.g.
H2O + D → P + H2) (ref. 38) and lead to a lower catalytic activity.
This was proved by the steady drop in the reaction rate when H2O
was co-fed during CO2 hydrogenation (Supplementary Fig. 10b).
To investigate further the prospect of the In2O3/HZSM-5 bifunc-
tional catalyst in industrial applications, the catalytic performance
for CO2 hydrogenation to C5+ hydrocarbons was evaluated using
a pellet catalyst under industrially relevant conditions. The dry
catalyst powders were compressed by a high-pressure agglomeration
technique to obtain both In2O3 and HZSM-5 pellets in a
cylindrical shape with a diameter of 3.0 mm and a height of
3.5 mm (Φ3.0 × 3.5 mm). The catalytic performance of the
well-mixed In2O3 and HZSM-5 pellets (In2O3/HZSM-5 mass
ratio = 1:2) was examined with tail-gas recycling (Supplementary
Fig. 11), commonly used in industry for a more efficient utilization
of the feed39,40. As shown in Fig. 5a, the pellet catalyst exhibited a
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
ARTICLES
55 similar performance to that of the granule catalyst under the same
reaction conditions. With an increasing recycle ratio, defined as
50
the flow rate of the recycled tail gas over that of the original feed
Conversion and selectivity (%)
45
gas, both CO2 conversion (from 8.7 to 18.2%) and C5+ hydrocarbon
40
selectivity (from 78.0 to 84.1%) increased, whereas CO selectivity
35
decreased substantially from 44.5 to 30.0%. The CO concentration
30
in the feed gas would obviously grow with an increasing recycle
25
ratio as the recycled tail gas contained a large amount of CO. To
20
study the effect of CO on the performance of CO2 hydrogenation,
15 CO was added into the feed gas of the CO2/H2 mixture with the
10 CO/(CO2 + CO) ratio increased from 0 to 100%. Increasing the
5 CO concentration was found to boost the activity of CO2 hydrogen-
ation to C5+ hydrocarbons, as shown in Fig. 5b. According to our
DFT calculations, the formation of oxygen vacancies on the
In2O3(110) surface by CO reduction is energetically much more
favourable than H2 reduction (Supplementary Fig. 4b), which is
4.0
consistent with the experimental observations (Supplementary
3.5 Fig. 6c and Supplementary Table 2). In addition, the adsorption
strength followed the order CO2 > H2 ≫ CO at a relatively low
C5+ yield (mmol h–1 gcat–1)
3.0
oxygen-vacancy coverage (Supplementary Fig. 4c). Consequently,
2.5
CO can increase the number of active sites (oxygen vacancies),
2.0 and then promote the CO2 hydrogenation activity and counterba-
1.5
lance the efficient annihilation of vacancies by CO2. However, we
did not detect any C5+ hydrocarbon at CO/(CO2 + CO) = 100%
1.0 (CO/H2) within eight hours, because In2O3 was reduced to the met-
0.5
and this metallic phase was unable to catalyse CO2 hydrogenation19.
With the above oxide/zeolite bifunctional catalyst for CO2 hydro-
genation to hydrocarbons, the hydrocarbon distribution can be
easily tuned through the shape selectivity of the zeolite. When
SAPO-34 was chosen as the active phase for C−C coupling, the
selectivity to lower olefins (C2=−C4=, generally referring to ethylene,
propylene and butylene) reached 76.9% in hydrocarbons with only
4.4% of CH4 at a CO2 conversion of 34.1% (Supplementary Fig. 12).
In addition, the main hydrocarbon products became liquefied pet-
roleum gas (C3o−C4o, referring to C3 and C4 paraffins) when the
Beta zeolite was used in combination with In2O3. Additionally, the
catalytic activity depended on the amount of the active vacancies,
which could be increased substantially by the introduction of
modifiers and/or the use of a suitable support (such as ZrO2).
Conclusions
In summary, we discovered a bifunctional catalyst composed of par-
tially reduced In2O3 and HZSM-5 that could convert CO2 directly
into liquid fuels with an excellent selectivity for value-added pro-
ducts. The C5+ selectivity reached 78.6% with only 1% CH4 at a
CO2 conversion of 13.1%. We demonstrated that the CO2 conver-
sion could be manipulated by controlling the surface structure of
the oxide and the mass ratio of the oxides/zeolite. The proximity of
the two components played a crucial role to suppress the undesired
RWGS reaction and obtain a high C5+ selectivity. Industry-relevant
tests using the pellet catalyst were carried out to show that tail-gas
recycling could improve further the catalytic performance for CO2
hydrogenation to C5+ hydrocarbons, which suggests a promising
prospect for industrial applications.
Methods
Catalyst preparation. Various oxides were prepared by a co-precipitation method.
HZSM-5 zeolites were prepared by the hydrothermal route with ethylamine as the
template. For the preparation of the composite catalyst presented in Fig. 2d, the In2O3
and HZSM-5 were pressed, crushed and sieved to granules in the range of 40–60 mesh
(granule sizes of 250–400 µm). Then, the granules of the two samples were mixed
together by shaking in a vessel. For the preparation of the composite catalyst presented
in Fig. 2e, the In2O3 and HZSM-5 were mixed in an agate mortar for 20 min. Then, the
mixed sample was pressed, crushed and sieved to particles in the range of 40–60 mesh.
Catalyst characterization. Catalysts were characterized by in situ XRD, nitrogen
physisorption, X-ray fluorescence spectroscopy, scanning electron microscopy, TEM
5
ARTICLES
and high-resolution TEM (HRTEM), H2 , CO2 and ammonia TPD, as well as H2 and
CO temperature-programmed reduction techniques. In situ NAP–XPS was
performed on a SPECS Surface Nano Analysis. The facility is composed of two
chambers, an analysis chamber and a quick ample load–lock chamber. The analysis
chamber is equipped with a PHOIBOS NAP hemispherical electron energy analyser,
a microfocus monochromatized Al-Kα X-ray source with a beam size of 300 µm, a
SPECS IQE-11A ion gun and an infrared laser heater.
Catalytic evaluation. Activity measurements in the hydrogenation of CO2 were
carried out in a continuous-flow, high-pressure, fixed-bed reactor (internal diameter
of 12 mm). Prior to the reaction, the catalyst was pre-treated in situ at 400 °C for 1 h in
pure Ar (150 ml min−1). After the reactor was cooled down to 340 °C, the reactant gas
mixture with a H2/CO2/N2 ratio of 73/24/3 and a pressure of 3.0 MPa was introduced
into the reactor. The catalytic reaction for CH3OH conversion was performed in the
same reactor. For the experiments with tail-gas recycling, the catalytic performance of
the pellet catalyst (15 g) was investigated in our pilot-scale fixed-bed reactor (internal
diameter 19 mm, length 1,180 mm (Supplementary Fig. 11)), which was equipped for
operation at industrial working conditions with a recycled tail gas. The effluents were
analysed quantitatively online with a Shimadzu GC-2010C gas chromatograph
equipped with thermal conductivity and flame-ionization detectors. The CO2
conversion was calculated by an internal normalization method. The hydrocarbon
distribution presented in this work was calculated on a molar carbon basis.
DFT calculations. Periodic DFT calculations were carried out with the Vienna ab
initio simulation package using the Perdew–Burke–Ernzerhof exchange-correlation
functional and projector augmented wave potentials.
Data availability. All the data that support the findings of this study are available
within the paper and its Supplementary Information files, or from the corresponding
author on reasonable request.
Received 23 January 2017; accepted 5 May 2017;
published online 12 June 2017
References
1. Kothandaraman, J. et al. Amine-free reversible hydrogen storage in formate salts
catalyzed by ruthenium pincer complex without PH control or solvent change.
ChemSusChem 8, 1442–1451 (2015).
2. Aresta, M., Dibenedetto, A. & Angelini, A. Catalysis for the valorization of
exhaust carbon: from CO2 to chemicals, materials, and fuels. Technological use
of CO2. Chem. Rev. 114, 1709–1742 (2014).
3. Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to
liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).
4. Li, C.-S. et al. High-performance hybrid oxide catalyst of manganese
and cobalt for low-pressure methanol synthesis. Nat. Commun. 6, 6538 (2015).
5. Graciani, J. et al. Highly active copper–ceria and copper–ceria–titania catalysts
for methanol synthesis from CO2. Science 345, 546–550 (2014).
6. Scirè, S., Crisafulli, C., Maggiore, R., Minicò, S. & Galvagno, S. Influence of the
support on CO2 methanation over Ru catalysts: an FT-IR study. Catal. Lett. 51,
41–45 (1998).
7. Moret, S., Dyson, P. J. & Laurenczy, G. Direct synthesis of formic acid from
carbon dioxide by hydrogenation in acidic media. Nat. Commun. 5, 4017 (2014).
8. Studt, F. et al. Discovery of a Ni–Ga catalyst for carbon dioxide reduction to
methanol. Nat. Chem. 6, 320–324 (2014).
9. Gao, S. et al. Partially oxidized atomic cobalt layers for carbon dioxide
electroreduction to liquid fuel. Nature 529, 68–71 (2016).
10. Yin, Z. et al. Highly selective palladium–copper bimetallic electrocatalysts for the
electrochemical reduction of CO2 to CO. Nano Energy 27, 35–43 (2016).
11. Dixneuf, P. H. Bifunctional catalysis: a bridge from CO2 to methanol. Nat. Chem.
3, 578–579 (2011).
12. Sakakura, T., Choi, J.-C. & Yasuda, H. Transformation of carbon dioxide. Chem.
Rev. 107, 2365–2387 (2007).
13. Montoya, J. H., Peterson, A. A. & Nørskov, J. K. Insights into C–C coupling in
CO2 electroreduction on copper electrodes. ChemCatChem 5, 737–742 (2013).
14. Aresta, M., Dibenedetto, A. & Angelini, A. The changing paradigm in CO2
utilization. J. CO2 Util. 3–4, 65–73 (2013).
15. Benson, E. E., Kubiak, C. P., Sathrum, A. J. & Smieja, J. M. Electrocatalytic and
homogeneous approaches to conversion of CO2 to liquid fuels. Chem. Soc. Rev.
38, 89–99 (2009).
16. Rodemerck, U. et al. Catalyst development for CO2 hydrogenation to fuels.
ChemCatChem 5, 1948–1955 (2013).
17. Dorner, R. W., Hardy, D. R., Williams, F. W. & Willauer, H. D. Heterogeneous
catalytic CO2 conversion to value-added hydrocarbons. Energy Environ. Sci. 3,
884–890 (2010).
18. Ye, J. Y., Liu, C. J., Mei, D. H. & Ge, Q. F. Active oxygen vacancy site for
methanol synthesis from CO2 hydrogenation on In2O3(110): a DFT study. ACS
Catal. 3, 1296–1306 (2013).
19. Martin, O. et al. Indium oxide as a superior catalyst for methanol synthesis by
CO2 hydrogenation. Angew. Chem. Int. Ed. 55, 6261–6265 (2016).
6 NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.2794
20. Kim, J., Choi, M. & Ryoo, R. Effect of mesoporosity against the deactivation of
MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process.
J. Catal. 269, 219–228 (2010).
21. Liu, Z. Y. et al. Solvent-free synthesis of c-axis oriented ZSM-5 crystals with enhanced
methanol to gasoline catalytic activity. ChemCatChem 8, 3317–3322 (2016).
22. Olsbye, U. et al. Conversion of methanol to hydrocarbons: how zeolite cavity and
pore size controls product selectivity. Angew. Chem. Int. Ed. 51, 5810–5831 (2012).
23. Olsbye, U., Bjørgen, M., Svelle, S., Lillerud, K.-P. & Kolboe, S. Mechanistic insight
into the methanol-to-hydrocarbons reaction. Catal. Today 106, 108–111 (2005).
24. Van Speybroeck, V. et al. Advances in theory and their application within the
field of zeolite chemistry. Chem. Soc. Rev. 44, 7044–7111 (2015).
25. Khodakov, A. Y., Chu, W. & Fongarland, P. Advances in the development of
novel cobalt Fischer–Tropsch catalysts for synthesis of long-chain hydrocarbons
and clean fuels. Chem. Rev. 107, 1692–1744 (2007).
26. Van der Laan, G. P. & & Beenackers, A. A. C. M. Kinetics and selectivity of the
Fischer–Tropsch synthesis: a literature review. Catal. Rev. 41, 255–318 (1999).
27. Xiang, Y. Z. & Kruse, N. Tuning the catalytic CO hydrogenation to straight- and
long-chain aldehydes/alcohols and olefins/paraffins. Nat. Commun. 7, 13058 (2016).
28. Behrens, M. et al. Performance improvement of nanocatalysts by promoter-
induced defects in the support material: methanol synthesis over Cu/ZnO:Al.
J. Am. Chem. Soc. 135, 6061–6068 (2013).
29. Gao, P. et al. Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via
hydrotalcite-like precursors for CO2 hydrogenation to methanol. J. Catal. 298,
51–60 (2013).
30. Fujiwara, M., Kieffer, R., Ando, H. & Souma, Y. Development of composite
catalysts made of Cu–Zn–Cr oxide zeolite for the hydrogenation of carbon-
dioxide. Appl. Catal. A 121, 113–124 (1995).
31. Jeon, J.-K., Jeong, K.-E., Park, Y.-K. & Ihm, S.-K. Selective synthesis of C3–C4
hydrocarbons through carbon-dioxide hydrogenation on hybrid catalysts composed
of a methanol synthesis catalyst and SAPO. Appl. Catal. A 124, 91–106 (1995).
32. Fujiwara, M., Satake, T., Shiokawa, K. & Sakurai, H. CO2 hydrogenation for C2+
hydrocarbon synthesis over composite catalyst using surface modified HB
zeolite. Appl. Catal. B 179, 37–43 (2015).
33. Inui, T., Kitagawa, K., Takeguchi, T., Hagiwara, T. & Makino, Y. Hydrogenation
of carbon-dioxide to C1–C7 hydrocarbons via methanol on composite catalysts.
Appl. Catal. A 94, 31–44 (1993).
34. Martin, O. et al. Zinc-rich copper catalysts promoted by gold for methanol
synthesis. ACS Catal. 5, 5607–5616 (2015).
35. Jiao, F. et al. Selective conversion of syngas to light olefins. Science 351,
1065–1068 (2016).
36. Cheng, K. et al. Direct and highly selective conversion of synthesis gas into lower
olefins: design of a bifunctional catalyst combining methanol synthesis and
carbon–carbon coupling. Angew. Chem. Int. Ed. 55, 4725–4728 (2016).
37. Zecevic, J., Vanbutsele, G., de Jong, K. P. & Martens, J. A. Nanoscale intimacy in
bifunctional catalysts for selective conversion of hydrocarbons. Nature 528,
245–254 (2015).
38. Fu, X. Z., Clark, L. A., Zeltner, W. A. & Anderson, M. A. Effects of reaction
temperature and water vapor content on the heterogeneous photocatalytic
oxidation of ethylene. J. Photochem. Photobiol. A 97, 181–186 (1996).
39. Lloyd, L. Handbook of Industrial Catalysts (Springer, 2007).
40. Subramani, V. & Gangwal, S. K. A review of recent literature to search for an
efficient catalytic process for the conversion of syngas to ethanol. Energy Fuels
22, 814–839 (2008).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21503260,
21573271, 91545112 and 11227902), the Shanghai Municipal Science and Technology
Commission, China (14DZ1207602, 16DZ1206900 and 15DZ1170500), the Ministry of
Science and Technology of China (2016YFA0202802) and the Chinese Academy of Sciences
(QYZDB-SSW-SLH035). We thank Z. Liu and Y. Han for the assistance with in situ NAP–
XPS, located at the State Key Laboratory of Functional Materials for Informatics, Shanghai
Institute of Microsystem and Information Technology, Chinese Academy of Sciences.
Author contributions
P.G., L.Z. and Y.S. conceived the project, analysed the data and wrote the paper. P.G., S.L.
and W.W. drafted the manuscript. P.G. and S.D. prepared the samples. S.L. performed DFT
calculations. Z.L. and H.W. studied the effect of the integration manner. X.B., M.Q. and C.Y.
performed the catalytic evaluation. S.D., Z.L., X.B. and J.C. characterized the samples. All
the authors discussed the results and commented on the manuscript.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permissions information is available online at www.nature.com/reprints. Publisher’s note:
Springer Nature remains neutral with regard to jurisdictional claims in published maps
and institutional affiliations. Correspondence and requests for materials should be addressed to
L.Z. and Y.S.
Competing financial interests
The authors declare no competing financial interests.