Applied Catalysis A: General 401 (2011) 46–55

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Applied Catalysis A: General

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

Study on the preparation of Cu/ZnO catalyst by sol–gel auto-combustion method

and its application for low-temperature methanol synthesis
Lei Shi a , Kai Tao a , Ruiqin Yang b , Fanzhi Meng a , Chuang Xing a , Noritatsu Tsubaki a,c,∗
a
Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
b
Zhejiang Provincial Key Lab. for Chem. & Bio. Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science &
Technology, Hangzhou 310023, PR China
c
JST, CREST, Sanbancho 5, Chiyoda-ku, Tokyo 102-0075, Japan

a r t i c l e i n f o a b s t r a c t

Article history: A series of the as-burnt and the burnt Cu/ZnO catalysts were prepared by a sol–gel auto-combustion
Received 9 December 2010 method using metal nitrates with the mole ratio of Cu/Zn = 1/1 (noted as M, M = Cu + Zn) and citric acid
Received in revised form 16 April 2011 (noted as CA). When the xerogels were burnt in the argon atmosphere, H2 and CH4 which were came
Accepted 27 April 2011
from the decomposition of the citric acid, were the reducing agents and were used in the redox process
Available online 10 May 2011
for synthesizing metallic Cu from Cu2+ in the chelated compound. The XRD patterns revealed that all the
as-burnt catalysts with different M/CA molar ratios were converted into pure Cu and ZnO species. TPR
Keywords:
analysis of the as-burnt catalyst illustrated that almost no hydrogen was consumed. It proved that Cu2+ in
Low-temperature
Methanol synthesis
the chelated compound was absolutely reduced to metallic Cu in the as-burnt catalyst. The effects of M/CA
Auto-combustion molar ratio on the properties of catalysts were studied by TG-DTA, FT-IR, Raman spectrum, XRD, SEM-
Cu/ZnO EDS, BET, and N2 O chemisorption techniques. The activity of the as-burnt catalysts without reduction
Metallic catalysts was investigated for low-temperature methanol synthesis from syngas containing CO2 using ethanol as a
promoter at 443 K and 5.0 MPa for 12 h. The total carbon conversion increased with increasing the content
of citric acid and reached a maximum for the as-burnt Cu/ZnO catalyst C0.8 with M/CA = 1/0.8, and then
decreased. The variation trend was in accordance with that of the copper (Cu0 ) surface area. Comparing
with the burnt catalyst C0.8-air after reduction, the methanol selectivity of the as-burnt Cu/ZnO catalyst
was much lower owing to lower hydrogenation activity of the ethyl formate. The as-burnt catalyst C0.8
was also used in continuous low-temperature methanol synthesis at 443 K and 5.0 MPa for 40 h. The
total carbon conversion was stable after 15 h and no obvious deactivation during 40 h reaction, but the
methanol selectivity was still not high.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction The present authors proposed a new method of low temperature

Methanol was widely used as a feedstock for the chemical indus-
tries and at the same time as an alternative fuel which was used in
fuel cells [1–3]. Methanol was industrially produced under high-
temperature and high pressure (523–573 K, 8.0–10 MPa), mainly
using Cu/ZnO catalysts developed by ICI Co. However, the efficiency
of methanol synthesis was severely limited by thermodynamics
because methanol synthesis was an extremely exothermic reaction.
Therefore, developing a low-temperature process for methanol
synthesis will greatly reduce the production cost and high one-pass
CO conversion will become available at low temperature.
∗ Corresponding author at: Department of Applied Chemistry, School of Engineer-
ing, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan.
Tel.: +81 76 445 6846; fax: +81 76 445 6846.
E-mail address: tsubaki@eng.u-toyama.ac.jp (N. Tsubaki).
synthesis of methanol from CO/CO2 /H2 on Cu/ZnO based catalyst
using alcohol as a catalyst and solvent, by which methanol was
produced at 443 K and 5.0 MPa [4–7]. As the used alcohol solvent
contained a small amount of water, it was considered that this
new low-temperature process could directly use low-grade syngas
containing CO2 and H2 O, without purification.
It was generally known that the particle size, surface area, metal-
lic surface area and composition of the catalyst were important
factors to the catalytic activity. A linear relationship between the
catalytic activity and the metallic Cu surface area of Cu/ZnO cata-
lyst was proved by Chinchen et al. [8]. To increase furthermore the
activity and selectivity of Cu/ZnO based catalyst for the new low-
temperature methanol synthesis, its preparation method should
be improved. In recent years, various methods were developed to
prepare Cu/ZnO based catalysts with large surface area and copper
surface area, which were believed to have a high catalytic activity
for methanol synthesis from CO (CO2 ) hydrogenation [6,9,10].

0926-860X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2011.04.043
 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55 47

Mixing of metal nitrate and citric acid

Ammonia Solution

pH value 7, transparent blue solution

Refluxing at 353 K for 4 h

Evaporating at 343 K

Dark blue viscous gels

Drying at 393K for 40h

Porous polymeric xerogel

Calcining at 523-723 K in argon, Calcining at 523-723K in air,

auto-combustion auto-combustion

Porous and loose pure Cu/ZnO catalyst Porous and loose CuO/ZnO

Fig. 1. Schematic flow chart of the catalysts prepared by a sol–gel auto-combustion method.

Recently, the sol–gel auto-combustion technique had emerged
as an attractive method for the production of high purity and crys-
talline oxide powders [11–17]. For the first time, Jiang et al. had
used citric acid–nitrate auto-combustion method to prepare pure
metals and alloys [18]. Wolf et al. presented a glycine–nitrate com-
bustion method to prepare nanopowders of pure nickel [19] and
copper–nickel alloys [20]. For the first time, we improved this novel
technology to directly prepare metallic catalyst. And for the first
time we used the as-burnt catalyst in the catalytic reaction without
further reduction. This technique was based on a chemical sol–gel
process combined with subsequent combustion process. An aque-
ous solution containing the desired metal salts and organic fuel
formed a gel through a sol–gel process, and then the gel was ignited
to combust, giving a voluminous and fluffy product with a large
surface area. In this process, citric acid was generally used as a
complexant to form a homogeneous precursor gel.
There were few reports [21–23] on the combustion methods of
the preparation of CuO based catalysts for methanol synthesis and
reforming of methanol [24]. However, the reported CuO based cat-
alysts had to be further reduced with hydrogen at high temperature
to obtain metallic Cu. The extra cost for reduction energy and engi-
neering made the whole catalyst preparation process inefficient.
In the present work, the as-burnt Cu/ZnO catalysts were pre-
pared by one-step sol–gel auto-combustion method, and applied
directly without hydrogen reduction in low-temperature methanol
synthesis reaction from the syngas containing CO2 .
(wt.%) to reach a pH value of 7. Stirring and refluxing at 353 K for
4 h ensured the citric acid completely chelating with the metal ions.
Subsequently, the neutralized solution was evaporated at 343 K
on a hot plate with continuously stirring, until dark blue viscous
xerogels were formed. Then the xerogels were dried at 393 K for
40 h. Next, the xerogels was treated in two ways, respectively. One
way was that the xerogels were put into a ceramic tube oven and
the temperature was increased up to about 493 K in the argon
atmosphere, leading to the ignition of the xerogels. The xerogels
burnt in a self-propagating combustion manner until all xerogels
completely burnt out to form a loose product. After that, the tem-
perature was continuously increased to 723 K and maintained for
1 h in the argon atmosphere. The as-burnt catalysts were directly
used for low-temperature methanol synthesis without hydrogen
reduction. Another way was that the xerogels with M/CA = 1/0.8
(noted as C0.8-air ) was put into a muffle oven and the temperature
was increased up to about 493 K in the air atmosphere, leading
to the ignition of the xerogels. After that, the temperature was
continuously increased to 723 K and maintained for 1 h in the air
atmosphere. The precursors were then reduced by a flow of 5%
hydrogen in nitrogen at 523 K for 10 h and successively passivated
by 1% oxygen diluted by nitrogen. As for a reference, the as-burnt
C0.8 which was also reduced by a flow of 5% hydrogen in nitrogen
at 523 K for 10 h and successively passivated by 1% oxygen diluted
by nitrogen was noted as C0.8-reduction .

2.2. Characterization of catalysts

2. Experimental
2.1. Preparation of catalysts
Schematic flow chart of the catalyst prepared by a sol–gel
auto-combustion method was shown in Fig. 1. Analytical-grade
Cu(NO3 )2 ·3H2 O (≥99%), Zn(NO3 )2 ·6H2 O (≥99%) and citric acid were
used as raw materials. The metal nitrates with the mole ratio of
Cu/Zn = 1/1 (noted as M, M = Cu + Zn) and citric acid (noted as CA)
were firstly dissolved in the distilled water according to different
M/CA molar ratios 1:0.5, 1:0.8, 1:1 and 1:1.5, denoted as C0.5 , C0.8 ,
C1 and C1.5 . The solutions were adjusted using ammonia of 28%
The thermal decomposition behaviour of the xerogels was char-
acterized by thermogravimetic and differential thermal analysis
(DTA/TGA 60, Shimadzu) at a heating rate 10 K/min from 293 to
1173 K in the argon atmosphere.
XRD patterns were obtained on a Rigaku RINT 2400 X-ray
diffractometer in the air atmosphere, using monochromatic Cu K␣
radiation, scanning 2 from 20◦ to 80◦ , and at 40 kV and 40 mA.
The Cu crystalline average size was calculated by Scherrer formula:
D = K/(ˇcos ), where D was the averaged dimension of crystallites,
K was the Scherrer constant 0.89,  was the wavelength of X-ray
(Cu K␣ = 0.154 nm), and ˇ was the width of the peak at half height.
48 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55
Fig. 2. The flow-type batch configuration for low-temperature methanol synthesis.
Infrared spectrum was recorded in the air atmosphere with a
Shimadzu Fourier Transform Infrared Spectrophotometer (FTIR-
8400).
Micro-Raman analysis of specimens was performed in the air
on a multichannel bench Renishaw InVia Reflex spectrometer
coupled with a Peltier-cooled CCD detector. The instrument was
equipped with a 514 nm diode laser for excitation, with a maxi-
mum output power of 100 mW and the power of the laser could
be decreased to 10% of maximal output power. The spectrum was
centred to 520 cm−1 over a time of 1 s with the diffraction grat-
ing of 1200 grooves/mm. The samples were scanned from 800 to
2000 cm−1 (the spectrum region that provided the most valuable
data on the microstructure of the amorphous carbon). All samples
were measured five times to check the reproducibility of spectrum
and to enhance the accuracy of the data by accumulation.
TPR experiments were carried out by catalyst analyzer BELCAT-
B, using 0.035 g burnt catalysts with 5% hydrogen diluted by
argon at atmospheric pressure. Before reduction, the catalysts were
heated at 323 K in flowing argon for 2 h. Then, the 5% hydrogen
(50 ml/min) was passed over the catalyst sample, and the tem-
perature was linearly raised from 298 K to 723 K at a heating rate
of 5.0 K/min. Water, formed during the reduction, was trapped by
molecular sieves 3A. The effluence gas was analyzed by a thermal
conductivity detector (TCD), with argon used as a reference.
The physical structures of the catalysts, as well as compositional
analysis and surface morphology observation, were measured by
scanning electron microscopy (SEM) (JEOL, JSM-6360 LV) with
energy-diffusive X-ray spectroscopy (EDX) (JEOL, JED-2300). The
samples for this analysis were firstly coated with a platinum layer
on the surface by an auto fine coater (JEOL, JFC-1600).
The copper (Cu0 ) surface area (SCu ) was determined by a nitrous
oxide (N2 O) pulse method as described elsewhere [6].
The surface area of the catalysts was determined by N2 physical
desorption at 77 K, using a Micromeritics NOVA 1000 SP surface
area and porosimetry analyzer. Samples were degassed at 473 K
prior to acquiring the adsorption isotherm. The surface areas were
calculated according to the BET method, using 0.164 nm2 as the
cross-sectional area of the nitrogen molecule.
2.3. Catalytic activity tests
A batch reactor with 80 ml inner volume and a stirrer was used to
study the catalytic activity. The catalyst of 1 g and 40 ml of ethanol
were firstly poured into the autoclave. The air inside was purged
by the reactant gas, Ar/CO/CO2 /H2 = 3.13/33/5.23/58.64, then the
pressure in the reactor was raised to 5.0 MPa at 298 K and the reac-
tion took place at 443 K for 12 h. The stirring speed was fixed at
2000 rpm to prevent the diffusion controlled regime. A continu-
ous methanol synthesis (as shown in Fig. 2) was also conducted at
443 K and 5.0 MPa for 40 h, using a flow-type batch reactor with
80 ml inner volume and with 3 g catalyst as well as 40 ml ethanol.
All products were determined on GC–MS (Shimadzu GCMS 1600). A
TCD (Shimadzu GC-320) was used to analyze gaseous products and
a FID (Shimadzu GC-8A) was used to analyze liquid products. The
CO, CO2 , total carbon conversions and the selectivity of the liquid
products were calculated as follows:
(CO/Ar in feed − CO/Ar in effluent)
CO conv. = 100 × (1)
(CO/Ar in feed)
(CO2 /Ar in feed − CO2 /Ar in effluent)
CO2 conv. = 100 × (2)
(CO2 /Ar in feed)
a b
Total carbon conv. = CO conv. × + CO2 conv. × (3)
(a + b) (a + b)
(a, b were the contents of CO, CO2 in the feed gas)
The selectivity of the liquid products was calculated as follows:
Pi yield
Pi selectivity = 100 ×  (4)
Pi yield
(Pi was the mol number of each liquid product)
3. Results and discussion
3.1. TG-DTA analysis of the citric acid and the xerogels with
different M/CA molar ratios to study the auto-combustion process
Thermal behaviour of the xerogels with different molar ratios
of metal nitrates (noted as M, M = Cu + Zn) to citric acid (noted
as CA) was investigated by TG-DTA measurements in the argon
atmosphere and in the air atmosphere. The results of the TG-DTA
analysis were shown in Fig. 3. The DTA plots of Fig. 3A presented
two endothermic peaks at 440 and 483 K, and one exothermic
peak at 743 K. The endothermic peak at 440 K could be assigned
to the melting of the citric acid, and there was no weight loss.
Another endothermic peak at 483 K came from the decomposi-
tion of citric acid [25], releasing CH4 , H2 , H2 O and CO2 , resulting
 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55 49

400 400
1.0 A 300 1.0 B
TG TG 300
0.8 200 0.8 200

Weight loss

Weight loss
0.6 100 0.6 100

μV
DTA

μV
DTA
0.4 0 0.4 0
-100 -100
0.2 0.2
-200 -200
0.0 0.0
400 600 800 1000 400 600 800 1000
Temperature (K) Temperature (K)
400 400
1.0 C 300 1.0 D 300
TG TG
0.8 200 0.8 200
Weight loss

Weight loss
0.6 100 0.6 100

μV
DTA

μV
DTA
0.4 0 0.4 0
-100 -100
0.2 0.2
-200 -200
0.0 0.0
400 600 800 1000 400 600 800 1000
Temperature (K) Temperature (K)
400 400
1.0 E 1.0 F
TG 300 TG 300
0.8 200 0.8 200
Weight loss

Weight loss
0.6 100 0.6 DTA 100
μV

μV
DTA
0.4 0 0.4 0
-100 -100
0.2 0.2
-200 -200
0.0 0.0
400 600 800 1000 400 600 800 1000
Temperature (K) Temperature (K)

Fig. 3. TG-DTA curves of (A) citric acid, and the xerogels burnt in argon with the different M/CA molar ratios of (B) 1:0.5, (C) 1:0.8, (D) 1:1, (E) 1:1.5 and the xerogel burnt in
air with M/CA molar ratio of (F) 1:0.8.

in a large weight loss. The exothermic peak arose from the pyrol-
ysis of the residue organics at higher temperature. At last, 10%
weight of carbonic residue was left, as observed from the TG
curve.
The DTA plots in Fig. 3B–F presented three endothermic peaks,
and two or three exothermic peaks. The first endothermic peak at
about 323 K could be assigned to the evaporation of the remained
water in the gel. The second endothermic peak at 393 K arose from
desorption of chemically adsorbed water. The third endothermic
peak at 443 K came from the decomposition of NH4 NO3 produced
by pH adjustment of the solution. All the DTA plots in Fig. 3B–F pre-
sented one sharp exothermic peak at about 493 K in a very narrow
temperature range and at the same time the TG plots showed an
abrupt weight loss, which indicated that the combustion process
of xerogels happened as a severe redox reaction wherein citric acid
acted as reductant, and nitrate ions and Cu2+ in the chelated com-
pound acted as oxidant. During this combustion process, a large
amount of gases such as H2 , H2 O, CH4 , NO, CO2 , NH3 , NO2 were
liberated according to the literatures [18,26]. H2 and CH4 were
the reducing agents that could be used in the redox process for
obtaining metallic Cu from Cu2+ in the chelated compound. The
whole reduction process could be separated in four steps: (1) the
decomposition of NH4 NO3 at about 440 K, some NO3 − still left in the
xerogels; (2) generation of CH4 and H2 by the decomposition of cit-
ric acid at the beginning of 483 K; (3) severe redox process between
CH4 –H2 and NO3 − at about 493 K; (4) reduction of metallic Cu from
Cu2+ in the chelated compound by CH4 and H2 .
The second exothermic broad peaks from about 650 to 800 K in
Fig. 3B–E arose from the pyrolysis of the residue organics. Compli-
cated carbonic residues left in the as-burnt catalysts were further
proved by FT-IR, Raman and SEM-EDS.
As well known, the redox process was strongly influenced by
the ratio of oxidant to reductant. Decreasing the content of reduc-
tant made the redox process more severe. The fierceness and the
flame temperature of the combustion process were strongly influ-
enced by the original M/CA molar ratio [13–15]. As shown in Fig. 3B,
the combustion process was the most severe for the catalyst C0.5
with M/CA = 1/0.5 than others, consequently there was only one
sharp exothermic peak and the residue organics decomposed at the
same time. With increasing the content of the citric acid, the flame
temperature was lower, and the combustion was much gentler. As
compared in Fig. 3C–E, the second exothermic broad peak became
larger gradually. It was considered that more complicated carbonic
residue which was derived from the pyrolysis of the residue organ-
ics, was left in the as-burnt catalyst with increasing the content of
citric acid.
The DTA plots of the xerogel burnt in the air atmosphere with
M/CA = 1/0.8 were compared in Fig. 3F. The DTA plots presented
three exothermic peaks. One sharp exothermic peak at about 493 K
in a very narrow temperature range was derived from the combus-
tion process in the air atmosphere. As O2 was a kind of oxidant and
participated in the redox reaction during the combustion process,
the xerogel burnt in the air atmosphere was more severe than that
in argon (as compared in Fig. 3C). The second exothermic peaks at
about 590 K arose from the amorphous carbon oxidation which was
in accordance with the experiment results reported by Liu et al. [27]
and Pranda et al. [28]. Amorphous carbon oxidation was a sustain-
ing heat releasing process in the air. The third exothermic peak at
50 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55

A G-band
D-band
2376 1770 820
B 1620

Intensity Counts
3180 3034 1400 1384
Transmittance

820 A
C 3180 2376 1770 1620 1384 B
1720 1400
D 3034 C
2376 1770 1384 820 D
1720 E
3034 1400
2376 1770 820
1384 F
3180 1720 1620
3034 1400
4000 3500 3000 2500 2000 1500 1000 500 800 1000 1200 1400 1600 1800 2000
Wavenumber (cm-1) Raman Shift (cm-1)

Fig. 4. FT-IR spectrum of the xerogels with different M/CA molar ratios of (A) 1:0.5, Fig. 6. Raman analysis of the as-burnt catalysts (A) C1.5 , (B) C1 , (C) C0.8 , (D) C0.5 and
(B) 1:0.8, (C) 1:1 and (D) 1:1.5. the burnt catalysts (E) C0.8-air , (F) C0.8-reduction after 10 h reduction by 5% hydrogen.

about 653 K was derived from the pyrolysis of the residue organics
in air.
3.2. FT-IR analysis of the xerogels with different M/CA molar
ratios and the burnt catalysts
The FT-IR spectrum of the xerogels with different M/CA molar
ratios was compared in Fig. 4. A broad absorption band at around
3180 cm−1 indicated the presence of adsorbed moisture [29]. The
band at 2376 cm−1 was attributed to the absorption of CO2 [29,30].
The bands at 820 and 1384 cm−1 were assigned to the NO3 − and
the band at 3034 cm−1 was assigned to O–H group [13,29,30]. Two
bands occurred near 1620 and 1400 cm−1 , representing the asym-
metric stretching and symmetric stretching vibrations for carboxyl
ions (COO− ), while the bands at 1720 and 1770 cm−1 were from the
free carboxylic group [13,31]. Citric acid had two types of carboxyl
groups, one inner carboxyl group (1770 cm−1 ) and two terminal
free carboxyl groups (1720 cm−1 ). There were two bands at 1720
and 1770 cm−1 in Fig. 3B–D, but no band at 1720 cm−1 in Fig. 4A,
indicating that two terminal free carboxyl groups were completely
chelated in the xerogel with M/CA = 1/0.5.
Fig. 5 shows the FT-IR spectrum of the as-burnt catalysts with
different M/CA molar ratios and the burnt catalyst C0.8-air after
reduction. It was clearly observed that there were no NO3 − (820
and 1384 cm−1 ) bands and carboxyl bands (1720 and 1770 cm−1 )
for all the burnt catalysts. These findings clarified that all the NO3 −
and carboxyl group took part in the reaction of combustion and the
A and adsorbed on the surface of the as-burnt catalysts. Decreasing
B proved by TG-DTA and XRD patterns. High temperature might lead
16501550
Transmittance
NO3 − provided an in situ oxidizing environment for the decompo-
sition of the citric acid.
There were almost no bands in Fig. 5A. It implied that lit-
tle carbonic residue left in the as-burnt catalyst C0.5 . Bands from
about 1100–1650 cm−1 in Fig. 5B, 1100–1700 cm−1 in Fig. 5C, and
1100–1700 cm−1 in Fig. 5D were presented. The bands at 1428,
1534, 1551 and 1582 cm−1 were attributed to carbonates species
(COOO) [32,33], and those at about 1650 cm−1 to C–O stretching
vibration of bicarbonate [33]. It was clear that with increasing
the initial content of citric acid in the xeogels, the FT-IR bands
of the as-burnt catalyst increased gradually. It inferred more car-
bonic residues left in the as-burnt catalysts with the increased
content of citric acid. There were two small bands at about 1350 and
1550 cm−1 which were attributed to the symmetric and asymmet-
ric stretches of (OCO) in a carboxylate species [32–35] that came
from the imcomplete decomposition of citric acid in Fig. 5E. The
bands in Fig. 5E were smaller than those in Fig. 5B. It proved that
less carbonic residues were left in the catalyst C0.8-air than C0.8 , and
the pyrolysis of residue organics was relatively complete in air than
in argon.
A small peak and a bigger peak at 2235 cm−1 were observed
in Fig. 5C and D. Some papers [36–38] reported that the bands
in the 2200–2260 cm−1 region possibly arised from isocyanate
and/or nitrile intermediates formed by the reaction of NOx with
CH4 . And at higher temperature, these surface species were hardly
detectable. The results were accordance with our experiment phe-
nomenon. In the auto-combustion process, a large amount of gases
such as H2 , H2 O, CH4 , NO, CO2 , NH3 , NO2 were liberated. NO and
NO2 with CH4 might form isocyanate and/or nitrile intermediates
the content of the citric acid, the combustion process was more
severe and the flame temperature was higher, which was already
to the decomposition of isocyanate and/or nitrile intermediates. So
1100 there were no bands at 2235 cm−1 in the FT-IR spectrum of the as-

C burnt catalyst C0.5 and C0.8 because of higher flame temperature. A

2235 small peak and a bigger peak at 2235 cm−1 were observed only in
D 1700 1576 1100 Fig. 5C and D.

2235
1750 3.3. Raman analysis of the as-burnt catalysts and the burnt
1576 1100 catalysts after reduction
E

1550 1350 The Raman spectrum of the as-burnt catalysts was shown in
4000 3500 3000 2500 2000 1500 1000 500 Fig. 6A–D in the region from 800 to 2000 cm−1 . Two relatively
broad Raman bands at about 1340 and 1590 cm−1 which were
Wavenumber (cm-1)
corresponded to the D (disordered) and G (graphitic) bands of
Fig. 5. FT-IR spectrum of the as-burnt catalysts (A) C0.5 , (B) C0.8 , (C) C1 , (D) C1.5 and the amorphous carbon [39–42], were exhibited in Fig. 6A–C. With
the burnt catalyst (E) C0.8-air after reduction. decreasing the content of citric acid, the intensity of the bands
 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55 51

Table 1
Cu The EDS analysis of the as-burnt catalysts with different M/CA molar ratios.
ZnO
Catalysts Surface element content (atomic ratio %)a

C O Cu Zn
A
C0.5 22.54 15.26 32.82 29.38
B C0.8 29.62 20.47 26.54 23.37
C1 44.30 17.10 22.03 16.23
C C1.5 58.54 10.14 16.35 14.97
D C0.8-air 8.80 32.00 29.60 29.60
C0.8-reduction 29.03 19.98 25.58 25.41

E a
Determined by element analysis.

F
30 40 50 60 70 80
2θ (º)
Fig. 7. XRD patterns of the as-burnt catalysts (A) C0.5 , (B) C0.8 , (C) C1 , (D) C1.5 and
the burnt catalysts (E) C0.8-air , (F) C0.8-reduction after 10 h reduction by 5% hydrogen.
at 1340 and 1590 cm−1 decreased gradually in Fig. 6A–C. There
were almost no bands in Fig. 6D. It was clear that the amount of
the amorphous carbon left on the surface of the as-burnt catalysts
decreased with the increased M/CA molar ratios. The Raman spec-
trum of the burnt catalysts C0.8-air after reduction was compared in
Fig. 6E. No bands were found, proving that the amorphous carbon
was completely burnt in the air atmosphere. The Raman spectrum
of the as-burnt catalyst C0.8-reduction after reduction was almost the
same to that of the as-burnt catalyst C0.8 , suggesting that the amor-
phous carbon could not be eliminated by 5% hydrogen during 10 h
reduction at about 523 K.
The XRD patterns of the catalyst C0.8-air after reduction for 10 h
by a flow of 5% hydrogen was compared in Fig. 7E. Cu crystallite size
of the catalyst C0.8-air which was presented in Table 2, was a little
larger than the as-burnt catalyst C0.8 . The result was in accordance
with the DTA plots in Fig. 3C and F. When the xerogel was burnt
in the air, O2 was as a kind of oxidant participating in the redox
process. More oxidant taking part in the combustion process made
the flame temperature higher. Higher temperature resulted in the
larger Cu particle size. Cu crystallite size of the catalyst C0.8-reduction
which was reduced by 5% hydrogen for 10 h at about 523 K was
nearly the same as that of the as-burnt catalyst C0.8 without reduc-
tion. It inferred that the metallic Cu in the as-burnt catalyst C0.8 was
generated in the auto-combustion process and the reduction of the
as-burnt catalyst C0.8 at 523 K could not lead to the increasing of Cu
crystallite size.
3.5. SEM-EDS analysis of the as-burnt catalysts and the burnt
catalysts after reduction

3.4. XRD analysis of the as-burnt catalysts and the burnt catalysts
after reduction
Fig. 7A–D shows the XRD patterns of the as-burnt catalysts with
different M/CA molar ratios. All diffraction peaks of the as-burnt
catalysts were indexed to Cu and ZnO phase. There was no impu-
rity observed. These findings evidently indicated that the CuO phase
was absolutely reduced to metallic Cu by H2 and CH4 produced from
the combustion process, and the xerogels had been converted into
Cu/ZnO catalysts in the combustion process. Cu crystallite size of
the catalysts with different M/CA molar ratios calculated by Scher-
rer formula was presented in Table 2. With the increased content
of citric acid (CA), Cu particle size decreased gradually. It could be
found that Cu particle sizes were closely related to the M/CA moral
ratio, which played an important role on the flame temperature
in the auto-combustion process. Decreasing the content of the cit-
ric acid made the flame temperature higher and the combustion
process more severe. Higher temperature resulted in the larger Cu
particle size. These results were in accordance with combustion
fierceness degree illustrated by the TG-DTA curves in Fig. 3.
Table 2
Batch reaction for methanol synthesis using the as-burnt Cu/ZnO catalysts.
SEM micrographs of the as-burnt catalysts with different M/CA
molar ratios were compared in Fig. 8A–D. All the as-burnt catalysts
exhibited highly porous microstructure, but the morphology was
different. The as-burnt catalyst C0.5 in Fig. 8A showed a foamy fila-
ment and spongy in nature owing to higher flame temperature and
abundant gases releasing in a split second. For the as-burnt cata-
lyst C0.8 in Fig. 8B, the sample had a large amount of small pores,
whereas the as-burnt catalyst C1 in Fig. 8C exhibited more com-
pact structure than C0.8 on the surface. The as-burnt catalyst C1.5
in Fig. 8D presented ordered polymerization on the surface and a
large pore microstructure in the body, which might be caused by the
excess amount of the citric acid. The unchelated citric acid changed
to quasi-solid state at 440 K, and then surrounded the xerogels. The
gases were not easy to be liberated in the combustion process from
the xerogels because of the surface coverage by the citric acid with
quasi-solid state, finally forming larger pores. As compared from
Fig. 8A to D, the surface color of the as-burnt catalysts changed
darker gradually, which was in accordance with the Raman results.
With the increased content of the citric acid, more amorphous car-
bon was left on the surface of the as-burnt catalysts. The color of

Catalysts SBET a (m2 /g) SCu b (m2 /g) Cuc Conversion (%) Selectivity (%) Yield (%)

Dia. (nm) CO CO2 Ctotal CH3 OH HCOOC2 H5 CH3 OH HCOOC2 H5

C0.5 6.4 1.70 68 24.6 53.2 28.6 3.4 96.6 1.0 10.2
C0.8 26.4 7.69 36 63.1 78.1 65.2 10.6 89.4 6.9 58.3
C1 31.5 6.17 31 58.4 77.7 61.1 11.5 88.5 7.0 54.1
C1.5 27.7 2.80 25 42.5 67.1 45.6 15.7 84.3 7.2 38.4
C0.8-air 18.4 4.93 45 59.2 79.3 62.0 60.4 39.6 37.4 24.5
C0.8-reduction 25.6 7.32 37 60.5 76.4 62.7 10.6 89.4 6.6 56.05

Reaction conditions: T = 443 K, P = 5.0 MPa, catalyst weight: 1 g, ethanol solvent: 40 ml, stirring speed: 2000 rpm, reaction time: 12 h, syngas:
Ar/CO/CO2 /H2 = 3.13/33/5.23/58.64.
a
Determined by N2 physical adsorption–desorption at 77 K.
b
Determined from N2 O pulse chemisorption.
c
Calculated by Scherrer formula.
52 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55
Fig. 8. SEM micrographs of the as-burnt catalysts (A) C0.5 , (B) C0.8 , (C) C1 , (D) C1.5 and the catalysts (E) C0.8-air , (F) C0.8-reduction after 10 h reduction by 5% hydrogen.
the as-burnt catalysts also changed from wine red to dark gray with
the increased content of citric acid. For the catalyst C0.8-air in Fig. 8E,
the sample had a large amount of small pores, and the distribu-
tion of the small pores was relatively uniform. The SEM image of
C0.8-reduction in Fig. 8F was nearly the same with that in Fig. 8B, full
of small pores.
The EDS analysis of the as-burnt catalysts with different M/CA
molar ratios was listed in Table 1. A part of carbonic residues stayed
on the as-burnt catalyst surface, which was associated with the con-
tent of the citric acid. Increasing the content of citric acid resulted
in the increased content of carbonic residues which were derived
from the pyrolysis of the residue organics on the surface, and the
decreased content of Cu and ZnO. This trend implied that more car-
bonic residues were left on the surface of the as-burnt catalysts
with increasing the initial content of citric acid in the xerogels.
These results were in accordance with those in FT-IR and Raman
analysis. The EDS analysis of the catalyst C0.8-reduction was nearly
the same with the as-burnt catalyst C0.8 . It inferred that Cu2+ in the
chelated compound was absolutely reduced to metallic Cu during
the combustion process in the argon atmosphere with M/CA = 1/0.8.
This result was accordance with XRD result. However, the amount
of the carbonic residues left in C0.8-air after reduction significantly
decreased comparing with the as-burnt catalyst C0.8 . Because a
large amount of amorphous carbon was burnt in the air atmo-
sphere, as the second exothermic peak shown in Fig. 3F. There was
almost no amorphous carbon left in the catalyst C0.8-air which was
already proved by Raman analysis.
3.6. TPR analysis of the as-burnt catalyst C0.8 and the burnt
catalyst C0.8-air
The TCD signal in terms of hydrogen consumption from H2 -TPR
of the burnt catalyst was shown in Fig. 9. There was only one peak
for the burnt catalyst C0.8-air before reduction in Fig. 9A at about
508 K, which was corresponded to the reduction of CuO to metallic
Cu. The shape of the peak was narrow and symmetrical, indicated
a homogeneous particle size distribution [43,44]. It implied that
CuO phase of the burnt catalyst C0.8-air dispersed homogeneously,
which was in accordance with the SEM image with uniform small
pores. The TPR profiles of the catalyst C0.8-air after 10 h reduction
by a flow of 5% hydrogen was shown in Fig. 8B. There was only
a little broad peak at about 470 K, which was derived from small
 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55
Consumption of H2 (a.u.)
A
B
C
300 350 400 450 500 550 600 650 700
Temperature (K)
Fig. 9. TPR profiles of the burnt catalysts (A) C0.8-air before reduction, (B) C0.8-air after
reduction, and (C) as-burnt catalyst C0.8 .
quantities of CuO oxidized by 1% oxygen. The TPR profiles of the as-
burnt catalyst C0.8 in Fig. 9C was nearly the same as that in Fig. 9B.
It inferred that all the Cu phase in the as-burnt catalyst C0.8 which
was burnt in the argon atmosphere was almost reduced to metallic
Cu. This result was in accordance with that of XRD and EDS.
3.7. Activity of the catalysts
The activity of the as-burnt catalysts and the burnt catalysts
reduced by a flow of 5% hydrogen in nitrogen at 523 K for 10 h
was investigated for the low-temperature methanol synthesis from
syngas containing CO2 using ethanol as a promoter at 443 K and
5.0 MPa for 12 h. The synthetic route was a new method of low-
temperature methanol synthesis [4,45] which allowed using solid
catalysts, as well as syngas containing CO2 and H2 O directly from an
industrial reformer or biomass gasifier without deep purification,
and could be operated at significantly low temperature.
Characterization results and the batch reaction records of the
as-burnt Cu/ZnO catalysts were shown in Table 2. It was shown
that the BET surface areas of the as-burnt catalysts increased with
increasing the citric acid content at first and reached a maximum
for the as-burnt catalysts C1 with M/CA = 1/1, and then decreased
furthermore. With increasing the content of citric acid, there were
more gases liberated out which led to the porous structure, but
the excess citric acid resulted in surplus of the carbonic residues,
which coated on the as-burnt catalysts and caused the decreasing
of the surface areas. The variation trend of the BET surface areas
of the as-burnt catalysts was similar with that of Cu crystalline
change except the as-burnt C1.5 . The as-burnt catalysts were con-
sisted of metallic Cu, ZnO and a part of carbonic residues which
were already proved by FT-IR and Raman analysis. The BET surface
areas were influenced by Cu crystalline size and the amount of the
carbonic residues. Increasing the initial content of the citric acid in
the xerogels, more carbonic residues were left in the as-burnt cata-
lysts, which led to the decreased BET surface areas of the catalysts.
There was a balance point between the content of citric acid and
Cu crystalline size, at which, the as-burnt catalyst had the biggest
BET surface area.
Only CO and CO2 were the carbon-containing gas-phase prod-
ucts, and only methanol and ethyl formate were the liquid-phase
products. It could be found that the total carbon conversion
increased with increasing the content of citric acid and reached
a maximum for the as-burnt catalysts C0.8 with M/CA = 1/0.8, and
then decreased furthermore. The variation trend was similar to that
of the copper (Cu0 ) surface area. This phenomenon was in good
accordance with the literature data [8,46,47], because higher Cu
surface area provided more active sites, and Cu0 was the active site
for the rate-determining step in this low-temperature methanol
53
Fig. 10. The mechanism for the synthesis reaction of low-temperature methanol
from syngas (CO/CO2 /H2 ) using ethanol as promoter (B was the as-burnt catalysts
Cu/ZnO).
synthesis. On the other hand, it was notable that the methanol
selectivity increased gradually with the increased content of cit-
ric acid. This trend was closely related to the crystallite size change
of Cu in Table 2. It was considered that the methanol selectivity
was associated with the crystallite size of Cu. Smaller crystallite
size of Cu was in favor of methanol formation, exhibiting higher
hydrogenation ability, although its SCu value was smaller as shown
in Table 2, partly owing to the higher carbonic residues coverage as
shown in Table 1 and Fig. 5D.
The activity and the selectivity of the burnt catalysts after reduc-
tion were also compared in Table 2. The characterization results and
the batch reaction records of the burnt catalyst C0.8-reduction were
similar to those of the as-burnt catalyst C0.8 . All the CuO phase was
reduced to metallic Cu by CH4 and H2 during the auto-combustion
process in the argon atmosphere. But for the burnt catalyst C0.8-air
after reduction, the methanol selectivity was remarkably promoted
from 10.6% to 60.4%, although the total carbon conversion was
slightly lower than that of the as-burnt catalyst C0.8 . The proposed
mechanism [5,7,32] for the low-temperature methanol synthesis
from syngas (CO/CO2 /H2 ) using ethanol as promoter (B was the as-
burnt catalysts Cu/ZnO) was shown in Fig. 10. Cu+ and ZnO were the
active sites for the formation of formate and ethyl formate, but only
Cu0 was active for hydrogenation of the ethyl formate. As proved
by FT-IR and EDS, there were more carbonic residues left in the as-
burnt catalyst C0.8 than in C0.8-air . Carbonic residues might influence
the activity of ethyl formate hydrogenation. The activity of the as-
burnt Cu/ZnO catalysts for the ethyl formate hydrogenation should
be improved in the low-temperature methanol synthesis reaction
in the future study.
As listed in Table 2, the as-burnt catalysts and the burnt catalysts
were more active for methanol synthesis from CO2 hydrogenation,
although the content of CO2 was only 5.23%. As had been proved
[48–50], a metallic Cu–Zn surface alloy was a catalytically active
species for the methanol synthesis from CO2 and H2 . The high activ-
ity of CO2 hydrogenation prepared by auto-combustion method
might be owing to the high temperature treatment during com-
bustion process to form Cu–Zn alloy, as the combustion method
here was conventionally used in producing the alloys and metal
oxide powders.
The continuous reaction results for low-temperature methanol
synthesis at 443 K and 5.0 MPa for 40 h using the as-burnt catalyst
C0.8 were presented in Fig. 11 and Table 3. The conversion of CO,
CO2 and the total carbon were stable after 15 h. The total carbon
TOF was 1.6 × 10−3 s−1 calculated by N2 O pulse method. The selec-
tivity of methanol and ethyl formate was calculated by analyzing
the liquid products which were the plus of those in the cold trap
54 L. Shi et al. / Applied Catalysis A: General 401 (2011) 46–55
Table 3
Continuous reaction result for low-temperature methanol synthesis with the as-burnt catalyst C0.8 .
Catalyst Conversion (%)
CO CO2 Ctotal
C0.8 18.4 −1.7 15.5
Reaction conditions: T = 443 K, P = 5.0 MPa, catalyst weight: 3 g, solvent: ethanol 40 ml, stirring speed: 2000 rpm, reaction time: 40 h, flow rate: 20 ml/min, syngas:
Ar/CO/CO2 /H2 = 3.13/33/5.23/58.64.
a
Based on N2 O pulse method. TOF was the total carbon turnover frequency.
20
15
Conversions (%)
CO 2
10
CO
5 C total
0
10
20 30 40
-5
-10
Time on stream (40 h)
Fig. 11. Variations of CO, CO2 , and total carbon conversions with reaction time for
the continuous synthesis of methanol.
and the autoclave after the reaction. Fig. 11 expressed the time-on-
stream activity change of the reaction during 40 h. The analysis on
the effluent gas after the trap exhibited that only CO, CO2 , and H2
exist and no alcohols and esters appeared. At the initial stage of the
reaction, as 40 ml dead volume of the reactor and 5 ml cold trap was
filled of pressurized feed gas, the apparent conversions were low
but increased gradually. After 15 h, the conversions were stable. CO
conversion was about 17%, while CO2 conversion was about −2%.
The total carbon conversion was about 15%. At the initial 15 h, the
CO2 conversion dropped to minimum −12%, and then increased
again to about −2%. The negative CO2 conversion meant that CO
was first converted to CO2 through the water-shift reaction, and
then CO2 hydrogenation to methanol. The balance between CO2
formation and formate formation was reached after 15 h.
4. Conclusion
A series of the as-burnt and the burnt Cu/ZnO catalysts after
reduction were prepared by a sol–gel method using metal nitrates
with the mole ratio of Cu/Zn = 1/1 and citric acid. During the auto-
combustion process in the argon atmosphere, a large amount of
gases such as H2 , H2 O, CH4 , NO, CO2 , NH3 , NO2 were liberated.
H2 and CH4 were the reducing agents that could be used in the
redox process for synthesizing metallic Cu from Cu2+ in the chelated
compound. The XRD patterns revealed that all the as-burnt cata-
lysts with different M/CA molar ratios were converted into pure Cu
and ZnO species. TPR analysis of the as-burnt catalyst illustrated
that almost no hydrogen was consumed. It proved that Cu2+ was
absolutely reduced to metallic Cu in the as-burnt catalyst.
The effects of M/CA molar ratio on the properties of catalysts
were studied by TG-DTA, FT-IR, Raman, XRD, SEM-EDS, BET and
N2 O chemisorption techniques. The results of the TG-DTA in argon
showed that the fierceness and the flame temperature of the auto-
combustion process were strongly influenced by the initial M/CA
molar ratio in the xerogels. The auto-combustion process was con-
sidered as a severe redox process, wherein citric acid acted as
reductant, and nitrate ions and Cu2+ in the chelated compound
acted as oxidant. Increasing the content of citric acid, the com-
bustion process was much gentler and the flame temperature was
TOFa (10−3 s−1 ) Selectivity (%) Yield (%)
CH3 OH HCOOR CH3 OH HCOOR
1.6 39.6 51.4 6.1 8.0
much lower. The xerogels burnt in the air atmosphere was more
severe than that in argon, as O2 was a kind of oxidant and par-
ticipated in the redox reaction during the combustion process. The
exothermic peak of the amorphous carbon oxidation was also found
in DTA curves. The SEM images illustrated that all the catalysts
exhibited highly porous microstructure, but the morphology was
different. EDS, FT-IR and Raman analysis showed that more car-
bonic residues and amorphous carbon were left in the as-burnt
catalysts with the increased content of the citric acid. There were
no amorphous carbon and a little carbonic residue left in the burnt
catalyst C0.8-air . Cu particle size calculated by Scherrer formula was
influenced by the flame temperature, and became lager in the as-
burnt Cu/ZnO catalysts with increasing the M/CA molar ratios. The
BET surface areas of the as-burnt catalysts which were influenced
by Cu crystalline size and the amount of the carbonic residues,
increased with increasing the citric acid content at first and reached
a maximum for the as-burnt catalysts C1 with M/CA = 1/1, and then
decreased furthermore.
The methanol synthesis reactions were conducted using the
as-burnt Cu/ZnO catalysts without further reduction from syngas
containing CO2 using ethanol as promoter at 443 K and 5.0 MPa
for 12 h. The total carbon conversion increased by decreasing the
M/CA molar ratio and reached a maximum for the as-burnt cata-
lyst C0.8 with M/CA = 1/0.8, and then decreased furthermore. The
variation trend was in accordance with that of the copper (Cu0 )
surface area. Comparing with the burnt catalyst C0.8-air after reduc-
tion, the methanol selectivity of the as-burnt Cu/ZnO catalyst was
much lower according to lower hydrogenation activity of the ethyl
formate. The as-burnt catalyst C0.8 was used in continuous low-
temperature methanol synthesis at 453 K and 5.0 MPa for 40 h. The
total carbon conversion was stable after 15 h and no obvious deac-
tivation during 40 h reaction, but the methanol selectivity was also
not high.
This novel auto-combustion method [18] which was used to
prepare pure metals and alloys, was for the first time introduced
to prepare metallic catalysts without further reduction. This novel
auto-combustion method will open a new window to prepare
metallic catalysts, especially the catalysts which was difficult to
be reduced at high temperature.
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