JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 51, Issue 1, January 2023

Online English edition of the Chinese language journal

Cite this article as: J Fuel Chem Technol, 2023, 51(1), 120−128 RESEARCH PAPER

Formic acid assisted synthesis of Cu-ZnO-Al2O3 catalyst

and its performance in CO2 hydrogenation to methanol
JIANG Xiu-yun, YANG Wen-bing, SONG Hao, MA Qing-xiang*, GAO Xin-hua,
LI Peng, ZHAO Tian-sheng*

State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering,
Ningxia University, Yinchuan 750021, China

Abstract: The Cu/Zn/Al precursor by coprecipitation was treated with formic acid and then calcined in N 2 to obtain Cu-ZnO-Al2O3
catalyst (CZA) for the CO2 hydrogenation to methanol. XRD, BET, TG-DSC, SEM, H2-TPR, N2O titration, XPS-AES and CO2-TPD
characterization techniques were used to analyze the phase composition, structural properties of the catalyst, the Cu specific surface
area, the dispersion and valence of the Cu species. The results showed that the formic acid treatment tuned the ratio of Cu + and Cu0,
increased the number of medium-strong base sites in the catalyst, and raised the selectivity of methanol. Under reaction conditions of
W/F(H2/CO2=70/23)=10 g∙h/mol, t=200 ℃ and p=3 MPa, using Cu-ZnO-Al2O3 treated under HCOOH/Cu/(molar ratio)=0.8, the CO2
conversion and the methanol selectivity were 6.7% and 76.3%, respectively.
Key words: formic acid treatment; Cu-ZnO-Al2O3; CO2 hydrogenation; methanol

The burning of fossil fuels releases a large amount of CO 2, dissociation of H2 and significantly improve the methanol
which leads to serious greenhouse effect and causes global selectivity of catalyst. Although these two types of catalysts
warming, glacier melting, extreme weather and other have good catalytic performance for CO2 hydrogenation to
environmental problems, affecting human social activities. methanol, they have high equipment requirements, large
Therefore, the reduction and utilization of CO2 have always production costs, and are more difficult to use for industrial
been the focus of research[1,2]. As a potential carbon resource, large-scale production. In contrast, copper-based catalysts
CO2 has its C element in the highest oxidation state, and can have good catalytic performance, low price and high
be converted into bulk basic chemicals by H2 reduction, such performance. In the 1960s, the British ICI company first
as methanol, methane, dimethyl ether, etc.[3,4]. Methanol is a applied the Cu-ZnO-Al2O3 catalyst to industrial methanol
very potential product as a base organic chemical feedstock synthesis (syngas to methanol)[10], because of its excellent
and a liquid fuel additive[5,6]. The conversion of CO2 into hydrogenation capacity for C=O bonds[11], so the
methanol to realize the utilization of CO2 has become a Cu-ZnO-Al2O3 catalyst has also become the main research
relatively active research field[7]. object of CO2 hydrogenation to methanol. It was found that
At present, the catalyst systems used in CO2 hydrogenation the catalyst had low methanol selectivity and easy sintering
to methanol mainly include copper-based catalysts, precious inactivation in the process of catalytic CO2 hydrogenation to
metal catalysts and other catalysts. Hu et al.[8] used MoS2 as a methanol[12,13]. Therefore, researchers added different
catalyst to catalyze the hydrogenation of CO2 to methanol, and additives, such as Mg[14], Mn[15], Fe[16], changed carriers, such
CO2 dissociation was promoted by utilizing the sulfur vacancy as ZrO2[17], SiO2[18], and optimized preparation methods and
rich in MoS2 itself, so as to selectively synthesize methanol conditions[19] to improve the specific surface area, active site
through hydrogenation of CO2, thus the selectivity of dispersion and surface alkalinity of the catalyst, so as to
methanol was improved. Han et al.[9] loaded Pt on In2O3 as the improve catalytic CO2 hydrogenation to methanol
active site in the catalyst for the hydrogenation of CO 2 to performance.
methanol. The results show that Pt can promote the In recent years, studies have shown that both Cu + and Cu0

Received: 02-Apr-2022; Revised: 20-May-2022.

Foundation items: Supported by National Natural Science Foundation of China (22169014, 21766027), Natural Science Foundation of Ningxia (2022AAC03040,
2021AAC03108) and Graduate Innovation Project of Ningxia University (GIP2020053).
*Corresponding author. Tel: 0951-2062393, E-mail: maqx@nxu.edu.cn, zhaots@nxu.edu.cn.
DOI: 10.1016/S1872-5813(22)60041-0
Copyright © 2023, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128

in Cu-based catalysts are active sites for CO2 hydrogenation to Cu:ZnO:Al2O3=4:3:3) was prepared by co-precipitation
methanol, and the amount of them directly affects the method: a mixture solution (1 mol/L) of Cu(NO3)2·3H2O,
conversion of CO2 and the formation of methanol. Wang et Zn(NO3)2·6H2O and Al(NO3)3·9H2O, and the same
al.[20] synthesized the Cu/SiO2 catalyst through ammonia concentration solution (1 mol/L) of Na2CO3 precipitant, were
evaporation, and believed that Cu+ was the active component added dropwise to a certain amount of deionized water under
that activated and converted CO2, and a higher Cu+/(Cu0+Cu+) vigorous stirring. The temperature was kept at 70 ℃ and pH =
ratio could improve methanol selectivity. Dong et al. [21] 7 ± 0.2 during precipitation, and after the precipitation was
prepared Cu/Zn/Zr catalyst by co-precipitation-reduction completed, the obtained seriflux was further stirred for 2 h.
method, and controlled the Cu0/Cu+ ratio in the catalyst by The final suspension was aged at 30 ℃ for 12 h, filtered and
changing the NaBH4 content to improve the activity of the washed, and dried for 12 h at 80 ℃.
catalyst. Shi et al.[22] have used formic acid assisted solid-state Formic acid treatment precursor: formic acid was separately
synthesis Cu/ZnO catalyst for syngas to produce methanol. added to a certain mass of catalyst precursor and ground to a
The solid phase reaction of formic acid as a reducing agent homogeneous mixture (HCOOH to Cu molar ratio of 0, 0.4,
with metal nitrate can form metal-formic acid precursors 0.8, 1.2, 2.4). Then the sample was dried at 120 ℃ for 10 h,
(H-COO-M), which decomposes CO during the calcination calcined in N2 atmosphere at a heating rate of 2 ℃/min to 350 ℃
process and reduces Cu2+ to Cu0. The Cu/ZnO catalyst for 3 h, and passivated at room temperature for 4 h
obtained has high activity and methanol selectivity. (passivation gas O2/N2 (1%/99%). The obtained catalyst was
In this experiment, the formic acid-assisted synthesis of named xf-CZA (x is the molar ratio of HCOOH and Cu). After
Cu-ZnO-Al2O3 catalyst was used to catalyze the all the catalyst samples were pressed, granulated and screened,
hydrogenation of CO2 to synthesize methanol, and the Cu2+ in 20–40 mesh catalysts were selected for activity evaluation and
the Cu/Zn/Al precursor was reduced to Cu + and Cu0 during the characterization analysis.
calcination process of the inert atmosphere by using formic
acid treatment, which changed the interaction between 1.3 Catalyst characterization
elements in the catalyst and improved the catalytic
performance of the catalyst. This process eliminates the high The crystal phase composition of the catalyst was recorded
temperature H2 reduction of the traditional catalyst, reduces by continuous scanning with Bruker’s D8 Advance X-ray
the consumption of H2, and has certain economic benefits. At diffractometer (Germany) with Cu-Kα ray radiation source. It
the same time, the effects of different formic acid amount on was operated at 40 kV and 40 mA and scanned over the 2θ
the structural properties, CO2 conversion and methanol range of 10°−85°.
selectivity of the catalysts were investigated. The specific surface area and pore size of the catalyst were
analyzed by JW-BK122F specific surface and aperture
1 Experimental analyzer (Beijing, Jingwei Gaobo). Prior to the analysis, the
sample (0.2 g, 20–40 mesh) was degassed at 300 ℃ for 2 h in
1.1 Materials and instruments flowing N2, and then measured by the static volume method at
–196 ℃, and the relative nitrogen pressure 10–8–10–1. The
Copper nitrate trihydrate (Cu(NO3)2·3H2O, A.R) was specific surface area was calculated by BET method.
purchased from Shanghai Macklin Biochemical Co., Ltd; zinc Temperature programmed reduction (TPR) was
nitrate hexahydrate (Zn(NO3)2·6H2O, A.R), aluminum nitrate characterized by automated programmed temperature
nonahydrate (Al(NO3)3·9H2O, A.R), sodium carbonate chemical adsorption instrument (AutoChem II.2920) from
(Na2CO3, A.R), and formic acid (HCOOH, 88%, A.R) were Micromerics. The sample (0.05 g, 20–40 mesh) was placed in
purchased from Sinopharm Chemical Reagent Co., Ltd. a U-shaped quartz tube, heated to 150 ℃ (ramp rate:
Fixed-bed Microreactor was purchased from Beijing 10 ℃/min), purged in He stream for 1 h, then reduced to room
ZXblue evaluation unit technology development Co., Ltd., temperature, switched with 10% H2/Ar flow, and heated again
with reaction tube inner diameter of 8 mm and tube length of to 400 ℃ (10 ℃/min). Record the reduction curve online
506 mm; product analysis was executed on the GC-9560 gas simultaneously.
chromatography purchased from Shanghai Huaai Temperature-programmed desorption (TPD) was carried
Chromatography analysis Co., Ltd. out using AutoChem II.2920 with a German Pfeiffer online
mass spectrometry analyzer (ThermoStar). The sample (0.05 g,
1.2 Catalyst preparation 20–40 mesh) was placed in a U-shaped quartz tube, heated to
200 ℃ (10 ℃/min) in a flow of He, and switched H2/CO2/Ar
The Cu/Zn/Al catalyst precursor (mass ratio = 70:23:7 flow to pretreat for 2 h. After the pretreatment, the
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128

temperature was reduced to 50 ℃, followed by purging with Methanol selectivity: sCH3 OH =1−sCO (8)
He flow for 1 h, and further the CO2 was switched for surface Methanol yield: wCH3OH =xCO2 ×sCH3OH (9)
reaction 1 h. Finally, the catalyst was heated to 400 ℃ where Ai represents the peak area of component i, μV∙s; fi
(10 ℃/min) in He flow, and the CO2 desorption curve was represents the relative correction factor of component i.
recorded synchronously by MS.
The exposed specific surface area (SCu) and dispersion of 2 Results and discussions
Cu (DCu) were also studied by the AutoChem II 2920
instrument. The sample (0.05 g, 20–40 mesh) was placed in a 2.1 Characterization of catalysts
U-shaped quartz tube and heated to 300 ℃ (10 ℃/min) in a
10% O2/He stream for 3 h, then reduced to room temperature. Figure 1 shows the XRD diffractograms of the catalysts
Then the sample was heated to 400 ℃ (10 ℃/min) in the 10% before and after the reaction. As observed in Figure 1(a), the
H2/Ar flow, after reducing for 1 h, the sample was cooled to precursor prepared by co-precipitation method is a
50 ℃ in Ar flow, switched over 10% N2O/Ar flow surface hydrotalcite-like structure Cu3Zn3Al2(OH)6CO3·4H2O
reaction, and then purged with He flow after the completion. (PDF#37-0629). Before the reaction, the 0f-CZA catalyst only
Finally, switched to 10% H2/Ar flow and heated up again to has a weak diffraction peak of CuO at 35.8°(PDF#45-0937),
400 ℃ (10 ℃/min). Record the change curve online indicating that the crystallinity of CuO is poor[23,24]. The
simultaneously. The reaction equation is as follows: characteristic diffraction peaks of Cu2O appear in the
CuO + H2 → Cu + H2O (1) 0.4f-CZA catalyst at 2θ of 36.4°, 42.3° and 61.4°,
2Cu + N2O → Cu2O + N2 (2) corresponding to the (111), (200), and (220) crystal planes of
Cu2O + H2 → 2Cu + H2O (3) Cu2O (PDF#05-0667), respectively. For the 0.8f-CZA catalyst,
the amount of consumed H2 in equation (1) was denoted as X, in addition to the enhanced characteristic diffraction peaks
and the consumption of H2 in equation (3) was denoted as Y. It intensity of Cu2O, the characteristic diffraction peaks of Cu
can be measured: appear at 2θ = 43.3°, 50.4° and 74.0°, corresponding to the
Cu dispersion is: D = (2Y/X) × 100% (4) (111), (200) and (220) crystal planes of Cu (PDF# 04-0836),
2
The surface area of Cu is: S = 1353 × Y/X (m /g) (5) respectively. For the 1.2f-CZA catalyst, all diffraction peaks
Thermal decomposition of the catalyst precursors was are further enhanced. When the HCOOH/Cu value is further
studied by using thermal analyzer (SETSYS16) of Setaram increased to 2.4, only the diffraction peaks of Cu can be
France. The catalyst was heated from room temperature to observed. These results indicate that with the increase of the
800 ℃ (10 ℃/min) in N2 flow and recorded the curves online. amount of formic acid, the reducing gas released
during calcination gradually increases, which leads to the
1.4 Catalytic test copper species in the catalyst continuous reduction, from Cu2+
to Cu+ and then continue to Cu0.
The activity evaluation of the catalyst for CO2
hydrogenation to methanol was carried out on the micro
fixed-bed reactor. 1 g catalyst diluted with 2 g quartz sand
(both in 20–40 mesh) was placed in a stainless steel tube
reactor. The N2 atmosphere was heated up to the reaction
temperature, and the catalyst activity evaluation was started by
switching the feed gas H2/CO2/Ar=70/23/7. Evaluation
conditions: W/F=10 g∙h/mol (W is catalyst mass, g; F is the
feedstock gas velocity, mol/h), t=200 ℃, p=3.0 MPa, in-line
reaction time TOS=48 h. The gas products were quantitative
analyzed online with a gas chromatograph, and the sampling
interval was 2 h. The material balance of the reactive activity
data of the catalyst was calculated based on carbon, using Ar
as the internal standard. The CO2 conversion, CH3OH
selectivity and yield were calculated by an internal
normalization method as showed below:
Ain in out out
CO2 /AAr −ACO2 /AAr Fig. 1 XRD patterns of xf-CZA catalysts
CO2 conversion: xCO2 =( )×100% (6)
Ain in
CO2 /AAr (a): Before reaction; (b): After reaction
fCO Aout
CO 1−xCO2
CO selectivity: sCO = × (7)
fCO Aout
CO2 xCO2
2
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Table 1 Texture property parameters of catalysts

Catalyst SBET/(m2·g−1) DCu/% a SCu/(cm2·g−1)a

0f-CZA 66.9 8.5 57.7

0.4f-CZA 59.3 6.7 45.5

0.8f-CZA 47.1 5.8 39.4
1.2f-CZA 38.5 4.9 33.6
2.4f-CZA 13.1 2.5 16.8
a: Calculated by N2O titration; DCu: Dispersion of Cu; SCu: Specific surface
area of Cu particle

No diffraction peaks of any form of Zn and Al oxide can be

found before and after the reaction, indicating that both of
them exist in an amorphous phase or highly dispersed[25].
Figure 2 shows the thermogravimetric analysis curves of
the dried precursors. It can be seen from Figure 2(a) that the
weight loss of the 0f-CZA catalyst precursor can be attributed
to the decomposition of each stage of the hydrotalcite-like
structure. Phase I mass loss occurs between 50–150 ℃ as the
Fig. 2 Thermal analysis curve of precursor samples evaporation of water molecules physically adsorbed. Phase II
(a): TG; (b): DSC mass loss occurs between 150–250 ℃ for the removal of
water molecules between layers of hydrotalcite-like. Phase III
mass loss occurs between 250–550 ℃, which is the
dehydration of hydroxyl groups in hydrotalcite-like and the
removal of interlayer carbonate ions. Phase IV mass loss
occurs between 550–650 ℃ as the decomposition of
copper-oxycarbonates, which is formed during the
decomposition of hydrotalcite-like structure[26,27]. The
catalysts for the treatment of formic acid, in addition to the
decomposition of hydrotalcite-like in each stage, the phase II
of the catalysts have the decomposition of the metal–formic
acid precursors into metal oxides, CO and other substances.
According to the DSC curves in Figure 2(b), all catalysts have
endothermic peaks at about 175 ℃ and 285 ℃. For the
0f-CZA catalyst precursor, this is classified as the
decomposition of hydrotalcite-like structure, while for the
formic acid-treated catalyst precursors, it contains the
decomposition of hydrotalcite structure and metal-formic acid
precursors, in which a large amount of CO and CO 2 are
released. And the reductive gas CO undergoes a violent redox
Fig. 3 N2 adsorption-desorption isotherms and pore diameter reaction with Cu2+ in the catalyst, resulting in an exothermic
distribution of xf-CZA catalysts peak occurred at around 210 ℃[22,28,29].
(a): N2 adsorption-desorption isotherm; (b): Pore diameter distribution Figure 3 shows the adsorption-desorption isothermal curves
and pore sizes distribution of the catalysts before the reaction.
As exhibited in Figure 1(b) that all catalysts have obvious As shown in Figure 3(a), all catalysts exhibit typical class IV
Cu characteristic diffraction peaks at 2θ = 43.3° after the isothermal absorption and desorption curves. At low relative
reaction, which may be due to the presence of a large amount pressures, the curves are relatively stable because the process
of H2 in the reaction gas itself, which can reduce the catalyst is reversible monolayer adsorption[30], and at high relative
at the reaction temperature. Weak characteristic diffraction pressures (0.5–1.0), H3 type hysteresis ring appears,
peaks of Cu2O and CuO appear at 2θ= 36.4° and 32.5°, indicating that the catalysts have slit hole with layered
corresponding to the (111) crystal plane of Cu 2O and the (110) structure and mesoporous structure.
crystal plane of CuO, respectively.
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Fig. 4 SEM images of xf-CZA catalysts

(a): 0f-CZA; (b): 0.4f-CZA; (c): 0.8f-CZA; (d): 1.2f-CZA; (e): 2.4f-CZA

two Gaussian peaks, of which the reduction peak around 252 ℃

is the reduction of surface CuO and the reduction peak of 307 ℃
is the reduction of bulk CuO[34]. For formic acid-treated
catalysts, combined with the previous XRD analysis, it can be
seen that Cu species in these catalysts are mixed in multiple
valence states and the reduction peaks appear at different
temperatures, which can be attributed to the reduction of Cu+ to
Cu0 at lower temperatures and Cu2+ to Cu0 at higher
temperatures[35]. It is observed that the reduction peaks at the
higher temperature gradually move towards the low temperature
Fig. 5 H2-TPR profiles of xf-CZA catalysts
with the increase of formic acid content, indicating that the
formic acid treatment can change the interaction between Cu
As can be seen from Figure 3(b), the pore sizes of all
species and Zn and Al oxides, and promote the reduction of
catalysts are almost distributed at 20–50 nm, indicating that
catalysts. The reduction peak area is decreases gradually, that is,
the catalysts have stacked mesoporous pores [31,32]. Table 1 lists
the hydrogen consumption of the catalysts are decreases
the parameters of the texture property parameters of catalysts.
gradually, indicating that part of the Cu species in the catalyst
As can be seen from the table, the specific surface area of
has been reduced to Cu0 during the calcination process, which is
catalysts gradually decreases with the value of HCOOH/Cu
consistent with the XRD characterization.
increase, and the specific surface area (SCu) and the dispersion
Figure 6 shows the XPS-AES spectra of the catalysts before
(DCu) of the metal Cu determined by the N2O reaction
and after the reaction, which are used to analyze the chemical
adsorption method also show a decreasing trend.
states of Cu species on the catalyst surface. According to
Figure 4 shows the SEM images of the catalysts before the
Figure 6(a), XPS peaks of 0f-CZA catalyst appear at the
reaction. As can be seen from the Figure, the catalysts show
binding energies of 934.5 and 954.4 eV, corresponding to Cu
irregular lamellar structure distribution. For 0.4f-CZA and
2p3/2 and Cu 2p1/2, respectively. Combine with the satellite
0.8f-CZA catalysts, the lamellar structure is basically
peak of Cu2+ around 940–945 and 960–963 eV, which is the
maintained, but agglomeration occurs with the increase of the
charge shock generated by the interaction of the valence
amount of formic acid to 2.4f-CZA catalyst, which leads to
orbital electrons of the Cu2+ ion with the spilled
the reduction of catalyst specific surface area, consistent with
photoelectrons, indicating that the presence of Cu2+ on the
the BET characterization results.
catalyst surface[36]. After the formic acid treatment, the Cu2+
Figure 5 shows the H2-TPR curves of the catalysts before the
peak intensity on the surface of the catalysts decreases
reaction. As the reduction temperatures of ZnO and Al2O3 are
significantly with the increase of formic acid, and gradually
higher than this temperature range[33], the reduction peaks in the
moves to the direction of low binding energy, indicating that
Figure 5 all belong to the reduction of Cu species. For the
Cu2+ is gradually reduced to Cu0/Cu+[37,38], which is consistent
0f-CZA catalyst, there is only one large reduction peak
with the XRD and H2-TRR characterization results of the
attributed to the reduction of CuO, which can be divided into
catalysts before the reaction.
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128

Fig. 6 XPS patterns of xf-CZA catalysts

(a): Cu 2p XPS of fresh xf-CZA; (b): Cu 2p XPS of spent xf-CZA; (c): Auger Cu LMM of fresh xf-CZA; (d): Auger Cu LMM of spent xf-CZA

Table 2 Copper component analysis on catalyst surface

Fresh catalyst Kinetic energy /eV Kinetic energy /eV
Cu0/(Cu+ + Cu0) Spent catalyst Cu0/(Cu+ + Cu0)
Cu+ Cu+ Cu0 Cu+ Cu0
0f-CZA 916.9 919.1 0.20 0f-CZA 916.9 918.9 0.41
0.4f-CZA 916.9 919.0 0.31 0.4f-CZA 916.6 918.3 0.59
0.8f-CZA 916.7 918.6 0.40 0.8f-CZA 916.6 918.5 0.63
1.2f-CZA 916.8 918.8 0.44 1.2f-CZA 916.6 918.7 0.67
2.4f-CZA 916.7 918.6 0.62 2.4f-CZA 916.9 918.9 0.65

In Figure 6(b), weak satellite peaks of Cu2+ on the catalysts

after the reaction, indicating that there is still a small amount
of Cu2+ on the catalysts surface after the reaction, which can
be attributed to that the presence of by-product water during
the reaction process may oxidize the copper on the surface of
the catalyst and lead to the presence of a small amount of Cu 2+.
In addition, a part of copper is oxidized due to the contact
between catalysts and air during the characterization process.
The XPS peaks around 952.6 eV and 932.7 eV corresponding
to Cu 2p3/2 and Cu 2p1/2 can be attributed to Cu0 or Cu+.
Fig. 7 CO2-TPD profiles of the xf-CZA catalysts
Considering the small differences in binding energies of
Cu0 and Cu+, the XPS spectra cannot be distinguished, so the
Table 3 Activity evaluation of xf-CZA catalyst
Cu LMM Auger electron spectra are determined for further
Catalyst xCO2 /% sCH3 OH /% sCO /% wCH3 OH /%
identification and quantification. As shown in Figure 6(c) and
0f-CZA 7.6 60.2 39.8 4.5
(d), a shoulder-width and asymmetrical Cu LMM XAES
0.4f-CZA 7.2 64.8 35.2 4.7
energy spectrum appears, which is fitted to two overlapping
0.8f-CZA 6.7 76.3 23.7 5.1
Cu LMM Auger kinetic energy peaks assigned to Cu + and
1.2f-CZA 6.1 77.9 22.1 4.7
Cu0[39]. Table 2 summarizes the peak positions of Cu + and Cu0
2.4f-CZA 2.8 80.2 19.8 2.2
on the surface of the catalysts and the ratio of Cu 0/(Cu++Cu0).
Reaction conditions: H2/CO2/Ar = 70/23/7, W/F = 10 g·h/mol, p = 3.0 MPa, t =
200 ℃, TOS = 48 h
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calcination process and the contact between Cu and ZnO

interface is increased, which may contribute to the formation
of more low-coordination oxygen ions O2–[44] on the surface of
the catalysts, and the change of electron effect between
elements promotes the interaction of metal-oxygen pairs. Thus,
the distribution of medium-strong basic sites on the catalysts
surface is increased[45].

2.2 Catalytic performance

Fig. 8 Relationship between the catalytic performance of xf-CZA The catalytic performance of catalysts is summarized in
catalyst and reaction time Table 3. As can be seen from the table, formic acid treatment
Reaction conditions: H2/CO2/Ar = 70/23/7, W/F = 10 g·h/mol, p = 3.0 MPa, t has a significant effect on the activity of the catalyst. With the
= 200 ℃, TOS = 48 h increase of the molar ratio of HCOOH/Cu, the selectivity of
methanol is significantly improved, while the CO2 conversion
As can be seen from the table, the proportion of Cu 0 in the decreased slightly, and the methanol yield shows a trend of
catalysts gradually increases with the increase of formic acid increasing first and then decreasing. When HCOOH/Cu =0.8,
content, indicating that more reducing gas to reduce Cu the conversion of CO2 is 6.7%, the selectivity of methanol
species to Cu0. For the catalysts after the reaction, based on reaches 76.3%, and the yield of methanol is up to 5.1% which
the value of Cu0/(Cu++Cu0) on the surface of the catalysts, it is is the highest value in the experiment. When the content of
obvious that the surface of the catalysts after formic acid formic acid is further increased, the activity of the catalyst
treatment occupies a large proportion of Cu 0, which is decreased. The results show that proper amount of formic acid
consistent with the XRD of the catalysts after the reaction. treatment could improve the structural properties and catalytic
Figure 7 shows the CO2-TPD desorption profiles of the activity of the catalysts.
catalysts before the reaction, which are used to analyze the Figure 8 shows the change of catalytic performance with
surface basicity of the catalysts. The peak area in the figure in-line reaction time. As can be seen from the figure, the
reflects the amount of basic site, and the peak position reflects activity of all catalysts is basically stable after 20 h of reaction,
the intensity of basicity, which corresponds to the CO2 and the CO2 conversion and methanol selectivity show no
adsorption capacity of the catalyst and the formation of obvious downward trend after 48 h of reaction, indicating that
different intermediates during the reaction process. It can be the catalysts have good stability.
seen from the figure that all catalysts have similar desorption
effects on CO2, and all have desorption peaks at 50–350 ℃, of 3 Conclusions
which the CO2 desorption peak of 50–150 ℃ is α peak,
representing the weak alkaline site, and the desorption peak of A series of Cu-ZnO-Al2O3 catalysts were prepared by
150–300 ℃ is the β peak, representing the medium-strong formic acid treatment catalyst precursor for the CO2
basic site. The intermediate of CO2 formation on the weak hydrogenation to methanol. It is found that formic acid
basic site (α peak) is bicarbonate species, which is difficult to treatment can change the interaction between the elements in
hydrogenate and easy to desorption and re-convert to CO2. the catalysts, make the reduction temperature of Cu 2+ species
The bidentate carbonates intermediate formed by CO2 at the move to the low temperature direction and the number of
medium-strong basic site (β peak) is gradually hydrogenated medium-strong basic sites of the catalyst increase, which is
by dissociated H atoms into HCOO, H2COO, H2COOH conducive to the reduction of the catalysts and the formation
and H2CO, and finally the C=O bond of H2CO is activated of methanol. Moreover, formic acid treatment can reduce Cu 2+
and reacts with the H atoms on the surface to form to the active centers Cu+ and Cu0, and the ratio of Cu+ to Cu0
methanol[40,41]. According to Figure 7, compared with 0f-CZA, in the catalysts can be regulated by changing the molar ratio of
the number of weak basic sites on the catalyst after formic HCOOH/Cu to further improve methanol selectivity and
acid treatment decreases, while the number of medium-strong catalyst activity. The highest CH3OH yield (5.1%) is obtained
basic sites is increase, which is conducive to methanol when the molar ratio of HCOOH/Cu is 0.8 at 200 ℃ and 3.0
generation. The medium-strong basic sites on the surface of MPa.
the catalyst are related to the metal-oxygen pairs (Cu-O, Zn-O,
Al-O, etc.) and the low-coordination oxygen ion O2– on the Declaration of Competing Interest
surface[42,43]. After the formic acid treatment, the CuO of the
catalysts is gradually reduced to Cu 2O and Cu during the
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128

The authors declare no conflict of interest. [14] Zhang F, Zhang Y L, Liu Y, Gasem K A M, Chen J Y, Chiang F
K, Wang Y G, Fan M H. Synthesis of Cu-ZnO-Al2O3/Mg
References catalysts on methanol production by different precipitation
methods. Mol Catal, 2017, 441: 190–198.
[1] Woodard D L, Davis S J, Randerson J T. Economic carbon cycle [15] Lin Min, Na Wei, Ye H C, Huo H H, Gao W G. Effect of
feedbacks may offset additional warming from natural additive on CuO-ZnO/SBA-15 catalytic performance of CO2
feedbacks. Proc Natl Acad Sci USA, 2019, 116(3): 759–764. hydrogenation to methanol. J Fuel Chem Technol, 2019, 47(10):
[2] Gao X H, Lu P F, Chen G H, Guo X Y, Liang J, Ma Q X, Zhang 1214–1224.
J L, Fan S B, Zhao T S. Performance of K-Fe3O4/Ni-AlMCM-41 [16] Cai W J, Chen Q, Wang F, Li Z C, Yu H, Zhang S Z, Cui L, Li C
tandem catalyst for CO2 hydrogenation to long-chain M, Comparison of the promoted CuZnMxOy (M: Ga, Fe)
hydrocarbons. J Fuel Chem Technol, 2021, 49(10): 504–512. catalysts for CO2 hydrogenation to methanol. Catal Lett, 2019,
[3] Ra E C, Kim K Y, Kim E H, Lee H, An K, Lee J S. Recycling 149(9): 2508–2518.
carbon dioxide through catalytic hydrogenation: Recent key [17] Arena F, Mezzatesta G, Zafarana G, Trunfio G, Frusteri F,
developments and perspectives. ACS Catal, 2020, 10(19): Spadaro L. How oxide carriers control the catalytic functionality
11318–11345. of the Cu-ZnO system in the hydrogenation of CO2 to methanol.
[4] Porosoff M D, Yan B H, Chen J G. Catalytic reduction of CO 2 Catal Today, 2013, 210: 39–46.
by H2 for synthesis of CO, methanol and hydrocarbons: [18] Chen K, Yu J, Liu B, Si C C, Ban H Y, Cai W J, Li C M, Li Z,
Challenges and opportunities. Energy Environ Sci, 2016, 9(1): Fujimoto K. Simple strategy synthesizing stable CuZnO/SiO2
62–73. methanol synthesis catalyst. J Catal, 2019, 372: 163–173.
[5] Sehested J. Industrial and scientific directions of methanol [19] Lo I C, Wu H W. Methanol formation from carbon dioxide
catalyst development. J Catal, 2019, 371: 368–375. hydrogenation using Cu-ZnO-Al2O3 catalyst. J Taiwan Inst
[6] Olah G A. Beyond oil and gas: The methanol economy. Angew Chem E, 2019, 98: 124–131.
Chem Int Ed, 2005, 44(18): 2636–2639. [20] Wang Z Q, Xu Z N, Peng S Y, Zhang M J, Lu G, Chen Q S,
[7] Jiang X, Nie X W, Guo X W, Song C S, Chen J G. Recent Chen Y M, Guo G C. High-performance and long-lived Cu/SiO2
advances in carbon dioxide hydrogenation to methanol via nanocatalyst for CO2 hydrogenation. ACS Catal, 2015, 5(7):
heterogeneous catalysis. Chem Rev, 2020, 120(15): 7984–8034. 4255–4259.
[8] Hu J T, Yu L, Deng J, Wang Y, Cheng K, Ma C, Zhang Q H, [21] Dong X S, Li F, Zhao N, Xiao F K, Wang J W, Tan Y S. CO 2
Wen W, Yu S S, Pan Y, Yang J Z, Ma H, Qi F, Wang Y J, Zheng hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts
Y P, Chen M S, Huang R, Zhang S H, Zhao Z C, Mao J, Meng prepared by precipitation-reduction method. Appl Catal B:
X Y, Ji Q Q, Hou G J, Han X W, Bao X H, Wang Y, Deng D H. Environ, 2016, 191: 8–17.
Sulfur vacancy-rich MoS2 as a catalyst for the hydrogenation of [22] Shi L, Shen W Z, Yang G H, FanX J, Fan X J, Jin Y Z, Zeng C Y,
CO2 to methanol. Nat Catal, 2021, 4(3): 242–250. Matsuda K J, Tsubaki N. Formic acid directly assisted
[9] Han Z, Tang C Z, Wang J J, Li L D, Li C. Atomically dispersed solid-state synthesis of metallic catalysts without further
Ptn+ species as highly active sites in Pt/In 2O3 catalysts for reduction: as-prepared Cu/ZnO catalysts for low-temperature
methanol synthesis from CO2 hydrogenation. J Catal, 2020, 394: methanol synthesis. J Catal, 2013, 302: 83–90.
236–244. [23] Witoon T, Permsirivanich T, Chareonpanich M.
[10] Li M J, Tsang E. Bimetallic catalysts for green methanol Chitosan-assisted combustion synthesis of CuO-ZnO
production via CO2 and renewable hydrogen: A mini-review and nanocomposites: effect of pH and chitosan concentration. Ceram
prospects. Catal Sci Technol, 2018, 8(14): 3450–3464. Int, 2013, 39(3): 3371–3375.
[11] Yang Y X, Evans J, Rodriguez J A, White M G, Liu P. [24] Li L, Mao D S, Yu J, Guo X M. Highly selective hydrogenation
Fundamental studies of methanol synthesis from CO2 of CO2 to methanol over CuO-ZnO-ZrO2 catalysts prepared by a
hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄). surfactant-assisted co-precipitation method. J Power Sources,
Phys Chem Chem Phys, 2010, 12(33): 9909–9917. 2015, 279: 394–404.
[12] Wu J G, Saito M, Takeuchi M, Watanabe T. The stability of [25] Liu Y, Gao Z H, Hao S H, Li S S, Huang W. Effect of pH value
Cu/ZnO-based catalysts in methanol synthesis from a CO2-rich on the catalytic performance of Cu-ZnO-Al2O3-LDHs catalysts
feed and from a CO-rich feed. Appl Catal A: Gen, 2001, in the synthesis of C2+ alcohol. Acta Pet Sin (Pet Proc Sect),
218(1/2): 235–240. 2018, 34(4): 716–722.
[13] Liang B L, Ma J G, Su X, Yang C Y, Duan H M, Zhou H W, [26] Gao P, Li F, Zhao N, Wang H, Wei W, Sun Y H. Preparation of
Deng S L, Li L, Huang Y Q. Investigation on deactivation of Cu-ZnO-Al2O3/(Zr)/(Y) catalyst form hydrotalcite-like
Cu-ZnO-Al2O3 catalyst for CO2 hydrogenation to methanol. Ind precursors and their catalytic performance for the hydrogenation
Eng Chem Res, 2019, 58(21): 9030–9037. of CO2 to methanol. Acta Phys-Chim Sin, 2014, 30(6):
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128

1155–1162. [37] Li J C, Wang L G, Hui X, Zhang C J, Cao Y, Xu S, He P, Li H Q.

[27] Xiao S, Gao P, Yang H Y, Xia L, Zhang J M, Chen Z W, Wang H. Effective hydrogenation of carbonates to produce methanol over
Preparation of layered Cu-ZnO-Al2O3 catalyst and its catalytic a ternary Cu-ZnO-Al2O3 catalyst. RSC Adv, 2020, 10(22):
performance for CO2 hydrogenation to methanol. J Shanghai 13083–13094.
Univ (Nat Sci Ed), 2016, 22(2): 218–230. [38] Yu J F, Yang M, Zhang J X, Zimina A, Pruessmann T, Zheng L,
[28] Shi L, Sun D, Wang Y X, Tan Y S, Li J, Yan S R, Fang R G, Grunwaldt J D, Sun J. Stabilizing Cu + in Cu/SiO2 catalysts with
Tsubaki N. Formic acid assisted synthesis of highly efficient a shattuckite-like structure boosts CO2 hydrogenation into
Cu/ZnO catalysts effect of HCOOH/Cu molar ratios. Catal Sci methanol. ACS Catal, 2020, 10(24): 14694–14706.
Technol, 2016, 6: 4777–4785. [39] Yang S Q, He J P, Zhang N, Sui X W, Zhang L, Yang Z X.
[29] Lu P, Chizema L G, Hondo E, Tong M L, Xing C, Lu C X, Mei Effect of rare-earth element modification on the performance of
Y F, Yang R Q. CO2 hydrogenation to methanol via In-situ Cu/ZnAl catalysts derived from hydrotalcite precursor in
reduced Cu/ZnO catalyst prepared by formic acid assisted methanol steam reforming. J Fuel Chem Technol, 2018, 46(2):
grinding. Chem Select, 2019, 4(19): 5667–5677. 179–188.
[30] Chen M Z, Wang L Y, Yu X H, Zhao Z. Preparation of MnO 2 [40] Dasireddy V D B C, Likozar B. The role of copper oxidation
under different hydrothermal conditions and its catalytic state in Cu-ZnO-Al2O3 catalysts in CO2 hydrogenation and
performance for soot combustion. Ind Catal, 2018, 26(10): methanol productivity. Renewable Energy, 2019, 140: 452–460.
56–63. [41] Gao P, Li F, Zhao N, Xiao F K, Wei W, Zhong L S, Sun Y H.
[31] Zhang Y F, Yang W B, Ma Q X, Gao X H, Zhang J L, Li P, Zhao Influence of modifier (Mn, La, Ce, Zr and Y) on the
T S, Li R. Effect of carbon nitride addition on Cu-ZnO-Al2O3 performance of Cu-ZnO-Al2O3 catalysts via hydrotalcite-like
catalytic performance for CO2 hydrogenation to methanol. Acta precursors for CO2 hydrogenation to methanol. Appl Catal A:
Pet Sin (Pet Proc Sect), 2021, 37(3): 508–517. Gen, 2013, 468: 442–452.
[32] Liu R W, Qin Z Z, Ji H B, Su T M. Synthesis of dimethyl ether [42] Printtto F, Ghiotti G, Durand R, Tichit D. Investigation of acid
from CO2 and H2 using a Cu-Fe-Zr/HZSM-5 catalyst system. base properties of catalysts obtained from layered double
Ind Eng Chem Res, 2013, 52(47): 16648–16655. hydroxides. J Phys Chem B, 2000, 104(47): 11117–11126.
[33] Clausen B S, Steffensen G, Fabius B, Villadsen J, Feidenhans R, [43] Leon M, Diaz E, Bennici S, Vega A, Auroux A. Adsorption of
Topsoe H. In situ cell for combined XRD and on-line catalysis CO2 on hydrotalcite-derived mixed oxides: Sorption
tests: Studies of Cu-based water gas shift and methanol catalysts. mechanisms and consequences for adsorption irreversibility. Ind
J Catal, 1991, 132(2): 524–535. Eng Chem Res, 2010, 49(8): 3663–3671.
[34] Li S Z, Guo L M, Ishihara T. Hydrogenation of CO2 to methanol [44] Yang H Y, Gao P, Zhang C, Zhong L S, Li X P, Wang S, Wang H,
over Cu/AlCeO2 catalyst. Catal Today, 2020, 339: 352–361. Wei W, Sun Y H. Core-shell structured Cu@m-SiO2 and
[35] Hou X, Xu C, Liu Y. Improved methanol synthesis from CO 2 Cu/ZnO@m-SiO2 catalysts for methanol synthesis from CO2
hydrogenation over CuZnAlZr catalysts with precursor hydrogenation. Catal Commun, 2016, 84: 56–60.
pre-activation by formaldehyde. J Catal, 2019, 379: 147–153. [45] Witoon T, Numpilai T, Phongamwong T, Donphai W, Boonyuen
[36] Zhang L, Lei J T, Tian Y, Hu X, Bai J, Liu D, Yang Y, Pan L W. C, Warakulwit C, Chareonpanich M, Limtrakul J. Enhanced
Effect of precursor and precipitant concentration on the activity, selectivity and stability of a CuO-ZnO-ZrO2 catalyst by
performance of CuO/ZnO/CeO2-ZrO2 catalyst for methanol adding graphene oxide for CO2 hydrogenation to methanol.
steam reforming. J Fuel Chem Technol, 2015, 43(11): Chem Eng J, 2018, 334: 1781–1791.
1366–1374.