Article

Effect of Oxide Coating on Performance of

Copper-Zinc Oxide-Based Catalyst for Methanol
Synthesis via Hydrogenation of Carbon Dioxide
Tetsuo Umegaki 1, *, Yoshiyuki Kojima 1, : and Kohji Omata 2, :
Received: 3 September 2015 ; Accepted: 9 November 2015 ; Published: 16 November 2015
Academic Editor: Alfons Baiker
1 Department of Materials & Applied Chemistry, College of Science & Engineering, Nihon University,
1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308, Japan; kojima.yoshiyuki@nihon-u.ac.jp
2 Department of Materials Science, Interdisciplinary Faculty of Science and Engineering,
Shimane University, 1060, Nishikawatsu-Chou, Matsue, Shimane 690-8504, Japan;
omata@riko.shimane-u.ac.jp
* Correspondence: umegaki.tetsuo@nihon-u.ac.jp; Tel.: +81-3-3259-0810; Fax: +81-3-3293-7572
: These authors contributed equally to this work.

Abstract: The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for
methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial
catalyst was coated with various oxides by a sol-gel method. The influence of the
types of promoters used in the sol-gel reaction was investigated. Temperature-programmed
reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper
species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than
that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the
catalysts prepared using L(+)-arginine. These observations indicated that the copper species were
weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared
using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine.
Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity
at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity
at low temperatures. At high temperature the conversion over the silica-coated catalyst does
not significantly change with reaction temperature, while the conversion over the zirconia-coated
catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the
durability depends on hydrophilicity of the oxides.

Keywords: oxide coating; copper-zinc oxide based catalyst; methanol synthesis; hydrogenation of
carbon dioxide; hydrophilicity of oxides

1. Introduction
Special attention has been paid to the sequestration of carbon dioxide by conversion to liquid
compounds as a means of mitigating the environmental impact of this gas. In this context, the
catalytic conversion of carbon dioxide to methanol via hydrogenation using heterogeneous catalysts
has attracted enormous interest for its central role in carbon dioxide utilization [1–3]. Methanol can
be used not only as the starting feedstock for many other useful chemicals but also as an alternative
source in the production of liquid fuels. On an industrial scale, the production of methanol is
generally achieved using Cu/ZnO/Al2 O3 catalysts from synthesis gas, which is obtained via the
steam reforming of natural gas and mainly contains carbon monoxide and hydrogen along with
a small amount of carbon dioxide [4–8]. When there is no appreciable production of dimethyl ether,

Materials 2015, 8, 7738–7744; doi:10.3390/ma8115414 www.mdpi.com/journal/materials

Materials 2015, 8, 7738–7744

the reactions that this gas mixture undergoes are: the synthesis of methanol from carbon dioxide
(Reaction (1)), the reverse water gas shift reaction, RWGS (Reaction (2)), and the “dry” methanol
synthesis reaction from carbon monoxide (Reaction (3)) [9]:

CO2 ` 3H2 ØCH3 OH ` H2 O ∆H298 K “ ´49.58 kJ¨ mol´1 (1)

CO2 ` H2 ØH2 O ` CO ∆H298 K “ 41.12 kJ¨ mol´1 (2)

Materials 2015, 8, page–page 

(Reaction  (1)),  the  reverse  water  gas  shift  reaction,  RWGS  (Reaction  (2)),  and 
CO ` 2H2 ØCH3 OH ∆H298 K “ ´90.55 kJ¨ mol´the  1 “dry”  methanol 
(3)
synthesis reaction from carbon monoxide (Reaction (3)) [9]: 
The stability of the catalyticCO2 + 3Hactivity of the copper-based
2↔CH3OH + H2O 
catalysts
ΔH298 K = −49.58 kJ·mol −1  is affected by (1)  the feed
containing a CO2 /CO molar ratio more than unity. Furthermore, water is produced during methanol
CO2 + H2↔H2O + CO  ΔH298 K = 41.12 kJ·mol−1  (2) 
synthesis via carbon dioxide hydrogenation (Reaction (1)) and RWGS (Reaction (2)) accelerates the
CO + 2H2↔CH3OH  ΔH298 K = −90.55 kJ·mol−1  (3) 
oxidation and deactivation of active sites, which is the influence of the water by-product produced
The  stability 
via the hydrogenation ofof  the  catalytic 
carbon dioxide activity  of  the 
[10–14]. Thecopper‐based 
number ofcatalysts  is  affected 
active sites by  the 
decreases feed  inactive
when
containing a CO2/CO molar ratio more than unity. Furthermore, water is produced during methanol 
copper compounds, such as copper oxide, sintered active copper species, and copper with strongly
synthesis via carbon dioxide hydrogenation (Reaction (1)) and RWGS (Reaction (2)) accelerates the 
adsorbedoxidation and deactivation of active sites, which is the influence of the water by‐product produced 
water molecules, are formed. Generally, mixing or coating the catalyst with inorganic
materialsvia the hydrogenation of carbon dioxide [10–14]. The number of active sites decreases when inactive 
such as silica is a promising technique to reduce the negative effect of water vapor [15–17].
Thecopper compounds, such as copper oxide, sintered active copper species, and copper with strongly 
present study investigated the effect of oxide coating on catalytic activity and durability of
adsorbed 
a commercial water  molecules, 
copper-zinc are  formed. 
oxide-based Generally, 
catalyst for themixing  or  coating  the 
hydrogenation of catalyst 
carbon with  inorganic 
dioxide to methanol.
materials such as silica is a promising technique to reduce the negative effect of water vapor [15–17]. 
The influence of preparation conditions such as the type of promoter (ammonia or L(+)-arginine)
The present study investigated the effect of oxide coating on catalytic activity and durability of 
used for a commercial copper‐zinc oxide‐based catalyst for the hydrogenation of carbon dioxide to methanol. 
the sol-gel reaction for the coating oxide on the commercial catalyst was also investigated.
The  influence  of  preparation  conditions  such  as  the  type  of  promoter  (ammonia  or  L(+)‐arginine) 
2. Results and Discussion
used for the sol‐gel reaction for the coating oxide on the commercial catalyst was also investigated. 

The2. Results and Discussion 
morphologies of oxide-coated F04M catalysts prepared using various promoters were
examined using TEM. The pristine F04M catalyst consists of finely dispersed particles with the
The  morphologies  of  oxide‐coated  F04M  catalysts  prepared  using  various  promoters  were 
diameters of approximately 20 nm (Figure 1a), while the oxide-coated catalysts prepared with
examined  using  TEM.  The  pristine  F04M  catalyst  consists  of  finely  dispersed  particles  with  the 
ammoniadiameters 
consist of 
ofapproximately 
the particles20 ofnm  F04M catalyst
(Figure  loosely
1a),  while  covered with
the  oxide‐coated  silica
catalysts  with low
prepared  with contrast
(Figure 1b,d,f).
ammonia  These results
consist  indicateof 
of  the  particles  that thecatalyst 
F04M  F04M loosely 
catalyst weakly
covered  bonded
with  withlow 
silica  with  thecontrast 
oxide  coating
(Figure 1b,d,f). These results indicate that the F04M catalyst weakly bonded with the oxide coating 
with ammonia. However, the oxide-coated catalyst prepared with L(+)-arginine consisted of the
with  ammonia.  However,  the  oxide‐coated  catalyst  prepared  with  L(+)‐arginine  consisted  of  the 
accumulated fine particles of pristine F04M catalyst covered with a silica (Figure 1c,e,g). These results
accumulated fine particles of pristine F04M catalyst covered with a silica (Figure 1c,e,g). These results 
indicate that the F04M catalyst strongly bonded with the oxide coating with L(+)-arginine.
indicate that the F04M catalyst strongly bonded with the oxide coating with L(+)‐arginine. 

Figure  1.  TEM  images  of  pristine  F04M  catalyst  (a)  and  F04M  catalyst  coated  with  silica  (b,c),   
TEM images of pristine F04M catalyst (a) and F04M catalyst coated with silica (b,c),
Figure 1.zirconia (d,e), and titania (f,g) using ammonia (b,d,f) and L(+)‐arginine (c,e,g). 
zirconia (d,e), and titania (f,g) using ammonia (b,d,f) and L(+)-arginine (c,e,g).
In  order  to  obtain  information  about  the  reducibility  of  active  copper  species,   
temperature‐programmed  reduction  (TPR)  profiles  observed  upon  treatment  of  the  as‐prepared 
In order to obtain information about the reducibility of active copper species,
samples  in  H2  are  obtained  by  thermogravimetric  analysis  (TGA).  Figure  2  shows  the  derivative 
temperature-programmed reduction (TPR) profiles observed upon treatment of the as-prepared
thermogravimetry (DTG) curves of the as‐prepared samples. The curves contained one main domain 
samples near 560 K. From the reduction profile of pristine F04M catalyst in Figure 2, clearly defined peaks 
in H2 are obtained by thermogravimetric analysis (TGA). Figure 2 shows the derivative
assigned to copper species at around 560 K appeared in the DTG curve [18–24]. Compared with the 
thermogravimetry (DTG) curves of the as-prepared samples. The curves contained one main domain
result of the pristine F04M catalyst, the peak temperatures in the profile of the oxide‐coated catalysts 
using  ammonia  were  lower  (Figure  2A),  while  the  temperatures  in  the  profile  of  oxide‐coated 
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Materials 2015, 8, 7738–7744

near 560 K. From the reduction profile of pristine F04M catalyst in Figure 2, clearly defined peaks
assigned to copper species at around 560 K appeared in the DTG curve [18–24]. Compared with the
result of the pristine F04M catalyst, the peak temperatures in the profile of the oxide-coated catalysts
using ammonia were lower (Figure 2A), while the temperatures in the profile of oxide-coated
catalysts using L(+)-arginine were higher (Figure 2B), and the reduction peak of the copper species of
the oxide-coated catalysts was very broad. In other words, the temperatures depend on the strength
Materials 2015, 8, page–page 
of the bond between the oxide and F04M catalyst, and the bond strength of the samples prepared
Materials 2015, 8, page–page 
with L(+)-arginine was higher than that of the samples prepared with ammonia. Figure 2A,B also
catalysts using L(+)‐arginine were higher (Figure 2B), and the reduction peak of the copper species of 
the oxide‐coated catalysts was very broad. In other words, the temperatures depend on the strength 
show temperature peaks at 553.6, 547.1, and 555.0 K for the catalysts coated with silica, zirconia, and
catalysts using L(+)‐arginine were higher (Figure 2B), and the reduction peak of the copper species of 
of the bond between the oxide and F04M catalyst, and the bond strength of the samples prepared 
the oxide‐coated catalysts was very broad. In other words, the temperatures depend on the strength 
titania using ammonia, respectively. On the other hand, the temperature peaks of the catalysts coated
with L(+)‐arginine was higher than that of the samples prepared with ammonia. Figure 2A,B also 
of the bond between the oxide and F04M catalyst, and the bond strength of the samples prepared 
with silica, zirconia, and titania using L(+)-arginine were 585.0, 591.0, and 590.0 K, respectively. It is
show temperature peaks at 553.6, 547.1, and 555.0 K for the catalysts coated with silica, zirconia, and 
with L(+)‐arginine was higher than that of the samples prepared with ammonia. Figure 2A,B also 
reportedtitania using ammonia, respectively. On the other hand, the temperature peaks of the catalysts coated 
that reconstruction of the active copper particles occurred with the addition of TiO2 [25–27].
show temperature peaks at 553.6, 547.1, and 555.0 K for the catalysts coated with silica, zirconia, and 
The result
with  indicates
silica,  thatand 
zirconia,  the active
titania  copper
using  species
L(+)‐arginine  were in the591.0, 
585.0,  TiOand 
2 -coated catalyst
590.0  K, 
titania using ammonia, respectively. On the other hand, the temperature peaks of the catalysts coated  prepared
respectively.  It  is  using
reported that reconstruction of the active copper particles occurred with the addition of TiO
L(+)-arginine show
with  silica,  broader
zirconia,  and dispersion
titania  using than those in
L(+)‐arginine  the585.0, 
were  pristine
591.0, catalyst.
and  590.0 These  [25–27]. 
results indicate
K,  respectively. 
2 It  is  that
The  result  indicates  that  the  active  copper  species  in  the  TiO2‐coated  catalyst  prepared 
reported that reconstruction of the active copper particles occurred with the addition of TiO using   
2 [25–27]. 
the temperatures depend on the oxide coating over the catalyst.
L(+)‐arginine show broader dispersion than those in the pristine catalyst. These results indicate that 
The  result  indicates  that  the  active  copper  species  in  the  TiO2‐coated  catalyst  prepared  using   
Methanol synthesis from the hydrogenation of carbon dioxide was tested over the oxide-coated
the temperatures depend on the oxide coating over the catalyst. 
L(+)‐arginine show broader dispersion than those in the pristine catalyst. These results indicate that 
catalyststhe temperatures depend on the oxide coating over the catalyst. 
after pre-reduction procedures. Figure 3 shows the temperature dependence of the
Methanol synthesis from the hydrogenation of carbon dioxide was tested over the oxide‐coated 
conversion of
catalysts  carbon dioxide over
after  pre‐reduction  the oxide-coated
procedures.  catalysts.
Figure  3  shows  The conversion
the  temperature 
Methanol synthesis from the hydrogenation of carbon dioxide was tested over the oxide‐coated  dependence  depends
of  the  on the
conversion 
catalysts.catalysts 
In theafter  of  carbon 
entire dioxide 
temperature
pre‐reduction  over  the  oxide‐coated 
region, Figure 
procedures.  catalysts. 
the conversion
3  shows  the  The 
over conversion  depends 
the oxide-coated
temperature  on 
of  the 
dependence catalysts the  using
catalysts. 
conversion  In of 
the  entire dioxide 
carbon  temperature 
over  region, 
the  the  conversion 
oxide‐coated  over The 
catalysts.  the  oxide‐coated 
conversion  catalysts on 
depends  using 
the  that the
ammonia was higher than that over the catalysts using L(+)-arginine. These results show
ammonia 
catalysts.  was  higher 
In  the  than 
entire  that  over  region, 
temperature  the  catalysts  using  L(+)‐arginine. 
the  conversion  These  results catalysts 
over  the  oxide‐coated  show  that  the 
using 
bond strength between the oxide and the commercial catalyst influences the catalytic activity.
bond strength between the oxide and the commercial catalyst influences the catalytic activity.   
ammonia  was  higher  than  that  over  the  catalysts  using  L(+)‐arginine.  These  results  show  that  the 
bond strength between the oxide and the commercial catalyst influences the catalytic activity.   
(A) (B)
F04M F04M
(A) (B)
F04M F04M
[a.u.][a.u.]

(a)
[a.u.][a.u.]

(d)
(a) (d)
DTGDTG

DTGDTG

(b) (e)
(b) (e)
(f)
(c)
(f)
(c)

373 473 573 673 373 473 573 673

Temp. [K] Temp. [K]
373 473 573 673 373 473 573 673
Temp. [K]
Figure 2. DTG curve registered upon H Temp. [K]
2‐TPR of F04M catalyst coated with silica (a,d), zirconia (b,e), 
Figure 2. DTG curve registered upon H2 -TPR of F04M catalyst coated with silica (a,d), zirconia (b,e),
and titinia (c,f) using ammonia (A) and L(+)‐arginine (B). 
Figure 2. DTG curve registered upon H2‐TPR of F04M catalyst coated with silica (a,d), zirconia (b,e), 
and titinia (c,f) using ammonia (A) and L(+)-arginine (B).
and titinia (c,f) using ammonia (A) and L(+)‐arginine (B). 
25
(b)
25
(b) (f)
20 (a)

(f)
[%] [%]

20 (a) (d)
CO2 conversion

15
(d)
CO2 conversion

15 (g)
10 (e)
(g)
10 (e)
5 (c)

5 (c)
0
480 500 460 520
0
Reaction Temp. [K]  
480 500 460 520
Reaction Temp. [K]
Figure 3. CO2 conversion over pristine F04M catalyst (a) and F04M catalyst coated with silica (b,c),   
zirconia (d,e), and titania (f,g) using ammonia (b,d,f) and L(+)‐arginine (c,e,g). Reaction conditions: 
Figure 3. CO2 conversion over pristine F04M catalyst (a) and F04M catalyst coated with silica (b,c),   
CO2 conversion
Figure 3.3 MPa, W/F = 5 g·h over
−1·mol −1, Hpristine F04M catalyst (a) and F04M catalyst coated with silica (b,c),
2/CO2/Ar = 72/24/4 (molar ratio). 
zirconia (d,e), and titania (f,g) using ammonia (b,d,f) and L(+)‐arginine (c,e,g). Reaction conditions:   
zirconia 3 MPa, W/F = 5 g·h
(d,e), and titania (f,g)
−1·mol using
−1, H ammonia (b,d,f) and L(+)-arginine (c,e,g). Reaction conditions:
2/CO2/Ar = 72/24/4 (molar ratio). 
Comparing 
3 MPa, W/F = 5 g¨ hthe 
´1 ¨ conversion 
mol´1 , H2 /CO among  the  oxide  coatings,  the  silica‐coated  catalyst  showed  the 
2 /Ar = 72/24/4 (molar ratio).
highest activity in the high temperature region, while the zirconia‐coated catalyst and titania‐coated 
Comparing  the  conversion  among  the  oxide  coatings,  the  silica‐coated  catalyst  showed  the 
highest activity in the high temperature region, while the zirconia‐coated catalyst and titania‐coated 
3
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Materials 2015, 8, 7738–7744

Comparing the conversion

Materials 2015, 8, page–page  among the oxide coatings, the silica-coated catalyst showed the
highest activity in the high temperature region, while the zirconia-coated catalyst and titania-coated
catalyst had high activity in the low temperature region. These results indicate that the temperature
catalyst had high activity in the low temperature region. These results indicate that the temperature 
profile of the conversion depends on the nature of the catalyst’s oxide coating.
profile of the conversion depends on the nature of the catalyst’s oxide coating. 
In order to verify the durability of the oxide-coated catalysts, they were tested for long reaction
In order to verify the durability of the oxide‐coated catalysts, they were tested for long reaction 
times. Figure
times.  Figure 4 4 
shows thethe 
shows  conversion of carbon
conversion  dioxide
of  carbon  over theover 
dioxide  oxide-coated catalyst using
the  oxide‐coated  ammonia.
catalyst  using 
For comparison, the conversion over pristine F04M catalyst is also shown in this
ammonia. For comparison, the conversion over pristine F04M catalyst is also shown in this figure.  figure. The
time course of the conversion depends on the catalyst’s oxide coating. The conversion over the
The time course of the conversion depends on the catalyst’s oxide coating. The conversion over the 
silica-coated catalyst does not significantly change in terms of reaction time, while the conversion
silica‐coated catalyst does not significantly change in terms of reaction time, while the conversion 
over the zirconia-coated catalyst and the titania-coated catalyst decrease up to 2 h before remaining
over the zirconia‐coated catalyst and the titania‐coated catalyst decrease up to 2 h before remaining 
constant up to 8 h. These results indicated that the silica-coated catalyst has a suitable activity for
constant up to 8 h. These results indicated that the silica‐coated catalyst has a suitable activity for 
long reaction
long  reaction times.
times. The
The silica-coated catalyst
silica‐coated  shows
catalyst  almost
shows  the same
almost  conversion
the  same  per weight
conversion  of F04 of 
per  weight  M 
(«23%) compared with the F04M catalyst, and the silica-coated catalyst did not significantly
F04 M (≈23%) compared with the F04M catalyst, and the silica‐coated catalyst did not significantly  reduce
the catalytic activity. Table 1 shows product selectivity over the pristine F04M and the oxide-coated
reduce the catalytic activity. Table 1 shows product selectivity over the pristine F04M and the oxide‐coated 
catalysts. As shown in Table 1, carbon monoxide and methanol are produced over all of the catalysts.
catalysts. As shown in Table 1, carbon monoxide and methanol are produced over all of the catalysts. 
Methanol selectivity over the silica-coated catalyst and the titania-coated catalyst was higher than
Methanol selectivity over the silica‐coated catalyst and the titania‐coated catalyst was higher than 
that over the pristine F04M catalyst, while the selectivity over the zirconia-coated catalyst was the
that over the pristine F04M catalyst, while the selectivity over the zirconia‐coated catalyst was the 
same as that over the pristine F04M catalyst. These results indicated that silica and titania coatings on
same as that over the pristine F04M catalyst. These results indicated that silica and titania coatings 
the F04M catalyst effectively improved methanol selectivity. It is reported that the addition of TiO2 
on the F04M catalyst effectively improved methanol selectivity. It is reported that the addition of TiO
improves the methanol selectivity because of the reconstruction of the active copper particles and/or
improves the methanol selectivity because of the reconstruction of the active copper particles and/or 
its acid-base property, which controls the stability of the reaction intermediate [25–27].
its acid‐base property, which controls the stability of the reaction intermediate [25–27]. 

 
Figure 4. Time course of CO
Figure 4. Time course of CO22 conversion over pristine F04M catalyst (a) and F04M catalyst coated 
conversion over pristine F04M catalyst (a) and F04M catalyst coated
with 
with silica  (b), zirconia
silica (b), zirconia (c),
(c), and
and titania
titania  (d). 
(d). Reaction 
Reaction conditions: 
conditions: 523 523 
K, K,  3  MPa, 
3 MPa, W/F W/F 
= 5= g¨5 hg·h
´1 −1 ·mol´1
¨ mol
−1, 
,
H22/CO
H /CO2/Ar = 72/24/4 (molar ratio). 
2 /Ar = 72/24/4 (molar ratio).

Table 1. Product selectivity over the various catalysts. 
Table 1. Product selectivity over the various catalysts.
Catalyst  CO Selectivity (%) CH3OH Selectivity (%) 
Catalyst CO Selectivity (%) CH3 OH Selectivity (%)
F04M  62.1  37.9 
F04M
SiO2 coat  62.1
53.1  37.9
43.9 
SiO2 coat 53.1 43.9
ZrO 2 coat 
ZrO2 coat
61.7 
61.7
38.3 
38.3
TiOTiO
2 coat 
2 coat 45.3 
45.3 54.7 
54.7
Reaction conditions: 523 K, 3 MPa, W/F = 5 g·h −1·mol
Reaction conditions: 523 K, 3 MPa, W/F = 5 g¨ h´1 ¨ mol ´1−1, , H 2/CO2/Ar
H2 /CO 2
/Ar = 72/24/4 (molar ratio). 
= 72/24/4 (molar ratio).

In order to determine differences in activity, the oxide‐coated catalysts were characterized by 
In order to determine differences in activity, the oxide-coated catalysts were characterized by
FTIR spectroscopy to assess their hydrophilicity. Figure 5 shows the FTIR spectra for the oxide‐coated 
FTIR spectroscopy to assess their hydrophilicity. Figure 5 shows the FTIR spectra for the oxide-coated
catalysts  prepared  with  ammonia.  The  zirconia‐coated  catalyst  and  the  titania‐coated  catalyst 
displayed a band of the H–O–H bond at around 1640 cm−1 [28], while the silica‐coated catalyst lacked 
this band. These results indicated that the silica‐coated catalyst had a relatively low hydrophilicity 
7741
compared with the zirconia‐coated catalyst and the titania‐coated catalyst because the oxide with low 

4
Materials 2015, 8, 7738–7744

catalysts prepared with ammonia. The zirconia-coated catalyst and the titania-coated catalyst
displayed a band of the H–O–H bond at around 1640 cm´1 [28], while the silica-coated catalyst lacked
this band. These results indicated that the silica-coated catalyst had a relatively low hydrophilicity
comparedMaterials 2015, 8, page–page 
with the zirconia-coated catalyst and the titania-coated catalyst because the oxide with low
hydrophilicity probably reduced the influence of the steam by-product. Therefore, the silica-coated
hydrophilicity probably reduced the influence of the steam by‐product. Therefore, the silica‐coated 
catalystcatalyst had a higher durability than the zirconia‐coated catalyst or titania‐coated catalyst. 
had a higher durability than the zirconia-coated catalyst or titania-coated catalyst.

(c)

(b)
Intensity [a.u.]

(a)

H-O-H

1650 1450 1250

Wave number [cm-1]  
FigureFigure 5. FTIR spectra of F04M catalyst coated with silica (a), zirconia (b), and titania (c). 
5. FTIR spectra of F04M catalyst coated with silica (a), zirconia (b), and titania (c).
3. Experimental Section 
3. Experimental Section
3.1. Catalyst Preparation 
3.1. Catalyst Preparation
Various  oxides  (silica,  zirconia,  titania)  were  coated  on  commercial  copper‐zinc  oxide‐based 
catalyst (JGC Catal. Chem. Ltd.; Kanagawa, Japan, F04M) by a sol‐gel method. An aqueous solution 
Various oxides (silica, zirconia, titania) were coated on commercial copper-zinc oxide-based
catalystof ammonia (Kanto Chemical Co., Tokyo, Japan, 28 wt % solution, >99.0%) or L(+)‐arginine (Wako 
(JGC Catal. Chem. Ltd.; Kanagawa, Japan, F04M) by a sol-gel method. An aqueous
Chemical  Co.,  Osaka,  Japan,  >99.0%)  were  mixed  with  0.5  g  of  F04M  in  ethyl  alcohol,  then 
solution of ammonia (Kanto Chemical Co., Tokyo, Japan, 28 wt % solution, >99.0%) or L(+)-arginine
tetraethoxysilane (Wako Pure Chem. Co., Osaka, Japan, >99.0%), zirconium butoxide (Sigma‐Aldrich 
(Wako Co. St. Louis, MO, USA, LLC., 80 wt % solution in 1‐butanol), or titanium‐n‐butoxide (Wako Pure 
Chemical Co., Osaka, Japan, >99.0%) were mixed with 0.5 g of F04M in ethyl alcohol,
then tetraethoxysilane (Wako Pure Chem. Co., Osaka, Japan, >99.0%), zirconium butoxide
Chem. Co., Osaka, Japan, >97.0%) was added to the solution, followed by stirring at 323 K for 3 h and 
centrifuging at a rotation speed of 6000 rpm for 5 min. 
(Sigma-Aldrich Co. St. Louis, MO, USA, LLC., 80 wt  % solution in 1-butanol), or titanium-n-butoxide
(Wako Pure Chem. Co., Osaka, Japan, >97.0%) was added to the solution, followed by stirring at
3.2. Characterization 
323 K for 3 h and centrifuging at a rotation speed of 6000 rpm for 5 min.
The  morphology  of  the  oxide‐coated  catalysts  was  observed  using  a  Hitachi  FE2000  (Hitachi 
High‐Tech. Co., Tokyo, Japan) transmission electron microscope (TEM) operated at an acceleration 
3.2. Characterization
voltage of 200 kV. The temperature‐programmed reduction–thermogravimetric analyses (TPR–TGA) 
Thewere performed with a Rigaku TG8120 (Rigaku Co., Tokyo, Japan) instrument. TPR profiles were 
morphology of the oxide-coated catalysts was observed using a Hitachi FE2000
(Hitachirecorded 
High-Tech. Co.,
by  passing  Tokyo,
a  10  vol  %  HJapan) transmission
2  in  Ar  (260  electron
mL·min−1)  through  the microscope (TEM)
sample  (~2  mg)  operated
heated  at  a  at
constant rate of 5 K·min
an acceleration voltage of 200−1  up to 1173 K. 
kV. The temperature-programmed reduction–thermogravimetric
analyses (TPR–TGA) were performed with a Rigaku TG8120 (Rigaku Co., Tokyo, Japan) instrument.
3.3. Catalytic Activity 
TPR profiles were recorded by passing a 10 vol % H2 in Ar (260 mL¨ min´1 ) through the sample
The catalysts were evaluated in a tubular stainless steel, fixed‐bed reactor (1/2′′ i.d) equipped 
(~2 mg) heated at a constant rate of 5 K¨ min´1 up to 1173 K.
with a temperature‐programmed control unit and a K‐type thermocouple. Each sample was loaded 
between  two  layers  of  quartz  wool  in  the  reactor.  Before  experiment,  the  catalyst  was  firstly   
3.3. Catalytic Activity
pre‐reduced at 553 K and atmospheric pressure in a hydrogen stream (1 vol % H2 in Ar) and cooled 
Theto desired temperature. Subsequently, synthesis gas (H
catalysts were evaluated in a tubular stainless 2/COsteel, fixed-bed reactor (1/211 i.d) equipped
2/Ar = 72/24/4 (molar ratio)) was introduced 

at W/F = 5 g·h ·mol , at a pressure of 3.0 MPa using a mass flow controller (Brookhaven). The effluent 

−1 −1
with a temperature-programmed control unit and a K-type thermocouple. Each sample was loaded
gases  were  analyzed  by  two  GC‐TCD  (Shimadzu  GC‐8A,  Shincarbon  ST  column  and  Shimadzu   
between two layers of quartz wool in the reactor. Before experiment, the catalyst was firstly
GC‐8A,  FlusinT  column).  Conversion  and  selectivity  were  calculated  by  internal  standard  and   
pre-reduced at 553 K and atmospheric
mass‐balance methods. CO pressure in a hydrogen stream (1 vol % H2 in Ar) and
2 conversion was calculated as follow:   
cooled to desired temperature. Subsequently, synthesis gas (H2 /CO2 /Ar = 72/24/4 (molar ratio))
5
was introduced at W/F = 5 g¨ h´1 ¨ mol´1 , at a pressure of 3.0 MPa using a mass flow controller

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Materials 2015, 8, 7738–7744

(Brookhaven). The effluent gases were analyzed by two GC-TCD (Shimadzu GC-8A, Shincarbon
ST column and Shimadzu GC-8A, FlusinT column). Conversion and selectivity were calculated by
internal standard and mass-balance methods. CO2 conversion was calculated as follow:

CO2 conversion “ 1 ´ FrCO2 sout {FrCO2 sin

Maximum error margin of the conversion in this study was ˘ 7%.

4. Conclusions
This study investigated the effect of oxide coatings on the activity of copper-zinc oxide-based
catalyst for methanol synthesis via the hydrogenation of carbon dioxide. A commercial copper-zinc
oxide-based catalyst was coated with various oxides (silica, zirconia, titania) by a sol-gel based
method. In this study, the influence of preparation conditions such as kinds of promoters (ammonia
or L(+)-arginine) on the sol-gel reaction was investigated. From the result of TPR-TGA, the reduction
peak assigned to the copper species of the oxide-coated samples prepared using ammonia shifted
to lower temperatures than that of the pristine F04M catalyst, while the copper reduction peaks
shifted to higher temperatures for the oxide-coated samples prepared using L(+)-arginine, indicating
that the copper species that were more weakly bonded with oxide were more easily reduced. The
coated catalyst prepared with ammonia shows a higher conversion of carbon dioxide than the coated
catalyst prepared with L(+)-arginine, indicating that the catalyst with a weaker oxide bond has
a higher activity than the catalyst with a strong oxide bond. Among the oxide-coated catalysts
prepared using ammonia, the silica-coated catalyst displayed the highest activity in the high reaction
temperature region, while the zirconia-coated and titania-coated catalysts had high activities at low
reaction temperatures. At high reaction temperatures, the conversion over the silica-coated catalyst
did not significantly change with the reaction time, while the conversion over the zirconia-coated
and titania-coated catalysts decreased during the initial reaction time, indicating that the silica-coated
catalysts have a more suitable activity for long reaction times. The zirconia-coated catalyst and the
titania-coated catalyst displayed the band of the H–O–H bond, while the silica-coated catalyst did
not display the band, indicating that the silica-coated catalyst had a relatively low hydrophilicity
compared with the zirconia-coated and the titania-coated catalysts. The silica-coated catalyst,
therefore, had a high durability compared with the other oxide-coated catalysts.

Acknowledgments: This work was supported by an ALCA (Advanced Low Carbon Technology Research and
Development) project of Japan Science Technology Agency (JST) for funding.
Author Contributions: Tetsuo Umegaki conceived and designed the experiments; Tetsuo Umegaki performed
the experiments; Tetsuo Umegaki, Yoshiyuki Kojima, Kohji Omata analyzed the data.
Conflicts of Interest: The authors declare no conflict of interest.

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