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Deactivation feature of Cu/SiO2 catalyst in methanol decomposition

Article  in  International Journal of Hydrogen Energy · May 2019

DOI: 10.1016/j.ijhydene.2019.03.160

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Deactivation feature of Cu/SiO2 catalyst in

methanol decomposition

Shaojun Qing a,d, Xiaoning Hou a,d, Lindong Li a, Gang Feng c,

Xiang Wang c, Zhixian Gao a,*, Weibin Fan b
a
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China
b
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan,
030001, China
c
College of Chemistry, Nanchang University, Nanchang, 330031, China
d
University of Chinese Academy of Sciences, Beijing, 100049, China

article info abstract

Article history: The deactivation of Cu/SiO2 catalyst in methanol decomposition, which demonstrated a
Received 18 January 2019 unique characteristics with time on stream, was studied in this paper. Based on the vari-
Received in revised form ation of methanol conversion, three catalyst samples with different testing time were
12 March 2019 obtained, enabling dynamic investigation of the deactivation process in three stages. These
Accepted 16 March 2019 samples were fully characterized by BET, ICP-OES, XRD, TEM and H2-TPR techniques. The
Available online 19 May 2019 results indicated that copper sintering, coking and loss of silica all contributed to the
catalyst deactivation during the whole reaction process. It was found that the rate of both
Keywords: copper sintering and silica loss decreased with increasing the reaction time, while the
Cu/SiO2 coking rate decreased initially from 0 h to 200 h and then increased in the final stage from
Methanol decomposition 200 h to 296 h. The catalytic performance of regenerated samples showed that the deac-
Deactivation tivated catalyst with different testing time had nearly the same initial activity, but revealed
Copper sintering a big change with time on stream, especially for the 296 h tested sample. The findings
Coking obviously revealed that sintering of Cu slowed down while silica loss continued at
Loss of silica decreased rate after testing for 200 h, and the increased rate of coking might be due to
structural change of the catalyst. It was also found that the loss of silica had an accu-
mulating effect, i.e. drastic change of catalyst texture could be made due to gradual loss of
silica, which in turn led to fatal catalyst deactivation.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

reduction of environmental pollution become more and more

Introduction
In the twenty-first century, energy and environment as two
important issues have become important factors that deter-
mine the sustainable development of the economy of all
countries. In view of this, development of new energy and
important. The automobile industry is the second largest after
the petrochemical industry. The pollution caused by its tail
gas accounts for about 42% of the total air pollution. There-
fore, developing clean alternative fuels to achieve energy
conservation and environmental protection is of great signif-
icance. Methanol was thought to be a clean alternative fuel for

* Corresponding author.
E-mail address: gaozx@sxicc.ac.cn (Z. Gao).
https://doi.org/10.1016/j.ijhydene.2019.03.160
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
16668 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4
automobile, and it could be used in two ways. First, methanol
was directly used as engine fuel [1,2], or as the methanol fuel
cell vehicles [3]. Second, methanol was converted into
hydrogen using the technology of methanol steam reforming,
and then used for the hydrogen fuel cell vehicles [4].
For the direct use of the methanol as a fuel, the actual
result is not ideal, mainly due to the low calorific value of its
unit volume and high vaporization latent heat. Instead, using
the hydrogen-rich gases as a fuel, which are produced by
methanol decomposition with using the heat of automobile
exhaust onboard of a vehicle, the thermal efficiency of the
engine can be improved greatly. It has been reported that the
efficiency of hydrogen-rich gases is 60% higher than that of
gasoline, and 34% higher than that of methanol [1]. In view of
this, study of methanol decomposition on-board is very
important for the technology of directly using methanol as
engine fuel for vehicle.
The core technology of methanol decomposition (CH3-
OH ¼ 2H2þCO) is the catalyst, and there are two main catalyst
systems, namely noble metal catalyst [5] and non-noble metal
catalyst [6,7]. Among these systems, the copper-based cata-
lysts have been widely studied and used, as they are cheap
and demonstrate good catalytic activity as well as high
selectivity for methanol decomposition [8e11]. However, the
short lifespan of copper based catalysts is a vital problem and
remains to be a great challenge for commercial applications.
As summarized in several literature reviews [12e14], the
deactivation of copper-based catalysts are due to several fac-
tors such as poisoning, coking, thermal sintering of copper
metal and physical damaging of the support.
According to Spencer [12,13], coke deposition is not a major
problem in CO/H2 involved reactions due to the low activity of
copper for breaking CeO bonds or for forming CeC bonds.
However, for methanol involved reactions, coking does cause
to catalyst deactivation as shown by several other papers
[15,16]. Cheng reported that the deactivation of Cu/Cr in
methanol decomposition was caused by carbonaceous depo-
sit and the deactivated catalyst could be completely regener-
ated by oxidation with O2 [15]. Jackson et al. found that the
retained material associated solely with copper was adsorbed
methanol/methoxy, and was more akin to a carbonate under
oxidizing conditions [16].
Solı's et al. studied copper based catalysts (CuMn2O4 and
CuCr2O4 spinel or CuO/CeO2 and CuO/ZnO) for methanol
steam reforming, and claimed that the catalyst deactivation
could be attributed to the concomitant effect of coke deposi-
tion and sintering [17]. A similar conclusion was also made for
steam reforming of dimethyl ether by Faungnawakij et al. [18].
Zhai et al. pointed out that coking was one reason for catalyst
deactivation in methanol synthesis, but the main cause was
the sintering of Cu particles [19].
Recently, Cu/SiO2 was studied for the hydrogenation of
dimethyl oxalate (DMO) to ethylene glycol by two research
groups. Lin et al. suggested that sintering of copper mainly
attributed to the unstable active centers, which were
caused by methanol, the CO split from methanol and the
oxidation of alcohol [20]. Wen et al. revealed that the loss
of silica from the Cu/SiO2 in the forms of TMOS played an
important role in the aggregation of copper particle, which
led to poor stability [21]. These two papers concluded that
the catalyst deactivation was due to the sintering of copper
metal particles.
In our previous work [22], we have shown that a Cu/SiO2
catalyst, which was prepared by the simple impregnation
method using a starch modified SiO2 as the support, demon-
strated superior catalytic performance for methanol decom-
position. After initial rapid loss of catalytic activity, the
catalyst revealed stable activity up to 200 h. Repeated prepa-
ration demonstrated same trend of catalytic behavior with the
stable activity changed within 5%. Unexpectedly, a slower
than the initial activity decrease was observed after 200 h,
showing a unique feature of deactivation mode, i.e. fast ac-
tivity loss-stable-slow activity loss. Thus, a further investiga-
tion was initiated aiming at a better understanding of how the
catalyst decay was happened. To this end, the copper particles
size, amount of coking and loss of silica of used catalysts with
different testing times were characterized and the regenera-
tion performance of used catalysts was also evaluated. The
obtained results revealed that the deactivation feature of Cu/
SiO2 catalyst for methanol decomposition resulted from
combination effects of Cu sintering, coking and loss of silica,
which will provide new insight on dealing with the behavior of
Cu-based catalysts.
Material and methods
Preparation of the support
SiO2 Powder (an industrial product from Chongqing jianfeng
industrial group Co., LTD, contained Fe with mass fraction of
0.02%), starch and deionized water were mixed by a kneader,
and then the mixture was extruded as a strip. The obtained
strip was dried in air for 10 h at 100  C. For the above prepa-
ration, the mass fraction of SiO2 and starch was controlled to
be 85.0% and 15.0%, respectively.
Preparation of the catalyst
CuO/SiO2 catalyst with 18.4% Cu loading (wt of Cu per gram of
catalyst) was prepared by equivalent-volumetric impregna-
tion method. First, the support was impregnated with an
aqueous solution of Cu(NO3)2 for 24 h. Subsequently, the
mixture was dried at 120  C in air for 12 h. The dried sample
was calcined at 300  C in air for 2 h at the heating rate of 3  C/
min, and the obtained sample was named as CuO/SiO2. The
reduced form was performed in pure H2 at 300  C for 2 h and
denoted as Cu/SiO2-R. The tested samples were denoted as
Cu/SiO2-X, where “X” was the testing time in hours. The re-
generated samples of used catalysts were named as Cu/SiO2-
X-O, which were obtained by calcining the used catalysts at
300  C in air for 2 h.
Catalyst characterization
The specific surface area of the catalysts was characterized on
a nitrogen adsorption system (JW-BK122W). The samples were
pre-treated at 80  C for 1 h under vacuum, then the
adsorptionedesorption isotherm was determined at liquid
nitrogen temperature of 196  C.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4
The reducibility of fresh and regenerated catalysts was
investigated by hydrogen temperature programmed reduction
(H2-TPR) on a FINESORB-3010C multi-function adsorption in-
strument. For each run, a catalyst sample of 30 mg was loaded
into a quartz tube and pretreated at 300  C in Ar for 30 min,
then cooled to room temperature (RT). Subsequently, H2-TPR
was started from RT to 400  C at a heating rate of 10  C/min in
10% H2/Ar. A thermal conductivity detector (TCD) was used to
monitor the consumption of H2.
To identify the crystalline phases and estimate the relative
crystallinities, the samples were characterized by the X-ray
diffraction patterns (XRD) on a Rigaku MiniFlexIIdesktop X-ray
diffractometer. The analysis condition is 30 KV and 15 mA in a
2q range of 10e80 at a scanning rate of 5 /min with Cu Ka
radiation. With the XRD data, the Cu or CuO crystalline size
was calculated by Scherrer equation [D ¼ Kl/(b cos q), K ¼ 0.89,
l ¼ 0.154056 nm, b was the half height width of the diffraction
peak, q was the X-ray diffraction angle].
The high resolution transmission electron microscopy
(HRTEM) images of the catalysts were obtained by a JEM 2010
microscope operating at 200 kV. The samples were dispersed
in ethanol by ultrasonic for 30 min. One or two drops of the
obtained suspension liquid was deposited on copper grids
coated with amorphous carbon films.
The coke content was analyzed by using a vario EL CUBE
equipment. Under the procedure of oxidation at 1150  C in air
followed by reducing at 850  C, the carbon on the used cata-
lysts was finally converted into CO, which was detected by
TCD. The carbon content was calculated by the peak area with
the quantitative curve.
Copper content of fresh and regenerated catalysts was
analyzed by inductively coupled plasma optical emission
spectrometry (ICP-OES) on a Thermo iCAP6300. The obtained
data enable the calculation of silica content.
Catalyst testing
Catalyst testing was carried out in a 10 mL fixed-bed down-
flow reactor. Prior to catalytic reaction, the catalyst was
reduced in pure H2 at 300  C for 2 h. After that, methanol was
fed into the reactor with micro pump and the velocity was
3 mL/h. The products were analyzed by the gas chromato-
graph with thermal conductivity detectors. The reaction
conditions were 300  C, atmospheric pressure, weight hourly
space velocity (WHSV) of 1.56 h1.
Results
Catalytic performance
The catalytic and regeneration performance of Cu/SiO2 for
methanol decomposition was shown in Fig. 1. On the fresh Cu/
SiO2 catalyst, the methanol decomposition showed a complex
conversion change tendency within 296 h. The methanol
conversion decreased rapidly from 98.4% to 77.2% during the
first 20 h, then decreased very slowly up to 200 h, and, then
decreased fast from 71.6% to 45.6% in the third stage up to
296 h. Obviously, the decrease rate at the last phase was lower
than that of the first phase.
16669
Fig. 1 e Variation of methanol conversion with time on
stream on fresh and regenerated Cu/SiO2 catalysts
(t ¼ 300  C, WHSV ¼ 1.56 h¡1, p ¼ 0.01 MPa).
In order to investigate the cause for the unique deactiva-
tion feature, the catalysts after testing for 20 h and 296 h in
methanol decomposition were regenerated by calcining at
300  C in air for 2 h, then the obtained samples Cu/SiO2-20-O
and Cu/SiO2-296-O were evaluated under the same condi-
tions. The results (Fig. 1) showed that the initial methanol
conversion could be completely restored even after testing for
296 h. The variation of conversion with time on stream of
regenerated sample Cu/SiO2-20-O was similar to that of fresh
catalyst within a testing of 80 h, but the long term tested Cu/
SiO2-296-O showed drastic changes. These results indicated
that the deactivated catalyst could be regenerated with the
initial conversion being restored, but the conversion varied
with time on stream in a different manner for the long time
tested catalyst, which might be accounted for by the accu-
mulating effect of silica loss as will be detailed later.
Characterization of catalyst samples
The specific surface area and pore diameter of fresh and re-
generated catalysts were listed in Table 1. The data showed
that the specific surface area decreased while the average pore
diameter of regenerated samples increased with increasing
the reaction time, indicating the structure change of the cat-
alysts after testing for methanol decomposition.
To identify the phase composition of the catalyst samples,
XRD characterization was carried out, and the patterns for
samples in their reduced forms were shown in Fig. 2a. The
broad diffraction peak in the range of 2q ¼ 15e31 can be
assigned to SiO2 [23,24], and the diffraction peaks at around
2q ¼ 43.27 , 50.40 and 74.13 are ascribed to the (111), (200),
(220) planes of metallic Cu, respectively, which are similar to
those of cubic Cu (JCPDS no.04-0836) [25,26].
For tested samples, the Cu peak intensified with narrowed
peak width, suggesting increased Cu particle size. The copper
crystalline size, which was calculated from the XRD data of
the (111) peak broadening by Scherrer equation, was listed in
Table 1. The copper crystalline sizes in Cu/SiO2-R and Cu/SiO2-
296 were also obtained by TEM/HRTEM technique. As shown
16670 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4

Table 1 e Physicochemical properties and chemical compositions of fresh, tested and regenerated samples.
Sample dCua/nm Cb wt% S m2/g Dpore nm dCuOc/nm Cud wt% SiO2 wt%
e
Cu/SiO2-R 8.0 0.53
Cu/SiO2-20 8.9 1.24
Cu/SiO2-200 11.6 2.76
Cu/SiO2-296 11.8 5.42
SiO2-20 e 2.71 e e e e e
CuO/SiO2 104.2 34.5 8.6 17.2 78.5
Cu/SiO2-20-O 101.9 40.6 6.2 19.5 75.7
Cu/SiO2-200-O 83.2 50.5 6.4 32.6 59.2
Cu/SiO2-296-O 74.0 54.7 7.1 38.7 51.7
a
Cu crystalline size was calculated from the XRD data (Fig. 2a) of the (111) peak broadening by Scherrer equation.
b
Carbon deposit.
c
Crystalline size of CuO was calculated from the XRD data (Fig. 2b) of the (111) peak broadening.
d
Determined by ICP-OES, wt of Cu per gram of catalyst; e) the support was modified by starch, so the fresh catalyst contained a few of carbon.

in Fig. 3(b and e), the Cu (111) plane with a d-spacing of
0.208 nm was identified [22,27]. The copper particles in Cu/
SiO2-R were in the range of 4.13e9.83 nm with average particle
size of 7.66 nm (Fig. 3c). With Cu/SiO2-296, the copper ranged
from 7.2 nm to 19.2 nm, giving an average value of about
12.5 nm (Fig. 3f). The calculated crystalline size from XRD was
8.0 nm for Cu/SiO2-R and 11.8 nm for Cu/SiO2-296, respec-
tively. It could be found that there existed a small difference
between the two methods, but both revealed the same sin-
tering trend for the tested sample. Hence, the use of size data
derived from one method seemed reliable when the variation
trend was solely considered.
After oxidative treating of the tested catalysts with air at
300  C for 2 h, the regenerated samples were also charac-
terized by XRD (Fig. 2b). As expected, only diffraction peaks
attributed to CuO and SiO2 were observed. Surprisingly, all
the calculated crystalline size of CuO in Table 1 were found
to be smaller than that of fresh CuO/SiO2 (see discussion
section).
By comparing the SiO2 peak intensity in Fig. 2a and b,
big changes could be noticed with tested samples. This can
be attributed to structural change or loss of SiO2 during
methanol transformation and this results was consistent
with the change of specific surface area and pore diameter
(Table 1).
From the H2-TPR profiles (Fig. 4), it could be found that
the reduction peak area of Cu/SiO2-20-O, Cu/SiO2-200-O and
Cu/SiO2-296-O, normalized by catalysts amount, were larger
than that of CuO/SiO2, demonstrating increased copper
content in the tested catalysts, and thus the reduction peak
area increased with increasing the reaction time. These
results were further confirmed by the characterization of
ICP-OES. The data (Table 1) showed that the copper content
in the CuO/SiO2, Cu/SiO2-20-O, Cu/SiO2-200-O and Cu/SiO2-
296-O were 17.2%, 19.5%, 32.6% and 38.7%, respectively.
Combined with the change of specific surface area and pore
diameter and XRD results (Fig. 2), it can be concluded that
the change of copper content was caused by the loss of
SiO2.
Apart from sintering of Cu and loss of silica, coking also
took place during the reaction. Quantitative analysis of coke
deposition in the tested catalysts was also performed, and
the results were listed in Table 1. It was obvious that coke
formation was obvious and its amount increased gradually
with time on stream up to 296 h. Over the SiO2 support, the
methanol conversion decreased from about 20.0% to 3.2%
within 20 h, and the coke formation was three times larger
as compared with that of Cu/SiO2-R.

Discussion

Characteristics of Cu sintering

The sintering behavior of metals has been found to be affected

by many parameters, such as temperature, atmosphere,
support, metal-support interactions, metal loading, pore
structure, poisons and so on. According to Spencer [13], the
predominant sintering mechanism of metals is vacancy
diffusion, which suggests a relationship with cohesive energy.
Combined with the order of stability for metals
(Ag < Cu < Au < Pd < Fe < Ni < Co < Pt < Rh < Ru < Ir < Os < Re),
it is not hard to understand that the copper-based catalysts
Fig. 2 e a) XRD patterns of reduced catalyst and tested
are more liable to sintering than other commonly used
samples; b) XRD patterns of fresh and regenerated
metallic catalysts, such as Ni and Fe [13,28].
samples.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4
Fig. 3 e TEM/HRTEM images of Cu/SiO2-R (a, b) and Cu/SiO2-296 (d, e). and the particle size distribution of Cu/SiO2-R (c) and
Cu/SiO2-296 (f).
Among many factors, temperature seems to have the
largest impacts on metal sintering. Generally, the sintering
liability can be indicated by the Tamman temperature of a
metal. When the temperature reaches near this value, the
migration ability of a metal is enhanced [29]. Copper metal has
a pretty low Tamman temperature of 405  C [30], so the
Fig. 4 e TPR profiles of fresh catalyst and regenerated
samples.
16671
copper-based catalysts have to be used at relative low-
temperatures, usually less than 300  C.
Therefore, in this study, all the investigations were
performed at a relatively high temperature of 300  C in
order to study the sintering behavior of Cu/SiO2 catalyst
effectively. The size of copper metal can be obtained by
both XRD and TEM characterizations. The obtained average
copper particle size with TEM method (Fig. 3) showed about
6% differences as compared with that of calculated from
XRD data (Table 1). Hence, the XRD derived copper crys-
talline size data for all samples have been used to investi-
gate the sintering behavior of copper.
From the listed data (Table 1), the average sintering rate
for a certain testing period can be calculated as shown in
Fig. 5a. The results showed that the copper sintering rate
decreased with increasing the reaction time. Bartholomew
reported that the sintering rate of supported metals such as
Ni and Pt decreased with increasing reaction time [29].
Based on quantitative GPLE treatments of the sintering ki-
netics, the sintering rate would become very slow after a
certain time, which seems to be applicable for our Cu/SiO2
system. Hence, with the fresh Cu/SiO2-R catalyst, it can be
speculated that the sintering rate is fast during the initial
testing period. In fact, the observed sintering rate was
pretty big during the initial period and became very small
after 200 h (Fig. 5a).
16672 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4
Fig. 5 e a) Average sintering rate of copper particles, b) Average silica loss rate and c) average coking rate.
Loss of silica and coke formation
The content of SiO2 decreased drastically with prolonged
testing time (Table 1), suggesting the loss of silica was
happened during the whole reaction process. This phenome-
non of dynamic silica loss was also evidenced by character-
izations with H2-TPR, XRD and N2-BET. Since the loss of silica
was serious in methanol atmosphere, we denote this phe-
nomenon as the methanol catastrophe. As reported in a pre-
vious literature [21], methanol could react with silica to form
tetramethoxysilane, which led to the loss of silica. In view of
this result, the reason of the silica loss in this study may be
also caused by the same mechanism. Based on the content of
SiO2, the average of silica loss rate was calculated and the data
was shown in Fig. 5b. It could be found that although the loss
of silica existed during the whole reaction process, the
average of silica loss rate decreased with increasing the re-
action time.
For the coke formation, it is generally thought that coking
is not serious on copper catalysts as compared to nickel, iron
and cobalt catalysts and acidic catalysts [12]. However, our
results revealed carbon deposition was obvious on Cu/SiO2
catalyst for methanol decomposition as shown in Table 1.
This may be attributed to the support, which was an industrial
product containing few impurities. To verify this issue, the
starch modified SiO2 support was tested for methanol
decomposition under the same conditions for Cu/SiO2-R. The
results showed that the coke formation within 20 h was three
times larger as compared with that of fresh Cu/SiO2-R (Table
1). This result also indicated that coking was hindered by
introduction of Cu on the support.
Based on the amount of carbon deposit (Table 1), the
average coking rate was calculated and the data are shown in
Fig. 5c. The average coking rates at the three stages, from 0 to
20 h, 20e200 h and 200e296 h, were 0.355, 0.084 and 0.277
mg  h1g-cat.1, respectively (Fig. 5c). These data indicated
that the coking rate was fast during the initial and the final
period. These abnormal findings may be caused by the loss of
SiO2 support. After the initial fast coking stage, coke might
cover most of the active sites on the support surface, which
led to a decreased coking rate during the second stage. In the
third stage, the accumulated loss of silica caused structural
change of the support (Table 1), and thus induced accelerated
the coke formation.
Deactivation feature of Cu/SiO2 catalyst
As shown in Fig. 1, on the Cu/SiO2 catalyst, methanol
decomposition showed a complex conversion change ten-
dency that was characterized by one rapid decrease in the
first 20 h, very small decline between 20 h and 200 h, and
then accelerated decrease after 200 h. The two serious
deactivation stages, from 0 to 20 h and 200e296 h, had one
common feature of fast coking rate (Table 1 and Fig. 5c). In
view of this, coking was thought to be one of the main
reasons for the deactivation in these two stages. Except for
this, copper sintering was obvious during the stage from
0 to 20 h (Table 1 and Fig. 5a), while the accumulated loss
of silica was not big. In contrast, during the stage from
200 h to 296 h, the results completely reversed. Therefore, it
could be concluded that the catalyst deactivation was
mainly caused by the copper sintering and coking during
the stage from 0 h to 20 h, and by loss of silica and coking
from 200 h to 296 h, respectively. However, this conclusion
could not be applied to the stage from 20 h to 200 h, as the
copper sintering, coking and loss of silica all existed, but
the deactivation was not obvious. This phenomenon re-
flected that the active sites of Cu/SiO2 for methanol
decomposition might not be solely copper surface, which
deserved further in-depth investigation.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 6 6 7 e1 6 6 7 4
Catalyst regeneration
The tested catalysts can be regenerated by oxidation treat-
ment with air. With such a treatment, carbon deposits are
burned off while sintered copper is oxidized to CuO. XRD
characterization data revealed that the size of CuO particles
become even smaller than that of fresh catalyst (Table 1).
Previously, we have demonstrated CuO in Cu/SiO2 can be
reshaped by Reduction-Oxidation (RO) treatment, resulting in
an annular morphology consisting of even smaller nano CuO
particles [24]. The above results indicate that Reaction-
Oxidation process had similar effects as the RO treatment,
probably via a mechanism involving the Kirkendal effect
[31,32]. Consequently, the following reduction of the regen-
erated sample would give rise to a highly dispersed Cu cata-
lyst, which is confirmed by the completely restored initial
conversion rate as shown in Fig. 1. Although the sintered
copper can be regenerated, the catalytic performance with
time on stream varied depending on the former testing time.
When the catalyst was tested for 20 h, copper sintering and
coking was serious, but the loss of silica was not obvious, so
the catalyst could be completely regenerated. However, for
Cu/SiO2-296 catalyst, the loss of silica was serious, so the
texture of the catalyst changed drastically as compared to that
of fresh catalyst, thus the methanol conversion varied with
time on stream in a different manner. These results reflected
the huge impacts of SiO2 loss on the long term catalytic
performance.
Advices for preventing Cu/SiO2 catalyst deactivation
Based on the results of this study, it could be known that
the deactivation of Cu/SiO2 catalyst for methanol decom-
position was mainly caused by the copper sintering, coking
and loss of silica. Amongst the three causes, silica loss,
which showed an accumulative effect, was the most fatal
one that seriously affect the regeneration behavior. In our
view, the deactivation of Cu/SiO2 could be partially retarded
in several ways. First, the copper sintering could be effec-
tively delayed by decreasing the reaction temperature,
enhancing the interaction between the copper and support
by controlling preparing conditions [33] or modifying the
catalyst with second component. The study of using Ni to
modify the Cu/SiO2 for methanol decomposition has been
done in our lab, and the obtained results showed that the
catalytic stability was greatly enhanced. Second, the results
of this research showed that the coking was mainly caused
by the SiO2 support, which might be related to the impu-
rities in SiO2. In view of this, the impurities should be
analyzed and the effect of each impurity for the coking
should be researched. This data will provide more infor-
mation for the selectivity and control of SiO2 support.
Third, as shown in Ref. [21], the silica loss was 15% after
testing for 300 h (3.0 MPa, 473 K, H2/DMO ¼ 150, 0.3 h1),
while in our study (0.01 MPa, 573 K, 1.56 h1) the silica loss
is about 34% after testing for 296 h. Based on these data, it
could be known that the reaction conditions had great ef-
fect on the reaction of methanol with silica oxide. There-
fore, this reaction could be controlled by adjusting the
reaction conditions.
16673
Conclusions
In conclusion, using Cu/SiO2 to catalyze the methanol
decomposition, serious deactivation was happened both in
the initial stage from 0 to 20 h and the final stage from 200 to
296 h, demonstrating a dynamic feature of the deactivation
process. The catalyst deactivation in the initial stage was
mainly caused by the copper sintering and coking, while in the
final it was largely resulted from coking and loss of silica. The
deactivated catalyst with testing for 20 h in methanol
decomposition could be completely regenerated, but the
deactivated catalyst tested for 296 h could not be completely
regenerated due to substantial loss of silica. The concept of
methanol catastrophe was introduced to emphasize the
gradual loss of Si and the irreversible structural changes that
led to fatal deactivation after a certain time and to varied
catalytic behavior of the regenerated catalyst.
Acknowledgments
This work has been financially supported by the National
Natural Science Foundation of China (no. 21503254 and
21673270).
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