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Contents lists available at ScienceDirect

Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Hydrothermally stable MOFs for CO2 hydrogenation over iron-based

catalyst to light olefins
Shen Hua , Min Liua , Fanshu Dinga , Chunshan Songa,b,** , Guoliang Zhangc, Xinwen Guoa,*
a
State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian
116024, PR China
b
EMS Energy Institute, PSU-DUT Joint Center for Energy Research and Department of Energy & Mineral Engineering, Pennsylvania State University, University
Park, PA 16802, United States
c
College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310014, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Two types of hydrothermally stable MOFs, ZIF-8 and MIL-53(Al) with different size and morphology,
Received 28 October 2015 were prepared and used as supports for catalysts for synthesis of hydrocarbons from CO2 hydrogenation.
Received in revised form 15 February 2016 XRD patterns proves that all these two types of MOFs materials could be stable under the reaction
Accepted 23 February 2016
conditions (P = 3 MPa; T = 573 K) with water as byproduct. MOFs as a novel porous materials show
Available online xxx
excellent properties on catalysis compared with traditional supports g-Al2O3 and the type of MOF
supports has a significant impact on the activity and selectivity of Fe catalysts for CO2 hydrogenation. Due
Keywords:
to the acidity of supports, ZIF-8 supports show different levels of considerable light olefins selectivity,
MOFs
CO2 hydrogenation
while all MIL-53 supports nearly could not obtain light olefins. The light olefins selectivity of ZIF-8 is also
affected by the secondary reaction of hydrogenation during the internal diffusion process. In this article,
catalyst with high active and high light olefins selectivity was obtained just by modulating the MOFs
supports.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction method, CO2 catalytic hydrogenation to hydrocarbons is one of the

Owing to the global greenhouse effect which is related to the
rising level of CO2 in the atmosphere, carbon dioxide capture,
storage and utilization technologies (CCSU) have been of great
environmental importance and received global attentions in recent
years [1–5]. Hence, there has been increasing pressure for
countries and scientists to curb CO2 emissions and to develop
efficient CO2 capture and utilization systems. Meanwhile, the
problem of depleting fossil resources, in particular coal and
petroleum, calls for the development of sustainable energy in a
variety of directions. From this point of view, it is a promising
strategy to convert CO2 in various chemical approaches to make
value-added chemical products [6–9], like thermal, electrochemi-
cal, and photochemical conversion of CO2 to fuels and value-added
products [10–12]. And among the paradigms in CO2 utilization
* Corresponding author. Fax: +86 411 84986134
** Corresponding author at: EMS Energy Institute, PSU-DUT Joint Center for
Energy Research and Department of Energy & Mineral Engineering, Pennsylvania
State University, University Park, PA 16802, United States. Fax: +1 814 865 3573.
E-mail addresses: csong@psu.edu (C. Song), guoxw@dlut.edu.cn (X. Guo).
potential approaches [13–15].
Metal organic frameworks (MOFs) are a class of hybrid
materials built from the coordination of metal ions or clusters
with organic ligands [16–19]. In the past two decades, MOFs have
received a large amount of attention from researchers, mainly due
to their structural variety and highly tunable physicochemical
properties. As a kind of porous materials with large pore volumes
and high surface areas, MOFs have shown great promise for a
number of diverse applications such as gas separation [20,21], drug
delivery [22] and catalysis [23–26]. Hydrothermal stability is a
pertinent issue to address MOFs for many catalytic applications
[27]. Low et al. [28] compared and mapped the steam stabilities of
general MOFs through energy assessed using molecular modelling
of the ligand displacement by water molecules and experimental
results. It is reported that MIL-53(Al) and ZIF-8 have excellent
hydrothermal stability which can be stable at more than 300  C in
the existence of steam. This makes MOFs potential support under
high temperature and high pressure catalytic reactions.
CO2 hydrogenation over iron-based catalyst has been shown to
proceed via a two-step process, with initial conversion of CO2 to CO
via the reverse water gas shift reaction (RWGS) followed by CO
hydrogenation into hydrocarbons as in Fischer–Tropsch synthesis
reaction (FTS) [29,30]. Many researchers have studied the effect of

http://dx.doi.org/10.1016/j.jcou.2016.02.009
2212-9820/ ã 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009
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2 S. Hu et al. / Journal of CO2 Utilization xxx (2015) xxx–xxx
promoters and bimetallic catalyst depending on iron-based
catalyst [14,15,31,32]. The support is also an important factor
which could influence the reaction. The synthesis of MOFs with
controllable size and morphologies is fascinating for different
applications [33–36]. Herein we choose iron-based catalysts for
the CO2 hydrogenation and hydrothermal stable MOFs with
different size and morphologies as support. The support with
different physicochemical properties shows a great effect on the
catalyst activity and selectivity. In the present work, a series of
MIL-53(Al) and ZIF-8 with different size and morphology as
hydrothermally stable support were prepared and tested for CO2
hydrogenation to hydrocarbons. The result shows a great differ-
ence in the CO2 conversion and light olefin selectivity.
2. Experimental
2.1. Materials and chemicals
1,4-Benzenedicarboxylic acid (H2BDC), 2-methylimidazole and
a-Fe2O3 (30 nm beads) was purchased from Aldrich. Aluminum(III)
chloride hexahydrate (AlCl3
6H2O), Zinc nitrate hexahydrate
(ZnNO3
6H2O), N,N-dimethylformamide (DMF), methanol
(CH3OH) and ammonia solution (NH3
H2O) were obtained from
Shanghai Chemical Reagent Inc. of the Chinese Medicine Group.
Deionized water was purchased from Dalian University of
Technology. All chemicals were used as received without further
purification.
2.2. Synthesis of MIL-53(Al) with different morphology
MIL-53(Al) was accomplished using a solvothermal synthesis
method. In a typical synthesis, AlCl3
6H2O (1.51 g, 6.2 mmol) and
H2BDC (1.01 g, 6.2 mmol) were added in 60 mL water. After stirring
and ultrasonic concussion for 5 minutes, the mixture was moved to
a 100 mL Teflon-lined steel autoclave and placed in an oven at
150  C for 3 days under static conditions. After cooling, the white
solid product was washed with H2O and DMF and then isolated by
centrifugation. The sample was then activated in boiling DMF for
5 h in order to remove the remaining unreacted reactant trapped in
the pores. After drying overnight in a vacuum oven at 50  C, the
sample was calcined at 200  C for 6 h to remove the free solvents.
The morphology-controlled MIL-53(Al) was obtained using a
solvothermal route in a DMF–H2O mixed solvent with H2BDC and
AlCl3
6H2O as the organic linker and metal source, respectively
[35] (see Supporting information) The MIL-53(Al) synthesized in
pure H2O was named support 1 (S1).
2.3. Synthesis of ZIF-8 with different size
ZIF-8 crystals with different size were synthesized as previously
reported with little modulation [1,37,38]. Three different solvent
systems were used to obtain size variant ZIF-8 crystals, named ZIF-
8(a), ZIF-8(b) and ZIF-8(c). ZIF-8(a) was synthesized using
ZnNO3
6H2O (1.49 g, 5.0 mmol) and 2-methylimidazole (0.82 g,
10.0 mol) as metal source and organic linker dissolved into 50 mL
methanol with 5 mL NH3
H2O added. ZIF-8(b) and ZIF-8(c) were
synthesized in pure methanol or DMF using ZnNO3
6H2O (0.74 g,
2.5 mmol) and 2-methylimidazole (0.82 g, 10.0 mol) as the
reactants, respectively. The mixture of reactants and solvents
was moved to a 100 mL Teflon-lined steel autoclave and placed in
an oven at 150  C for 24 hours under static conditions. The obtained
products were dealt with the same processing method as MIL-53
(Al). ZIF-8(a), ZIF-8(b) and ZIF-8(c) were named support 2, 3 and 4
(S2, S3 and S4)
Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009
2.4. Preparation of Fe2O3/MOF catalysts
Size- and morphology-controlled MIL-53 and ZIF-8 were used
as the support materials. The Fe2O3/MOF catalysts were prepared
by the solid grinding method using nano a-Fe2O3 and the above
supports to obtain 21 wt% of Fe2O3 loading, respectively. The
obtained catalysts were named catalyst 1–4 (C1–C4) correspond-
ing to S1–S4. For control experiment, g-Al2O3 was used as a kind of
support to compare with the MOFs, and the prepared catalyst was
named catalyst 5 (C5).
2.5. CO2 hydrogenation reaction
The catalytic hydrogenation of carbon dioxide was carried out
in a pressurized fixed-bed flow reactor (inner diameter 8 mm)
where a weighed 1 g catalyst (mixed with 5 g quartz sand sieved by
20–40 mesh) was loaded for each test. Prior to the reaction, the
catalyst was pre-treated by reduction with H2 at 573 K overnight.
After the reduction, the feed gas was changed to the mixture of
carbon dioxide and hydrogen under the reaction conditions of n
(H2)/n(CO2) = 3 (molar ratio); P = 3 MPa; T = 573 K and the space
velocity was 3600 ml g 1 h 1. Considering the hydrothermal
stability of MOF materials, the reaction temperature was detailed
investigated to obtain the highest catalyst activity on the premise
of guarantee the stability of supports (see Supporting information).
Products were analyzed by an on-line FULI GC97 gas chromato-
graph. CO, CO2 and CH4 were analyzed on a carbon molecular sieve
column with TCD detector, while CH4 and C2–C8 hydrocarbons
(C2+) were analyzed by a flame ionization detector (FID) with a
HayeSep Q column. Chromatograms of FID and TCD were
correlated through CH4, and product selectivity was obtained
based on carbon.
2.6. Catalyst characterization
Powder X-ray diffraction (XRD) patterns of fresh and used
catalysts were recorded on a Rigaku SmartLab(9) diffractometer,
using Cu Ka X-rays at a scanning rate of 8 /min between 5 and 80 .
The tube voltage and current used were 40 kV and 100 mA. The size
and morphology of samples were characterized using field-
emission scanning electron microscopy (NOVA NanoSEM 450) at
an accelerating voltage of 10.0 kV. The sorption properties of the
samples were determined by N2 adsorption on a Quantachrome
AUTO-SORB-1-MP sorption analyser at liquid nitrogen tempera-
ture. Prior to the measurements, the samples were degassed at
150  C for 8 h. NH3-TPD experiments were carried on ChemBET
Pulsar TPR/TPD equipment (Quantachrome, USA). The sample was
dried in flowing helium (99.99%, 60 mL/min) at 300  C for 0.5 h
prior to NH3 adsorption. NH3 adsorption took place at 100  C until
saturation, and then, the sample was flushed with helium at the
same temperature for 1 h. TPD measurement was conducted from
100  C to 400  C, with a heating rate of 10  C/min.
3. Results and discussion
3.1. Morphology characterization
Fig. 1 clearly shows the SEM images of MOF supports and Fe2O3
loaded catalysts. MIL-53(Al) was like a kind of rhomboid crystal
(Fig. 1 S1) with the side length of around 1–2 mm. A series of ZIF-
8 crystals with different sizes were prepared by varying the specific
synthesis conditions, mostly the solvent, and all the other reaction
conditions remained the same. The obtained ZIF-8 crystals reveal a
change of their morphologies from random ball and ellipsoidal
shapes to regular rhombic dodecahedra with the changes of size
from 150 nm to 300 nm to finally 2 mm (Fig. 1 S2, S3 and S4). The
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S. Hu et al. / Journal of CO2 Utilization xxx (2015) xxx–xxx 3

Fig. 1. SEM images of the samples (S1: MIL-53(Al), S2: ZIF-8(a), S3: ZIF-8(b), S4: ZIF-8(c), C1: Fe2O3/S1, C2: Fe2O3/S2).
CO2 conv. & product sel. (%)

100
CO2 conv.
C5+
80 C2-C4
0

=
C2-C4
60 CH4
CO

40

20

0
C1 C2 C3 C4 C5 NS
Catalyst
Fig. 2. CO2 conversion and product selectivity over different catalysts (C1: MIL-53(Al)/Fe2O3, C2: ZIF-8(a)/Fe2O3, C3: ZIF-8(b)/Fe2O3, C4: ZIF-8(c)/Fe2O3, C5: Fe2O3/g-Al2O3,
NS: Fe2O3 without support).

Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009
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images of C1 and C2 show clearly that the active component
(30 nm beads of Fe2O3) was homogeneously dispersed on the
surface of S1 while S2 was sufficiently mixed with Fe2O3 because
the size of S2 was relatively smaller compared to S1. The SEM
images of MIL-53(Al) synthesized in DMF–H2O mixed solvent
demonstrate a way to control the size and morphology of MIL-53
(Al) crystals (Fig. S1).
3.2. Catalytic hydrogenation of CO2 into hydrocarbons
Catalytic activity and product selectivity of the five catalysts are
shown in Fig. 2. a-Fe2O3 mixed with quartz sand was used to
compare with the five catalysts with different supports, which was
named none support (NS) and the data were also shown in Fig. 2.
On the whole, all these four kinds of MOFs supported catalysts
from C1 to C4 show superior catalytic activity and better product
selectivity compared with g-Al2O3 (C5). The selectivity of
byproduct CO over C1–C4 is significantly less than C5 which

after reaction
MIL-53
C1(Al)
♣-Fe3O4 before reaction

♦-Fe2O3

♣
♣ ♣ 10 20 30 40 50 60 70 80
♣ ♣
♣

♦
♦ ♦

♦ ♦ ♦♦ ♦ ♦

after reaction
C1
ZIF-8(a) before reaction
♣-Fe3O4
♦-Fe2O3

♣
10 20 30 40 50 60 70 80
♣
♣ ♣ ♣ ♣
Intensity(a.u.)

♦
♦ ♦
♦ ♦♦
♦ ♦ ♦

after reaction
ZIF-8(b)
C3 before reaction
♦-Fe2O3
♣-Fe3O4

♣ ♣ ♣ ♣
♣ 10 20♣ 30 40 50 60 70 80

♦
♦
♦ ♦
♦ ♦♦ ♦ ♦

after reaction
C4
ZIF-8(c)
♣-Fe3O4 before reaction

♦-Fe2O3
♣

♣ ♣
♣
♣ 10 20 30 ♣ 40 50 60 70 80
♣

♦
♦ ♦
♦ ♦♦
♦ ♦ ♦

30 40 50 60 70
2 Theta(degree)
2 The ta(degree)
Fig. 3. XRD patterns of fresh and used catalysts (C1: MIL-53(Al)/Fe2O3, C2: ZIF-8(a)/Fe2O3, C3: ZIF-8(b)/Fe2O3, C4: ZIF-8(c)/Fe2O3).

Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
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represents a deepening of the reaction, together with the Table 1

Sorption data of MOFs supports (S1: MIL-53(Al), S2: ZIF-8(a), S3: ZIF-8(b), S4: ZIF-8
additional rise in selectivity of C2+ hydrocarbons. All the three
(c)).
ZIF-8 with different size and morphology supported catalysts (C2–
C4) show higher CO2 conversion than MIL-53 (C1). Meanwhile, Sample SBET (m2/g) Smicro (m2/g) Vmicro (cm3/g) Vtotal (cm3/g)
there exists a huge difference on the selectivity of light olefins S1 1535 1524 0.57 0.59
between C1 and C4. As C2–C4 show different levels of considerable S2 1900 1856 0.67 0.89
S3 1918 1897 0.68 0.73
light olefins selectivity, while C1 nearly could not obtain light
S4 1821 1793 0.62 0.69
olefins, neither the other MIL-53 with controllable size and
morphology supported catalyst (see Supporting information). Measured by N2 adsorption at 77 K and all these data were calculated from the
desorption branch. The total pore volumes of all samples have been calculated at a
Moreover, the selectivity of CH4 over C1 is obviously higher than
p/p0 value of 0.995.
the others. Focusing on C2–C4, the CO2 conversion increased with
the crystal size enlarging, while the selectivity of light olefins
decreased, together with the additional rise in selectivity of C2–C40
hydrocarbons. A similar phenomenon occurred in the series of
MIL-53(Al) supported catalysts (see Supporting information). From
the result of NS, it is found that the light olefins selectivity is really
high and the CO2 conversion and CO selectivity is similarly with C5.

3.3. X-ray diffraction

The framework structures of fresh and used catalysts were

determined using X-ray diffraction (Fig. 3). All the XRD patterns
show that the framework of MIL-53(Al) and ZIF-8 were mostly
maintained after the reaction with little decrease in the
crystallinity which confirmed that both of these two types of
MOFs supports were stable enough under the selected reaction
conditions. It proves that it is feasible to use hydrothermally stable
MOFs for high temperature and high pressure catalytic reactions
with generated water. The characteristic peaks of a-Fe2O3 were
observed in the XRD patterns before reaction. After the CO2
hydrogenation reaction, the XRD patterns of these used catalysts
exhibited the characteristic peaks of magnetite (Fe3O4).
3.4. Sorption properties
Porosity is a unique characteristic of MOFs. Their microporous
structures provide high surface areas and large pore volumes,
together with a large variety of pore dimensions and topologies,
which have triggered an extensive investigation into their
application for gas separation and storage, drug delivery and
catalysis [2]. To evaluate the sorption properties of these four kinds
of MOFs supports, nitrogen sorption isotherms at 77 K were
measured. The four MOFs supports have a similar micropore
adsorption/desorption isotherms (Fig. 4), while their total BET
Fig. 5. Porous structures of MIL-53(Al) and ZIF-8.
surface areas were different from each other, which is depended on
the types of MOFs materials. As shown in Table 1, the total BET
surface areas (SBET) of three kinds of ZIF-8 crystals are similar to
each other ranging from 1821 to 1918 m2/g, which are higher than
MIL-53(Al) (1535 m2/g). The surface areas of these two types of
MOFs were mostly contributed by the micropore surface areas.
MIL-53(Al) was reported to have breathing effects and the channel
dimensions become 8.5  8.5 Å [2] when the pores were empty
[39]. ZIF-8 was known to have SOD (sodalite) topology with large
cavities of 11.4 Å and small apertures of 3.2 Å [38]. (Fig. 5) All these
four MOFs supports belong to microporous materials, which
means that the active component (30 nm beads of Fe2O3) was not
able to get into the channels through solid grinding synthesis
method and the Fe2O3 beads were supposed to disperse on outside
surface of the supports which were confirmed by SEM images
(Fig. 1).

900
S1
800
Volume(cm /g STP)

S2
700 S1
S2
Al2O3
3

600 S3
Intensity(a.u.)

500
S4
400

300

0.0 0.2 0.4 0.6 0.8 1.0

Relative pressure(p/p0)
Fig. 4. N2 adsorption/desorption isotherms of MOFs supports (S1: MIL-53(Al), S2: 150 200 250 300 350 400 450
ZIF-8(a), S3: ZIF-8(b), S4: ZIF-8(c)) For construction convenience, the y values are Temperature(°C)
modulated by adding specific numbers to the original data, S1(+320), S2(+240), S3
(+120). Fig. 6. NH3-TPD profiles of S1,S2 and Al2O3 (S1: MIL-53(Al), S2: ZIF-8(a)).

Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009
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Scheme 1. Proposed schematic of the reaction.
3.5. NH3 chemisorption of catalysts
The acidity of S1, S2 and Al2O3 was determined by temperature-
programmed desorption of ammonia (NH3-TPD). Compared with
Al2O3, the two kinds of MOFs supports S1 and S2 show much
weaker peak intensity. And it is also found that sample S1 exist two
main distinct ammonia-desorption peaks at around 200  C and
340  C, which are ascribed to the weak acidic sites and the strong
acidic sites, respectively. Meanwhile the sample S2 almost show no
acidity as there is no obvious peaks observed and S1 has much
weaker acidity than Al2O3. It is known that the acidity of catalysts is
conducive to the hydrogenation reactions, so the light olefins
selectivity over C1 in this article is quite low (Fig. 2). By contrast,
g-Al2O3 is a normal acidic support, and the selectivity of light
olefins in the reaction of CO2 hydrogenation to hydrocarbons is
almost zero compared to NS which none support was used (Fig. 6).
3.6. Proposed assumption
In consideration of the chosen supports, all the different kinds
of MOFs exists a large amount of organic components in the
structure. Therefore, MOFs show a great CO2 adsorption property
[40,37] which makes a contribution to the occurrence and
deepening of the reaction. As is shown in Fig. 2, the catalysts
with MOFs as supports have a higher CO2 conversion and a lower
CO selectivity which attributed to the stronger CO2 adsorption. Due
to the acidity of MIL-53(Al) and Al2O3, the effect of hydrogenation
in this reaction is obviously enhanced and the selectivity of alkanes
is extremely high with almost no olefins detected. When talked
about ZIF-8, it is known for the excellent ability of hydrogen
storage [38,41,42]. It can be supposed that there exists adequate
amount of H2 in the pores and channels of ZIF-8. Alkenes,
generated on the surface of ZIF-8, transfer through the inner of ZIF-
8 and the secondary reaction of hydrogenation happened during
this process which leads to a result that the selectivity of alkenes
over different ZIF-8 as supported catalysts decreases with increase
in particle size. It can be seen that the C2+ product selectivity over
different ZIF-8 is almost the same except the ratio of alkanes and
alkenes, which proves that alkanes was partially generated by the
hydrogenation of alkenes (Scheme 1).
4. Conclusions
To explore more applications for MOFs as excellent materials, a
series of ZIF-8 and MIL-53(Al) with different sizes and morphol-
ogies were prepared and used as hydrothermally stable supports
for catalysts for CO2 hydrogenation to hydrocarbons. Through our
work we could find that, MOFs as a novel porous materials show
excellent properties on catalysis compared with traditional
Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009
supports such as g-Al2O3. And even with mechanical mixing,
the type of MOF supports has a significant impact on the activity
and selectivity of Fe catalysts for CO2 hydrogenation. The chosen
two types of MOFs show significant difference on the selectivity of
light olefins due to the acidity of supports, ZIF-8 supports show
different levels of considerable light olefins selectivity, while all
MIL-53 supports nearly could not obtain light olefins. Among the
3 different ZIF-8 supports, the larger crystals correspond to lower
olefin selectivity which is mainly affected by the secondary
reaction of hydrogenation during the internal diffusion process,
the selectivity of alkenes decreases with increases in particle size.
It is proposed that hydrothermally stable MOFs could be a
promising supports in high temperature and high pressure
catalytic reactions to obtain higher activity and better product
selectivity.
Acknowledgments
This work was supported by the State Key Program of National
Natural Science Foundation of China (Grant No. 21236008). We
thank Dr. T. Loiseau for proving the breathing effect of MIL-53 in
Fig. 5 (Chem.-Eur. J. 2004, 10, 1373).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcou.2016.02.009.
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Please cite this article in press as: S. Hu, et al., Hydrothermally stable MOFs for CO2 hydrogenation over iron-based catalyst to light olefins, J. CO2
Util. (2016), http://dx.doi.org/10.1016/j.jcou.2016.02.009