Renewable and Sustainable Energy Reviews 44 (2015) 508518

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Recent development in catalytic technologies for methanol synthesis

from renewable sources: A critical review
Khozema Ahmed Ali, Ahmad Zuhairi Abdullah n, Abdul Rahman Mohamed
Low Carbon Economy Group, School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia

art ic l e i nf o a b s t r a c t

Article history: In the current era of energy crises, alternative feedstock such as methanol are commonly used as fuels
Received 27 January 2014 and solvents in various industries. Methanol is commonly produced from non-renewable sources.
Received in revised form Recently, sustainable methanol synthesis via innovative and efcient catalytic processes has drawn a lot
4 December 2014
of attention and research is currently aimed at nding a suitable catalyst for optimized production at
Accepted 3 January 2015
commercial scale. Nowadays, one of the main interests is catalytic synthesis of methanol from CO2. This
work presents a critical review on innovative catalysts for methanol synthesis, research progress for
Keywords: their development and their use in the catalytic process. It also provides an overview on recent
Catalytic methanol synthesis development in methanol synthesis from syngas, CO2 hydrogenation and photo-catalytic reduction of
Renewable energy
CO2. The use of various reactors, the inuence of preparation method, support, promoter, different type of
Carbon dioxide
catalysts used, their properties and performance during methanol synthesis are also thoroughly reviewed.
Hydrogenation
Syngas & 2015 Elsevier Ltd. All rights reserved.
Photoreduction

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
2. Methanol synthesis through CO2 hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
2.1. Effect of catalyst preparation method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
2.2. Effect of promoter on the catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
2.3. Effect of support on catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
2.4. Other catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
3. Catalyst for methanol synthesis from syngas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
3.1. Effect of catalyst preparation method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
3.2. Effect of promoter on catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
3.3. Other catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
4. Catalyst for methanol synthesis from photo reduction
of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
4.1. Effect of promoter on catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
4.2. Effect of catalyst preparation method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
4.3. Other catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
5. Analysis of catalyst system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516

1. Introduction

n
Corresponding author. Methanol is a widely used and globally distributed product
E-mail address: chzuhairi@usm.my (A.Z. Abdullah). with number of industrial applications. It is also very important

http://dx.doi.org/10.1016/j.rser.2015.01.010
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
due to the current depletion of fossil fuel resources. It is con-
sidered to be an ideal alternative fuel due to fast dismissing oil and
gas resources [1]. In chemical industry, commercial uses of
methanol include the production of formaldehyde, aromatics,
ethylene, methyl tertiary butyl ether (MTBE), acetic acid and other
chemicals [2]. There is also a growing demand for methanol in fuel
application such as production of dimethyl carbonate (DMC),
biodiesel production, the direct blending into gasoline and it could
provide conventional energy storage for fuel cell applications due
to its cleaner emissions as compare to fossil fuel resources [3].
Figs. 1 and 2 illustrate data regarding the worldwide methanol
consumption and its industrial demand.
The commercial production of methanol is mainly from fossil
fuel based syngas that generally contains CO and H2 with small
traces of CO2. Meantime, the high temperature and pressure
requirement for this process has a serious impact on the environ-
ment [5]. Over the past decades, researchers have been focusing
on the potential of CO2 hydrogenation to produce methanol. CO2 is
an important greenhouse gas that is the main causal agent for
climate change and global warming [6]. In this regard, its utiliza-
tion is an attractive way to reduce CO2 concentration in the
atmosphere [7].
In addition, according to the Kyoto Protocol, some industria-
lized countries and European community are committed to reduce
their greenhouse gas emissions [8]. The emission level must be
reduced by 5% below their emission level in 1990 during a ve
year period (20082012). Three market-based mechanisms were
offered to help in achieving the targets i.e. (i) emission trading
Fig. 1. Methanol consuming industries [4].
Fig. 2. Trend in methanol demand for a 10 year period [3].
509
known as the carbon market, (ii) clean development mechanism
(CDM) and (iii) joint implementation (JI) [9]. Even though carbon
dioxide is readily available, it is thermodynamically stable, coupled
with its standard free energy of formation (G1  394.359 kJ/
mol) [10]. Large energy source is required in reduction/splitting
process. It is also well establish that the methanol can be readily
produced through CO and CO2 hydrogenation [11].
Recently, the main interest in methanol synthesis is to develop
highly efcient and innovative catalysts. In this regard, a number of
investigations have been conducted to develop catalysts with large
surface area, high active site dispersion and smaller particle size in
order to increase activity and selectivity. Among these, Cu-based
catalysts have been given great attention. A work by Zhang et al. [12]
showed that the addition of metal ions onto Cu-based catalyst
increased the activity and stability of the catalysts. Hong [13] found
that the properties and performance of Cu-based catalyst could be
adjusted by varying preparation parameters and methods. In the
work of Robinson and Moi [14], it was proven that besides the active
site on which the reaction occurred, type and structure of the
support also had an inuence on the methanol synthesis. Even with
all these ndings, there is still a need for enhancement of Cu-based
catalyst and also the preparation of new catalysts to address draw-
backs of currently available catalysts. Ideal catalyst properties
include a primary component that shows good selectivity and
activity towards the desired product, a support that not only
provides good conguration and stability but also has some mod-
ulating interaction between the primary component and promoter,
and a promoter that further enhances the catalyst ability. All these
objectives could be achieved by using a robust preparation method.
Similarly, another environmentally friendly way to produce
methanol that has been gaining more attention is photocatalytic
reduction of CO2 with water in the presence of light irradiation. An
attractive feature of photocatalysis is that it occurs under relatively
mild conditions with readily available and relatively cheap source
of reactant. By using suitable semiconductor material as a catalyst,
the absorption of light energy generates electron and holes needed
for the reduction reaction. In this case, CO2 can be reduced to
useful chemicals such as formic acid, formaldehyde, methane and
methanol [15]. To date, a number of catalysts have been investi-
gated for photocatalysis such as ZnS, CdS, ZrO2, TiO2, MgO and ZnO
[16]. Among these catalysts, TiO2 has been widely used due to its
high catalytic activity [17] and comparable band energy (3.2 eV) to
the reduction potential of CO2 [18].
Even though TiO2 is a good catalyst for methanol production,
one of the most challenging tasks is to have enhanced efciency in
the photochemical process. Methanol yield from this process is
still competitive to the yield by syngas or hydrogenation process.
Looking at the thermodynamics of the reaction, 228 kJ of energy
is required to convert one mole of CO2 to methanol with six
electrons to convert C4 in CO2 to C2  in methanol. In addition,
with poor visible light response from TiO2, signicant improve-
ment is necessary in order to upgrade this process to an industrial
scale. One of the prominent ways is by modifying TiO2 catalyst
with other metals and semiconductors. Since this is still a new
research area, there are only few reported studies that involve
modication of TiO2 catalyst. Further innovation in TiO2 catalysts
as well as the use of other semiconductor is vital in enhancing the
efciency of the process.
2. Methanol synthesis through CO2 hydrogenation
2.1. Effect of catalyst preparation method
Currently, the synthesis of methanol is rather promising due to
its dramatic economic values and signicance for use as alternative
510 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
fuel. The chemical conversion of CO2 via catalytic reaction especially
hydrogenation of CO2 is recently becoming attractive because it may
lead to the production of commercial compounds like formic acid,
methanol, carbon monoxide, methane, and other hydrocarbons [19].
Eq. (1) represents the hydrogenation of CO2 into methanol as below.
CO2 H22CH3OH H2O
Among the studied catalysts, Cu-based catalyst is considered
one of the most popular choices for methanol synthesis due to its
improved and better activity [20]. It is also reported that due to the
sensitive structure of the catalyst, even a slight change in the
preparation method may cause considerable effects on the cata-
lytic performance and yield [21]. Conventional catalyst prepara-
tion methods include co-precipitation, impregnation and sol gel
which are sensitive to pH, time consuming and are restricted by
deviation from stoichiometry [22]. In order to overcome such
drawbacks and to enhance the performance of synthesized cata-
lysts, novel preparation methods are recommended e.g. the pre-
paration of Cu/ZnO/Al2O3 catalysts through decomposition of M
(Cu,Zn)-ammonia complexes (DMAC) under sub-atmospheric
pressure at various temperatures [23]. In this regard, XRD patterns
indicated that precursor prepared at medium temperature (343 K)
contained more aurichalate phase than those synthesized at any
other temperature. Rich aurichalate phase could improve Cu
dispersion and also formed small and homogenous CuO and ZnO
crystalline for higher activity [24]. The catalyst with this phase also
showed high stability and activity after calcination [25]. The BET
surface area and particle size of the catalyst were smaller com-
pared to the other catalyst which is consistent with the view that
aurichalate phase led to smaller Cu particle size. The high tempera-
ture CO2 release peak based on the EGA was ascribed to secondary
decomposition of hydroxyl carbonate that could restrain the Cu
particle growth, thus maintaining the activity of the catalyst [26].
Guo [27] on the other hand reported the effect of glycine
content in combustion synthesis method on CuO/ZnO/ZrO2 (CZZ)
catalyst properties and catalytic performance for methanol synth-
esis. Similarly, combustion synthesis method is an attractive
technique to synthesize metal oxide as it offers precise stoichio-
metric ratio, low cost, and short reaction time [28]. Glycine, a
molecule with zwitterionic character can be an ideal complexion
agent for various types of metal. Such characteristics can complex
metal ions with varying ionic size that helps in preventing
selective precipitation and maintain the compositional homoge-
neity [29].
However, SEM images were used to study changes in morphol-
ogy as the glycine contents during the combustion were varied
from 50% to 150% of stoichiometry [29]. This observation was
consistent with XRD pattern and BET surface area. The data
regarding effect of glycine content on the physicochemical proper-
ties and catalytic performance of the catalyst are presented in
Table 1. It is clearly seen that particle size, methanol selectivity and
yield show volcanic trends with the increase in glycine content
while the surface area shows an inverse trend. As for ZrO2 support,
variation in glycine content effected its phase formation. For low
Table 1
Physicochemical properties and catalytic performance of CZZ catalysts [30].
Catalysts CuO crystallite SBET n(m-ZrO2)/n CH3OH
size (nm) (m2/g) (t-ZrO2) selectivity (%)
50 CZZ 16.0 17.8 0.85 71.1
75 CZZ 19.7 4.8 3.30 80.0
100 CZZ 25.3 3.3 10.30 82.1
125 CZZ 23.0 4.8 0.49 79.1
150 CZZ 19.5 5.5 0.07 78.9
glycine content (50%), both monoclinic, m-ZrO2 and tetragonal
t-ZrO2 phase were observed. A maximum m-ZrO2 was observed
when the stoichiometry content (100%) was used. In contrast, the
intensity for t-ZrO2 was higher for 125% and 150% CZZ. Based on
these results, methanol selectivity did not only depend on Cu
surface area but also on the ZrO2 phase.
(1)
According to Wang [23], the introduction of CO2 into the
mother liquid during the aging process in co-precipitation method
for Cu/ZnO/Al2O3 catalyst preparation could improve the activity
and physiochemical properties of the catalyst. During the aging
process, the reaction (2) occurs by releasing OH  ion that
increases the pH value [24,30]. The introduction of CO2 according
to reactions (3) and (4) can avoid the pH change. Constant pH is
found to improve physiochemical properties and catalytic perfor-
mance of the catalyst [26].
CuNO3 2 3CuOH2 s 2CO23  -2Cu2 OH2 CO3 s 2OH  2NO3
2
H2 O CO2 -2H CO23  3
OH  H -H2O (4)
The introduction of CO2 in the aging process can increase the
surface area, pore volume. At the same time, it avoids the
agglomeration of smaller particle into larger aggregates and also
inhibits the crystalline growth. In the absence of CO2, the XRD
pattern of the precursor showed low intensity of stable hydro-
xycarbonate phase which indicates the decomposition of this
phase during aging process. In addition, the use of CO2 promotes
the formation of stable hydroxycarbonate phase.
According to Zhuang [31], fractional precipitation (FP), solid-
state reaction (SS), impregnation precipitation (IP)) not only
affected the interaction between Cu and ZrO2 in Cu/ZrO2 catalyst
but they also affected the reducibility and physical structure of the
catalyst. The preparation method mostly affects the surface area
and the pore structure of the catalyst. The catalyst prepared using
FP method catalyst has generally larger surface area and wider
pore distribution where as catalyst prepared via impregnation (IP)
method has smaller surface area and more centralized pore
distribution. The interaction between ZrO2 and copper oxide
causes the change in microscopic state of Cu surface. In IP method,
the catalyst exhibited better CO2 conversion and methanol yield.
Furthermore, it is noted that the catalyst performance here is
mainly determined by the strong interaction between Cu and ZrO2
rather than the surface area.
2.2. Effect of promoter on the catalyst system
It is well noted in literature that the catalytic performance of
bimetallic catalyst is considered better than monometallic catalyst
and therefore, it has attracted the research attention for further
development. The purpose of introducing metal/metal compound
to the catalyst is to better tune the selectivity and to enhance the
activity of the catalyst [32]. Wang [11] reported the effect of
promoter on Cu based catalyst activity. The study focused on the
key difference between Cu based catalyst with different promoters
and its effect on copper crystalline size. It is well established that
CH3OH
crystalline size has a direct correlation with the catalyst activity
yield (%)
[33]. Among the catalysts prepared, the CuZnAlZr catalyst showed
8.5 the highest space time yield (STY) for methanol synthesis over the
3.9 whole temperature range (463513 K). The presence of Al and Zr
2.9 reduced the crystallinity of copper which increased the catalytic
4.0
4.7
activity. Meanwhile, the introduction of Mn increased the copper
crystalline and reduced the catalyst activity. Based on the TEM
 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
images, ring like structures were observed with metallic copper
forming the rings and ZnO particles occupying the middle area.
This structure provided more active sites for methanol synthesis
and improves the catalyst stability by making it harder to sinter
and it was attributed to the metallic copper coating by ZnO
particle [11].
Other than that, the addition of aurum has also been found to
affect the performance of Cu-based catalyst. In the work by
Mierczynski [34], 20% Cu/Cr2O3/3Al2O3 gave the highest methanol
yield and 5% Au20% Cu/Cr2O3/3Al2O3 showed the highest selec-
tivity for methanol synthesis. High selectivity could be due to the
formation of AuCu alloy and that Au particle in the catalyst that
served as nucleation center for Cu crystallization. Low yield of
methanol for AuCu catalyst might be ascribed by low dispersion
of Au particle obtained from using classical impregnation method
[35]. To further improve the Cu/ZrO2 catalyst performance, the
catalyst was doped with various amounts of La [27]. The surface
area of the catalyst increased with the increase in La loading due
to the formation of surface defects that hinders the crystallization
and grain growth of CuO and ZrO2. As for the Cu surface area SCu,
there was a decrease with increasing La loading. This is because
with high La loading, the position of Cu was occupied by La. The
catalyst activity was found to have correlation with SCu. Mean-
while, the selectivity for methanol was related to the distribution
of basic site on the catalyst surface.
In another investigation, Zhang [36] reported the effect of TiO2,
SiO2, and TiO2SiO2 promoters on the performance of CuO/ZnO/
Al2O3 catalyst for methanol synthesis (Table 2). According to him,
TiO2, SiO2, and TiO2SiO2 promoted CuO/ZnO/Al2O3 catalysts
exhibited better catalytic activity than the one without promoter.
Among these, TiO2SiO2 promoted catalyst had the highest CO2
conversion and methanol yield. The XRD results indicated that the
promoters enhanced the dispersion of CuO and ZnO based on
larger BET and Cu specic surface area. This well dispersion of
ZnO increased the interaction between CuO and ZnO, leading to
better activity [37]. The H2-TPR showed that TiO2SiO2 promoted
catalyst not only enhanced the dispersion, but also increased the
CuO reduction temperature which led to higher catalytic perfor-
mance [38].
The addition of CeO2 to Cu/ZrO2 and Cu/ZnO catalyst reported
by Bonura [39] showed a negative effect on activity but enhanced
the selectivity of the catalyst. The introduction of CeO2 might
cause a decline in the surface area of the catalyst and increase in
pore volume and average pore diameter. These properties might
have been contributed by the poor thermal and chemical stability
of CeO2 and strong interaction between CeO2 and support [40].
In the work done by Samei [41], the addition of colloidal silica
and metal oxides (Mn, Ga and Zr oxides) was found to increase
the CuO/ZnO/Al2O3 catalyst activity and stability. Based on the
temperature-programmed reduction (TPR) curves, the addition of
SiO2 increased the reduction temperature of the catalyst. Further
increase in reduction temperature was observed with the introduc-
tion of metal oxide together with SiO2. The increase in reduction
Table 2
CuO/ZnO/Al2O3 BET surface area and performance for methanol synthesis [36].
Catalysts SBET CO2 CH3OH CH3OH
(m2/g) conversion (%) selectivity (%) yield (%)
CuO/ZnO/Al2O3 26.32 15.81 23.31 3.69
TiO2/CuO/ZnO/ 33.69 20.24 27.15 5.50
Al2O3
SiO2/CuO/ZnO/ 37.77 16.10 25.29 4.07
Al2O3
TiO2SiO2/CuO/ 42.72 40.70 41.17 16.76
ZnO/Al2O3
511
temperature resulted in better Cu dispersion or smaller Cu particles.
The BET surface area and pore volume was also increased with the
addition of SiO2. The methanol yield was greater with the presence
of SiO2 due to its ability to reduce catalyst deactivation by suppres-
sing the crystallization of the constituents during the reaction.
Catalyst deactivation is normally caused by the water formation
along with methanol during methanol synthesis [42]. The stability
and activity were even better when ZrO2 and Ga2O3 were added as
they improved the specic surface area and specic activity per unit
Cu surface area.
2.3. Effect of support on catalyst system
It is reported that other than the metallic active site, support
may also plays a vital role to modulate and enhance the catalyst
performance [43]. The work of Maniecki [44] showed the effect of
various support (CrAl3O6, FeAlO3, and ZnAl2O4) on the catalytic
activity of Cu based catalyst for methanol synthesis. Comparison of
catalytic activity indicated that the 20% Cu/ZnAl2O4 catalyst had
the highest selectivity and activity, with 20% Cu/FeAlO3 catalyst
showed the lowest selectivity and activity. In addition, FeAlO3
support had higher BET surface area compared to ZnAlO3 even at
higher calcination temperature. The better catalyst activity of Cu/
ZnAlO3 was due to the synergetic effect of support and Cu
composition which is shown in the XRD pattern.
Similarly, Mierczynski [44] investigated the inuence of sup-
port composition of copper supported catalysts containing 20 wt%
Cu over (Al2O3, ZnAl2O4, ZnAlO2.5, Zn2AlO3.5 and ZnO) on the
structure of the catalysts and their catalytic activity in methanol
synthesis. The high yield and selectivity of methanol obtained
from Cu/ZnAl2O4 catalyst suggested that Cu Zn sites were the
active site for methanol synthesis. Higher Cu/ZnO ratio increased
the catalyst activity. The optimum ratio for this catalyst was
reported as 0.72 for Cu/ZnO and 0.5 for Al/Zn. These results were
further conrmed by the TPR prole for 20% Cu/ZnAl2O4. The IR
spectrum indicated that bidentate formate was directly hydro-
genated to methanol through methoxy synthesis. The main inter-
mediate species during methanol synthesis are b-HCOO-groups
and hydrogenation of this species is the rate-limiting step of the
reaction [45].
However the work by Jia [46] showed that copper content had
an inuence on the structural properties and catalytic perfor-
mance of pre-reduced LaMn1  xCuxO3 (0 r xr1) when used for
methanol synthesis. Methanol selectivity and CO2 conversion were
the highest at 50% copper content (x 0.5). For this composition,
an interaction between Cu and Mn was observed. This interac-
tion provided ne dispersion of active site (Cu ) to absorb more
CO2 and inhibit further reduction of Cu to Cu0. Catalyst with
higher copper content showed lower activity due to lack of
interaction between Cu and Mn and the failure of perovskite
structure to form completely.
2.4. Other catalyst system
Conventional Cu-based catalysts have been extensively studied
for futher improvement in methanol synthesis. The use of alter-
native catalysts containing active sites other than Cu is rarely
investigated due to low selectivity and activity. However, there are
few studies that indicate the opposite [46]. In the work done by
Grabowski [47], Ag/ZrO2 catalyst showed good performance in
methanol synthesis. It was found that both selectivity and activity
did not have any correlation with Ag0 dispersion and content.
Instead, it showed dependency toward t-ZrO2 phase content and
Ag /Zr ratio. This revealed that methanol synthesis did not occur
on the metallic Ag surface but on Ag sites. The rate of methanol
formation increased with the increase in t-ZrO2 phase content and
512 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
Ag concentration. The Ag active sites were stabilized by the
oxygen vacancies in the t-ZrO2 phase. It was also noted that the
introduction of ZnO had no signicant effect on the methanol yield
which differed from the behavior of Cu-based catalyst.
Kong [48] on the other hand reported the development of co-
precipitate type of Pd-decorated multiwalled carbon nanotubes
(MWCNT)-promoted Pd-Ga2O3 catalyst. Combining metal catalyst
with MWCNT could increase the catalyst selectivity and activity
due to its advantagoues features such as excellent performance for
H2 adsorption, high thermal conductiviy, large surface area, and
highly graphitized tube wall and nano sized channels [49]. High
methanol yield and selectivity was observed for the doped Pd
Ga2O3 compared to the undoped catalyst. This result could be
related to the CNTs excellent adsorption/activation of H2 [13]. The
presence of CNTs also increased the stability of the catalyst as
there was no catalyst deactivation after about 200 h of reaction.
Ahmed [7] investigated methanol synthesis using ordered
layered double hydroxides (LDH) consisting Zn and/or Cu. The
catalyst was further enhanced by the addition of Al or Ga. The
advantages of using LDH are the sorption capacity for CO2 in
the layered space and tunable semiconductor properties based on
the choice of metal cations. The main product form is CO and
methanol. The highest selectivity and yield for methanol were
achieved using [Zn1.5Cu1.5Al(OH)8]2 (CO3)2  mH2O catalyst. Com-
parison with other catalysts indicated that Cu was the active site
for methanol formation. The addition of Ga increased methanol
formation whereas the introduction of Al favored CO formation.
3. Catalyst for methanol synthesis from syngas
3.1. Effect of catalyst preparation method
Detailed studies on Cu/ZnO/Al2O3 catalyst including the effects
of precipitation parameters and aging process on the activity of
catalyst have been reported [20]. Such studies mainly focused on
Cu and ZnO effect in methanol synthesis. Al2O3 is known to be
useful for inhibiting sintering of metal particle, accelerating the
adsorption and activation of CO. It also improves the stability of
the catalyst. However, extensive research works on such aspects
are quite limited.
According to Bai [50], it was found that the preparation of ZrO2
support had considerable effects on the methanol synthesis. The
catalyst prepared using alcogel/thermal treated with nitrogen
method (CuO/ZrO2-AN) showed better catalyst performance than
the one obtained through conventional precipitation method
(CuO/ZrO2-CP). In this regard, the good performance of CuO/
ZrO2-AN catalyst was attributed to the larger surface area, which
allowed better dispersion of the active Cu species. Other than that,
calcination temperature of the support and Cu/ZrO2 also affected
the catalyst activity. Higher calcination temperature might
increase the growth of ZrO2 particle and reduce the surface area.
These are undesirable because of the low dispersion of active
species leading to reductions in the conversion of CO and selec-
tivity towards methanol.
Effects of aluminum emulsion and its preparation method on
the performance of the copper-based catalyst modied with
aluminum precursor has been investigated by Wang [23]. In this
investigation, the activity of these catalysts was compared with
that of traditional catalyst prepared using pseudo boehmite (AB-3)
and commercial catalyst (GA-4). It was found that, the catalyst
prepared using aluminum emulsion (AF-1) showed the highest CO
and CO2 conversion as well as the highest selectivity for methanol.
The precursor of (AF-1) catalyst had high rosasite phase (Cu,
Zn)2CO3(OH)2 which could promote catalyst activity. Subsequent
calcinations caused the generation of sosoloid of CuO and ZnO by
Table 3
Effect of calcination time and temperature on methanol synthesis [55].
Calcination Calcination Deactivation CH3OH Highest STY
temperature (K) time (h) rate (%) selectivity (%) (g/kgcat h)
573 4.0 6.33 99.3 157.4
623 0.5 2.09 99.3 161.5
623 1.0 0.48 99.5 165.4
623 2.0 0.43 99.4 172.2
623 3.0 0.48 99.4 159.8
623 4.0 1.01 99.3 169.1
673 4.0 1.83 99.2 116.9
the decomposition of rosasite phase [51]. As for the aluminum
emulsion preparation, signicant effect on the morphology of the
catalyst could be observed. Emulsion prepared using normal
precipitation method showed uniform size distribution, lower
crystallization degree and high Cu /Cu0 ratio. The ratio of Cu /
Cu0 was responsible for good catalytic activity as both Cu metal
and Cu2O were required for an active catalyst [52]. This high
synergy between CuO and ZnO resulted in higher catalytic activity.
The aluminum precursor also strengthened the CuOZnO and
CuOalumina interaction and increased the reduction temperature
of Cu species.
Meanwhile, co-precipitation method is generally used to
synthesize Cu/ZnO catalyst for low temperature methanol synth-
esis from syngas with alcohol in which solvent and promoter
usually have some problems. It was found that the precursor
experienced signicant sintering during drying [38]. To overcome
this problem, Meng [53] proposed the use of supercritical CO2 (SC-
CO2) to extract the solvent from the catalyst precursor to avoid
agglomeration of the catalyst structure. The Cu/ZnO catalyst pre-
pared by SC-CO2 drying method showed excellent performance for
methanol synthesis from syngas compared to the conventional Cu/
ZnO catalyst. The presence of water in the catalyst precursor could
enlarge the pore size and destroy the structure of the catalyst
during calcination. With SC-CO2 drying method, water can be
extracted by maintaining the precursor structure, thus improving
the dispersion of Cu active site [54]. Based on such ndings, drying
temperature and pressure were deemed the main parameters that
inuence the catalyst performance. An optimum temperature and
pressure of 308 K and 8 MP gave maximum BET and Cu specic
surface areas. In the liquid phase methanol synthesis, the use of gas
phase Cu/ZnO/Al2O4 catalyst has shown effective activity but it lacks
in stability. Thus far, not much attention has been given on the
effect of preparation parameter on the stability of liquid phase Cu/
ZnO/Al2O4 catalyst.
Zhang [55] reported that both calcinations temperature and
time could inuence the catalyst activity and stability. As shown in
Table 3, the best calcinations temperature and time were found to
be 623 K and 2 h, respectively. The XRD, DTG and TPR data showed
that the catalyst prepared at lower calcinations temperature and
shorter calcinations time did not fully decompose [56]. When the
calcinations temperature was sufciently high and time was
sufciently long, weaker interaction between CuO and ZnO species
was caused by sintering of CuO species [57]. Stronger interaction
between CuO and ZnO led to better performance of the catalyst.
3.2. Effect of promoter on catalyst system
Previously, many of the catalysts developed are strong base
catalysts which have low industrial application as the feedstock for
industrial methanol synthesis such as gas from methane reformer
or coal gasier generally contains traces of CO2. A study conducted
by Tian et al. [58] showed that combination of solid catalyst (copper
magnesia) and homogeneous catalyst (potassium formate) enhanced
 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
Fig. 3. Reaction pathway for methanol formation [58].
low temperature methanol synthesis from syngas containing traces
of CO2. When the catalysts were used separately, low CO conversion
and high selectivity of methanol were found for Cu/MgO catalyst,
whereas potassium formate catalyst showed high CO2 conversion
but no methanol formation. Higher CO and CO2 conversions were
achieved when Cu/MgO was combined with HCOOK catalyst.
According to the reaction pathway postulated (Fig. 3), the synergy
between HCOOK for the esterication process and Cu/MgO for
hydrogenolysis process was crucial for high methanol yield.
In a similar work, Na compounds such HCOONa, Na2CO3,
NaHCO3, and NaOH have been found to have an effect on methanol
synthesis using Cu/MgO catalyst [59]. Among the promoters,
Na2CO3 showed the highest selectivity and yield of methanol.
The chemical interaction between alkali and coppermagnesium
surface improved the hydrogenolysis activity of the catalyst and
formed active site more easily. As the loading of Na2CO3 was
increased, the efciency of the catalyst increased up to a peak
point of 9 wt% Na2CO3 and then decreased. Increasing loading of
Na2CO3 resulted in increasing concentration of methyl formate
which is desirable for methanol synthesis. However, with higher
loading, the methanol yield was reduced due to the excessive
alkali that could cover some part of hydrogenolysis site on the
catalyst surface. Even with good activity towards methanol yield, it
is noteworthy that the catalyst activity dropped signicantly after
a short period of time. For further enhancement in catalytic
activity and stability, exploration works to modify the catalysts
could be performed with the addition of metal and metal oxides.
Meshkini [60] carried out a study on the effect of metal oxides
(Mn, Mg, Zr, Ce, Ba, Cr, and W) on the Cu/ZnO/Al2O4 catalyst. Using
design of experiment, the effect of each promoter and their
interaction could be obtained. It was found that the addition of
Ce reduced the activity and stability of the catalyst, whereas the
addition of Mn and Zr showed desirable effects. When only Mn
was added, there was only improvement in the activity. In the case
of Zr addition, the effect was more towards the stability of the
catalyst. Thus, the addition of both promoters created a synergy
that enhanced both catalytic activity and stability. Mn and Zr are
also structural promoters as they could improve the dispersion of
Cu particles on the surface of the catalyst.
3.3. Other catalyst system
The catalyst developed for methanol synthesis has been tested
in packed bed reactor. Researchers have found that uidized bed
reactor is not only better in terms of good heat transfer and less
expensive to manufacture, it can also limit diffusion limitation as
usually smaller sized catalyst particles are used. Since common
xed bed reactor catalyst is not suitable to be used in uidized bed
reactor [61], a series of CuZnZr catalysts with different composi-
tions have been developed to have good catalytic activity and
mechanical strength [11]. For methanol synthesis reaction, the
catalyst with a composition of Cu:Zn:Zr 4.5:1.5:3 had the highest
activity and attrition resistance. The SEM images of the catalyst
showed that the particles were nearly spherical which was in
agreement with Pham [62] that reported spherical particles
were more attrition resistant than non-spherical particles. Overall
513
stability of the catalyst was also good as no deactivation was
observed after few hours.
As catalyst pallet and particle packed beds are sensitive to
temperature and has low single pass conversion, Phan [63]
conducted a study on methanol synthesis using Cu-based mono-
liths. Monolithic catalysts give higher mechanical strength, low
pressure drop and also enhanced heat and mass transfer due to
straight channel and thin walls [64]. The work was focused on the
effects coating technique (CuO/ZnO/Al2O3 slurry coating, Al2O3
solgel coating with impregnated CuOZnO, Al2O3, colloidal coat-
ing with impregnated CuOZnO, Al2O3, colloidal coating and
depositionprecipitation) for Cu-based catalyst onto steel mono-
lith for methanol synthesis. The result indicated that, the Cu-based
monolith prepared by slurry coating via two-stage co-precipitation
showed better Cu dispersion which translated into higher catalytic
activity as compared to the other coating methods. It even showed
superior activity compared to the powder catalyst used in a xed
bed reactor. This could be due to the good thermal properties and
low pressure drop displayed by the monolith.
Other than monoliths, the use of long carbon nano tubes (CNTs)
has been reported to enhance the methanol yield [65]. The
addition of long CNTs to Cu/Zn/Al/Zr catalyst created a catalyst
with large surface area that provides more dispersion of the Cu/Zn
active site. Other than that, CNTs could also reversibly adsorb and
store considerable amount of H2, which can later be spillover to
the active sites to increase the hydrogenation reaction [66].
4. Catalyst for methanol synthesis from photo reduction
of CO2
Photo catalytic method employs the principle of photosynth-
esis in plant, in which plants absorb carbon dioxide together with
sunlight and water to produce carbohydrate energy for themselves
and oxygen as the by-product. Photo catalysis is dened as a
process where one or more reaction steps occur by the electron
pairs hole created when a source of energy (light energy) is
illuminated on the surfaces of semiconductors. Methanol can be
synthesized from CO2 according to the reactions below, in which
water serves as hydrogen source [7].
CO2 H2O-CH3OH 3/2O2 (5)
H2O 2p -1/2O2 2H (6)
 n n
H2 O-eaq ; H ; OH; H ; H2 ; H2 O 7
4.1. Effect of promoter on catalyst system
Even though TiO2 catalyst generally shows good selectivity and
product yield as compared to the other catalysts, the yield is still
considered to be low. The goal of increasing the yield has driven
studies to be conducted for further improvement in the catalyst
activity. One of the prominent ways is by doping TiO2 catalyst with
other metals and semiconductors. Tseng et al. [67] studied the
effect of copper loading on TiO2. The yield of methanol was greatly
increased and was much higher compared to that of the sol gel
derived TiO2 and commercial Degussa P25. The photo catalytic
activity of Cu/TiO2 was improved due to the lowering of recombi-
nation probability for holeelectron pairs. The supported Cu
facilitated in the redistribution of electric charge and the Schottky
barrier of Cu and TiO2. Slamet et al. [68] reported the doping of
TiO2 with CuO. CuO was found to be the most active dopant
compared to other copper species because it has the highest
potential redox. High Cu loading (optimum loading of 3 wt% Cu)
514 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
increased the efciency of the catalyst as Cu served as active site
and good electron trapper. Catalyst with more than 3 wt% Cu
reduced the methanol yield due to its shading effect by which the
photo excitation capacity of TiO2 was inhibited.
Wang [11] investigated the visible light ( 4420 nm) photo-
reduction of CO2 using CdSe quantum dots (QD) sensitized Pt/TiO2
heterostructured catalysts. It was found that the QDs uniform
dispersion and close/direct contact with TiO2 was important for
efcient separation across the CdSe and TiO2 heterojunction.
The distribution can be observed from SEM image and EDS
analysis. The Quantum connement of the dots shifts the conduc-
tion band of CdSe to higher energies, which facilitates charge
injection into TiO2. According to the redox potential, this shift is
also favorable for the injected electron to initiate the reduction of
CO2 with water, thus increasing the catalyst activity. Other than
that, the product composition was also dependent on the metal
co-catalyst (in this case Pt) as H2 was the main product when Fe
was used.
Luo [69] reported the effect of Cu and Ce doping on methanol
synthesis. Three types of TiO2 co-doped catalyst, CeCu/TiO2, Cu
Ce/TiO2, and (CeCu)/TiO2 were synthesized. It was observed that
the sequence in which the metals were impregnated signicantly
affected the surface area of the catalyst, the structure of the
catalyst and the phases formed on the surface of the catalyst. Of
the three types of catalyst, CuCe/TiO2 showed the highest yield of
methanol. This was due to the well-proportioned Cu and Ce on the
surface of the catalyst [67] as compared to the other two. Similar
increase in methanol yield was observed when TiO2 was doped
with Ag [17]. The introduction of Ag increased the specic surface
area of Ag-modied catalyst as compared to pure TiO2 catalyst.
However, the major factor that inuenced the activity of the
catalyst was the Ag concentration. The catalytic activity of the
Ag/TiO2 catalyst increased with the increase in the Ag dopant
concentration. The highest yield for methanol was obtained with
7 wt% Ag/TiO2 catalyst. For catalysts having Ag concentrations up
to 5%, more effective electron hole pair was generated due to the
decrease of absorption edge created by Ag impurity inside TiO2. As
for catalysts having Ag concentrations of more than 5%, the
formation of metal cluster inside TiO2 formed a Schottky barrier
at the metalsemiconductor interface that decreased the electron
hole recombination rate [70].
TiO2 nanotubes (TNTs) are less preferred over TiO2 powders for
photoreaction due to low quantum efciency and low energy
absorption properties [71]. However, TNTs performance can be
improved with the addition of CdS or Bi2S3 [72]. The visible light
absorption of TNTs is greatly enhanced through the modication
with CdS and Bi2S3. It is theoretically due to smaller band gap of
CdS and Bi2S3 as compared to TNTs. On the other hand, the surface
area and the CO2 absorption capacity of the catalyst experienced
reductions when CdS and Bi2S3 were added. Despite these draw-
back, TNTsBi2S3 showed the highest methanol yield followed by
TNTsCdS and TNTs. This high yield was attributed to the forma-
tion of heterojunction structure which improved the separation of
electron and holes. This prevented charge recombination and
prolonged the lifetime of the photo carrier [73].
Narrow band semiconductor compounds FeTiO3 was coupled
with TiO2 to enhance visible light response and at the same time
improve electronhole separation [74]. For both UVvis and visible
light irradiation, FeTiO3/TiO2 (FTC) catalyst exhibited better photo-
catalytic activity than the bare TiO2 and Degussa P25 catalyst. The
improvement in catalyst activity may be attributed to junction
effect between two semiconductors and the narrow band gap of
FeTiO3 [75]. It was also reported that increasing loading of FeTiO3
caused a reduction in methanol yield. The high concentration of
metal content might form recombination centers that could lead
to reduction in photocatalytic efciency.
4.2. Effect of catalyst preparation method
Cobalt-phthalocyanine (CoPc) has been used as a sensitizer to
enhance the TiO2 catalyst performance under visible light irradia-
tion but the product yield was still low. Further enhancement in
catalytic activity could be achieved by in-situ CoPcTiO2 synthesis
method [76]. Through the in-situ synthesis process, the reactants
(Co salt and 1,2-dicyanobenzene) were isolated homogenously in
pores of TiO2, that limited long distance movement and collision
between molecules. The distribution of CoPc molecules into the
pores of TiO2 matrix created a cage effect that prevented the
CoPc molecules from migrating to adjacent pores, which could
successfully avoid dimerization and aggregation of the molecules
[77]. This contact enhanced the catalytic activity as the efciency
of electronhole produced by CoPc and electron trapping by TiO2
increased. Other than that, this method also ensured that the
particle sizes obtained were uniform and had optimum diameter
that gave maximum catalytic efciency [65].
In a work by Koci [17], TiO2 particles were prepared using sol
gel and precipitation methods. Anatase TiO2 particles with crystal-
lite sizes ranging from 4.5 nm to 29 nm were synthesized using
both methods. There was a change observed in band gap energy
with the variation of TiO2 particle sizes with the largest band gap
energy (  3.14 eV) for catalyst having smaller particle size pre-
pared by precipitation method. The smallest band gap energy
( 3 eV) was recorded by the catalyst having larger particle size
prepared using sol gel method [78]. As for methanol yield, the
highest yield was obtained with the catalyst prepared using
precipitation method with particle size of 14 nm. Usually, the
catalyst activity depends on surface area and band gap energy
[79]. However in this case, the particle aggregation [80], size
quantization effect [55] and increased surface electronhole
recombination [79] could overshadow the major effects. The
competing effect of charge carrier dynamic, specic surface area
and light absorption efciency of the catalyst prepared by pre-
cipitation method determined the better catalyst.
4.3. Other catalyst system
Besides TiO2, other semiconductors with narrow band gap that
can give good selectivity for CO2 photoreduction is Cu2O. Li et al.
[72] investigated photocatalytic reduction of CO2 to methanol
using Cu2O/SiC catalyst under visible light radiation. SiC is well
known for its strong reduction performance [81]. Thus, it was
postulated that the combined effect of Cu2O and SiC could increase
the catalyst performance. The result showed that Cu2O/SiC had the
best photocatalytic performance as compared to Cu2O and SiC.
This good performance was attributed by the potentials of con-
duction bands of Cu2O and SiC that are more negative than those
of methanol yield in water and also the large average pore
diameter and small particle size of SiC.
The narrow band gap and much more negative conduction
bands potentials has made CdS and Bi2S3 ideal for methanol
synthesis under visible light irradiation [82]. In the work by Li
et al. [72], Bi2S3 modied CdS catalyst showed higher methanol
yield compared to CdS and Bi2S3 alone. Based on the UVvis
response, the enhanced visible light response of the catalyst could
be attributed to the presence of Bi2S3. The introduction of Bi2S3
also increased the specic surface area and the average pore
volume of CdS. Fig. 4 shows the mechanism for the catalyst. Since
the conduction band potentials of CdS and Bi2S3 are more negative
than those of methanol yielded from CO2, CO23  , and H2CO3, both
could serve as CO2 reducing agent. As for the oxidation of H2O,
only CdS served as the oxidation agent because it has a more
positive valence band potential.
 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
Fig. 4. Mechanism of photoreduction of CO2 to methanol [72].
lnNbO2 has also shown good catalytic activity under visible
light radiation. Better activity has been achieved with the addition
of NiO and Co3O4 co-catalysts [83]. The effect of pretreatment has
also been investigated. Without any pretreatment, 1 wt% NiO
lnNbO3 had the highest methanol yield while with pretreatment,
0.5 wt% NiOlnNbO3 showed the highest methanol yield. The
pretreatment causes ultra ne NiO particles to aggregate to form
large particles on lnNbO3 surface. This induced the formation of
positive electronhole which is undesirable in CO2 photoreduction
process. As for 0.5% lnNbO3, the presence of shellcore structure
with NiO thin shell and metallic Ni core acted as bias for electron
transfer from lnNbO3 to NiO layer. Comparing NiO with Co3O4,
higher methanol yield was obtained with NiO co-catalyst without
pretreatment. The difference in activity might be due to the redox
property of Co cations that served as good recombination centers
[84]. NiOlnNbO3 showed high activity because of the presence of
tiny NiO particles and small amount of Nb2O5.
5. Analysis of catalyst system
Most of the catalyst developments carried out for CO and CO2
hydrogenation are on Cu-based catalysts. It is clear that all the
parameters discussed earlier have signicant effects on the cata-
lyst activity. The issue arises as some of the works reported are not
in agreement with other works. In the case of Cu active site, even
though many studies have been conducted, the nature of the
active site is yet to be fully understood and there are still
controversies regarding the roles of active sites. Some researcher
suggests that the catalytic activity is proportional to the surface
area of metallic Cu (Cu0) [85]. This is based on the fact that only
Cu0 was observed on the surface of Cu(1 0 0) [86] and that the
catalyst activity increased as the Cu0 increased up to Cu/ZnO ratio
of 8 and then decreased [87]. Works by Chinchen [88] on the other
hand concluded that large fraction of Cu0 surface was covered by
oxygen containing species and that the activity of the catalyst was
independent of Cu0 surface area. This result was supported when
Cu ion was found dissolved in ZnO matrix and the rod-like
catalyst structure with more Cu had higher catalytic activity than
that of the platelets [89]. When comparing methanol synthesis on
oxidized Cu(1 0 0) with clean Cu(1 0 0), Szanyi and Goodman [90]
concluded that Cu was the active site that governed the catalyst
activity. Even with all this disagreement, it is well established that
the activation of CO/CO2 and homogenous splitting of H2 occur on
Cu or Cu0. Knowing this information is important so that when
support and promoters are added to the catalyst, the improvements
515
expected from them are clear. This is vital for better understanding
and further enhancement of the catalyst.
A good supports must be able to provide large surface area for
better dispersion of active site [91]. It also helps in terms of
improving the interaction between active site and promoter,
modulating the adsorption strength between reactant molecules
and catalyst surface, which inuences catalyst selectivity [38] and
also avoiding catalyst poisoning and sintering [92]. From the work
described above, the supports used have provided one or more
criteria for a good support but none could fulll all the necessary
criteria. Among the supports, Zn-based and Zr-based supports
have shown the best improvement on the stability and activity of
the catalyst. It has been observed that heterogeneous splitting of
hydrogen occurs on ZnO surface and it serves as hydrogen
reservoir which enhances the reaction by reverse spillover of
hydrogen from ZnO [93].
The adsorption of hydrogen is greater when ZnO is combined
together with Cu metal [94]. Few studies have also suggested that
ZnO support is an active component in methanol synthesis [95].
ZnO support provides ZnCu active site by mitigating to the Cu
surface [96]. Other than that, ZnO can also absorb poisonous
species available in the feed gas such as H2S. As for Zr-based
support, the interaction between Cu active site and ZrO2 changes
the morphology of the catalyst from monoclinic crystal phase to
tetragonal crystal phase [97]. This special structure and can
improve the stability of the catalyst and it is the main reason for
increasing interest in Zr support even tough methanol yield is
lower than Zn-support. Good thermal resistance of Zr further
increases its stability that is essential under reducing and oxidiz-
ing atmospheres [98]. Since methanol synthesis catalysts are
structurally sensitive, they are often modied with the addition
of promoter to further enhance the selectivity, activity and
stability.
Most of the metal and metal oxides described above show
positive improvement but there are few that do not show any
enhancement in the catalyst properties. It may be inaccurate to say
that these promoters are unfavorable as combination of different
parameters could also affect the nal result. Preparation method,
support [99], and promoter precursor [100] are few parameters
that could interfere and hinder the promotional effect of the
promoter. Work by Rynkowski and Gomez [101] showed that
classical impregnation method led to low dispersion of Au particle
on Cu-based catalyst which resulted in low catalytic activity. The
interaction between promoter and support was reported by
Boujana [102]. Different FT-IR spectra were obtained when Pt
was added on different support which indicated that the catalyst
had different properties.
Metals such as Zn, Al, Zr, Mg and metal oxides such as SiO2,
TiO2, Al2O3, can be regarded as promoters that have shown good
improvement for Cu catalyst. Even so, researchers are still engaged
in the search for a new promoter that can produce a better
methanol synthesis catalyst. In order to achieve that, problems
related to active site, effect of support and interaction of support,
promoter and active site must be overcome rst [100].
In order to produce an optimum catalyst, the inuence of
preparation method and preparation conditions must also be fully
understood. Reports on various improvements for conventional
preparation method and preparation condition as well as novel
preparation method are available in literature. However, issues
such as sensitivity towards pH, catalyst preparation time and cost,
and effect of calcination temperature and time for co-precipitation
method have been unsatisfactorily addressed. Many of the works
have resulted in signicant enhancement in stability and activity
of the catalyst.
Varying the pH value in catalyst preparation can affect the
phase composition of the precursor. Li and Inui [103] found that
516 K.A. Ali et al. / Renewable and Sustainable Energy Reviews 44 (2015) 508518
constant pH was important to have very ne inter-dispersion of
CuO and ZnO after calcination. In addition, novel preparation
method for low temperature methanol synthesis catalyst and
improvement of liquid phase methanol synthesis catalyst showed
promising prospect to overcome thermodynamic limitation of the
synthesis process. Since the reaction is exothermic, reaction heat
should be remove to avoid reduction in catalytic activity [104].
Methanol synthesis at low temperature can overcome this pro-
blem by offering high heat transfer efciency, high conversion per
pass and low operating cost [105]. Another way to overcome this
limitation is by using membrane dual-type reactor [106]. This type
of reactor can also enhance kinetic limited reaction. It also ensures
lower catalyst deactivation and better control of stoichiometrical
feed. Higher reactant conversion can be achieved by removing
products from reaction zone and reactants permeation to the
reaction zone, while sintering can be minimized by removing
water using permselective membrane [40].
The availability of H2 gas and the poisonous nature of CO are
the main drawbacks for methanol synthesis from CO and CO2
hydrogenation. From the environmental point of view, these
processes are undesirable because of the energy requirement to
produce H2 and syngas. This requirement is usually met by fossil
fuel burning which increases environmental problems such as
emission of greenhouse gasses. On the other hand, methanol
synthesis from CO2 and H2O using light irradiation at ambient
temperature and pressure is a good approach environmentally.
Much of the work done so for is focused on semiconductors with
narrow band gap energy. Semiconductors are chosen based on
their band gap position and electron acceptor species and electron
donor species redox potentials [107]. Reaction using visible light
irradiation is made possible by the introduction of dopant and
variation in synthesis method for the semiconductors. These
improvements have also lowered the electron and hole recombi-
nation rate that can affect methanol yield. In order to have high
catalytic activity, low recombination rate is required. This means
that more electron and hole can migrate to the surface for reaction
to occur. A good photocatalyst should be able to improve charge
separation to increase the life time of charge carrier. It should also
enhance the efciency of charge carrier and prevent charge carrier
recombination [72]. Thus far, most of the researches have focused
on improving the catalyst activity by introducing metals or other
semiconductor materials. However, the methanol yield is not as
high as yield from CO and CO2 hydrogenation. Therefore, other
factors that could affect the catalyst performance should be
explored and investigated. Factors such as the inuence of TiO2
facet on the catalyst activity and its effect and interaction with the
metal introduced can be investigated [45]. The current available
preparation method can be further modied so that TiO2 with
specic facet that show good methanol selectivity can be synthe-
sized. Other than that, most of the work done so far has neglected
the due mention on stability and deactivation of the catalyst. This
is important to ensure that the catalyst has good reusability and
can be used for long and continuous process. Therefore, it clear
that even tough methanol can be synthesized from CO2 and H2O,
there still much to be done before it can be applied in industry.
6. Conclusions
In this paper, the advancement and innovations in the catalyst
system and the effect on the efciency for methanol synthesis
have been discussed. Based on reported ndings, it can be
concluded that an effective catalyst should have a large surface
area. The large surface area will give rise to better dispersion of
active metal to enhance the performance of the catalyst. For that,
the right selection of support is vital as there are some interactions
between active metal and support that can affect the physico-
chemical properties of the catalyst. The same can be said in the
case of promoter selection. Thus a proper understanding between
these interactions must be developed to obtain a tailor made
catalyst for this application. Other than that, the catalyst devel-
oped must also have good stability. This feature is rarely discussed
in literature so far. A catalyst that has high stability is important
when it comes to industrial application. Therefore, these aspects
together with the molecular interaction mechanism should be the
focus of future studies.
Acknowledgement
A Long Term Grant Scheme (LRGS) from Ministry of Education
Malaysia (203/PKT/6723001) to support this work is gratefully
acknowledged.
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