Journal of CO2 Utilization 15 (2016) 83–88

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Journal of CO2 Utilization

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

Synthesis of methanol and dimethyl ether from the CO2 hydrogenation

over Cu
ZnO supported on Al2O3 and Nb2O5
Renata J. da Silvaa , Allan F. Pimentelb , Robson S. Monteirob,c , Claudio J.A. Motaa,b,d,*
a
Universidade Federal do Rio de Janeiro, Escola de Química, Av. Athos da Silveira Ramos, 149, CT Bloco E, 21941-909 Rio de Janeiro, Brazil
b
Universidade Federal do Rio de Janeiro, Instituto de Química, Av. Athos da Silveira Ramos, 149, CT Bloco A, 21941-909 Rio de Janeiro, Brazil
c
Catalysis Consultoria Ltda., Av. das Américas 7837, 22793-081 Rio de Janeiro, Brazil
d
INCT Energia & Ambiente, UFRJ, 21941-909, Brazil

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

Article history: We report the synthesis, characterization and catalytic evaluation of Cu
ZnO catalysts supported on Al2O3
Received 27 October 2015 and Nb2O5, as acidic materials, to study the CO2 hydrogenation to methanol and dimethyl ether. The
Received in revised form 8 January 2016 catalysts were prepared by precipitation or impregnation of the metals over the supports. They were
Accepted 31 January 2016
characterized by different techniques, such as XRF, BET area, TPD of n-butylamine, XRD and TPR. Catalytic
Available online 11 February 2016
tests were performed in an automated catalytic unit coupled to a gas chromatograph with FID and TCD
detectors. Different conditions of temperature and pressure were studied. It could be observed that the
Keywords:
choice of the synthesis method affects the activity and selectivity of the CO2 hydrogenation, at the
Methanol
Dimethyl ether
conditions used in this work. The catalyst prepared by impregnation of the metals over the Al2O3 support
CO2 hydrogenation was the most active and selective to dimethyl ether. This result can be explained by the better and lower
Al2O3 temperature reducibility of CuO particles along with higher density of acid sites and strength of the
Nb2O5 alumina support.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction commodities such as formaldehyde and acetic acid [15,16]. DME

Carbon dioxide (CO2) capture and utilization for the manufac-
ture of high value-added products is gaining increased importance,
due to the necessity to reduce the emissions of this greenhouse gas
in the atmosphere [1–8]. The hydrogenation of CO2 is a synthetic
route of special interest, as it may be used to synthesize fuels and
chemicals, thus constituting an important area of research widely
explored in recent years [9,10]. In this context, the hydrogenation
of CO2 to methanol and dimethyl ether (DME) appears as an
excellent option, as these products might find applications either
as fuels or chemicals [11–14].
Methanol is an important raw material [12,15,16]. It can be used
directly as fuel or in the production of biodiesel [17]. The Methanol
to Gasoline (MTG) process [18] has been commercialized in the
1980’s. Nevertheless, the process was adapted to produce ethene
and propene, the so-called, Methanol to Olefins (MTO) [19,20], due
to the higher added-value of the olefins compared with gasoline.
Methanol is also used in the production of important chemical
* Corresponding author at: Universidade Federal do Rio de Janeiro, Escola de
Química, Av. Athos da Silveira Ramos, 149, CT Bloco E, 21941-909 Rio de Janeiro,
Brazil.
E-mail address: cmota@iq.ufrj.br (C.J.A. Mota).
may be used in diesel engines to replace the petrodiesel.
Furthermore, it is considered greener than diesel, because it is
virtually free from sulfur and aromatics, emitting less CO, SOx and
particulates. Presently, methanol is synthesized from syngas, a
mixture of CO and H2, which in turn is produced from natural gas or
coal. DME may be produced through the acid-catalyzed dehydra-
tion of methanol or directly from syngas, using bifunctional
catalysts [13]. Additionally, methanol and DME can also be
produced from the catalytic hydrolysis of chloromethane over
metal-exchanged zeolites [21–23], thus avoiding the production of
syngas, which is highly energy demanding.
There are many studies on the CO2 hydrogenation to methanol
[13]. An industrial plant has been built in Iceland producing
hydrogen from geothermal energy. On the other hand, the direct
conversion of CO2 to DME is still poorly studied compared with its
direct production from syngas [10,24]. The synthesis of methanol
from CO2 often uses Cu
ZnO unsupported catalysts, together with
different promoters [10,25–29]. The commercial catalyst for the
methanol synthesis from syngas is constituted of 50–70% CuO, 20–
50% ZnO, and 5–20% of promoter, in this case, Al2O3 [28]. Other
oxides, such as chromium, magnesium, rare earths, gallium or
zirconium can be used as promoters too [26,30,31].
The CO2 hydrogenation to methanol is limited by thermody-
namics [32], with the equilibrium being favored to the products at

http://dx.doi.org/10.1016/j.jcou.2016.01.006
2212-9820/ã 2016 Elsevier Ltd. All rights reserved.
84 R.J. da Silva et al. / Journal of CO2 Utilization 15 (2016) 83–88
Cu.ZnO
CO2 + 3H2 CH3OH + H2O
Scheme 1. Synthesis of methanol from CO2 hydrogenation.
high pressures and low temperatures (Scheme 1). We have shown
that the traditional Cu
ZnO catalyst, promoted with Al2O3, operates
on the thermodynamic limit at 270  C and 50 bar [33,34]. However,
the catalytic activity is significantly reduced when lower temper-
atures are used, which suggests the existence of kinetic limitations
for this type of catalysts [33,34].
Cu
ZnO supported on different solid acids, such as g-alumina,
ZSM-5 or other zeolites have been used in the direct synthesis of
DME from syngas [35,36]. A bifunctional catalyst must be used to
perform the hydrogenation of CO2 to methanol and, in the
sequence, the dehydration of methanol to DME (Scheme 2), which
is performed by the acid sites of the catalyst [37–39]. Although it is
of great importance to control the temperature of the system, the
production of DME from methanol does not have severe
thermodynamic limitations [24].
Here, we report the synthesis and characterization of Cu
ZnO
catalyst supported on acidic materials (Al2O3 an Nb2O5) to study
the CO2 hydrogenation to methanol and DME.
2. Experimental
The catalysts were prepared by precipitation or impregnation of
Cu(NO3)2
3H2O (99% purity) and Zn(NO3)2
6H2O (98% purity), both
from Sigma–Aldrich, over g-alumina (Al2O3), Puralox MP2218 from
Evonik, and calcined niobium oxide (Nb2O5), obtained from
amorphous hydrated niobium pentoxide (Nb2O5
nH2O—72.6%
Nb2O5) supplied by CBMM (Companhia Brasileira de Metalurgia
e Mineração, Brazil), as solid acid supports. Prior to impregnation
or precipitation of the metal precursors, the hydrated niobium
pentoxide was calcined at 550  C for 2 h in order to stabilize the
structure and avoid the possible formation of metal niobates, due
to strong metal-support interaction [40]. The alumina support was
used without any previous thermal treatment.
In the precipitation method, 1.9 g of copper nitrate and 2.3 g of
zinc nitrate (metal atomic ratio of 1:1) were dissolved in 500 mL of
deionized water and put in contact with 10 g of alumina or the
calcined niobium oxide. The system was subjected to stirring and
1 mol L 1 solution of NaOH (99% purity) was added dropwise until
pH 7. At the end, the system was aged for one hour at room
temperature before filtration, washing and drying. The catalysts
prepared by precipitation are denoted with (p).
In the impregnation method, the solution containing the copper
and zinc cations was put in contact with the alumina or niobium
oxide support and vigorously stirred for 24 h at room temperature.
Then, the water was carefully evaporated on a rotary evaporator at
60  C and reduced pressure. The catalysts prepared by impregna-
tion are denoted with (i).
All catalysts prepared, either, by precipitation or impregnation
were calcined at 550  C for 2 h prior to the catalytic runs.
The catalyst composition was obtained by X-ray florescence
(PW2400 Philips equipped with Rh tube 3 KW). The textural
characterization was carried out by N2 physisorption on a
Micromeritics ASAP 2020 equipment. X-ray diffraction was
performed on a Shimadzu 6000 instrument equipped with a Cu
Cu.ZnO
2 CO2 + 6H2 2 CH3OH + 2 H2O
+ a
"H "
2 CH3OH CH3OCH3 + H2O
Scheme 2. Synthesis of DME from CO2 hydrogenation over bifunctional catalyst.
Ka target, operating at 40 kV and 30 mA. Standard powder
diffraction patterns were gathered for 2u angles ranging from
5 to 80 at a scanning speed of 4 /min. Temperature Programmed
Reduction (TPR) was carried out at a home-made system, using a
mixture of 1.7 mol% of H2 in Argon. The acidity of the catalyst was
determined by temperature programmed desorption of n-butyl-
amine, following a procedure described elsewhere [41].
CO2 hydrogenation reactions were carried out in a PID high
pressure automatic flow unit, coupled with an Agilent 7890A gas
chromatograph equipped with Flame Ionization (FID) and Thermal
Conductivity (TCD) detectors. An on-line system was used to
analyze the products of the reaction on a Plot/Q column
(30 m  0.320 mm  20 mm). A stainless steel reactor was loaded
with 500 mg of catalyst and 500 mg of inert SiC, both sieved to 32–
115 mesh, to form a fixed bed. The catalysts were initially reduced
under a mixture of 10 mol% H2 in N2 in two steps. Initially, the
temperature was increased to 140  C at a rate of 1  C min 1,
remaining at this temperature for 5 h. Then, the temperature was
set to 270  C, using the same previous rate of 1  C min 1, and
remaining at this temperature for 2 h. After reduction, the
temperature was set to the desired value (250 or 270  C) and
the system was pressurized (30 or 50 bar) with a 1:3 molar mixture
of CO2 and H2 (25 vol.% CO2 and 75 vol.% H2), respectively. The
space velocity was kept constant at 10 h 1 and the reaction was
monitored for 8 h, without presenting any significant deactivation.
3. Results and discussion
Table 1 shows the results of chemical and textual character-
izations of the prepared catalysts. Except for the Cu
ZnO/Nb2O5 (p),
mostly catalysts presented atomic ratios of these metals close to 1.
The BET area of the supported catalysts was lower than the original
alumina and calcined niobium oxide supports. Calcined niobium
oxide showed a much lower BET area, which is attributed to the
high temperature thermal treatment used to stabilize it from an
amorphous hydrated niobium pentoxide [42]. However, there was
no significant difference in the areas for the precipitated or
impregnated catalysts considering the same support.
Table 2 shows the results of total acidity and acid strength
distribution of the catalysts in comparison to the original supports.
The alumina support has more acid sites than the calcined niobium
oxide and this property was reflected on the prepared catalysts.
Except for the Cu
ZnO/Nb2O5 (p) catalyst, the total acidity
increased with the presence of the metals. This may be explained
in terms of the adsorption of the probe molecule onto the metals
surface.
XRD analyses show that the synthesized catalysts present the
same diffraction patterns exhibited by the original supports
(Figs. 1 and 2). Prior to calcination, Nb2O5 is an amorphous
hydrated niobium pentoxide (Nb2O5
nH2O). Its thermal treatment
Table 1
Chemical and textural characterization of the catalysts.
Catalyst Metal (wt%)a BET area (m2/g)b
Cu Zn
Cu
ZnO/Al2O3 (p) 3.7 3.0 171
Cu
ZnO/Al2O3 (i) 3.7 3.2 168
Cu
ZnO/Nb2O5 (p) 3.1 4.7 30
Cu
ZnO/Nb2O5 (i) 2.6 2.8 32
Nb2O5c – – 42
Al2O3 – – 206
Determined by XRF.
b
Determined by N2 Physisorption.
c
Calcined at 550  C.
 R.J. da Silva et al. / Journal of CO2 Utilization 15 (2016) 83–88
Table 2
Acid strength distribution of the catalysts measured by n-butylamine thermodesorption. Values in mmol g
Catalyst Medium acid sites (150–299  C)
Cu
ZnO/Al2O3 (p) 0.28
Cu
ZnO/Al2O3 (i) 0.44
Cu
ZnO/Nb2O5 (p) 0.04
Cu
ZnO/Nb2O5 (i) 0.16
Nb2O5a 0.09
Al2O3 0.29
a
Calcined at 550  C.
at 550  C for 2 h turned it into the crystalline form as shown in
Fig. 2 [43,44].
Figs. 1 and 2 also show the XRD patterns of bulk CuO and ZnO,
showing that there is no conclusive evidence for the presence of
crystalline phases of these oxides in the supported catalysts. Both
preparation methods, by precipitation or impregnation, were
successful in generating well-dispersed amorphous or poorly
crystalline undetectable small particles of copper and zinc oxides.
This fact may be explained by the low amount of metals on the
catalysts, in the range of 3 wt.%.
Fig. 3 shows the TPR profiles of the prepared catalysts, as well as
of the bulk CuO as reference. The reduction profile of CuO is
characterized by a broad peak ranging from 200 to 400  C, which
encompasses the two-step reduction of copper oxide, namely, Cu+2
to Cu+1 and Cu+1 to Cu [45]. ZnO does not reduce at this
temperature range and its TPR profile is not shown. H2 consump-
tion was observed above 800  C for the catalysts supported on
Nb2O5 and may be ascribed to the reduction of the support.
CuO reducibility seems to be influenced by the nature of the
support and the preparation method. On Al2O3-supported
catalysts, the reduction temperature peak has shifted to lower
temperatures, which was much more pronounced on the
impregnated catalyst. Impregnation technique for supporting
metal particles tends to produce more aggregation of metal
clusters, as the result of the increasing viscosity of the metal
Fig. 1. XRD pattern of the catalysts supported on Al2O3.
85
1
of catalyst.
Strong acid sites (300–550  C) Total acidity
0.50 0.78
0.29 0.73
0.12 0.16
0.11 0.27
0.16 0.25
0.35 0.64
precursors solution during the drying process of solvent removal
[46]. Large aggregates might have a weaker interaction with the
support and then the reduction is facilitated.
Conversely, on Nb2O5-supported catalyst, the reduction tem-
perature peak has shifted to higher temperatures. CuO was much
more difficult to reduce when supported on calcined Nb2O5. Nb2O5
is a well-known reducible metal oxide support in the presence of
metal particles and strongly interacts with them. Even with the
previous thermal treatment, aiming the stabilization of its
structure, calcined Nb2O5 still strongly interacts with the metal
particles on the surface. For reducible oxides, such as TiO2, CeO2
and Nb2O5, the literature describes a phenomenon known as a
strong metal-support interaction (SMSI) [47], which might be the
main cause for shifting the CuO reduction peak to higher
temperatures.
Fig. 4 shows the results of CO2 conversion over the supported
catalysts. As expected, the conversion increases with the increas-
ing of the pressure as predicted by thermodynamics. The catalysts
were also more active at raising temperatures with increased
performance at 270  C, which indicates that at such low
conversions the reaction still responds to the temperature, because
the reaction is far from the equilibrium. The most active catalyst
was the Cu
ZnO/Al2O3 (i), showing 9% conversion at 270  C and
50 bar. The catalysts supported on Nb2O5 were significantly less
active, as well as the Cu
ZnO/Al2O3 (p).
86 R.J. da Silva et al. / Journal of CO2 Utilization 15 (2016) 83–88

Fig. 2. XRD pattern of the catalysts supported on Nb2O5.

As discussed earlier, TPR profiles showed that the nature of the
support and the preparation method strongly affected the CuO
reducibility. Other important point is the fact that for all catalysts,
the pre-activation reduction temperature was limited to 270  C for
2 h, in order to avoid metal particles sintering at much higher
reduction temperatures. This careful procedure prevented the
complete bulk reduction of CuO particles, with the generation of
Cu active sites only on the surface and, to some extent, to the
immediate underneath sub-surface layers. The number or density
of available Cu active sites as shown by the TPR profiles might
dramatically change, as the shifting to higher or lower reduction
temperatures seems to be governed by the nature of the support
and the preparation method.
The easiest reducibility of CuO on the Al2O3-supported and
impregnated Cu
ZnO catalyst showed that not only surface, but
possibly bulk CuO reduction has occurred. That might explain its

Fig. 3. TPR profiles of Nb2O5- and Al2O3-supported Cu
ZnO catalysts. Bulk CuO is also shown as reference. The dotted line represents the pre-activation reduction temperature
(270  C) of the catalysts.
 R.J. da Silva et al. / Journal of CO2 Utilization 15 (2016) 83–88
Fig. 4. CO2 conversion over CuZn-based supported catalysts. ( ) Cu
ZnO/Al2O3 (p); ( ) Cu
ZnO/Al2O3 (i); ( ) Cu
ZnO/Nb2O5 (p); ( ) Cu
ZnO/Nb2O5 (i).
higher activity expressed in terms of CO2 conversion, due to much
higher availability of Cu active sites. For catalyst prepared by
precipitation technique and for Nb2O5-supported Cu
ZnO catalysts,
the pre-activation reduction temperature was not high enough to
generate a higher density of Cu active sites resulting in a much
lower activity for those catalysts.
Table 3 compares the effect of temperature and pressure on the
selectivity. The formation of DME was observed only over Cu
ZnO/
Al2O3 (i) and Cu
ZnO/Nb2O5 (i). Comparing the Al2O3-supported
catalysts, Cu
ZnO/Al2O3 (p) produced only methanol, whereas
Cu
ZnO/Al2O3 (i) produced methanol and DME. This is a conse-
quence of the higher conversion observed over the later catalyst.
The same behavior was also observed for the catalysts supported
on Nb2O5, with Cu
ZnO/Nb2O5 (i) showing formation of DME at the
more severe reaction conditions.
It is possible to observe that the DME production is limited by
the activity of the catalyst. Thus, the DME selectivity increases for
higher conversions of CO2. Therefore, it is necessary to produce
sufficient amounts of methanol, which upon contact with the acid
sites of the support, can be dehydrated to DME. In the present
study, it seems that the acidity of the catalysts is well adjusted to
dehydrate the alcohol, as the acidity of the Al2O3 supported
catalysts were the same, but only one of them produced DME,
indicating that the production of methanol is the major factor
controlling the selectivity. Temperature and pressure have little
effect on the selectivity. It would be expected that DME selectivity
increases with temperature, as dehydration is endothermic.
Nevertheless, for Cu
ZnO/Al2O3 (i) the selectivity to DME did not
significantly increase with temperature. This may be explained by
the overall low conversion of the catalytic system, which impairs a
more precise evaluation of the effect of this parameter. On Cu
ZnO/
Nb2O5 (i), the increase in temperature led to the production of
DME, although in low selectivity.
Recently, a study of CO2 hydrogenation over Cu supported on
Al2O3 with different promoters was carried out [48]. Authors
observed conversions in the range of 9–12% at 250  C and 20 bar of
Table 3
Effect of temperature and pressure on selectivity.a
Catalyst 250  C/30 bar 250  C/50 bar
(%) MeOH (%) DME (%) MeOH
Cu
ZnO/Al2O3 (p) 100 – 100
Cu
ZnO/Al2O3 (i) 65 35 76
Cu
ZnO/Nb2O5 (p) 100 – 100
Cu
ZnO/Nb2O5 (i) 100 – 100
a
Reaction performed for 8 h and WHSV = 10 h 1.
87
pressure. CO was the major product with selectivity varying from
61 to 83% depending on the promoter used. Methanol selectivity
was within 13 to 36%, whereas methane was also formed in minor
amounts. DME was not observed and this may be due to the much
higher space velocity used, in the range of 1400–5000 h 1. The
amount of Cu was about three fold higher than the one used in this
study, which may explain the lower CO2 conversion observed in the
present study. Nevertheless, the much lower space velocity used in
the present work favored the formation of DME in the case of the
most active catalyst, prepared by the impregnation of Cu and Zn
over Al2O3. Therefore, besides the preparation method, the
adequate choice of experimental conditions is crucial to perform
the two consecutive reactions: methanol formation from CO2
hydrogentaion and its dehydration to DME. A low space velocity
provides more contact between the formed methanol and the
acidic support to catalyze the methanol dehydration to DME.
Oyola-Rivera and collaborators also studied the CO2 hydro-
genation to methanol and dimethyl ether at 270  C and 17 bar of
pressure, using Pd-based catalyst supported on Ga2O3 [37]. They
reported DME selectivity varying from 4 to 53%, whereas the CO2
conversion varied in the range of 5 to 14%. Apparently, the nature of
the Ga2O3 phase has a great influence on the selectivity to DME.
The main problem is the high costs of gallium, which may impair
its industrial utilization.
Our present results indicate that it is possible to hydrogenate
CO2 to methanol and dehydrate it to dimethyl ether over
traditional Cu
ZnO catalysts supported on acid meterials. The
proper choice of the preparation procedure and space velocity
seems critical for the production of DME. It is not completely clear
why impregnation of the metals leads to a better reducibility of the
CuO supported on Al2O3, but a combination of weaker interaction
with the support and the presence of large metal clusters might be
the reasons for such behavior. Additional experiments must be
carried out to study the interaction between the metal oxide
particles, as well as with the support.
270  C/30 bar 270  C/50 bar
(%) DME (%) MeOH (%) DME (%) MeOH (%) DME
– 100 – 100 –
24 65 35 69 31
– 100 – 100 –
– 100 – 95 5
88 R.J. da Silva et al. / Journal of CO2 Utilization 15 (2016) 83–88
4. Conclusions
Copper and zinc oxides supported on Al2O3 and Nb2O5 catalysts
were prepared by precipitation or impregnation of the metal
precursors. The atomic ratio of the metals was nearly to 1 for most
of the catalysts. The area of the catalysts decreased upon metal
impregnation or precipitation. The TPR profiles were similar for all
catalysts, except the catalyst prepared by impregnation of the
alumina support (Cu
ZnO/Al2O3 (i)), which showed a better
reducibility than the others. The XRD diffraction was similar to
the diffraction patterns of the original supports and did not show
evidence for the formation of CuO or ZnO crystalline phases,
indicating a good dispersion of the metals on the support.
The catalysts were evaluated in the CO2 hydrogenation. The CO2
conversion depended on the temperature and pressure used, being
higher at 270  C and 50 bar. The most active catalyst was the
Cu
ZnO/Al2O3 (i), showing 9% conversion at these conditions. This
result may be interpreted in terms of the better reducibility of this
catalyst compared with the others.
Formation of DME was observed only on the impregnated
catalysts, with the highest selectivity, around 35%, being observed
over the Cu
ZnO/Al2O3 (i). This result may be explained in terms of
the higher CO2 conversion on this catalyst, producing more
methanol. These data indicate that, under the reaction conditions
used, the formation of DME is mostly governed by the metal
activity of the catalyst to perform the CO2 hydrogenation, rather
than by the acid function, which seems to be well adjusted once
larger amounts of methanol are initially produced.
Acknowledgments
Authors thank CNPq,FAPERJ, CAPES and BNDES for financial
support.
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