Molecular Catalysis 537 (2023) 112887

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Preparation of CuZnZrAl catalysts by coprecipitation-ammonia method for

methanol steam reforming and the effect of promoters Y and Ce
Linfeng Li a, b, Jiayuan Chen a, b, Cuibing Zeng c, Quan Liu c, Hui Hu a, b, Qingming Huang a,
Xiaohui Chen a, b, *
a
National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002, China
b
School of Chemical Engineering, Fuzhou University, Fuzhou 350116, Fujian, China
c
Fujian Zhongyuan New Energy Co. Ltd., Fuzhou 350314, Fujian, China

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

Keywords: CuZnZrAl catalysts were synthesized by the co-precipitation and coprecipitation-ammonia methods and modified
Methanol steam reforming with Y and Ce promoters for the methanol steam reforming hydrogen production process. The physicochemical
Hydrogen properties of the catalysts were analyzed by XRD, BET, H2-TPR, and XPS methods. The methanol conversion, as
Coprecipitation-ammonia method
well as CO selectivity of MSR at different temperatures, were investigated, and its stability was probed using
CuZnZrAl catalysts
repeated start and stop test to simulate the onboard hydrogen production process. The results showed that the
methanol conversion of CuZnZrAl catalyst prepared by coprecipitation-ammonia method was 96.9% at a tem­
perature of 270◦ C, S/C molar ratio of 1.2, and WHSV of 2.6 h− 1, which was higher than that of 94.6% by the co-
precipitation method. In addition, the best catalytic performance was obtained for the catalyst with Ce promoter
addition using coprecipitation-ammonia method. The conversion was 100% at 270◦ C with a CO selectivity of
only 0.31%, and the conversion remained 98.7% after 20 reactions were repeated.

1. Introduction steam reforming(MSR) [7], partial oxidative reforming(POR) [8], and

autothermal reforming(ATR) [9] three systems.
Energy is the power source for human survival and development, and The MSR reaction process is shown below (Eq.(1)), usually accom­
today’s fossil fuels are increasingly exhausted [1]. Countries are panied by the water-gas shift (WGS, Eq.(2)) and methanol decomposi­
embracing the concept of carbon neutrality and setting related goals, so tion(MD, Eq.(3)) [10].
building a renewable energy system is a crucial issue facing humanity
CH3OH + H2O → CO2 + 3H2, ΔH= 49.5KJ mol− 1
(1)
today [2]. Hydrogen fuel cells are an efficient means of energy con­
version, but pure hydrogen is difficult to store and transport [3]. CO + H2O ⇆ CO2 + H2, ΔH= -41.17 KJ mol− 1
(2)
Therefore, proton exchange membrane fuel cells using low-carbon al­
cohols (methanol and ethanol) as raw materials have received extensive CH3OH → CO + 2H2, ΔH= 92.0 KJ mol− 1
(3)
attention [4].
The reaction formula of ATR is shown below (Eq.(4),‘p’ is not 0 or 1).
Methanol, the third-largest commercial chemical in the world after
For the first time, Huang et al. [11] found that the conversion of
ethylene and ammonia, is not only an important basic chemical raw
methanol over Cu-based catalysts increased significantly after adding
material but also can be used as a fuel. As the simplest saturated alcohol,
oxygen to the MSR system. Since then, the POR system has gradually
methanol, which is liquid at room temperature and pressure, is known as
been actively studied by scholars.
‘liquid hydrogen storage’. Compared with methane or liquefied petro­
leum gas, it is easier to store and transport and has a higher hydrogen-to- CH3OH+(1-P)H2O+1.5PO2→CO2+(3-P)H2, ΔH=49.5-241.8p KJ mol− 1
(4)
carbon ratio and lower activation temperature [5,6].
According to the different reforming oxidants, the methanol MSR is expected to be one of the hydrogen production technologies
reforming reaction for hydrogen production mainly includes methanol to become the hydrogen source of proton exchange membrane fuel cells
[12]. It is also one of the most anticipated hydrogen production

* Corresponding author.
E-mail address: chenxhfzu@fzu.edu.cn (X. Chen).

https://doi.org/10.1016/j.mcat.2022.112887
Received 10 October 2022; Received in revised form 17 December 2022; Accepted 17 December 2022
Available online 13 January 2023
2468-8231/© 2023 Elsevier B.V. All rights reserved.
L. Li et al.
methods. Its mild reaction conditions and high hydrogen content in the
product make it of great research value. Combined with microreactor
technology, it is expected to create an online mobile hydrogen produc­
tion technology suitable for automobiles.
There are two main types of catalysts currently used in MSR: copper-
based catalysts and precious-metal-based catalysts [13]. Copper-based
catalysts have good low-temperature reforming activity and can
generate hydrogen with high selectivity under suitable conditions,
which include CuO/SiO2 [14], CuO/ZnO/Al2O3 [15], CuO/ZnO/ZrO2
[16], CuO/ZnO/ZrO2/Al2O3 [17], etc. Therefore, it is widely used in
hydrogen production technology.
Different preparation methods and conditions significantly affect the
structure and properties of catalysts. The preparation methods of
copper-based catalysts mainly include the impregnation method, pre­
cipitation method, rapid decomposition method, complex combustion
method, etc., among which the co-precipitation method is the most
common [18]. The steps of the co-precipitation method are to mix the
nitrate solution with the alkaline solution. The main influencing factors
are the type of the precipitant, the concentration of the precursor and
the precipitant, the precipitation temperature, and the pH value [19].
In addition, the choice of different promoters also significantly im­
pacts the performance of the catalyst [20]. According to the research,
adding Zr, Ce, and La promoters to the CuO/A12O3 catalyst can promote
the dispersion of copper and effectively prevent the aggregation and
sintering of the copper lattice, which helps to improve the activity of the
catalyst and increase its stability [21].
After modification by adding Zr based on CuO/ZnO/Al2O3, the ac­
tivity and stability of the catalyst were improved [22]. On the one hand,
the addition of Zr is beneficial to the dispersion of Cu, avoids the for­
mation of CuAl2O4 spinel, increases the specific surface area of the
catalyst, and thus improves the activity of the catalyst. On the other
hand, the redox ability of the catalyst is improved, thereby enhancing
the stability of the catalyst [23].
The existing disadvantage of Cu-based catalysts is the insufficient
stability. Compared with noble metal catalysts, Cu is easier to sinter,
resulting in a lower specific surface area [24]. Especially in the scene of
on-board hydrogen production, repeated heating and cooling will
inevitably occur. Therefore, how to prepare Cu-based catalysts with high
stability is still the focus of current research.
In our experiments, the CuZnAlZr catalyst was prepared by the
coprecipitation-ammonia method, which was compared with the tradi­
tional co-precipitation method. Then, on the basis of CuZnZrAl, Y and Ce
promoters were added to prepare CuZnX(Y, Ce)ZrAl catalyst. The
methanol conversion and CO selectivity of MSR at different tempera­
tures were investigated. At the same time, different from previous
studies, we designed a new method for evaluating the stability of cata­
lysts. For the vehicle application of the catalyst, the evaluation method
of repeated start and stop was used to test the stability of the catalyst
under repeated heating and cooling.
2. Experimental
2.1. Catalyst preparation
2.1.1. Co-precipitation method
For the preparation of the CuZnAlZr catalyst by co-precipitation
route, 0.5 M solution of the Na2CO3 was added dropwise to 0.1 M so­
lution of a certain amount of metal nitrate (Cu(NO3)2⋅3H2O, Zn
(NO3)2⋅6H2O, ZrO(NO3)2⋅xH2O and Al(NO3)3⋅9H2O) with vigorous
stirring until pH=8. Stirring was continued for 2 h and then age for 12 h.
Afterwards, filtration and washed with 1 L of deionized water to elim­
inate the Na and nitrate residues, and dried at 110 ◦ C for 12 h. Finally,
calcined at 400 ◦ C for 2 h, pressed into tablets, and grind to 20-35 mesh.
Using the same method, CuZnYZrAl and CnZnCeZrAl catalysts were
prepared. The precursors of Y and Ce were Y(NO3)3⋅6H2O and (NH4)2Ce
(NO3)6, respectively.
2
Molecular Catalysis 537 (2023) 112887
2.1.2. Coprecipitation-ammonia method
0.5 M solution of the (NH4)2CO3 was added dropwise to 0.1 M so­
lution of a certain amount of metal nitrate with vigorous stirring until
pH=8. Then heated to 80 ◦ C to evaporate ammonia until pH=6(about 3
h). After that, removed the water bath and continue stirring for 2 h, then
aged, dried, calcined, and tableted, same as the co-precipitation method.
Meanwhile, as a comparison, CZZA catalyst was prepared using
(NH4)2CO3 as a precipitant using a co-precipitation method. The
composition of all prepared catalysts is listed in Table 1.
2.2. Catalytic activity test
A self-built fixed-bed reactor was used to evaluate the performance
of the catalyst in the MSR reaction at atmospheric pressure and 270 ◦ C.
The reactor was made of a quartz tube with an inner diameter of 6 mm
and an outer diameter of 8 mm. It was electrically heated by a vertical
tube furnace. 2 g of each catalyst (20-35 mesh) was loaded into the
reactor and secured with quartz wool at both ends of the reactor bed.
The catalyst was first reduced by flowing 10% H2/N2 over the catalyst at
270 ◦ C for 3 h before the reaction. The methanol-water mixed solution
with a molar ratio of 1 to 1.2 and a flow rate of 0.1 ml/min (WHSV
2.6h− 1) was first gasified and then entered into the fixed bed reactor.
The contents of CO, CO2, H2O, and methanol in the products were
analyzed online by gas chromatography (GC) and thermal conductivity
detector (TCD).
In addition, the catalyst was tested under repeated start and stop
conditions to test its stability. It was reacted at a temperature of 270◦ C,
S/C molar ratio of 1.2, and WHSV of 2.6 h− 1 for 2 h, then lowered to
room temperature and then heated to 270◦ C to continue the reaction
and this was repeated 20 times.
3. Results and discussion
3.1. XRD
The XRD pattern of the calcined catalyst is shown in Fig. 1. The figure
shows that all catalysts have CuO diffraction peaks at 2θ=38.8◦ , while
the diffraction peaks at 2θ=34.4◦ , 35.7◦ , 56.5◦ , etc. are all attributed to
the ZnO phase [25].
No diffraction peaks of ZrO2, Y2O3 and CeO2 were detected in the
samples with the promoter added, indicating that these particles are in
an amorphous state, which may inhibit the growth of CuO and ZnO
crystallites through buffering and sequestration. When (NH4)2CO3 is
used as a precipitant, a copper-ammonia complex (Cu(NH3)4)2+ is
formed. The complex is soluble in water, resulting in a large loss of Cu.
This may be the reason why CuO peak almost cannot be detected from
CZZA (Cop/(NH4)2CO3) in the red curve [16].
After adding CeO2, a diffraction peak belonging to CexZr1-xO2
appeared. It has been reported that CexZr1-xO2 has a good ability to store
and release oxygen and activate CO [26], which can reduce the CO
content in the product. Moreover, it can increase the rate of dehydro­
genation and dissociation of reactant methanol, thereby increasing the
reaction rate and the conversion rate of the reaction [27].
The CuO crystallite size of different catalyst samples is shown in the
Table 2. CuO crystallite size in the CZZA catalyst prepared using the
coprecipitation-ammonia method was 10.3 nm, significantly lower than
16.4 nm in the co-precipitation method. the addition of Y and Ce pro­
moters to the CZZA catalyst also showed different degrees of CuO
crystallite size reduction. The reduction was 13.7 nm with the addition
of Y, and 10.5 nm with the addition of Ce. The smallest CuO crystallite
size came from CZCZA (Co-Am) catalyst, which was 10.1 nm. The results
showed that the change of preparation method and the addition of
accelerant can reduce the crystallite size and improve the dispersion.
L. Li et al. Molecular Catalysis 537 (2023) 112887

Table 1
The names and composition of all prepared catalysts.
Catalysts Synthesis method Precipitating agent Metal composition (wt.%)

Cu Zn Y Ce Zr Al

CZZA(Cop/Na2CO3) Co-precipitation Na2CO3 30 50 0 0 15 5

CZZA(Cop/(NH4)2CO3) Co-precipitation (NH4)2CO3 30 50 0 0 15 5
CZZA(Co-Am) Coprecipitation-ammonia (NH4)2CO3 30 50 0 0 15 5
CZYZA(Cop) Co-precipitation Na2CO3 30 35 15 0 15 5
CZCZA(Cop) Co-precipitation Na2CO3 30 35 0 15 15 5
CZCZA(Co-Am) Coprecipitation-ammonia (NH4)2CO3 30 35 0 15 15 5

Fig. 1. XRD patterns of prepared catalysts. Fig. 2. H2-TPR patterns of prepared catalysts.

has an important influence on the catalyst activity [28]. As seen from the
Table 2 figure, only one reduction peak can be observed for all catalysts in the
CuO crystallite size, BET Specific area and Pore volume of prepared catalysts. temperature range of 50-600 ◦ C, which is the peak of Cu2+ being
Catalyst CuO crystallite size BET Specific area Pore volume (cm3 reduced to Cu0. It indicated that none of the oxides (ZnO, ZrO2, etc.) in
(nm) (m2 g− 1) g− 1) the catalysts except CuO were reduced. The reduction temperature of
CZZA(Cop) 16.4 73.55 0.31 the CZZA catalyst prepared by the co-precipitation method was 240.1◦ C,
CZZA(Co- 10.3 85.98 0.28 and the catalyst prepared using the coprecipitation-ammonia method
Am)
was 222.7◦ C, which was lower than that of the co-precipitation method.
CZYZA(Cop) 13.7 86.62 0.27
CZCZA(Cop) 10.5 91.58 0.21 And the reduction temperatures of the two catalysts after adding Y and
CZCZA(Co- 10.1 92.16 0.21 Ce promoters were 218.1◦ C and 213.5◦ C respectively, which were lower
Am) than the original CZZA catalyst. The lowest reduction temperature was
206.2◦ C from CZCZA(Co-Am) catalyst. The reduction peak shifted to­
ward the lower temperature, indicating that the CuO particles dispersed
3.2. BET
on the catalyst surface were more easily reduced. In other words, the
CuO particles in the CZCZA catalyst were smaller and better dispersed,
The BET specific surface areas and pore volume of the different
which was consistent with the XRD results.
catalysts are represented in Table 2. As can be seen from the table, the
specific surface area of the catalysts prepared using the coprecipitation-
ammonia method was 85.98 m2 g− 1, which was higher than that of those 3.4. XPS
prepared using the co-precipitation method. In addition, the specific
surface area of the catalysts increased to different degrees after adding The valence states of the surface species of CZCZA catalysts after
promoters. The specific surface area increased to 92.16 m2 g− 1 after the calcination, reduction, and reaction were analyzed using an X-ray
addition of Ce using coprecipitation-ammonia method. The specific diffraction photoelectron spectroscopy analyzer. Fig. 3a shows the 2p
surface area of the catalysts affects the dispersion of the active compo­ orbital electron binding energy spectrum of surface Cu. It can be seen
nents, which in turn affects the catalytic activity. This result indicated from the figure that the 2p3/2 and 2p1/2 electron binding energies of Cu
that the components in the CZCZA(Co-Am) catalyst were better after calcining were 933.9 eV and 953.6 eV, respectively [29], and a
dispersed, which was consistent with the XRD results. peak appeared at 936-946 eV, which were characteristic of Cu2+ [30].
After reduction, the shake-up peak disappeared, the 2p3/2 electron
3.3. H2-TPR binding energy of Cu decreased to 932.4 eV, and the peak was narrowed,
indicating that Cu2+ had been reduced to Cu+ or Cu0, which was
The H2-TPR spectra of different catalysts are shown in Fig. 2. Re­ consistent with the H2-TPR results. Moreover, the characteristic peak of
searchers have shown that the reduction performance of the catalysts 2p3/2 electron binding energy of Cu broadened after the reaction. This

3
L. Li et al.
Fig. 3. XPS (a) Cu 2p, (b) Ce 3d, (c)Zn 2p and (d)Zr 3d spectra of CZCZA catalysts.
indicated that some Cu0 and Cu+ have been oxidized.
Fig.3b shows the 3d orbital electron binding energy spectrum of Ce.
Two peaks at 882.7 eV and 902.6 eV were attributed to Ce3+, and two
peaks at 898.2 eV and 915.4 eV were attributed to Ce4+ [31], indicating
that Ce3+ and Ce4+ coexisted on the surface of the catalyst. During the
MSR reaction, oxygen vacancies are required for the decomposition of
H2O and the formation of H2, and surface oxygen species are required for
the dissociation and oxidation of methanol [32]. The coexistence of Ce3+
and Ce4+ can coordinate the redox process, enhance the oxygen storage
and release capacity of the catalyst, and provide oxygen vacancies and
surface oxygen. Therefore, it promotes the dissociation of methanol and
the decomposition of H2O and improves methanol conversion. In addi­
tion, CeO2 can oxidize the CO adsorbed on the catalyst surface to CO2,
thus reducing the CO selectivity.
Fig. 3c and Fig. 3d show the electron binding energy spectra of 2p
orbitals of Zn and 3d orbitals of Zr, respectively. From the figures, it can
be seen that the present states of Zn and Zr did not change before and
after the reduction and after the reaction, and existed on the catalyst
surface as ZnO and ZrO2, respectively.
4
Molecular Catalysis 537 (2023) 112887
3.5. SEM and EDX
Fig. 4 shows the SEM results of prepared catalysts. As shown in the
figure, all catalysts were spherical particles, and CZZA catalyst particles
had a more general agglomeration phenomenon with many particles
larger than 1 μm. After adding Y and Ce, the agglomeration phenomenon
was significantly weakened. Especially, after adding Ce, the catalyst
particles showed more regular small spheres with more homogeneous
size.
Energy dispersive X-ray (EDX) spectra and dot mapping micrographs
of promoted CZZA(Co-Am) and CZCZA catalysts are illustrated in Fig. 5.
The EDX results confirmed the coexistence of all metals on the catalyst
surface. Based on EDX dot-mapping micrographs of the catalysts, Cu, Zn,
Al, Zr and Ce were uniformly dispersed on the surface of the catalyst.
3.6. Catalytic activity
The performance of the catalysts at different temperatures at S/C
molar ratio of 1.2 and WHSV of 2.6 h− 1 is shown in Fig. 6. It can be seen
from the figure that the methanol conversion of all catalysts increased
with increasing temperature, because the MSR reaction is a heat-
absorbing reaction and increasing temperature is beneficial to the
 L. Li et al.
Fig. 4. SEM pictures of the (a) CZZA(Cop), (b) CZZA(Co-Am) (c) CZYZA(Cop) and (d) CZCZA(Cop) catalysts.
reaction. However, CO selectivity also increased with higher tempera­
ture, probably due to the fact that the WGS reaction is also heat
absorbing.
In the tested temperature range (190-290 ◦ C), the methanol con­
version of CZZA catalysts prepared by coprecipitation-ammonia method
was greater than that of the co-precipitation method in all cases.
Meanwhile, the addition of Y and Ce promoters resulted in significantly
higher methanol conversion and significantly lower CO selectivity.
Among them, the methanol conversion was 100% and CO selectivity was
0.31% at 270 ◦ C after the addition of Ce using coprecipitation-ammonia
mathod. It indicated that the addition of Ce improved the catalytic
performance of the MSR reaction.
3.7. Catalytic stability test
The stability of the catalyst in repeated start and stop tests are shown
in the Fig. 7. According to the results, the products on all catalysts were
mainly H2 and CO2, with a small amount of CO, and no other by-
products re generated.
It can be seen from the figure that the methanol conversion rate of
the CnZnZrAl catalyst prepared by the traditional co-precipitation
method was about 84.5% after the fifth reaction. Then the conversion
rate gradually decreased with the increase of the number of reactions.
After the 20th reaction, the conversion rate dropped to 82%.
Studies have shown that the main reason for the deactivation of Cu-
based catalysts is the thermal sintering of Cu crystallites [24]. A sudden
drop in conversion was observed for all catalysts after the first reaction.
It showed that the thermal sintering of Cu in the catalyst mainly occurs
during the first cooling or the second heating process. At this stage, the
Cu crystallites on the catalyst surface underwent severe sintering and
aggregation, resulting in a decrease in specific surface area and a
decrease in activity. We speculated that the reason for this phenomenon
may also include that during the test, we took the reaction tube out of
the reaction system after the reaction and exposed it to the air to cool
down naturally. At this time, part of the Cu0 in the catalyst was at a
higher temperature. It was oxidized to Cu2+ by oxygen in the air,
resulting in the loss of active centers. In the subsequent reaction process,
Realizar substituições, resfriamentos e manutenções após material esfriar em atmosfera redutora ou inerte
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Molecular Catalysis 537 (2023) 112887
the catalytic activity decreased slowly with the increase in the number of
reactions. In addition, in the third reaction, a slight recovery of meth­
anol conversion was observed, which may be due to the H2 in the re­
action product, which caused the catalyst to undergo a self-reduction
process.
The conversion rate of the catalyst prepared by the coprecipitation-
ammonia method was stable at about 85% in the subsequent reaction
test, which was higher than that of the traditional coprecipitation
method. This result may be attributed to the smaller catalyst crystallite
size and higher active phase dispersion of the catalyst prepared by the
coprecipitation-ammonia method under the same catalyst ratio, which
matched the characterization results.
In addition, after adding a second promoter such as Y and Ce based
on CZZA, the catalytic activity and stability were more obviously
improved. Among them, after adding Y, the methanol conversion rate
was 90% after 20 reactions. After adding Ce, the methanol conversion
rate in the first 10 reactions was always 100%, and the subsequent re­
actions began to decrease slowly. The conversion rate was 97% after 20
reactions, which was significantly higher than other catalysts. The best
stability came from the CZCZA(Co-Am) catalyst. The conversion rate
was 98.7% after 20 reactions. Therefore, after adding Ce, the activity
and stability of the catalyst were improved considerably. The reason for
this phenomenon may be that Y2O3, CeO2 and ZrO2 are in amorphous
state and they have good thermal stability of their own and do not sinter
easily. They are uniformly dispersed between CuO and ZnO particles
(EDX can prove this), which makes CuO better spaced apart from CuO
and ZnO, weakening the sintering of CuO.
The CO selectivity of different catalysts in the methanol steam
reforming to hydrogen reaction is shown in Fig. 8. Under the same re­
action conditions, the initial CO selectivity of the CZZA catalyst pre­
pared by the conventional co-precipitation method was 3.4%. With the
increase in reaction times, the CO selectivity gradually increased and
rose to about 7% after 20 reactions. The CO selectivity of the CZZA
catalyst prepared using the coprecipitation-ammonia method was about
6% after 20 reactions, which was slightly better than the former. In
addition, the CO selectivity of the catalysts had a more significant
decrease after the addition of Y and Ce promoters. The CO selectivity
L. Li et al.
Fig. 5. EDX analysis of the (a) CZZA(Co-Am) and (b) CZCZA(Cop) catalysts.
was maintained between 1-2% after 20 reactions with the addition of Y
promoter. In comparison, the CO selectivity was significantly reduced to
less than 1% with the addition of Ce promoter, which was significantly
lower than that of the CZZA catalyst without the addition of promoter.
The lowest CO selectivity came from the CZCZA (Co-Am) catalyst. CO
selectivity was 0.31% after 20 reactions. This indicated that the addition
of the accelerator Ce significantly reduced the CO selectivity.
It was reported that CeO2 has good oxygen storage and releases the
ability to oxidize the CO adsorbed on the surface to CO2, and the addi­
tion of ZrO2 can further enhance this ability [33]. In the study of Cao
et al. [34], it was confirmed that the good oxygen storage and release
ability helps to promote the water gas conversion reaction and inhibit its
inverse reaction, thus reducing the production of CO. This is consistent
with our experimental results. The significant reduction of CO selectivity
in CZCZA catalysts may be due to the combined effect of Ce and Zr to
improve the oxygen storage and release capacity of the catalysts.
6
Molecular Catalysis 537 (2023) 112887
4. Conclusion
In this study, CuZnZrAl catalysts were prepared by the co-
precipitation and coprecipitation-ammonia methods, respectively, and
modified with Y and Ce promoters based on CZZA catalyst for the MSR
process. The following conclusions were obtained.
The results showed when the reaction temperature increased, the
conversion of the MSR process was increased. Still, it also improved the
CO selectivity and increased the CO concentration in the tail gas.
It was demonstrated by XRD, BET, and H2-TPR that using the
coprecipitation-ammonia method can effectively improve the dispersion
of each component in the catalyst, resulting in smaller active component
crystallite size and larger catalyst specific surface area.
The addition of promoters Y and Ce improved the stability of the
CZZA catalyst. The catalyst was tested under repeated start and stop
conditions in this experiment. It was reacted at a temperature of 270◦ C,
L. Li et al. Molecular Catalysis 537 (2023) 112887

Fig. 6. Catalytic performance of prepared catalysts in MSR process.

Fig. 7. Methanol conversion vs. number of reaction repetitions at 270◦ C,

WHSV of 2.6 h− 1 and S/C molar ratio of 1.2. Fig. 8. CO selectivity vs. number of reaction repetitions at 270◦ C, WHSV of 2.6
h− 1 and S/C molar ratio of 1.2.

S/C molar ratio of 1.2, and WHSV of 2.6 h− 1 for 2 h, then lowered to
room temperature and then heated to 270◦ C to continue the reaction, Hu: Project administration, Writing – review & editing. Qingming
and this was repeated 20 times. After 20 reactions, the conversion of the Huang: Resources, Funding acquisition. Xiaohui Chen: Conceptuali­
catalyst with the addition of Y promoter increased from 82.9% to 91.6%, zation, Supervision.
and the conversion with the addition of Ce was 97.7% after 20 reactions.
The addition of Ce generated CexZr1-xO2, a composite oxide of Ce and
Zr, which had an important effect on the performance of the catalyst. Declaration of Competing Interest
The presence of CexZr1-xO2 might reduce the crystallite size of CuO, and
both CexZr1-xO2 and CeO2 had good oxygen storage and release ability, The authors declare that they have no known competing financial
which could oxidize CO in the reforming tail gas to CO2 and reduce the interests or personal relationships that could have appeared to influence
CO content in the product. The CZCZA(Co-Am) catalyst possessed the the work reported in this paper.
highest methanol conversion (100%) and the lowest CO selectivity
(0.31%) at a temperature of 270◦ C, S/C molar ratio of 1.2, and WHSV of Data availability
2.6 h− 1.
Data will be made available on request.
CRediT authorship contribution statement

Linfeng Li: Investigation, Writing – original draft, Visualization. Acknowledgements

Jiayuan Chen: Investigation, Visualization. Cuibing Zeng: Resources,
Funding acquisition. Quan Liu: Resources, Funding acquisition. Hui This work was supported by the National Natural Science Foundation
of China (Grant 21571036).

7
L. Li et al. Molecular Catalysis 537 (2023) 112887

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