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Cite This: Ind. Eng. Chem. Res. 2019, 58, 9030−9037 pubs.acs.org/IECR

Investigation on Deactivation of Cu/ZnO/Al2O3 Catalyst for CO2

Hydrogenation to Methanol
Binglian Liang,†,‡ Junguo Ma,† Xiong Su,† Chongya Yang,†,‡ Hongmin Duan,† Huanwen Zhou,§
Shaoliang Deng,§ Lin Li,† and Yanqiang Huang*,†,∥
†
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
‡
University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing 100049, China
§
Dalian Reak Science & Technology Co., Ltd., 327 Shunle Street, Lvshun Economic Development Zone, Dalian 116023, China
∥
Dalian National Laboratory for Clean Energy, Dalian 116023, China
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*
S Supporting Information

ABSTRACT: The catalytic performance of Cu/ZnO/Al2O3

(CuZnAl) catalyst for CO2 hydrogenation to methanol was
Downloaded via 188.68.0.160 on July 18, 2019 at 07:58:14 (UTC).

investigated over a period of 720 h time-on-stream, which

showed that the space time yield of CH3OH was decreased by
34.5% during the long-term testing. Different characterization
techniques, including X-ray diffraction (XRD), scanning
electron microscopy, high resolution transmission electron
microscopy, X-ray photoelectron spectroscopy (XPS), and N2O
adsorption experiments, were applied to study the deactivation
reasons. XRD and N2O adsorption experiments indicated that
there were no obvious changes in Cu particle size after the
CuZnAl catalyst was exposed to reaction atmosphere for 720 h,
while agglomeration took place on ZnO particles. XPS results
revealed that part of the metallic Cu was oxidized to Cu2+. The CuZnAl catalyst deactivation was proved to be due to the
comprehensive effect of Cu oxidation and ZnO species agglomeration during CO2 hydrogenation to methanol.

1. INTRODUCTION Catalysts possessing a good stability and longer lifetime have

The gradual increase in atmospheric CO2 concentration poses
a grand challenge to the global environment.1,2 There has been
an ongoing research upsurge in finding ways to stabilize
atmospheric CO2 levels by reducing CO2 production,
effectively transforming CO2, and/or effectively storing
CO2.3−8 CO2 utilization through catalytic conversion of CO2
to liquid fuels or other valuable chemicals has received
considerable attention from the viewpoint of environmental
protection and energy conservation issues.9−15 In particular,
the hydrogenation of CO2 to methanol was considered as one
of the most promising ways for CO2 utilization in a large
scale.16−24 As a kind of liquid fuel with high energy density,
methanol can act as an additive by being directly added into
gasoline and also as a key platform chemical for the
manufacture of several important chemicals such as form-
aldehyde, dimethyl ether, light olefins, acetic acid, and a wide
variety of other products.25 The synthesis of CH3OH by CO2
and H2 originating from renewable energy (wind, solar, or
biomass energy) can realize not only the utilization of CO2 but
also the storage of renewable energy into methanol.26 This
process fits in the vision of the powerful “liquid sunshine”
strategy which combines renewable energy with CO2 and
water to produce green liquid fuel.27
significant value for developing industrial processes. However,
the industrial application is always accompanied by a
deactivation behavior of the catalysts. Recognition and
exploration of the reasons for catalyst deactivation and then
developing catalysts with better stability appear to be extremely
important tasks. Previously, the reasons for deactivation on
CuZnAl catalyst in methanol synthesis from syngas have been
widely studied, which can be summarized as follows: (1)
catalyst poisoning resulted from the trace impurity in feed
gas;28,29 (2) Cu particle sintering was caused by the high
reaction temperature;30 and (3) carbon deposition.31 Recently,
benefiting from the development of modern characterization
techniques, there were some new observations for CuZnAl
catalyst deactivation in CO hydrogenation to methanol.
Lunkenbein et al. investigated the deactivation behavior of
CuZnAl catalyst for the synthesis of methanol over a time-on-
stream (TOS) period of 148 days. It was suggested that the
deactivation mainly resulted from the changes in the ZnO
moiety because ZnO acted as the most dynamic species, and
Received: March 20, 2019
Revised: April 19, 2019
Accepted: April 30, 2019
Published: April 30, 2019

© 2019 American Chemical Society 9030 DOI: 10.1021/acs.iecr.9b01546

Ind. Eng. Chem. Res. 2019, 58, 9030−9037
Industrial & Engineering Chemistry Research
only slight changes took place on the Cu nanoparticles.32 It is
noteworthy that there are differences for methanol synthesis
between CO hydrogenation and CO2 hydrogenation. During
CO2 hydrogenation to methanol, the in situ water generation
may accelerate the crystallization of Cu and ZnO components
in Cu/ZnO-based catalysts, which leads to the catalyst
deactivation.33 However, systematic understanding of the
details of the dynamic structural changes of the catalyst during
the deactivation period are still lacking, and the real
deactivation reasons need to be further investigated.
In this study, CuZnAl catalyst was evaluated for as long as
720 h in the catalytic hydrogenation of CO2 to methanol. The
change of catalyst structure during the operation was explored
in detail with the help of various characterization techniques,
and the reasons for catalyst deactivation were systematically
analyzed.
2. EXPERIMENTAL SECTION
2.1. Catalyst Evaluation. The CuZnAl catalyst was
provided by Dalian Reak Science and Technology Co., Ltd.
The activity evaluation of methanol synthesis from CO2
hydrogenation was carried out in a fixed-bed continuous-flow
reactor at high pressure. Typically, the catalyst (0.2 mL, 20−40
mesh) diluted with quartz sand (0.8 mL, 20−40 mesh) was
placed in a stainless steel tubular flow reactor (i.d. 10 mm).
Prior to reaction, the catalyst was reduced at 250 °C for 1 h in
pure hydrogen with a flow rate of 20 mL min−1 under
atmospheric pressure. After the reaction vessel was cooled, the
feed gas with a H2/CO2 ratio of 3/1 was introduced into the
reactor and adjusted to the setting pressure (typically 3 MPa),
followed by elevating the temperature to the desired value
(typically 200 °C) to initiate the reaction. The reaction
temperature was controlled by a thermocouple which was
located at the central position of the catalyst bed. The reaction
conditions were controlled as follows except for when specially
labeled: H2/CO2 = 3; pressure = 3 MPa; temperature = 200
°C; gas hourly space velocity (GHSV) = 9000 h−1. The
catalytic reaction data were collected after at least 10 h on
stream. The effluent gas products were kept at 120 °C to
prevent any condensation. The products were analyzed by two
online Agilent 7890B gas chromatograph instruments
equipped with a thermal conductivity detector (TCD) and a
flame ionization detector (FID), respectively. A carbon
molecular sieve (TDX-01) packed column was connected to
a TCD for H2, CO2, CO, and Ar analysis, while the FFAP
capillary column was connected to FID for CH4 and CH3OH
analysis. The selectivity to CH4 will not be mentioned in the
following study since it was below 1%. The activity of
methanol synthesis was evaluated by space time yield (STY) of
the methanol product, and the detailed calculation formulas
are detailed as follows.34
CO2 (in) − CO2 (out)
XCO2(%) = × 100%
CO2 (in)
CH3OH(out)
SCH3OH(%) = × 100%
CO2 (in) − CO2 (out)
STY(g CH OH/kgcat h)
3
FCO2(in) × XCO2 × SCH3OH × MCH3OH
= × 100%
Wcat
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where XCO2 is the CO2 conversion; SCH3OH is the CH3OH
selectivity; CO2(in) and CO2(out) are the amount of CO2 at
the inlet and outlet of the reactor, respectively; CH3OH(out)
is the amount of CH3OH at the outlet of the reactor; FCO2(in)
is the molar flow rate of CO2 at the inlet of the reactor;
MCH3OH is the molecular weight of methanol (32 g mol−1); and
Wcat is the used catalyst weight.
2.2. Catalyst Characterization. X-ray diffraction (XRD)
patterns were carried out on a PANalytical X’Pert-Pro powder
X-ray diffractometer, using Cu Kα monochromatized radiation
(λ = 0.1541 nm) with a scanning angle (2θ) of 10−80° at a
scan speed of 6° min−1. The voltage and current were operated
at 40 kV and 40 mA, respectively. The high resolution
transmission electron microscopy (HRTEM) and high angle
annular dark field scanning transmission electron microscopy
(HAADF-STEM) images were measured on a JEM-2000EX
(JEOL) microscope. Scanning electron microscopy (SEM)
images were recorded on a JSM-7800F microscope. X-ray
photoelectron spectroscopy (XPS) experiments were recorded
on an ESCALAB 250Xi spectrometer using a Al Kα (hυ =
1486.6 eV) X-ray source with a pass energy of 20 eV, and the
base pressure of the analysis chamber was less than 1 × 10−8
Pa. The binding energy was corrected for surface charging by
the C 1s peak at 284.6 eV as the charge calibration reference.
For XPS experiments, all samples were passivated in 1% O2/Ar
to avoid the severe oxidation in air. Chemisorption of the N2O
experiment was carried out by dissociative N2O adsorption at
50 °C following a procedure described by Van Der Grift et
al.,35,36 and the detailed experiment process is shown in the
Supporting Information.
3. RESULTS AND DISCUSSION
The STY of CH3OH for CuZnAl catalyst under certain
reaction conditions during CO2 hydrogenation to CH3OH
with a TOS of 720 h is displayed in Figure 1a. During the
initial period of 24 h, the STY of CH3OH almost remained
stable at 181.2 gCH3OH/kgcat·h, which was shown in the region
A of Figure 1a. This result is basically consistent with the
catalyst activity that has reacted for 10 h, shown in Figure 1b.
However, with the increase of TOS, catalyst deactivation took
place (region B). The STY of CH3OH showed a rapid
decrease of 25.1% from 181.2 to 135.8 gCH3OH/kgcat·h with the
reaction time prolonged to 350 h, indicating that the catalyst
deactivated severely at this stage. With the TOS further
prolonged to 720 h (region C), the STY of CH3OH altered
with only a slight decreasing tendency from 135.8 to 118.7
gCH3OH/kgcat·h. From the overall experiment result of 720 h
TOS, the STY of CH3OH experienced a significant decline by
34.5% from 181.2 to 118.7 gCH3OH/kgcat·h, indicating that a
deactivation occurred during the 720 h TOS. Furthermore, the
rate of deactivation in the first 350 h was obviously higher than
that of the latter period.
In order to study the deactivation reason for CuZnAl
catalyst on CO2 hydrogenation to methanol, the catalyst
structure at different reaction stages was systematically
analyzed. Figure 2 shows the XRD patterns of CuZnAl catalyst
at different stages (after H2 reduction; after reaction for 10 and
720 h). For the different stages of CuZnAl catalysts, there were
no diffraction peaks of Al2O3, which was possibly due to the
low content (less than 9%) of Al species and its high dispersion
in the catalyst. The peak at 26.5° was attributed to the (002)
DOI: 10.1021/acs.iecr.9b01546
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Industrial & Engineering Chemistry Research
Figure 1. STY of CH3OH over CuZnAl catalyst with the TOS of 720
h (a) and 10 h (b) in CO2 hydrogenation. Reaction conditions: H2/
CO2 = 3:1; temperature = 200 °C; pressure = 3.0 MPa; GHSV =
9000 h−1.
Figure 2. XRD patterns of CuZnAl catalyst at different stages: (a)
after H2 reduction, (b) after reaction for 10 h, and (c) after reaction
for 720 h.
plane of the graphite, which usually acts as the binder in the
forming process of the catalyst.37 Graphite will not be
considered in the following discussions since it is commonly
considered as an inert component with no contribution to
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catalytic activity.38 In the case of CuZnAl components, three
major diffraction peaks could be observed with 2θ values of
43.3°, 50.4°, and 74.1°, belonging to the (111), (200), and
(220) planes of metallic Cu (PDF no. 01-085-1326),
respectively.39 It is important to highlight that the peak
intensity of metallic Cu was markedly reduced after reaction,
which may reflect the change of Cu species. The average
particle size of Cu0 particles over the CuZnAl catalyst
calculated by the Scherrer equation are shown in Table 1. It
Table 1. Physicochemical Properties of CuZnAl Catalyst at
Different Stages
catalyst dCu (nm)a dZnO (nm)a N2O-SA (m2 g−1)
H2 reduction 11.7 7.2 45.4
10 h 7.9 7.7 54.2
720 h 7.8 10.7 16.7
a
The values of dCu and dZnO were calculated by the Scherrer equation.
has been reported that the aggregation of Cu particles is the
main reason for the deactivation on Cu-based catalyst in
methanol synthesis.30,31 A high temperature often led to the
increase in metal size because of sintering, Ostwald ripening, or
otherwise. However, for our case, it is interesting to note that
the average size of Cu particles was decreased from 11.7 to 7.9
nm after a reaction period of 10 h. This change was possibly
due to the reconstruction of Cu species during the initial
reaction stage. The size of the Cu particles was basically kept at
7.8 nm with the reaction prolonged from 10 to 720 h,
indicating that the dispersion of Cu was not changed
obviously. In other words, there was no obvious agglomeration
of Cu particles during the entire reaction process of CO2
hydrogenation. On this basis, it is proposed that the sintering
of Cu particles may not be the main deactivation reason for
CuZnAl catalyst for CO2 hydrogenation to methanol.
In addition, the 2θ values for other diffraction peaks at 31.9°,
34.6°, 36.4°, 47.7°, 56.8°, 63.1°, and 68.2° were attributed to
ZnO species.40,41 The peak with the highest intensity at 36.4°
was ascribed to the (101) plane of ZnO (PDF no. 01-079-
0205), the intensity of which was slightly increased after
reaction compared to the reduced sample. As calculated by the
Scherrer equation (Table 1), the particle size of ZnO was 7.2
nm for the reduced sample, which was slightly increased to 7.7
nm after a reaction time of 10 h and further grew up to 10.7
nm with the reaction time extending to 720 h. This
observation indicated that ZnO species was aggregated during
the reaction process, consistent with the previous report that
the generated water during CO2 hydrogenation may cause the
crystallization of ZnO.33 Therefore, the agglomeration of ZnO
species may be the main reason for the catalyst deactivation.
Recently, it was reported that chemisorption of the N2O
experiment is powerful for measuring the Cu surface area and
redox active sites on ZnO.32,42 Figure 3 shows the reduction
profiles of CuZnAl catalysts at different reaction stages after
N2O oxidation treatment at 50 °C. According to the calculated
hydrogen consumption in the second TPR of the CuZnAl
catalysts at different stages after N2O oxidation, the N2O-SA
values could be calculated and are summarized in Table 1. The
N2O-SA of H2-reduced CuZnAl catalyst was 45.4 m2 g−1, and
it was slightly increased to 54.2 m2 g−1 after reaction for 10 h,
which was likely to be due to the reconstruction of Cu species
consistent with the XRD results. More importantly, it should
be mentioned that the N2O-SA value was remarkably
DOI: 10.1021/acs.iecr.9b01546
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Figure 3. H2-TPR profiles of the CuZnAl at different stages after N2O

oxidation.

decreased to only 16.7 m2 g−1 with increasing the TOS to 720

h. Generally, the decrease of N2O-SA may be due to the
agglomeration of Cu particles for a long reaction time at high
temperatures. Nevertheless, the XRD results have revealed that
no significant changes happened on the Cu particles after
reaction for 10 and 720 h (Table 1). Therefore, other factors
may exist affecting the N2O-SA value. Since N2O-SA can
quantify the Cu surface area and redox active sites on ZnO,32,42
the decrease of N2O-SA was possibly due to the reduction in
the amount of partially reduced ZnO1−x sites. Combined with
the XRD results, the particle size of ZnO was enlarged over the
used catalyst after 720 h of TOS, being likely to lead to the
reduction of the amount of ZnO1−x sites and the decrease in
the N2O-SA value. Therefore, the decrease of N2O-SA further
proved the agglomeration of ZnO particles.
In order to explore the effect of morphology on catalytic
activity, SEM images of the CuZnAl catalyst at different
reaction stages were observed, as shown in Figure 4. The
sample after H2 reduction showed a granular morphology with
a particle size of approximately 40 nm. After reaction for 10
and 720 h, the catalyst nanoparticles maintained a granular
morphology, but the size decreased to approximately 25 nm,
which may be due to the reconstruction of the catalyst under
the atmosphere of CO2 and H2O which is consistent with the
changes in the Cu particle size obtained from the XRD result.
SEM images show that there were no obvious changes in
morphology during the reaction period from 10 to 720 h.
Figure 4. SEM images of the CuZnAl catalyst after: (a) H2 reduction,
Consequently, the morphology and the particle size of the (b) reaction for 10 h, and (c) reaction for 720 h.
catalyst may be spectators on the deactivation of the catalyst.
HAADF-STEM, TEM, and HRTEM characterizations
further illustrated the morphology of the CuZnAl catalyst at Al2O3 species (Figure 5g). The sample showed characteristic
different stages (Figure 5). The HAADF-STEM images spacings of 2.56 and 2.38 Å, representing the (104) and (110)
showed that Cu particles displayed a similar morphology as lattice planes of Al2O3.43 Although Al2O3 was not detected in
the bright spot region (Figure 5a−c). TEM images showed the XRD pattern, it could be observed in HRTEM images,
that the particles in the CuZnAl catalyst displayed good further indicating that Al2O3 possessed high dispersion. Figure
dispersion. The crystal size was in a range of 4 to 15 nm after 5g shows the expected spacing of 2.08 Å for the metallic Cu
H2-reduction treatment. Even after it was reacted for 10 and lattice planes of (111)44 and 2.47 Å for the ZnO planes of
720 h, the catalyst mantained its nanoparticle morphology and (101).45 The sample after reaction also kept a similar state in
the size showed a wide distribution which was similar to the the Cu lattice fringes, which suggested that the reaction
situation of the catalyst after H2 pretreatment. From the condition of 10 h had almost no influence on the Cu species,
HRTEM images, the H2-reduced catalyst consisted of consistent with the XRD result that only the intensity was
aggregated nanoparticles with the features of Cu, ZnO, and changed with no position shift. When the catalyst was
9033 DOI: 10.1021/acs.iecr.9b01546
Ind. Eng. Chem. Res. 2019, 58, 9030−9037
Industrial & Engineering Chemistry Research
Figure 5. HAADF-STEM, TEM, and HRTEM images of the CuZnAl catalyst after (a, d, g) H2 reduction, (b, e, h) reaction for 10 h, and (c, f, i)
reaction for 720 h.
evaluated for 720 h, the Cu and ZnO spacing were also
maintained, but the margin of Cu particles became indistinct,
which was possibly due to the oxidation of Cu species. Besides,
the overview image of the catalyst after 720 h TOS showed a
large region of crystalline ZnO particles, indicating the
agglomeration of ZnO during the reaction, which is consistent
with the results obtained from XRD patterns.
The chemical state of the Cu species and surface
composition of the CuZnAl catalyst at different stages were
investigated by XPS measurements (see Figure 6). The
calculated and deconvoluted results are shown in Table 2.
Figure 6a shows the energy region of the Cu 2p3/2 core level in
the fresh CuZnAl catalyst. The higher binding energy peak at
934.4 eV was assigned to Cu2+ in the CuO, indicating that the
Cu species mainly existed in the form of CuO for fresh
CuZnAl catalyst.46,47 The shakeup satellite peak at the high
binding energy of 941−945 eV was obviously observed, which
was an additional characteristic of Cu2+ compounds.48 For the
CuZnAl catalyst after H2 reduction, the binding energy of
932.5 and 934.5 eV were assigned to Cu0 and Cu2+,
respectively.48 Besides, the satellite peak further indicated the
existence of Cu2+ in the sample. Compared with the fresh
CuZnAl catalyst, the content of surface Cu2+ was reduced to a
great extent. There were no significant changes in the peak
position of Cu0 and Cu2+ in the catalyst after reaction for 10
and 720 h. However, the fraction of surface Cu2+ increased
from 17.4% to 22.6% after reaction for 10 h and further
significantly increased to 31.6% after 720 h TOS, indicating
that part of the surface Cu0 was oxidized to Cu2+ species during
the process of CO2 hydrogenation to methanol.
In addition, the surface Cu/Zn ratio was decreased from
1.42 to 0.76 when the fresh catalyst was reduced by H2, and it
9034
Article
was increased to 1.54 after reaction for 10 h, further remaining
at 1.43 with prolonging the reaction time to 720 h. The results
are in good agreement with the observation that the surface
Cu/Zn ratio would be decreased in the reductive atmosphere
and increased in the oxidative atmosphere.49 The changes in
the Cu/Zn ratio suggested that the catalyst treated in the CO2
hydrogenation condition was similar to that with the treatment
condition of an oxidizing atmosphere, further indicating that
the Cu species can be oxidized in a CO2 hydrogenation
atmosphere. CO2 hydrogenation to methanol reaction
contained a high concentration of in situ produced water.
Thus, the oxidation of Cu species was likely due to the
existence of CO2 and water.37,50 With prolonging the reaction
time, the oxidation degree of the Cu species was increased.
Consequently, the oxidation of the Cu species was possibly
another reason for the deactivation in CO2 hydrogenation to
methanol.
As determined from all the characterization results, the
structural changes of CuZnAl catalyst at different stages are
shown in Scheme 1. From the H2 reduction stage to the stage
after reaction for 10 h, the size of the Cu particles decreased
with a redispersion effect and ZnO species experienced a slight
agglomeration. Besides, the surface metallic Cu showed a
certain degree of oxidation. Further extending the reaction
time from 10 to 720 h, the size of Cu particles remained almost
unchanged while the size of ZnO particles was enlarged by
38.9% to 10.7 nm and further aggregated. It was also indicated
that the agglomeration of ZnO species has no significant effect
on the dispersion of Cu. Due to the lower Tammann
temperature of the Cu (405 °C), the agglomeration of Cu
species was mainly due to the high temperature. However, the
reaction temperature of CO2 hydrogenation is relatively low
DOI: 10.1021/acs.iecr.9b01546
Ind. Eng. Chem. Res. 2019, 58, 9030−9037
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Scheme 1. Schematic Representation of the Structure

Changes of CuZnAl Catalyst at Different Stages

4. CONCLUSIONS
The deactivation behavior of a CuZnAl catalyst in CO2
hydrogenation to methanol during 720 h TOS was systemati-
cally investigated, where the agglomeration of ZnO species and
the oxidation of metallic Cu were certified to be the main
reasons for catalyst deactivation. The particle size of Cu was
not changed obviously after 720 h TOS, which may be due to
the low reaction temperature during CO2 hydrogenation to
methanol, inferring that the Cu particle size can be recognized
as a spectator in deactivation. Therefore, it is crucial to stabilize
the structure of ZnO species and metallic Cu to improve the
catalyst lifetime for CO2 hydrogenation to methanol. It is
proposed that the regulation of the structural promoter and the
addition of hydrophobic promoter can help realize the
stabilization of ZnO species and the inhibition of metallic
Cu oxidation for further improving the stability of the catalyst.

■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b01546.
The detailed process of N2O chemisorption experiment
(PDF)
Figure 6. Cu 2p3/2 core-level spectra of (a) fresh CuZnAl, (b)
CuZnAl after H2 reduction, (c) CuZnAl after reaction for 10 h, and
(d) CuZnAl after reaction for 720 h.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: yqhuang@dicp.ac.cn. Fax: (+) 86-411-84685940.
Tel.: (+) 86-411-84379416.
(200 °C); therefore, the temperature-triggered aggregation of ORCID
Cu does not occur. Another interesting finding is that the Lin Li: 0000-0002-3036-0934
oxidation degree of metallic Cu was prominently increased. Yanqiang Huang: 0000-0002-7556-317X
Overall, the ZnO species showed agglomeration, and part of Notes
The authors declare no competing financial interest.

the surface metallic Cu was oxidized after a long period of
reaction, resulting in the loss of interfacial sites between ZnO
and Cu, which are considered as the active sites for methanol
synthesis from CO2 hydrogenation.20 Therefore, it can be
inferred that the oxidation of Cu species and the aggregation of
ZnO during reaction contribute to the deactivation of CuZnAl
catalyst.
■
ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program
of China (2016YFB0600902), the Dalian Science Foundation
for Distinguished Young Scholars (2016RJ04), the Dalian
National Laboratory for Clean Energy (DNL180401), and the
Youth Innovation Promotion Association CAS.

Table 2. Binding Energiesa of Core Electrons of Cu 2p3/2 and Surface Composition in the CuZnAl Catalyst at Different Stages
binding energy (eV)
catalyst satellite1 satellite2 Cu2+ Cu0 Cu2+ (%) Cu (%) Zn (%) Cu/Zn
fresh 944.3 941.9 934.4 − 100 58.7 41.3 1.42
H2 reduction 944.2 941.6 934.5 932.5 17.4 43.2 56.8 0.76
10 h 944.2 942.2 934.5 932.6 22.6 60.6 39.4 1.54
720 h 944.1 941.6 934.4 932.5 31.6 58.9 41.1 1.43

a
Unit in electronvolts (eV).

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9037 DOI: 10.1021/acs.iecr.9b01546

Ind. Eng. Chem. Res. 2019, 58, 9030−9037