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,
which leads to serious greenhouse effect and causes global
warming, glacier melting, extreme weather and other
environmental problems, affecting human social activities.
Therefore, the reduction and utilization of CO2 have always
been the focus of research[1,2]. As a potential carbon resource,
CO2 has its C element in the highest oxidation state, and can
be converted into bulk basic chemicals by H2 reduction, such
as methanol, methane, dimethyl ether, etc.[3,4]. Methanol is a
very potential product as a base organic chemical feedstock
and a liquid fuel additive[5,6]. The conversion of CO2 into
methanol to realize the utilization of CO2 has become a
relatively active research field[7].
At present, the catalyst systems used in CO2 hydrogenation
to methanol mainly include copper-based catalysts, precious
metal catalysts and other catalysts. Hu et al.[8] used MoS2 as a
catalyst to catalyze the hydrogenation of CO2 to methanol, and
CO2 dissociation was promoted by utilizing the sulfur vacancy
rich in MoS2 itself, so as to selectively synthesize methanol
through hydrogenation of CO2, thus the selectivity of
methanol was improved. Han et al.[9] loaded Pt on In2O3 as the
active site in the catalyst for the hydrogenation of CO 2 to
methanol. The results show that Pt can promote the
dissociation of H2 and significantly improve the methanol
selectivity of catalyst. Although these two types of catalysts
have good catalytic performance for CO2 hydrogenation to
methanol, they have high equipment requirements, large
production costs, and are more difficult to use for industrial
large-scale production. In contrast, copper-based catalysts
have good catalytic performance, low price and high
performance. In the 1960s, the British ICI company first
applied the Cu-ZnO-Al2O3 catalyst to industrial methanol
synthesis (syngas to methanol)[10], because of its excellent
hydrogenation capacity for C=O bonds[11], so the
Cu-ZnO-Al2O3 catalyst has also become the main research
object of CO2 hydrogenation to methanol. It was found that
the catalyst had low methanol selectivity and easy sintering
inactivation in the process of catalytic CO2 hydrogenation to
methanol[12,13]. Therefore, researchers added different
additives, such as Mg[14], Mn[15], Fe[16], changed carriers, such
as ZrO2[17], SiO2[18], and optimized preparation methods and
conditions[19] to improve the specific surface area, active site
dispersion and surface alkalinity of the catalyst, so as to
improve catalytic CO2 hydrogenation to methanol
performance.
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
methanol, and the amount of them directly affects the
conversion of CO2 and the formation of methanol. Wang et
al.[20] synthesized the Cu/SiO2 catalyst through ammonia
evaporation, and believed that Cu+ was the active component
that activated and converted CO2, and a higher Cu+/(Cu0+Cu+)
ratio could improve methanol selectivity. Dong et al. [21]
prepared Cu/Zn/Zr catalyst by co-precipitation-reduction
method, and controlled the Cu0/Cu+ ratio in the catalyst by
changing the NaBH4 content to improve the activity of the
catalyst. Shi et al.[22] have used formic acid assisted solid-state
synthesis Cu/ZnO catalyst for syngas to produce methanol.
The solid phase reaction of formic acid as a reducing agent
with metal nitrate can form metal-formic acid precursors
(H-COO-M), which decomposes CO during the calcination
process and reduces Cu2+ to Cu0. The Cu/ZnO catalyst
obtained has high activity and methanol selectivity.
In this experiment, the formic acid-assisted synthesis of
Cu-ZnO-Al2O3 catalyst was used to catalyze the
hydrogenation of CO2 to synthesize methanol, and the Cu2+ in
the Cu/Zn/Al precursor was reduced to Cu + and Cu0 during the
calcination process of the inert atmosphere by using formic
acid treatment, which changed the interaction between
elements in the catalyst and improved the catalytic
performance of the catalyst. This process eliminates the high
temperature H2 reduction of the traditional catalyst, reduces
the consumption of H2, and has certain economic benefits. At
the same time, the effects of different formic acid amount on
the structural properties, CO2 conversion and methanol
selectivity of the catalysts were investigated.
1 Experimental
1.1 Materials and instruments
Copper nitrate trihydrate (Cu(NO3)2·3H2O, A.R) was
purchased from Shanghai Macklin Biochemical Co., Ltd; zinc
nitrate hexahydrate (Zn(NO3)2·6H2O, A.R), aluminum nitrate
nonahydrate (Al(NO3)3·9H2O, A.R), sodium carbonate
(Na2CO3, A.R), and formic acid (HCOOH, 88%, A.R) were
purchased from Sinopharm Chemical Reagent Co., Ltd.
Fixed-bed Microreactor was purchased from Beijing
ZXblue evaluation unit technology development Co., Ltd.,
with reaction tube inner diameter of 8 mm and tube length of
506 mm; product analysis was executed on the GC-9560 gas
chromatography purchased from Shanghai Huaai
Chromatography analysis Co., Ltd.
1.2 Catalyst preparation
The Cu/Zn/Al catalyst precursor (mass ratio
Cu:ZnO:Al2O3=4:3:3) was prepared by co-precipitation
method: a mixture solution (1 mol/L) of Cu(NO3)2·3H2O,
Zn(NO3)2·6H2O and Al(NO3)3·9H2O, and the same
concentration solution (1 mol/L) of Na2CO3 precipitant, were
added dropwise to a certain amount of deionized water under
vigorous stirring. The temperature was kept at 70 ℃ and pH =
7 ± 0.2 during precipitation, and after the precipitation was
completed, the obtained seriflux was further stirred for 2 h.
The final suspension was aged at 30 ℃ for 12 h, filtered and
washed, and dried for 12 h at 80 ℃.
Formic acid treatment precursor: formic acid was separately
added to a certain mass of catalyst precursor and ground to a
homogeneous mixture (HCOOH to Cu molar ratio of 0, 0.4,
0.8, 1.2, 2.4). Then the sample was dried at 120 ℃ for 10 h,
calcined in N2 atmosphere at a heating rate of 2 ℃/min to 350 ℃
for 3 h, and passivated at room temperature for 4 h
(passivation gas O2/N2 (1%/99%). The obtained catalyst was
named xf-CZA (x is the molar ratio of HCOOH and Cu). After
all the catalyst samples were pressed, granulated and screened,
20–40 mesh catalysts were selected for activity evaluation and
characterization analysis.
1.3 Catalyst characterization
The crystal phase composition of the catalyst was recorded
by continuous scanning with Bruker’s D8 Advance X-ray
diffractometer (Germany) with Cu-Kα ray radiation source. It
was operated at 40 kV and 40 mA and scanned over the 2θ
range of 10°−85°.
The specific surface area and pore size of the catalyst were
analyzed by JW-BK122F specific surface and aperture
analyzer (Beijing, Jingwei Gaobo). Prior to the analysis, the
sample (0.2 g, 20–40 mesh) was degassed at 300 ℃ for 2 h in
flowing N2, and then measured by the static volume method at
–196 ℃, and the relative nitrogen pressure 10–8–10–1. The
specific surface area was calculated by BET method.
Temperature programmed reduction (TPR) was
characterized by automated programmed temperature
chemical adsorption instrument (AutoChem II.2920) from
Micromerics. The sample (0.05 g, 20–40 mesh) was placed in
a U-shaped quartz tube, heated to 150 ℃ (ramp rate:
10 ℃/min), purged in He stream for 1 h, then reduced to room
temperature, switched with 10% H2/Ar flow, and heated again
to 400 ℃ (10 ℃/min). Record the reduction curve online
simultaneously.
Temperature-programmed desorption (TPD) was carried
out using AutoChem II.2920 with a German Pfeiffer online
mass spectrometry analyzer (ThermoStar). The sample (0.05 g,
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
= 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
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128
Fig. 2 Thermal analysis curve of precursor samples
(a): TG; (b): DSC
Fig. 3 N2 adsorption-desorption isotherms and pore diameter
distribution of xf-CZA catalysts
(a): N2 adsorption-desorption isotherm; (b): Pore diameter distribution
As exhibited in Figure 1(b) that all catalysts have obvious
Cu characteristic diffraction peaks at 2θ = 43.3° after the
reaction, which may be due to the presence of a large amount
of H2 in the reaction gas itself, which can reduce the catalyst
at the reaction temperature. Weak characteristic diffraction
peaks of Cu2O and CuO appear at 2θ= 36.4° and 32.5°,
corresponding to the (111) crystal plane of Cu 2O and the (110)
crystal plane of CuO, respectively.
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
evaporation of water molecules physically adsorbed. Phase II
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
reaction with Cu2+ in the catalyst, resulting in an exothermic
peak occurred at around 210 ℃[22,28,29].
Figure 3 shows the adsorption-desorption isothermal curves
and pore sizes distribution of the catalysts before the reaction.
As shown in Figure 3(a), all catalysts exhibit typical class IV
isothermal absorption and desorption curves. At low relative
pressures, the curves are relatively stable because the process
is reversible monolayer adsorption[30], and at high relative
pressures (0.5–1.0), H3 type hysteresis ring appears,
indicating that the catalysts have slit hole with layered
structure and mesoporous structure.
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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
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128
Fig. 8 Relationship between the catalytic performance of xf-CZA
catalyst and reaction time
Reaction conditions: H2/CO2/Ar = 70/23/7, W/F = 10 g·h/mol, p = 3.0 MPa, t
= 200 ℃, TOS = 48 h
As can be seen from the table, the proportion of Cu 0 in the
catalysts gradually increases with the increase of formic acid
content, indicating that more reducing gas to reduce Cu
species to Cu0. For the catalysts after the reaction, based on
the value of Cu0/(Cu++Cu0) on the surface of the catalysts, it is
obvious that the surface of the catalysts after formic acid
treatment occupies a large proportion of Cu 0, which is
consistent with the XRD of the catalysts after the reaction.
Figure 7 shows the CO2-TPD desorption profiles of the
catalysts before the reaction, which are used to analyze the
surface basicity of the catalysts. The peak area in the figure
reflects the amount of basic site, and the peak position reflects
the intensity of basicity, which corresponds to the CO2
adsorption capacity of the catalyst and the formation of
different intermediates during the reaction process. It can be
seen from the figure that all catalysts have similar desorption
effects on CO2, and all have desorption peaks at 50–350 ℃, of
which the CO2 desorption peak of 50–150 ℃ is α peak,
representing the weak alkaline site, and the desorption peak of
150–300 ℃ is the β peak, representing the medium-strong
basic site. The intermediate of CO2 formation on the weak
basic site (α peak) is bicarbonate species, which is difficult to
hydrogenate and easy to desorption and re-convert to CO2.
The bidentate carbonates intermediate formed by CO2 at the
medium-strong basic site (β peak) is gradually hydrogenated
by dissociated H atoms into HCOO, H2COO, H2COOH
and H2CO, and finally the C=O bond of H2CO is activated
and reacts with the H atoms on the surface to form
methanol[40,41]. According to Figure 7, compared with 0f-CZA,
the number of weak basic sites on the catalyst after formic
acid treatment decreases, while the number of medium-strong
basic sites is increase, which is conducive to methanol
generation. The medium-strong basic sites on the surface of
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
surface[42,43]. After the formic acid treatment, the CuO of the
catalysts is gradually reduced to Cu 2O and Cu during the
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
The catalytic performance of catalysts is summarized in
Table 3. As can be seen from the table, formic acid treatment
has a significant effect on the activity of the catalyst. With the
increase of the molar ratio of HCOOH/Cu, the selectivity of
methanol is significantly improved, while the CO2 conversion
decreased slightly, and the methanol yield shows a trend of
increasing first and then decreasing. When HCOOH/Cu =0.8,
the conversion of CO2 is 6.7%, the selectivity of methanol
reaches 76.3%, and the yield of methanol is up to 5.1% which
is the highest value in the experiment. When the content of
formic acid is further increased, the activity of the catalyst
decreased. The results show that proper amount of formic acid
treatment could improve the structural properties and catalytic
activity of the catalysts.
Figure 8 shows the change of catalytic performance with
in-line reaction time. As can be seen from the figure, the
activity of all catalysts is basically stable after 20 h of reaction,
and the CO2 conversion and methanol selectivity show no
obvious downward trend after 48 h of reaction, indicating that
the catalysts have good stability.
3 Conclusions
A series of Cu-ZnO-Al2O3 catalysts were prepared by
formic acid treatment catalyst precursor for the CO2
hydrogenation to methanol. It is found that formic acid
treatment can change the interaction between the elements in
the catalysts, make the reduction temperature of Cu 2+ species
move to the low temperature direction and the number of
medium-strong basic sites of the catalyst increase, which is
conducive to the reduction of the catalysts and the formation
of methanol. Moreover, formic acid treatment can reduce Cu 2+
to the active centers Cu+ and Cu0, and the ratio of Cu+ to Cu0
in the catalysts can be regulated by changing the molar ratio of
HCOOH/Cu to further improve methanol selectivity and
catalyst activity. The highest CH3OH yield (5.1%) is obtained
when the molar ratio of HCOOH/Cu is 0.8 at 200 ℃ and 3.0
MPa.
Declaration of Competing Interest
 JIANG Xiu-yun et al. / Journal of Fuel Chemistry and Technology, 2023, 51(1): 120−128
The authors declare no conflict of interest.
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