Journal of CO₂ Utilization 36 (2020) 82–95

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Journal of CO2 Utilization

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

Enhanced catalytic performance of Zr modified CuO/ZnO/Al2O3 catalyst for T

methanol and DME synthesis via CO2 hydrogenation
Shoujie Rena, Xiao Fana, Zeyu Shanga, Weston R. Shoemakera, Lu Mab, Tianpin Wub,
Shiguang Lic, Naomi B. Klinghofferc, Miao Yud, Xinhua Lianga,*
a
Department of Chemical and Biochemical Engineering, Missouri University of Science and Technology, Rolla, MO 65409, United States
b
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439, United States
c
Gas Technology Institute, 1700 South Mount Prospect Road, Des Plaines, IL 60018, United States
d
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Zirconium (Zr) modified CuO/ZnO/Al2O3 (CZA) catalysts with different aluminum (Al) and Zr contents were
CO2hydrogenation synthesized by the co-precipitation method. The synthesized CuO/ZnO/ZrO2/Al2O3 (CZZA) catalysts were
Methanol comprehensively characterized and studied for methanol synthesis via CO2 hydrogenation. The CZZA catalyst
Dimethyl ether showed the highest methanol yield of 12.4 % at 220 °C and 2.76 MPa with an optimized catalyst composition of
CuO/ZnO/ZrO2/Al2O3 (CZZA)
Cu/Zn/Zr/Al (atomic ratio) at 4:2:1:0.5. The CZZA catalyst showed better activity than that of the CZA catalyst
Stability
and a superior stability for methanol synthesis. There was no decrease in the BET surface area and very little
coke formation for the spent CZZA catalyst, after 300 h of methanol synthesis. Bifunctional catalysts, composed
of CZZA and HZSM-5, were investigated for dimethyl ether (DME) synthesis directly from CO2 hydrogenation,
and a maximum DME yield of 18.3 % was obtained at a reaction temperature of 240 °C and a pressure of
2.76 MPa. The stability of the bifunctional CZZA and HZSM-5 catalyst during the DME synthesis also sig-
nificantly improved, as compared to that of the CZA and HZSM-5. A significant decrease in the BET surface area
and an increase in coking on the spent CZZA catalyst were observed after 100 h of DME synthesis, indicating a
detrimental effect on CZZA stability when a HZSM-5 catalyst was present. The changes in structural properties
(e.g., BET surface area and crystallinity) and coking for HZSM-5 could be responsible for the deactivation of the
bifunctional catalyst.

1. Introduction
Dimethyl ether (DME) has been considered to be a promising al-
ternative fuel and an important intermediate chemical used for the
production of other chemicals, such as methyl acetate [1,2]. The cata-
lytic conversion of syngas (CO and H2) to DME has been widely in-
vestigated during the last decade and a good yield has been achieved
[1,3,4]. Due to its extensive availability and a motivation to reduce
green-house gas emissions, CO2 has been selected as a building block in
producing useful chemicals and fuels [5–10]. CO2 hydrogenation with
H2 to produce DME is becoming of increasing interest to researchers
[11–13]. Compared to DME production from syngas, production with
CO2 involves a reverse water gas shift reaction, as a side reaction, as
well as CO2 hydrogenation to methanol and methanol dehydration to
DME.
A conventional catalyst used for methanol synthesis from syngas is
CuO/ZnO/Al2O3 (CZA), which has high activity [14–16]. This catalyst
is also the primary choice for CO2 hydrogenation to methanol and has
been investigated during the last several years [11,14,17,18]. Although
good activity has been achieved, the stability of CZA for CO2 hydro-
genation has not been sufficient [19–22]. Due to the hydrophilic
property of Al in the CZA catalyst, water generated in CO2 hydro-
genation to methanol and reverse water gas shift reactions can be ad-
sorbed onto the catalyst, which will reduce the activity. Large amounts
of produced water could accelerate catalyst deactivation. To improve
the stability of the hydrogenation catalyst, particularly with respect to
water resistance, some promoters, such as Fe, Pd, and Zr have been
investigated [23–26]. Zr, as a structural promoter, can prevent the
aggregation of CuO and ZnO, and favor the dispersion of CuO, thereby
improving the structural properties of catalysts [27,28]. Li et al. [29]
synthesized Zr doped catalysts and investigated the stability of the
catalysts for methanol synthesis from CO2. The Zr doped catalysts

⁎
Corresponding author.
E-mail address: liangxin@mst.edu (X. Liang).

https://doi.org/10.1016/j.jcou.2019.11.013
Received 31 May 2019; Received in revised form 24 October 2019; Accepted 8 November 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
S. Ren, et al.
showed an excellent tolerance against water vapor. It was also pointed
out that Zr could prevent the crystal growth of CuOx and reduce the
irreversible deactivation of catalysts.
Solid acid catalysts are generally used for methanol dehydration. In
direct CO2 hydrogenation to DME, bifunctional catalysts composed of
hydrogenation catalysts (e.g., CZA) and solid acid catalysts (e.g., HZSM-
5 or γ-Al2O3), which are similar to those used for syngas conversion to
DME, have been investigated [20,22,30–32]. However, detrimental
interactions, such as an ion exchange between hydrogenation and de-
hydration catalysts, have been reported and the presence of water could
enhance this undesirable effect. Catalyst deactivation and low product
yields have been significant challenges in the industrial application of
bifunctional catalysts [20,21,32].
Zr promoted catalysts have shown an improvement in CO2 con-
version to methanol. However, in direct DME synthesis from CO2 by
bifunctional catalysts, the methanol dehydration reaction produces a
significant amount of water, in addition to the water produced by CO2
hydrogenation to methanol and the reverse water gas shift reactions.
There have only been a few reports about the effects of Zr modified CZA
catalysts on the activity and stability of bifunctional catalysts in DME
synthesis from CO2, and the deactivation mechanism of bifunctional
catalysts composed of Zr-modified CZA and HZSM-5 was not fully un-
derstood. In this study, we modified a CZA catalyst by Zr and tested the
activity and stability for CO2 conversion to methanol and DME. The Zr
loading and Al loading in the catalyst were optimized. A long-term
stability test for methanol and DME synthesis was conducted to de-
termine the effect of Zr on catalyst stability. The spent catalysts were
also characterized to reveal the deactivation mechanism of the cata-
lysts.
2. Materials and methods
2.1. Materials
A Zr-modified CuO/ZnO/Al2O3 (CZZA) catalyst was synthesized by
the co-precipitation method. The precursors, including copper nitrate
(Cu(NO3)2 ·3H2O, 99 %), zirconium dinitrate oxide hydrate (ZrO
(NO3)2·xH2O), 99.9 %), zinc nitrate (Zn(NO3)2·6H2O, 98 %), aluminum
nitrate (Al(NO3)3·9H2O, 98 %), and sodium carbonate (Na2CO3, 99 %),
were purchased from Alfa Aesar (USA) and used to synthesize the CZZA
catalyst. Ammonia-ZSM-5 (molar ratio of SiO2/Al2O3 = 23:1, with a
surface area of 425 m2/g) was purchased from Alfa Aesar and used as a
precursor for the dehydration catalyst. Before being used, the ammonia-
ZSM-5 was calcined at 500 °C for 5 h to obtain HZSM-5. Admixed gas of
CO2 and H2, with a volume ratio of 1:3, was purchased from Airgas Inc.
(USA), and was used as feed gas for reactions.
2.2. CuO/ZnO/ZrO2/Al2O3 synthesis and bifunctional catalyst preparation
The co-precipitation method was used to synthesize a CZZA catalyst
[22]. A certain amount of metal nitrates (copper nitrate, zinc nitrate,
zirconium nitrate, and aluminum nitrate) were mixed and diluted with
deionized (DI) water to a final volume of 500 mL. The aqueous solution
of mixed metal nitrates and an aqueous solution of sodium carbonate
were simultaneously added dropwise into 400 mL of preheated DI water
(65−70 °C), under vigorously stirring at 400 rpm. The temperature was
kept at 65−70 °C and the pH value was kept at 6.5–7.0 during the co-
precipitation process. The pH value was immediately adjusted to 7.0 by
an aqueous solution of sodium carbonate at the end of co-precipitation.
Precipitates were then aged at 70 °C, for 30 min under vigorous stirring
at 400 rpm. After aging, the precipitates were filtered under reduced
pressure and rinsed several times with warm DI water. Next, the cata-
lyst (solid residues from filtration) was dried in an oven, at 110 °C
overnight, then calcined in air at 400 °C for 4 h, at a heating rate of
2 °C/min. To investigate the effects of precursor concentration on cat-
alytic performance, different concentrations of mixed aqueous nitrate
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Journal of CO₂ Utilization 36 (2020) 82–95
solutions (total metal concentration of mixed aqueous at 0.1, 0.4, 0.7,
and 1.0 M) and aqueous sodium carbonate solution (0.1, 0.4, 0.7, and
1.0 M) were used for catalyst synthesis and denoted as CZZA-x, in which
x stands for the concentration of solutions (the same concentrations of
nitrates and sodium carbonates) used for catalyst synthesis.
Bifunctional catalysts were prepared by physically mixing CZZA
powder and HZSM-5 powder. CZZA-0.1 was used for all experiments,
except when testing the effects of precursor concentration. For a cata-
lytic activity test, 0.5 g of CZZA powder and 0.5 g of HZSM-5 were used
for bifunctional catalyst preparation. For a HZSM-5 loading test, bi-
functional catalysts were prepared by fixing CZZA powder at 0.5 g and
varying HZSM-5 from 0.1 g to 0.5 g. In order to determine the deacti-
vation mechanism of CZZA and HZSM-5 in DME synthesis, the bi-
functional catalyst used for the stability test was prepared by physically
mixing pelletized CZZA (40–60 mesh) and HZSM-5 (40–60 mesh).
2.3. Catalyst characterization
Nitrogen adsorption and desorption of catalysts was determined by
a Quantachrome Autosorb-1. The Brunauer–Emmett–Teller (BET)
method was used to calculate the specific area of samples in a relative
pressure range of 0.05–0.25 of nitrogen adsorption and desorption
isotherms.
The reducibility of a CZZA catalyst was determined by hydrogen
temperature-programmed-reduction (H2-TPR) analysis, which was
performed using a Micromeritics Autochem II 2920 (Micrometritics
Instrument Corporation) under the following conditions: 25 mg sample,
10 % H2-Ar, with a flowrate of 20 mL/min, and heating rate of 10 °C/
min.
NH3 temperature-programmed desorption (NH3-TPD) was per-
formed with a Micromeritics Autochem II 2920 using the following
procedures. A 100 mg sample was pretreated at 350 °C, with a He flow
of 30 mL/min for 1 h, and then cooled to 50 °C. Ammonia (5 % NH3/
He) was introduced into the catalyst for 60 min at 50 °C. After that, the
sample was flushed with helium for 60 min to remove weakly adsorbed
NH3 and, then, the temperature was programmed to increase to 700 °C
at a rate of 10 C/min. The amount of ammonia in the effluent was
measured by TCD and quantitatively calibrated by NH3 pulses.
The metallic copper surface area, copper dispersion, and particle
size were determined by performing N2O-chemisorption using a
Micromeritics Autochem II 2920. The catalyst was first degassed at
250 °C for 2 h in pure He, then reduced at the same temperature for 2 h
in 10 % H2 in He. After the reduction, pure He was used to cool down
the catalyst to 50 °C. Then, gas was changed to a mixture of 1 % N2O in
He to start N2O-chemisorption. The stoichiometry of Cu:N2O was as-
sumed to be 2:1.
The textural structure and powder X-ray diffraction (XRD) patterns
of fresh and spent catalysts were determined by a Philips X'Pert PRO
PW3050 X-ray diffractometer, equipped with a Cu Kα radiation and a
graphite generator. The tube voltage and the current were at 45 kV and
40 mA, respectively. The scan range was 20–90°, with a scan rate at
0.5°min-1. X-ray absorption spectroscopy (XAS) was performed by using
the 9-BM beamline of the Advanced Photon Source at Argonne National
Lab, USA.
Images of reduced catalysts and spent catalysts were taken by a FEI
Tecnai F30 TEM, operated at 300 kV, to determine the microstructure.
Energy Dispersive X-Ray Spectroscopy (EDS) was used for element
mapping.
Coking content of spent catalysts was determined by a TA
Instruments Q50 thermogravimetric analyzer. In order to remove
moisture and absorbed CO2, catalysts were first heated to 100 °C, at a
heating rate of 10 °C/min, and kept at 100 °C for 60 min, with a N2 flow
rate of 100 mL/min. Then, the catalyst was heated to 1000 °C at the
same heating rate with air (100 mL/min) to determine the coking
amount.
S. Ren, et al.
2.4. Catalytic testing of methanol and DME synthesis
The activity of the synthesized catalysts was tested using a fixed-bed
reactor system as described in our previous reports [22,31]. To evaluate
the catalytic activity for methanol production, the CZZA powder cata-
lyst (0.5 g) was diluted by quartz sand (0.5 g, particle size of 60–120
mesh), with a mass ratio of 1:1. CZZA-0.1 was used for all experiments
except testing the effects of precursor concentration. The catalysts were
reduced at 250 °C for 10 h, with 20 mL/min of pure H2. The reactions
were performed at 200−260 °C, with pressure of 2.76 MPa, 6 mL/min
CO2, 18 mL/min H2, and space velocity of 823 h-1. The long-term sta-
bility tests for methanol synthesis were conducted at 220 °C, 2.76 MPa,
6 mL/min CO2, 18 mL/min H2, and 823 h-1 space velocity.
A bifunctional catalyst, composed of CZZA and HZSM-5, was used
for DME synthesis from CO2 hydrogenation. The bifunctional catalysts
were reduced at the same conditions as those used for methanol
synthesis. To optimize the reaction conditions for DME synthesis, re-
action temperatures of 220−280 °C and pressure of 2.76 MPa were
investigated. All reactions were tested with 6 mL/min CO2, 18 mL/min
H2, and 472−917 h-1 space velocity, depending on the HZSM-5
loading. Long-term stability tests for DME synthesis were conducted at
240 °C, 2.76 MPa, 6 mL/min CO2, 18 mL/min H2, and 472 h-1 space
velocity. The reaction products were analyzed by an on-line gas chro-
matography (SRI 8610C), as described previously [22]. CO2 conversion
( XCO2 ), product selectivity (SCO , SMeOH , and SDME) and yield (YCO , YMeOH ,
and YDME ) were calculated using equations described in a previous re-
port [22].
3. Results and discussion
3.1. Catalyst characterization
Specific surface areas of synthesized catalysts from different pre-
cursor concentrations were measured, based on the BET method, and
the results are presented in Table 1. The largest surface area of 109 m2/
g was obtained for a CZZA catalyst that was prepared with a precursor
concentration of 0.1 M. Increasing the precursor concentration, from
0.1 M to 0.4 M, resulted in a decrease in specific surface area. When the
precursor concentration was increased further, the specific surface area
did not decrease any more. Compared to the specific surface area of
CZA (i.e., 128 m2/g for a CZA catalyst prepared with a precursor con-
centration of 0.1 M) [22], the specific surface area of CZZA decreased
with Zr modification.
The reducibility of CZA catalysts and CZZA catalysts, prepared by
0.1 M concentration of precursor solutions, is shown in Fig. S1 in
Supplementary Material. The catalysts CZA-0.1 and CZZA-0.1 showed
similar H2-TPR profiles, with one single and clear reduction peak. The
reduction peak of CZA was at around 220 °C, while the peak of CZZA
was at around 245 °C, which were lower than that of pure CuO [29].
Compared to the CZA catalyst, Zr loading decreased the reducibility of
CuO.
Cu surface area, Cu dispersion, and Cu particle size of catalysts
prepared by different atomic ratios were calculated according to N2O-
chemisorption and the results are shown in Table S1. The catalyst with
Table 1
BET surface area and N2O chemisorption results of CuO/ZnO/ZrO2/Al2O3
catalysts prepared with different concentrations of precursors.
Catalyst BET surface Cu surface area Cu dispersion Cu particle
area (m2/g) (N2O) (m2/g) (%) size (nm)
CZA-0.1 128 59.3 16.3 5.8
CZZA-0.1 109 44.3 18.9 4.6
CZZA-0.4 99 33.7 12.2 7.2
CZZA-0.7 99 33.5 12.1 7.2
CZZA-1.0 101 31.1 11.2 7.7
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Journal of CO₂ Utilization 36 (2020) 82–95
Cu/Zn/Zr/Al atomic ratio of 4:2:1:0.5 has the highest Cu surface area
and Cu dispersion, but the smallest Cu particle size. Increasing Al
loading slightly decreased Cu surface area and Cu dispersion, while
increased the Cu particle size. Decreasing Zr loading to 0.5 or increasing
Zr loading to 1.5 from 1.0 also resulted in a decrease in Cu surface area
and Cu dispersion, and an increase in Cu particle size. These results
indicate that Cu/Zn/Zr/Al atomic ratio of 4:2:1:0.5 is the optimal for
CZZA catalyst.
The BET surface area and N2O chemisorption results of catalysts
prepared by different concentrations are shown in Table 1. Similar to
the results of specific surface areas, the largest Cu surface area and Cu
dispersion, and the smallest Cu particle size were 44.3 m2/g, 18.9 %,
and 4.6 nm, respectively, for the catalyst synthesized with the lowest
precursor concentration of 0.1 M. This suggested that the low precursor
concentration could provide increased Cu surface area and dispersion,
and a reduced Cu particle size. Increasing the precursor concentration
from 0.1 M to 0.4 M resulted in a significant decrease in Cu surface area
and dispersion and an increase in Cu particle size. With the further
increase of precursor concentration, a slight decrease in the Cu surface
area and dispersion and an increase in Cu particle size were observed.
Compared to a CZA catalyst, synthesized using the same method [22],
the addition of Zr reduced the Cu surface area and Cu particle size,
while it increased Cu dispersion, especially with a low precursor con-
centration. This can be explained by the fact that the addition of Zr in a
CZZA catalyst reduced the Cu content, as compared to that of CZA and,
therefore, improved the dispersion of Cu in the catalyst, which led to a
decrease of particle size. Meanwhile, due to the lower Cu content in the
CZZA catalyst, compared to that of the CZA, the Cu surface area, per
gram of catalyst, was reduced. For a catalyst prepared with a precursor
concentration of 0.1 M, the Cu surface area, Cu dispersion, and Cu
particle size were 59.3 m2/g, 16.3 %, and 5.8 nm for CZA, and 44.3 m2/
g, 18.9 %, and 4.6 nm for CZZA.
Compared to other published results [33–35], our synthesized cat-
alysts, especially those using the lowest precursor concentrations, had
good properties, such as high specific surface area, high Cu surface area
and Cu dispersion, and small Cu particle size. This could be attributed
to the large amount of initial water and low precursor concentration
during the co-precipitation process, which could improve particle dis-
persion and reduce precipitate aggregation during co-precipitation
[22].
The results of acidity characterization of bifunctional catalysts are
shown in Table S2. The peaks observed for bifunctional catalysts at
175−190 °C, 320−330 °C, and 500−520 °C corresponded to weak,
medium, and strong acidic sites. These acidic sites of bifunctional cat-
alysts were attributed to the presence of HZSM-5. CZZA-0.1 had more
medium acidic sites, as compared to other catalysts, that were prepared
by high precursor concentrations. However, the weak and medium
acidic sites of these catalysts contributed to over 92 % of total acidity,
which could be helpful in improving DME selectivity in methanol de-
hydration.
TEM and HRTEM images were taken and EDS mapping was done to
reveal the morphological properties and atomic distribution of reduced
CZZA-0.1 (Fig. 1a, b, and c). Previous reports identified that Zr im-
proved Cu dispersion and reduced the aggregation of Cu clusters [36].
In this study, a TEM image of reduced CZZA-0.1 shows nanoscale
particles (ca. 15 nm) with uniform distributions. Crystal fringes, cor-
responding to Cu (111), were observed and Cu nanoparticles were
dispersed homogeneously in the reduced catalysts. In addition, as seen
from EDS mapping, the elements of Zn, Zr, Al, and O in reduced CZZA-
0.1 were very well distributed, indicating that these elements were
homogeneously dispersed in the reduced catalyst. These results agree
well with previous findings [36,37].
XRD patterns of a reduced catalyst are shown in Fig. 2a. Diffraction
peaks at 43.3°, 50.5°, and 74.1°, corresponding to (111), (200), and
(220) planes of copper were observed. In addition, diffraction peaks at
31.8°, 34.4°, 36.3°, and 56.6°, corresponding to (100), (002), (101), and
S. Ren, et al.
Fig. 1. TEM, HRTEM, and EDS mapping images of reduced fresh CuO/ZnO/ZrO2/Al2O3 catalyst: (a) TEM, (b) HRTEM, and (c) EDS mapping.
(110) planes of zincite were observed. There were no peaks corre-
sponding to zirconium oxides and aluminum oxides, indicating that
zirconium oxides and aluminum oxides were either too highly dispersed
to form very small particles or existed as an amorphous phase in the
reduced CZZA catalysts. Previous studies pointed out that alloying of Zn
with Cu could improve CO2 hydrogenation [38,39]. Therefore, we
performed a XAS analysis of both reduced CZA and CZZA catalysts to
determine the interaction between Cu and Zn. However, we did not
observe any alloyed CuZn. As shown in Fig. 2b and c, there was no
significant shift in k space, indicating that Cu was not alloyed with any
other metals in either CZA or CZZA. This could have been due to the
low reduction temperature (250 °C), which could not result in bulk
alloy formation [40,41].
3.2. Catalytic activity for methanol synthesis
Fig. S2 shows the effect of space velocity on CO2 conversion, me-
thanol selectivity and yield. CO2 conversion, methanol selectivity, and
yield decreased with the increase of space velocity from 823 to 1235 h-
1
. This was attributed to the decrease in contact time between reactants
and catalysts, which resulted in insufficient hydrogenation of CO2. In
this study, a fixed flow rate of 24 sccm (mixture of H2 and CO2 at a
molar ratio of 3:1) was used for all catalytic activity tests.
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Journal of CO₂ Utilization 36 (2020) 82–95
3.2.1. Effects of Al content in CZZA on methanol synthesis
According to our previous report [22], the optimized atomic ratio of
Cu and Zn for a CuO/ZnO based catalyst was 2:1. In this study, in order
to investigate the effects of Al and Zr loadings, we fixed the composition
of Cu/Zn at a 4:2 molar ratio for catalyst synthesis. Al, as a structural
promoter present in a catalyst, can improve the dispersion of Cu and
enhance the synergistic effects between Cu and Zn [42]. The atomic
ratio of Cu/Zn/Zr was fixed at 4:2:1 and Al loading varied from 0.5 to
1.5. The catalytic performance of the catalysts is shown in Fig. 3.
CO2 conversion increased with the increase in reaction temperature,
while the methanol selectivity decreased. Although increasing the re-
action temperature enhanced the CO2 conversion, the highest methanol
yield was achieved at a relatively low reaction temperature (220 °C),
due to the relatively high CO2 conversion and high methanol selectivity
at that temperature. At reaction temperatures of 200 °C and 220 °C, CO2
conversion decreased when the Al loading increased from 0.5 to 1 and,
then, increased when the Al loading increased from 1 to 1.5. When the
reaction temperature increased to 240 °C and 260 °C, the amount of Al
had little effect on CO2 conversion. The methanol selectivity decreased
with the increase in Al loading. The highest selectivity for methanol was
64.9 % with an Al loading of 0.5 at 200 °C. Methanol yield also de-
creased with an increase of Al loading. The highest methanol yield was
12.4 %, with Al loading of 0.5 at 220 °C. In contrast to methanol, the CO
Fig. 2. XRD analysis (a, d) of CZZA and HZSM-
5, and extended x-ray absorption fine structure
(EXAFS) analysis (b, c) of reduced CZA and
CZZA catalysts in (b) k space and (c) R together
with EXAFS reference spectra of Cu foil. Spent
CZZA_100 h and spent HZSM-5_100 h were
spent catalysts after 100 h of reaction in DME
synthesis; spent CZZA_300 h was the spent
catalyst after 300 h of reaction in methanol
synthesis.
S. Ren, et al.
Fig. 3. Effects of Al content in CZZA catalysts on methanol synthesis and equilibrium data at the same reaction conditions: (a) CO2 conversion, (b) MeOH selectivity,
(c) MeOH yield, (d) CO selectivity, and (e) CO yield. Atomic ratios are presented as Cu/Zn/Zr/Al in charts. Equilibrium data were evaluated based on references
[43,44].
selectivity and yield increased with the increase in reaction tempera-
ture. Increasing Al loading resulted in an increasing trend in CO se-
lectivity and yield. The best Al loading was found to be 0.5 based on
these results.
3.2.2. Effects of Zr content in CZZA on methanol synthesis
Fig. 4 shows that CO2 conversion increased with an increase in re-
action temperature, from 200 °C to 220 °C, and then remained constant
when the reaction temperature increased further. The methanol se-
lectivity was similar when reaction temperatures were at 200 °C and
220 °C; however, it significantly decreased with the further increase in
the reaction temperature. Due to the low CO2 conversion, the methanol
yield at 200 °C was lower than that at 220 °C. Methanol yield sig-
nificantly decreased when the reaction temperature increased to 240 °C
and 260 °C, as compared to that at 220 °C. Similar CO selectivity was
observed at 200 °C and 220 °C. However, it significantly increased with
the increase in reaction temperature. The CO yield also increased with
the reaction temperature. These results indicated that the optimum
reaction temperature for methanol synthesis was 220 °C. At each
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Journal of CO₂ Utilization 36 (2020) 82–95
reaction temperature, a similar trend of CO2 conversion for different Zr
loadings was observed, indicating that Zr loading did not significantly
impact CO2 conversion. A similar or slight increase in methanol se-
lectivity and yield were observed when Zr loadings increased. At the
lowest Zr loading, the highest CO selectivity and yield were observed.
Increasing the Zr loading to 1, the CO selectivity and yield decreased.
Further increasing the Zr loading did not decrease the CO selectivity
and yield. Considering the effects of different Al loadings and Zr load-
ings, the optimized composition of CZZA was Cu/Zn/Zr/Al = 4:2:1:0.5
at atomic ratio, which is consistent to the results of N2O chemisorption
for CZZA catalysts.
3.2.3. Effects of precursor concentration during CZZA synthesis on
methanol synthesis
The effects of precursor concentration on CZZA catalysts for me-
thanol synthesis were also studied. As shown in Fig. 5a, precursor
concentration had no obvious effects on CO2 conversion. However,
precursor concentration influenced the methanol and CO selectivity.
The methanol selectivity decreased with increasing precursor
S. Ren, et al.
Fig. 4. Effects of Zr content in CZZA catalysts on methanol synthesis: (a) CO2 conversion, (b) MeOH selectivity, (c) MeOH yield, (d) CO selectivity, and (e) CO yield.
Atomic ratios are presented as Cu/Zn/Zr/Al in charts.
concentration, while the CO selectivity increased. There were only
minor effects on product yield; the CO yield increased slightly by an
absolute value of 1 % (from 7.5 to 8.5 %), with an increase of precursor
concentration from 0.1 M to 1.0 M, while methanol yield decreased
slightly by an absolute value of 1.3 % (from 12.4 to 11.1 %). These
changes could be attributed to the decrease in Cu surface area, when
the precursor concentration increased.
To understand the effects of catalyst chemo-physical properties on
catalytic performance, we did further regression analysis and plotted
graphics to show the relationship between catalytic activity and cata-
lyst chemo-physical properties (i.e., BET surface area, Cu surface area,
Cu dispersion, and Cu particle size) in both methanol synthesis and
DME synthesis. As shown in Fig. 5b-e, there was no linear relationship
between catalyst chemo-physical properties and catalytic activity (CO2
conversion, methanol selectivity, and yield) at the confidence level of
90 %. However, Cu surface area, Cu dispersion, and Cu particle size
weighed more on methanol selectivity (p < 0.2) than those on CO2
conversion and methanol yield.
We have summarized the literature results of methanol synthesis
from CO2 in Table S3 and made a comparison with the best results we
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Journal of CO₂ Utilization 36 (2020) 82–95
obtained in this study.
3.3. Catalytic activity for DME synthesis
3.3.1. Effects of Al content in CZZA on DME synthesis
As discussed in Section 3.2, the optimized atomic ratio of Cu/Zn/Zr/
Al for a methanol synthesis catalyst was 4:2:1:0.5. In order to under-
stand the effects of Al loadings on catalyst performance, we investigated
DME synthesis further. The CZZA catalyst composition had a fixed
atomic ratio of Cu/Zn/Al at 4:2:1 and Al loading varied from 0.5 to 1.5.
CZZA (0.5 g) and HZSM-5 (0.5 g), at a mass ratio of 1:1, was mixed to
form a bifunctional catalyst for DME synthesis.
As shown in Fig. 6, for all catalysts with different Al loadings, CO2
conversion and DME yield first increased with an increase in reaction
temperature from 220 °C to 240 °C, and then decreased with the in-
crease in reaction temperature from 240 °C to 280 °C. A relatively high
DME selectivity was observed at 220 °C and 240 °C, indicating that low
reaction temperature favored DME selectivity. When the reaction
temperature increased further, CO2 conversion, DME selectivity, and
yield greatly decreased, which was similar to our observation of DME
S. Ren, et al.
Fig. 5. Effects of precursor concentration on (a) methanol synthesis and (b, c, d, e) regression analysis between chemo-physical properties (i.e., (b) BET surface area,
(c) Cu surface area, (d) Cu dispersion, and (e) Cu particle size) and catalyst activity (i.e., CO2 conversion, methanol selectivity, and yield) in methanol synthesis.
synthesis from CO2 using CuO/ZnO/Al2O3 [22]. On the contrary, CO
selectivity and yield increased significantly with the increase in reac-
tion temperature. Similar methanol selectivity and yield were observed
at each reaction temperature, indicating that the reaction temperature
had no significant effects on methanol production.
Al loading had a significant effect on the CO2 conversion, product
selectivity, and yield. As shown in Fig. 6, CO2 conversion, DME se-
lectivity, and yield decreased with the increase in Al loading, from 0.5
to 1.5, for all synthesized catalysts at reaction temperatures of
220 °C–260 °C. At 280 °C, CO2 conversion remained similar, with Al
loading at 0.5 and 1.0, but greatly decreased when Al loading increased
to 1.5. DME selectivity and yield greatly decreased, first with the in-
crease in Al loading to 1.0 and, then, remained similar with a further
increase in Al loading to 1.5. The highest DME yield was 18.3 %, with a
CO2 conversion of 26.5 % and DME selectivity at 69.2 %, when the Al
loading was at 0.5 and the reaction temperature was 240 °C. CO se-
lectivity and yield increased with the increase in Al loading from 0.5 to
1 and, then, remained similar, when the Al loading increased further
from 1 to 1.5. Methanol selectivity and yield remained similar, with Al
loading at 0.5 and 1, and then increased with an Al loading of 1.5 at
reaction temperatures of 220 °C–260 °C. At reaction temperature of
280 °C, the Al loading of 1 showed a higher methanol selectivity and
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Journal of CO₂ Utilization 36 (2020) 82–95
yield than that of 0.5 and 1.
3.3.2. Effects of Zr content in CZZA on DME synthesis
As discussed in Section 3.2.1, the optimized Al loading was 0.5. We
further investigated the effects of Zr loadings on catalyst performance
for DME synthesis. The CZZA catalyst composition had a fixed atomic
ratio of Cu/Zn/Al at 4:2:0.5, and we varied Zr loading from 0.5 to 1.5.
CZZA (0.5 g) and HZSM-5 (0.5 g), at a mass ratio of 1:1, was mixed to
form a bifunctional catalyst for DME synthesis.
As shown in Fig. 7, the amount of Zr affected catalytic performance
and volcano trends for CO2 conversion, DME selectivity and yield were
observed with an increase in Zr loading at each reaction temperature,
except at 220 °C. The highest CO2 conversion, DME selectivity, and
yield were obtained when Zr loading was 1.0. On the contrary, CO and
methanol selectivity and yield showed reversed volcano trends with the
increase of Zr loading at each reaction temperature. Low CO selectivity
and yield were observed with Zr loading of 1.
Reaction temperature also had significant effects on CO2 conver-
sion, product selectivity, and yield. Our previous study of CZA catalyst
performance indicated that the optimum reaction temperature for DME
was 240 °C [22]. Similarly, the optimum reaction temperature for CZZA
was also 240 °C, and the highest DME yield achieved was 18.3 % when
S. Ren, et al. Journal of CO₂ Utilization 36 (2020) 82–95

Fig. 6. Effects of Al content in a CZZA catalyst on DME synthesis with equilibrium data at the same reaction conditions: (a) CO2 conversion, (b) DME selectivity, (c)
DME yield, (d) CO selectivity, (e) CO yield, (f) MeOH selectivity, and (g) MeOH yield. Atomic ratios are presented as Cu/Zn/Zr/Al in charts. Equilibrium data were
evaluated based on references [43,44].

the catalyst was composed of Cu/Zn/Zr/Al at 4:2:1:0.5 (atomic ratio).
The DME yield obtained was higher than those reported in previous
papers [12,22,25]. At reaction temperatures of 220 °C and 240 °C, re-
latively low CO selectivity and yield were obtained, indicating that the
low reaction temperature was unfavorable for CO production. Methanol
selectivity and yield showed a slight decrease trend with the increase in
reaction temperature.
3.3.3. Effects of precursor concentration during CZZA synthesis on DME
production
Similar to those of methanol synthesis (discussed in Section 3.2), the
CO2 conversion, DME selectivity, and DME yield slightly decreased with

89
S. Ren, et al. Journal of CO₂ Utilization 36 (2020) 82–95

Fig. 7. Effects of Zr content in CZZA catalyst on DME synthesis: (a) CO2 conversion, (b) DME selectivity, (c) DME yield, (d) CO selectivity, (e) CO yield, (f) MeOH
selectivity, and (g) MeOH yield. Atomic ratios are presented as Cu/Zn/Zr/Al in charts.

the increase in precursor concentration, while the CO selectivity in-
creased (Fig. 8 a). This could be due to the decreases in the BET surface
area, Cu surface area, and Cu dispersion with increasing precursor
concentration for CZZA synthesis. Since HZSM-5 in bifunctional cata-
lysts can efficiently convert methanol to DME, only a very small amount
of methanol was detected. Methanol selectivity and yield remained si-
milar for catalyst synthesis by different precursor concentrations.
We also did a regression analysis and plotted graphics to show the
relationship between catalytic activity and catalyst chemo-physical
properties in DME synthesis. As shown in Fig. 8b–f, the catalytic activity
in DME synthesis had no significant correlation with the BET surface
areas of the catalysts. However, there was a strong linear relationship
between catalyst chemo-physical properties (Cu surface area, Cu dis-
persion, Cu particle size, and total acid) and CO2 conversion/DME

90
S. Ren, et al. Journal of CO₂ Utilization 36 (2020) 82–95

Fig. 8. Effects of precursor concentration on (a) DME synthesis and (b, c, d, e, f) regression analysis between chemo-physical properties (i.e., (b) BET surface area, (c)
Cu surface area, (d) Cu dispersion, (e) Cu particle size, and (f) total acid) and catalyst activity (i.e., CO2 conversion, DME selectivity, and yield) in DME synthesis.

yield. At a confidence level of 90 %, the Cu surface area and Cu particle

size had significant effects on both CO2 conversion and DME yield. Cu
dispersion and total acid also had a significant effect on CO2 conver-
sion. These results suggested that the Cu properties (Cu surface area, Cu
dispersion, and Cu particle size) on the catalyst surface and the acidity
of the bifunctional catalyst were critical in determining CO2 conversion
to DME.
The literature results of DME synthesis from CO2, using bifunctional
catalysts, are summarized in Table S4. Compared to these literature
data, our synthesized bifunctional catalyst, composed of CZZA and
HZSM-5, showed a better performance than others. Again, the very
good chemo-physical properties of our synthesized CZZA could be a
major factor contributing to the excellent performance.

3.3.4. Effects of HZSM-5 loading on DME synthesis

Fig. 9. Effects of HZSM-5 loading (i.e., 0.1 g, 0.2 g, 0.3 g, and 0.5 g) on DME
synthesis.
The effects of HZSM-5 loadings on catalytic performance were also
investigated. Previous studies showed that HZSM-5 loading sig-
nificantly affected DME production; the DME production showed a
volcano pattern with HZSM-5 loading, when an optimum HZSM-5
loading was at 50 wt.% of a bifunctional catalyst [45]. However, in this

91
S. Ren, et al.
study, HZSM-5 loading did not affect CO2 conversion, as shown in
Fig. 9. HZSM-5 loading had a very small impact on CO and DME se-
lectivity. As a result, no significant changes in CO yield, methanol yield,
and DME yield were observed, even when the HZSM-5 loading was
reduced to less than 20 wt.% of the bifunctional catalyst. This indicated
that the effects of HZSM-5 loading on DME synthesis were not sig-
nificant when HZSM-5 loadings were between 0.1 to 0.5 g for a short
reaction time. The HZSM-5 loading could impact the long term stability
of the catalyst. These results were similar to our observations on DME
synthesis, using a bifunctional catalyst of CZA and HZSM-5 [31].
3.4. Catalyst stability for methanol and DME synthesis
3.4.1. Catalyst stability for methanol synthesis
Catalyst deactivation is a major issue in the commercialization of a
catalyst. In previous studies, the CZA catalyst has showed good activity,
but the stability of CZA was still undesirable [14,15,46,47]. The pre-
sence of Al in the catalyst made the catalyst hydrophilic, which resulted
in a decrease in catalytic activity due to water adsorption [48]. In this
study, a Zr-modified CZA catalyst (CZZA-0.1) showed improved stabi-
lity. After 300 h of reaction, CO2 conversion, methanol selectivity and
yield decreased from 20.8 to 20.0 %, from 62.1 to 58.5 %, and from
13.0 to 11.7 %, respectively. In contrast, the CZA catalyst (using 0.1 M
precursor concentration with Cu/Zn/Al atomic ratio of 6/3/1), pre-
pared in our lab, showed a considerable decrease in CO2 conversion,
methanol selectivity, and yield (Fig. 10); after 100 h of reaction, the
CO2 conversion, methanol selectivity, and methanol yield decreased
from 21.3 to 18.9 %, from 64.9 to 56.8 %, and from 12.8 to 10.8 %,
respectively. These results indicated that the CZZA catalyst was much
more stable than the CZA catalyst. That could be attributed to the hy-
drophobic property of Zr, which can repel produced water away from
the active sites of a catalyst and, thus, reduce the opportunity for Cu
oxidation by water [29].
Fig. 10. Comparison of catalyst stability between CZZA and CZA for methanol synthesis: (a) CO2 conversion, (b) MeOH selectivity, and (c) MeOH yield.
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Journal of CO₂ Utilization 36 (2020) 82–95
3.4.2. Catalyst stability for DME synthesis
To further understand the stability of a Zr-modified CZA catalyst for
DME synthesis, CZZA was mixed with HZSM-5 to form a bifunctional
catalyst and tested for 100 h. As shown in Fig. 11, the bifunctional
catalyst, prepared by Zr modified CZA (CZZA-0.1) and HZSM-5, was
more stable than CZA and HZSM-5, which was similar to the perfor-
mance for methanol synthesis. After 100 h of reaction, CO2 conversion
reduced from 27.1 to 24.1 % for the CZZA plus the HZSM-5 catalyst,
while CO2 conversion for the CZA plus HZSM-5 catalyst reduced from
26.2 to 22.0 %. After 100 h of reaction, the DME yield reduced from
18.5 to 14.1 % for CZZA plus the HZSM-5 catalyst, and the DME se-
lectivity was still over 58.7 %. These results suggested that Zr mod-
ification of the CZA catalyst could improve stability, which was con-
sistent with a previous report [49].
3.4.3. Characterization of spent catalysts
Coking and Cu sintering have been considered as major reasons for
catalyst deactivation. Previous studies pointed out the presence of
detrimental interactions, such as migration of metal ions between hy-
drogenation and dehydration catalysts, which could block acidic sites
[20,21,31,32]. To understand the deactivation mechanism of Zr mod-
ified CZA catalysts and HZSM-5 during CO2 conversion to DME, the
spent catalysts used in methanol synthesis (300 h) and DME synthesis
(100 h) were characterized. Before characterization, the bifunctional
catalyst used in DME synthesis was separated as spent CZZA and spent
HZSM-5 in order to clearly understand the deactivation of each catalyst.
As shown in Table 2, after 300 h of methanol synthesis, the specific
surface area of the spent CZZA was still similar to that of the fresh
catalyst; however, the Cu surface area and dispersion had significantly
decreased, while the Cu particle size had increased. For the spent CZZA
catalyst used in DME synthesis, the specific surface area had decreased
significantly after 100 h on stream; the Cu surface area and dispersion
had also significantly decreased and the Cu particle size had increased
for the CZZA catalyst used in DME synthesis. Compared to the spent
CZZA used in methanol synthesis, the spent CZZA catalyst used in DME
S. Ren, et al.
Fig. 11. Comparison of the catalyst stability of CZZA and CZA for DME synthesis: (a) CO2 conversion, (b) DME selectivity, and (c) DME yield.
synthesis showed a much lower Cu surface area and Cu dispersion, and
larger Cu particle size. These results indicated that the CZZA catalyst
tended to be less stable in DME synthesis, when mixed with HZSM-5. As
more water was generated in DME synthesis, this could have resulted in
hydrothermal sintering of Cu, thereby reducing the Cu surface area and
increasing Cu particle size, leading to the deactivation of CZZA. The
surface area of spent HZSM-5 also showed a significant decrease, as
compared to the fresh as-prepared powder catalyst (392 m2/g), which
could be one of major reasons for the deactivation of bifunctional cat-
alysts.
TGA analysis for these spent catalysts was also performed and the
results are shown in Fig. 12a. Due to Cu oxidation in the reduced fresh
CZZA, the TGA curve for fresh CZZA first increased until it reached
287 °C; after that, a slight decrease was observed, which could have
been due to the presence of a residual precursor during calcination
(360 °C). Compared to fresh CZZA, the spent CZZA (used in methanol
synthesis and DME synthesis) decreased with increasing temperature,
when the temperature was lower than 287 °C. One reason was that
some of the Cu in the spent catalyst had already been oxidized during
the reaction. Previous studies also found that the type of coke formed
depended on the oxidation temperature. Some small carbon molecules
formed unstable coke, which could be burned at a relatively low tem-
perature (less than 300 °C) [50,51]. Therefore, in this study the weight
loss before 287 °C could be attributed to these small carbon molecules.
Some more stable coke could be burned off at temperatures over 300 °C,
which was the primary reason for the catalyst deactivation. This coke
was hard to remove at relatively low regeneration temperatures. In this
Table 2
BET surface area and N2O chemisorption of spent CZZA and spent HZSM-5 catalysts.
Catalyst Reaction BET surface area (m2/g)
CZZA Fresh 109
CZZA Methanol synthesis, 300 h 106
CZZA DME synthesis, 100 h 76
HZSM-5 Fresh 392
HZSM-5 DME synthesis, 100 h 261
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Journal of CO₂ Utilization 36 (2020) 82–95
study, after 287 °C, the curves of the spent CZZA were almost parallel to
those of the fresh catalyst. The weight loss of spent CZZA (after 300 h of
methanol synthesis) between 287 °C and 900 °C in TGA analysis was
only about 0.05 %. For spent CZZA, after 100 h of reaction in DME
synthesis, the weight loss was about 0.15 % in the same temperature
range of TGA analysis, which was three times that for the spent CZZA
used in methanol synthesis. This result indicated that more coking
could be formed for the CZZA catalyst during DME synthesis. The
methoxy ions were intermediates in the formation of methanol and
could also be intermediates in the formation of coke precursors [52].
More methoxy ions were formed in DME synthesis than methanol
synthesis from CO2, which could result in more coke formation. How-
ever, the amounts of coking for both spent CZZA catalysts were very
small and, therefore, were unlikely to significantly impact performance,
as compared to the over 2 % coking on spent CZA catalysts reported in
the literature [50]. The amount of coking for spent HZSM-5 was about
1.87 % (Fig. 12b), which was much higher than that of the spent CZZA
catalyst. These results indicated that the coking on the HZSM-5 could be
responsible for the deactivation of the bifunctional catalyst.
After 300 h of methanol synthesis and 100 h of DME synthesis, the
active Cu sites in both spent CZZA catalysts were changed (Fig. 2a).
Peaks were observed 35.5° and 38.7° that corresponded to (002) and
(111) planes of tenorite, indicating that the copper active sites were
oxidized during long-term reaction. The comparison of XRD patterns
between fresh and spent HZSM-5 catalysts are shown on Fig. 2d. The
intensity of spent HZSM-5 reduced after 100 h of reaction for DME
synthesis, indicating that the crystallinity of HZSM-5 had decreased.
Cu surface area (N2O) (m2/g) Cu dispersion (%) Cu particle size (nm)
44.3 18.9 4.6
17.9 6.5 13.5
14.1 5.1 17.1
– – –
– – –
S. Ren, et al.
Fig. 12. TGA analysis of spent catalysts: (a) CZZA and (b) HZSM-5. Spent CZZA_100 h and spent HZSM-5 were catalysts after 100 h of reaction in DME synthesis at
240 °C and 2.76 MPa; spent CZZA_300 h was the catalyst after 300 h of reaction in methanol synthesis at 220 °C and 2.76 MPa.
Fig. 13. TEM, HRTEM, and EDS mapping images of spent CuO/ZnO/ZrO2/Al2O3 catalyst: (a) TEM, (b) HRTEM, and (c) EDS mapping.
The peaks of spent HZSM-5 also shifted, to a high degree, as compared
to those of fresh HZSM-5. This could be due to the unit cell dimension
change for the crystal induced by coking and the operating conditions
of high reaction temperature and pressure.
TEM and HRTEM images for spent catalysts showed an aggregation
of particles (Fig. 13a, 13b, and 13c). EDS elemental mapping also
showed that Cu on the surface had partially aggregated. These results
indicated that the Cu sintering occurred after a long-term reaction,
which led to the reduction of the Cu surface area and dispersion. This
observation was consistent with the results of N2O chemisorption for
Cu.
4. Conclusion
In this study, Zr modified CZA catalysts were synthesized by the co-
precipitation method. The effects of Al and Zr loading were investigated
in both methanol and DME synthesis from CO2 hydrogenation. The
optimized catalyst composition for methanol and DME synthesis was
4:2:1:0.5 for an atomic ratio of Cu/Zn/Zr/Al. The catalyst showed a
maximum methanol yield of 12.4 % at a reaction temperature of 220 °C
and a pressure of 2.76 MPa, and a maximum DME yield of 18.3 % at a
reaction temperature of 240 °C and pressure of 2.76 MPa, which were
much higher than those of the CZA catalyst. A long-term stability test
indicated that the CZZA catalyst had superior stability during methanol
synthesis and a significant improvement in stability for DME synthesis,
as compared to CZA. Characterization of the spent catalysts indicated
that the CZZA was less stable during DME synthesis than for methanol
synthesis. A significant decrease in the BET surface area and higher
coking in the HZSM-5 catalyst could be a primary reason for the de-
activation of the bifunctional catalyst for DME synthesis via CO2 hy-
drogenation.
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Journal of CO₂ Utilization 36 (2020) 82–95
Declaration of Competing Interest
The authors declare no competing financial interest.
Acknowledgements
This work was supported by the U.S. Department of Energy through
contract DE-AR0000806. We thank DOE ARPA-E Program Director, Dr.
Grigorii Soloveichik, for his assistance and support. Use of the
Advanced Photon Source (9-BM) by the Argonne National Laboratory,
was supported by the U.S. Department of Energy, Office of Basic Energy
Sciences, under Contract No. DE-AC02-06CH11357. We also thank Dr.
Xiaoqing He at the Electron Microscopy Core Facility, University of
Missouri-Columbia for TEM and EDS analysis.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jcou.2019.11.013.
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