Molecular Catalysis 456 (2018) 38–48

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Molecular Catalysis
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Component ratio dependent Cu/Zn/Al structure sensitive catalyst in CO2/ T

CO hydrogenation to methanol
⁎
Mohammad Sadeghiniaa, Ali Nemati Kharat Ghaziania, , Mehran Rezaeib
a
School of Chemistry, University College of Science, University of Tehran, 1417466191, Tehran, Iran
b
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, P.O. Box 8731751117, Kashan,
Iran

A R T I C LE I N FO A B S T R A C T

Keywords: A set of 16 series CuO/ZnO/Al2O3 ternary catalysts in four different groups with various compositions were
Methanol synthesis systematically synthesized through co-precipitation route and employed for the production of methanol from a
Coprecipitation mixture of H2, CO and CO2 at 50 bar and 250 °C. In each group, CuO/Al2O3 ratio was fixed in specific and
Component ratio constant value and CuO/ZnO ratio varied from 1.8 to 2.7. The ratio of CuO/Al2O3 was also varied from 5 to 11.
Cu/Zn/Al ternary catalyst
The prepared samples were characterized and analyzed to understand the relation between the catalytic activity
Interwoven nano-twin
and textural properties to develop a high active and stable catalyst for methanol synthesis. It was observed that
Structure sensitive
the sample with CuO/ZnO = 2.7 and CuO/Al2O3 = 9 as well as the samples having CuO/ZnO = 1.8 possessed
the best productivity and selectivity. The smallest Cu crystal sizes and the highest BET and Cu surface areas were
observed for the samples with a CuO/Al2O3 ratio of 9. Furthermore, the largest Cu crystal size and the lowest Cu
surface area were observed on the samples with CuO/ZnO = 1.8. Nevertheless, higher activities were observed
at CuO/ZnO = 1.8. It was also found that some interwoven nano-twins are formed at CuO/ZnO = 1.8, which in
turn accelerate the methanol productivity and improve the catalytic stability. Finally, the active catalysts were
compared with the commercial catalyst and the results showed a better catalytic performance for the prepared
samples in this article.

1. Introduction precipitation synthetic parameters. In both mentioned factors enormous

CuO/ZnO/Al2O3 catalysts do catalyze the low pressure-low tem-
perature conversion of CO, CO2 and H2 to methanol and have been
widely used for a long time [1–3]. Several routes have been reported to
prepare methanol synthesis catalysts including: co-precipitation of ni-
trate solution [4–7], complexation like oxalate [8,9], urea [10], citrate
and formate precursor [11,12], combustion synthesis [13] sol–gel or
colloidal methods [14,15], mechano-chemical synthesis [16], ultra-
sonic [17,18], etc. [19,20]. Among all preparation routes, co-pre-
cipitation of Cu/Zn/Al nitrates by Na2CO3 is a prominent and standard
technique employed for the industrial synthesis of methanol catalyst
[21]. By proper adjustment of the precipitation parameters like pH
[22,23], aging time and temperature [6,22,24–26] and varying the
components [27,28] a high efficient catalyst can be produced. This
ternary catalyst is a very sophisticated case and highly sensitive to even
small changes of the metal component and synthesis parameters [29].
Hence, for a rational design in industrially applied route, two critical
factors should be considered: the nominal metal composition and co-
differences in catalytic activities are possible. So, exact setting of syn-
thetic factors and optimized metal components are of crucial im-
portance for the final catalyst. Behrens et al. [30–35] have intensively
investigated CuO/ZnO system to evaluate the active phase for high
performance catalyst. In CuO/ZnO system, the most active precursor is
zincian-malachite [(CuxZn1-x)2(OH)2CO3, x > 0.3] wherein the most Zn
decoration into the precursor takes place. Zincian-malachite formation
severely depends on the synthetic parameters and critical Zn content
[1]. So, synthetic condition and nominal metal composition are em-
pirically chosen to reach the maximum amount of malachite phase. As
above mentioned, in binary CuO/ZnO system the most active catalysts
are prepared from zincian-malachite and if aluminum exists in a sig-
nificant amount, the ternary hydrotalcite phase will be observed after
co-precipitation [36]. Hence, aluminum presence in catalyst as a
structural promoter makes the composition more complex. Hoppener
[37], showed that different phases including: Hydrotalcite [(Cu,
Zn)6Al2CO3(OH)16.4H2O], Rosasite [(Cux, Zn1-x)2(OH)2CO3,
0.3 < x < 0.5] and zincian- malachite [(CuxZn1-x)2(OH)2CO3, x > 0.7]

⁎
Corresponding author.
E-mail address: anemati@ut.ac.ir (A. Nemati Kharat Ghaziani).

https://doi.org/10.1016/j.mcat.2018.06.020
Received 10 March 2018; Received in revised form 27 May 2018; Accepted 20 June 2018
2468-8231/ © 2018 Elsevier B.V. All rights reserved.
M. Sadeghinia et al. Molecular Catalysis 456 (2018) 38–48

are formed during co-precipitation of Cu/Zn/Al system depending on Where λ is the X-ray wavelength in nanometer (nm), β is the peak
the metal ratio in the initial metal nitrate solution. Furthermore, it is width of the diffraction peak profile at half-maximum height resulting
believed that the rosasite decomposition results in to highly active from small crystallite size in radians and K is a constant related to
catalyst and hydrotalcite is an excellent catalyst stabilizer resulting in crystallite shape, normally taken as 0.9. The value of β in 2θ axis of
formation of small Cu and ZnO particles in Cu/Zn/Al ternary system. diffraction profile must be in radians. Nitrogen adsorption-desorption
Similar to CuO/ZnO system, optimization of the metal content at the analysis was performed in a gas adsorption analyzer (BELSORP mini II)
first step is essential in ternary Cu/Zn/Al system and moving on the to calculate the specific surface area and pore size distribution.
edge of the optimized structure will conduct the final product to be the Reducibility of the catalysts and copper surface area and its dispersion
best efficient industrial catalyst. The work presented here is guided by were determined by the temperature programmed reduction (TPR) and
the aim of achieving and understanding the best optimized composition N2O chemisorption analyses in a Chemisorb 2750 (Micromeritics) in-
with the best activity and selectivity in the industrial catalytic synthesis strument. The exposed metallic copper surface area (SCu) in the reduced
of methanol. state was measured by the N2O/He (volume ratio 5:95) oxidation of Cu
to Cu+ followed by second H2 thermal programmed reduction as de-
scribed in [38,39]. The measurement was performed in a tubular quartz
2. Experimental reactor. Firstly, the catalyst was reduced completely at 300 °C. The
amount of hydrogen consumption in the first TPR was denoted as X
2.1. Catalyst preparation (CuO+H2→Cu+H2O). It was then purged with He and cooled to 50 °C.
Surface copper atoms were oxidized to Cu2O in N2O/He flow (volume
A set of 16 series CuO/ZnO/Al2O3 catalysts were synthesized using ratio 5:95, 30 ml/min) at 50 °C for 0.5 h. Finally, the catalyst was
co-precipitation route [38]. A solution of metal nitrate [Cu purged by He to remove the oxidants and cooled to room temperature
(NO3)2.3H2O, Zn(NO3)2.6H2O, Al(NO3)3.9H2O] with different metal to start another TPR run. Hydrogen consumption in the second TPR was
concentrations (total metal concentration = 1 M) was pumped at a denoted as Y (Cu2O+H2→2Cu+H2O). The dispersion of Cu and SCu
constant rate (5 cc/min) into a heated glass reactor containing 50 ml were calculated using the following equations [39].
H2O under stirring. Simultaneously, Na2CO3 solution (1 M) was
pumped at a constant rate (5 cc/min) into the reaction vessel. During D= (2×Y/X) ×100%, (2)
the precipitation step, pH and temperature were kept constant at 7 and SCu = 2×Y×Nav/(X×MCu×1.4 × 1019) = 1353×Y/X (m2/g) (3)
70 °C, respectively. After aging for 1 h, the blue precipitate turned into
the green precursor. After this step, the suspension was filtered and Where Nav is the Avogadro’s constant, MCu is the relative atomic mass of
washed with deionized water and the washed filter cake was then dried copper (63.456 g/mol), and 1.4 × 1019 is the copper atom surface
at 90 °C and the final product was obtained after calcination at 320 °C density per square meter.
for 3 h. The chemical composition of the prepared samples with various Morphologies of the samples were observed by SEM using a VEGA
CuO/ZnO and CuO/Al2O3 ratios are reported in Table 1. TESCAN microscope at an accelerating voltage of 5 kV, with a work
distance (WD) between 5 and 8 mm and magnifications in the range of
100–800,000. For determining chemical compositions of the crystal
2.2. Characterization techniques phases, energy-dispersive spectroscopy (SDD-EDS) was employed to
obtain the EDS spectra by means of an EDS DX-4 analysis system. A very
The crystalline structure of the samples was analyzed by X-ray dif- thin Pt film was used to provide a better conductivity of the sample.
fraction (XRD) method. XRD analyses were performed on a PANalytical High resolution transmission electron microscopic (HR-TEM) images
X’Pert-Pro X-ray diffractometer with Cu-Kα radiation were obtained on a JEM-2100UHR apparatus were used to study the
(λ = 0.15406 nm) at 45 kV and 40 mA to identify the crystal phases. surface morphology of the samples.
Scattering intensity was recorded in the range of 10° < 2θ < 90° for all
of the samples with a 2θ step of 0.03° and a count time of 2 s per step. 2.3. Catalytic evaluation
The diffraction patterns were indexed by the JCPDS (Joint Committee
on Powder Diffraction Standards) files. Cu crystallite sizes were calcu- Catalytic activity tests were performed in a continuous fixed-bed
lated using the well-known Scherrer equation: stainless steel reactor (internal diameter, 10 mm) at 5.0 MPa and
L= Kλ
(1) 250 °C. The reactor was charged with 1 g of the crushed and sieved
βCOSθ
catalyst particles (mesh 35–60). Prior to reaction, the catalyst was re-
Table 1 duced in a reducing gas mixture (5% H2 in 95% N2) at 240 °C and at-
The chemical composition of the prepared samples with various CuO/ZnO and mospheric pressure for 12 h. The feed gas (100 Nml/min) consisted of
CuO/Al2O3 ratios. 81.11 vol% H2, 9.94 vol% CO, and 8.95 vol% CO2 was introduced into
the reactor and the products and unreacted gases were analyzed by an
Sample CuO/ZnO CuO/Al2O3 CuO (% wt) ZnO (%wt) Al2O3 (%wt)
online gas chromatograph equipped with a two-column system con-
CZA-1 1.8 5 56.96 31.65 11.39 nected to a thermal conductivity detector (TCD) and a helium ionized
CZA-2 2.1 5 59.66 28.41 11.93 detector (HID), respectively. Methanol and water were analyzed by a Q
CZA-3 2.4 5 61.86 25.77 12.37 PLOT capillary column (30 m × 0.53 mm) and TCD, while unreacted
CZA-4 2.7 5 63.68 23.58 12.74
CZA-5 1.8 7 58.88 32.71 8.41
gasses and small amount of methane were determined by a Carboxen
CZA-6 2.1 7 61.76 29.41 8.83 1010 PLOT capillary column (30 m × 0.32 mm) and HID. Space time
CZA-7 2.4 7 64.12 26.72 9.16 yield (STY) and selectivity data were obtained using mass-balance
CZA-8 2.7 7 66.08 24.48 9.44 method.
CZA-9 1.8 9 60.00 33.33 6.67
CZA-10 2.1 9 63.00 30.00 7.00
CZA-11 2.4 9 65.45 27.27 7.27 3. Results and discussion
CZA-12 2.7 9 67.50 25.00 7.50
CZA-13 1.8 11 60.74 33.74 5.52 3.1. X-ray diffraction
CZA-14 2.1 11 63.81 30.39 5.80
CZA-15 2.4 11 66.33 27.64 6.03
CZA-16 2.7 11 68.43 25.35 6.22 Fig. 1a–d show the XRD patterns of the prepared catalysts. In each
figure CuO/ZnO ratio is constant and CuO/Al2O3 ratio was varied from

39
M. Sadeghinia et al.
Fig. 1. a–d X-ray diffraction patterns of the prepared ternary catalysts.
5 to 11. All samples showed corresponding CuO and ZnO diffraction
peaks and there is no evidence of Al2O3 diffraction peaks due to low
content of Al2O3 and low calcination temperature.
In all figures, the increase in Al content diminished the peak in-
tensities. The decrease in the intensity of the diffraction peaks can be
explained by the structural promoting effect of Al in catalysts. In fact,
Al2O3 acts as a structural spacer and in higher Al contents, catalysts
tend to be more amorphous. Another interesting point was observed in
samples with CuO/ZnO = 2.7. The intensity of the diffraction peaks
observed at 2θ = 45–50° corresponding to CuO and ZnO peaks was
lower compared to those observed in samples with different CuO/ZnO
ratios, indicating the smaller CuO crystallite sizes as reported in
Table 2.
3.2. BET and pore size distribution
Figs. 2a–d and 3a–d illustrate the N2 adsorption/desorption iso-
therms and pore size distributions, respectively. All samples showed
type IV isotherm, in which capillary condensation is accompanied by
hysteresis relating to mesoporous materials [40]. It can be seen that in
samples containing higher content of aluminum, the hysteresis loop was
observed at higher relative pressures (P/P°), indicating the larger pore
size in these samples. This issue can be seen in pore size distribution
curves (Fig. 3a–d). According to pore size distribution curves, the lar-
gest and smallest pore sizes are related to samples with CuO/Al2O3 = 5
and CuO/Al2O3 = 11, respectively. Usually aluminum is added to en-
hance the thermal stability and Cu dispersion [41–44] and insertion of
Al into CuO/ZnO system predominantly is accompanied by changing in
textural properties of catalysts. An optimum ratio of components should
be determined in which the sample possessed the best textural prop-
erties. According to Table 2, the BET surface area for the samples
synthesized at CuO/Al2O3 = 9 is higher than the other ratios.
40
Molecular Catalysis 456 (2018) 38–48
3.3. Temperature programmed reduction (TPR)
In ternary CuO/ZnO/Al2O3 system prior to reaction, the catalyst
should be activated by diluted H2. Activating of catalysts results in the
reduction of CuO to Cu. Thermal programmed reduction provides
useful information about reducibility behavior of the prepared samples.
According the literatures, in these types of catalysts, reduction could be
proceed in three steps [45–48]. To investigate the reducing behavior of
the prepared catalysts, all TPR profiles were deconvoluted qualitatively
by a Gaussian-type function. TPR profiles of the prepared samples are
depicted in Fig. 4a–d.
The deconvoluted plots illustrated three reduction peaks implying
that catalyst reduction takes place in three steps. Probably due to pre-
sence of different phases in the precursor [37], thermal decomposition
will result in different types of CuO. Copper in vicinity with the zinc and
aluminum oxides is the origin of synergetic effect, which in turn in-
fluences the reducibility of copper [49–52].
Both of zinc and aluminum can act as dispersive agents and besides
dispersing effect, ZnO can activate H2 and enhance the reducibility of
copper [51]. Based on Bahmani and coworkers′ study [53] with regard
to H2 access and reduction possibility, copper oxide species could be
divided into three categories of reducibility: highly dispersed CuO
particles, large particles with ZnO contact and large particles without
ZnO. They believed that the first reduction peak can be assigned to the
surface layer copper oxide (surface CuO) which was in direct contact
with ZnO species, the second reduction peak is related to an inter-
mediate layer (bulk-intermediate CuO) being directly influenced by
ZnO due to several atomic layer distance, whereas the third peak fitted
to reduction of core layer of copper oxide (bulk-core CuO). According to
the Fig. 3a–d, in each series at CuO/Al2O3 = 5, high temperature re-
duction peak related to bulk CuO species can be seen distinctly as a
shoulder. In fact, at higher Al contents, bulk core CuO species are
M. Sadeghinia et al. Molecular Catalysis 456 (2018) 38–48

Table 2
Textural properties of samples along with their productivity and selectivity.
Sample N2 adsorption/desorption N2O chemisorption XRD STY Selb c
χCO d
χCO 2

2 3 a
SBET (m /g) Vb (cm /g) SCu D (%) dCu (gMeOH/kgcat.h)
2
(mCu /gcat) (nm)

CZA-1 116.9 0.624 38.89 5.74 9.4 642.51 99.90 59.36 15.58
CZA-2 88.8 0.388 25.2 3.68 10.8 628.46 99.80 58.62 15.24
CZA-3 118.8 0.501 23.6 3.50 11.3 471.52 99.72 47.68 9.71
CZA-4 105.7 0.517 23.9 3.51 8.3 568.17 99.75 53.54 13.99
CZA-5 102.4 0.338 26.86 4.08 10.7 663.88 99.89 60.61 16.86
CZA-6 106.1 0.567 18.20 2.70 10.0 538.12 99.87 50.98 11.10
CZA-7 97.8 0.324 17.90 2.64 9.2 543.14 99.60 52.58 11.78
CZA-8 90.3 0.406 25.38 3.75 8.8 630.13 99.69 59.17 15.32
CZA-9 121.1 0.448 22.11 3.27 10.0 656.49 99.67 61.52 15.91
CZA-10 120.7 0.387 23.61 3.49 8.8 553.05 99.60 52.96 14.69
CZA-11 126.3 0.386 30.85 4.15 8.8 652.95 99.67 60.60 15.67
CZA-12 130.6 0.429 35.56 5.40 8.7 669.12 99.74 61.28 16.51
CZA-13 91.9 0.313 24.76 3.66 10.4 660.18 99.87 61.48 16.05
CZA-14 91.4 0.317 20.97 3.10 9.7 604.22 99.78 56.68 15.15
CZA-15 91.1 0.269 18.61 2.75 8.8 538.84 99.72 50.76 12.84
CZA-16 91.1 0.257 22.37 3.30 8.8 577.67 99.39 56.24 11.56
Commerciale 84.2 0.231 28.63 4.12 8.8 660.57 94.38 61.30 16.34

Note: All data relating to methanol production including: STY, selectivity, CO and CO2 conversion have been collected 1 h after reaching the reactor pressure to
50 atm. a: dispersion of metallic Cu, b: selectivity, c: CO conversion, d: CO2 conversion, e: MK-121 methanol synthesis catalyst.

formed in higher amounts compared to the other ratios and conse-
quently reduction peaks are shifted to elevated temperatures [49]. At
CuO/ZnO = 2.7 shouldered peak relating to bulk CuO has been merged
into the medium temperature peak.
It means that at this ratio bulk CuO exists in lower amount than the
other ratios. From XRD results it was found that CuO crystallite sizes at
CuO/ZnO = 2.7 were smaller and smaller particle sizes are originated
from well-dispersed particles. Usually, strong metal-support interaction
(SMSI) could be observed in well-dispersed particles arising from CuO/
ZnO synergetic effect [34]. Such strong metal-support interaction can
shift the reduction temperature to lower values. Since CuO particle sizes
at CuO/ZnO = 2.7 are the smallest, shoulder peak corresponding to

Fig. 2. a–d N2 adsorption-desorption of Cu/Zn/Al catalysts.

41
M. Sadeghinia et al. Molecular Catalysis 456 (2018) 38–48

Fig. 3. a–d Pore size distribution (BJH) of Cu/Zn/Al catalysts.

bulk CuO went shrinking and we expect SMSI to be higher at CuO/ other synthesized samples with CuO/ZnO = 2.7 possessed activity
ZnO = 2.7. Nevertheless, it is soon to deduce and this information are lower than the samples with CuO/ZnO = 1.8. For more investigation,
not sufficient to predict the most efficient catalyst. we measured the metallic copper surface areas. It has been proposed
that the active centers in CuO/ZnO/Al2O3 system are located on me-
tallic Cu sites and total activity is directly dependent to the copper
3.4. Catalytic performance
surface area [54,55].
N2O reactive frontal chromatography (N2O chemisorption) was
According to XRD and TPR results it was cleared that the smallest
performed to determine the metallic Cu surface area (Table 2) and the
crystallite sizes and higher CuO/ZnO synergetic effect could be ob-
results were plotted versus CuO/ZnO and CuO/Al2O3 ratios and illu-
tained at CuO/ZnO = 2.7 and BET and BJH results showed that at CuO/
strated in Fig. 5e. If a linear relationship between Cu surface area and
Al2O3 = 9, the highest surface areas were achieved. Hence, the pre-
STY exists, STY and Cu surface area diagrams (Fig. 5a and e) should be
pared samples at these ratios are expected to be the best catalysts from
superimposed together exactly. But it is seen that two diagrams could
the catalytic activity point of view. To investigate the catalytic activity
not be superimposed together. In Other words, there is no exact con-
and selectivity, all the samples were exposed to methanol synthesis test.
formity between two diagrams. Our study showed conflicting results
Fig. 5a to f illustrate the correlation of different properties to the CuO/
about linear relation between methanol productivity and Cu surface
ZnO and CuO/Al2O3 ratios. Fig. 5a and b deal with the relation between
area suggesting that there is no general correlation between methanol
CuO/ZnO and CuO/Al2O3 ratios and methanol productivity and se-
productivity and Cu surface area. It should be noted that the presence of
lectivity. From Fig. 5a, it can be observed that at CuO/Al2O3 = 9,
ZnO dramatically influences the N2O measurements. This effect can be
methanol productivity (STY) is slightly higher than those obtained at
explained by the presence of oxygen deficiencies, which are located at
other ratios. It seems logical; because prepared samples at this ratio
the Cu-ZnO interface and are prone to influence N2O measurement.
have the highest surface areas. Also the prepared samples with CuO/
N2O in fact probes the Cu surface plus the oxygen vacancies [56], and
ZnO = 1.8 are located in maximums in diagram. As it was expected, the
this phenomenon results in unreal estimation of exposed Cu surface
most catalytically active sample was obtained from intersection of
area. Based on new findings, necessary factors ensuring high perfor-
CuO/ZnO = 2.7 and CuO/Al2O3 = 9 (Fig. 5a). Another noticeable point
mance catalyst consist of strong metal-support interaction, high Cu
is about CuO/ZnO = 1.8. All prepared samples at CuO/ZnO = 1.8 have
surface area, defect and steps [35]. Hence, high Cu surface area is not
remarkable catalytic activity. More attention to Fig. 5a revealed that
the only parameter to ensure the high catalytic activity. According to
except the best sample (CZA-12) synthesized at CuO/ZnO = 2.7 and
second TPR in N2O chemisorption, two types of Cu+ in catalyst surface
CuO/Al2O3 = 9, the other samples synthesized at CuO/ZnO = 2.7 are
were observed in the samples.
not more catalytically active compared to the samples with CuO/
It is not contradictory result with those data obtained from TPR
ZnO = 1.8. In fact, according to XRD results and with envisaging the
profiles. Based on Dyatlov work [57] only 10% of surface is catalyti-
fact that at CuO/ZnO = 2.7, the size of copper particles is smaller, it
cally active and more than 60% of it consists of copper or brass and the
was expected that the catalytic activity is higher compared to the other
rest of surface pertains to aluminum oxide. Actually three types of Cu
ratios. However, unexpectedly we observed that except CZA-12, the

42
M. Sadeghinia et al.
Fig. 4. a–d Deconvoluted TPR profiles of the prepared samples.
can be found in the catalyst, in which two types of them are present at
the surface. During temperature programmed reduction, all types of Cu
are reduced completely and the peak deconvolution showed three types
of Cu. In N2O chemisorption after reducing all types of Cu species, N2O
is injected and only surface species of Cu are oxidized to Cu2O. It should
be noted that both of Cu and Cu+ are present in the activated catalyst
[58]. Cu+ and Zn2+ are isoelectronic and can produce solid solution.
Two peaks in second TPR in N2O chemisorption indicate that more than
one type of Cu+ may be present in the catalysts: particles formed by
extraction of Cu from the (Zn,Cu)O solid solution and particles formed
by reduction of CuO primary particles [59]. In other words, one type of
Cu+ has been dissolved in ZnO and another species is related to fine
dispersed Cu particles acts as a weak electron donor. Two mentioned
Cu+ types can be detected in second TPR. Fig. 8a and b show the
second TPR in N2O chemisorption for the best samples prepared at
CuO/ZnO = 2.7 and CuO/ZnO = 1.8 (CZA-12 and CZA-5), respec-
tively. It has been claimed that electron donor effect will be decreased
by increasing in CuO content and Cu dissolvation in ZnO is improved by
introducing a trivalent element like Al3+ [60].
In Fig. 8a (CZA-12) the second peak related to electron donor effect
has lower intensity due to more Cu content. Electron donor effect in
CuO/ZnO = 1.8 is higher than CuO/ZnO = 2.7. Hence, besides dis-
persing effect, ZnO can increase the electron donor effect in the sam-
ples. About the effect of particle size on the activity, we obtained some
contradictory results. For CuO/ZnO = 1.8, we observed that larger
particles are more catalytically active while for CuO/ZnO = 2.4 we
almost observed a reverse trend. By more attention to Table 2, it is seen
that both of CZA-3 and CZA-10 have the same Cu surface area but their
STYs are different. It can be interpreted from the mentioned facts: 1)
there is an optimum ZnO content, in which the highest catalytic activity
43
Molecular Catalysis 456 (2018) 38–48
is obtained [61,62]. The difference between the STYs of the CZA-3 and
CZA-10 samples is due to different contents of ZnO in theses samples
and 2) in fact, according to lower Cu surface areas and higher activities
in samples having CuO/ZnO = 1.8 compared to CuO/ZnO = 2.7, it can
be concluded that the strong metal-support interaction is higher in
CuO/ZnO = 1.8 and it is one of the main reason for higher catalytic
activity. The optimum Zn amount can be determined from the angular
position of the characteristic (20 1) XRD peak of the zincian-malachite
and it was found that near 28% ZnO, incorporation of Zn into zincian-
malachite system is maximum and Jahn-Teller distortions of MO6 unit
in malachite system is lower around this content and at higher Zn
amounts Zn-rich aurichalcite phase as a side product will be formed
[63]. In addition to the optimum amount of ZnO, the catalytic perfor-
mance also depends on the optimum amount of Al. Moreover Zn dec-
oration of Cu particles, homogeneous doping of ZnO by Al at low
contents could be taken place [64] which in turn reduces the band gap
and led to a defect rich material. This doping effect is appeared in
second TPR in N2O chemisorption. Second peak in second TPR is
sharper in the case of CuO/ZnO = 1.8.
Another feature about this ternary catalyst can be observed.
According to Table 2, CZA-10 and CZA-16 samples have nearly the
same Cu particle size and Cu surface area and their productivity is
expected to be the same; but productivity of these catalysts are dif-
ferent. This difference could be related to different morphologies [65].
Morphology could influence the Zn decoration and consequently the
productivity. In other words, both Cu particle size and morphology
affect the catalytic activity. Since catalytic activity depends on the size
and morphology of the particles, it is concluded that Cu/Zn/Al ternary
catalysts are structure sensitive [61,62]. It is reported that the size of Cu
particles influences the productivity and larger particles are more
M. Sadeghinia et al.
Fig. 5. (a) Correlation between CuO/Al2O3 and CuO/ZnO ratios and methanol production (b) methanol selectivity (c) Copper surface area (d) dispersion of copper
(e) conversion of carbon monoxide and (f) carbon dioxide conversion.
active. We observed this issue at CuO/ZnO = 1.8. Actually lower ac-
tivity for small particles is mainly due to changes in the copper surface
structure [62].
The coverage with zinc species might depend on the copper particle
size, and could result in a decreased activity for smaller copper parti-
cles. So decorating of Cu particles by reduced Zn particles becomes
weaker and results in a decreased activity. Larger CuO particles and its
lower contents accompanied by higher ZnO contents, ensure effective
Zn decorating into Cu particles and increase electron donor effect. In
the other hand homogeneous decoration and rich defect catalyst is
obtained at lower aluminum amounts. All these three mentioned issues
44
Molecular Catalysis 456 (2018) 38–48
are possible for CuO/ZnO = 1.8 and higher activity at this ratio could
be related to satisfy all these factors. Effect of the mentioned factors can
be monitored in second TPR and TEM results. Methanol productivity is
directly related to the CO and CO2 conversion. Therefore, STY, CO and
CO2 conversion diagrams are expected to be in the same pattern. This
issue is presented in Fig. 5e and f. Based on Table 2, CZA-12 and CZA-5
samples are the most active catalysts, but their atomic ratios are dif-
ferent. In continue, the mentioned important factors will be evaluated
for these two highly active cases to some extent. Since we were inter-
ested in to achieve the best-optimized catalyst which is useful in in-
dustrial application, we also conducted methanol production activity
M. Sadeghinia et al. Molecular Catalysis 456 (2018) 38–48

Fig. 6. SEM and EDS elemental mappings of CZA-5 (a) and CZA -12 (b).

test for commercial MK-121 methanol synthesis catalyst and compared
with our active samples. The relevant results are seen in Table 2 and
other discussions are mentioned in stability test section.
3.5. Scanning electron microscopy (SEM) and elemental mapping
Fig. 6a and b show the SEM images of CZA-5 and CZA-12. Moreover,
the chemical composition and element distribution information of the
samples were analyzed by SEM-EDS mapping scan. It can be observed
that, dispersion of Cu is more homogeneous for CZA-12 than CZA-5.
Less homogeneity with lots of pore spaces was observed, which is in
good agreement with Cu dispersion data (Table 2). Uneven distribution
of Cu in CZA-5 is the result of larger Cu nanoparticles. More uniform
distribution of Zn and Al is seen for CZA-5.
3.6. Transmission electron microscopy (TEM) and second TPR in N2O
chemisorption
Transmission electron microscopy provides supporting information
on the particle size distributions, morphology of catalytically active
nanoparticles, and thereby the distribution of surface sites. In addition,
some of structural properties including structural imperfections,
stacking faults, twin and boundaries can be investigated by TEM. It has
been reported that various structural imperfections can be found in Cu
particles larger than 5 nm, wherein the most typical imperfections are
twins and stacking faults [66]. As earlier mentioned, larger Cu particles
are more active. Two reasons come to mind: 1) decoration of Zn into Cu
particles takes place more easily in larger particles and 2) defects and
imperfections are more in larger particles. The latter can be probed by
TEM images. Fig. 7a–f show the TEM images of CZA-12 and CZA-5.
At first glance, wrinkle shaped dark bands or coarse tweed structure
arisen from twin boundaries and interwoven can be observed in TEM
images of CZA-5. Some of structural imperfections such as crystal dis-
orders, stacking faults, twin boundaries, kink and steps can be found
around coarse tweed structure. For example, along planes (002), the
stacking faults of CuO are visible as dark bands [67]. The coarse tweed
structure nearly was barely seen for CZA - 12. Some literatures referred
this coarse tweed structure as nano-twin [68]. These nano-twins are
located interior the grains and illustrated by arrows in the Fig. 7e.
The prepared catalysts exhibited here have relatively large CuO
particles and poorly crystalline ZnO, so the demonstrated crystalline
particles depicted in TEM images are majorly related to CuO nano-
particles. Furthermore, Fast Fourier Transform (FFT) imaging can de-
termine d spacing for more identification of CuO and ZnO particles. It
has been proved that high concentration of nano-twins in CuO are
stable under working condition [69]. Therefore, these coarse tweed
nano-structures originated from interwoven nano-twins are also stable
at working conditions and play a critical role in final activity of catalyst.
According to TEM images, for CZA-5, the intensity of the mentioned
nano-twins is higher than CZA-12. This issue is clearly seen in second
TPR of N2O chemisorption. Second peak in TPR is sharper for CZA-5
meaning that Cu+ is originated from defect rich catalyst. FFT images
for CZA-12 and CZA-5 showed different patterns. HRTEM for CZA-12
confirmed single crystalline nature of CuO and calculated d-spacing
from electron diffraction spots were recorded 0.23 nm and 0.25 nm
related to (111) and (002) planes, respectively. Fig. 7e showed FFT
imaging of a nano-twin in CZA-5. Four types of spots indicated by
different colors can be seen in nano-twin area. The calculated d-spacing
of 0.23 nm and 0.25 nm belongs to (111) and (002) planes of CuO. The
corresponding planes with d-spacing of 0.28 nm, 0.24 nm and 0.26 nm
are respectively assigned to (100), (002) and (101) planes of ZnO [70]
and the spot at 0.24 nm is related to ZnO. The spots at 0.27 nm, 0.31 nm
and 0.37 nm are related to hydrozincite Zn5(CO3)2(OH)6 that could not
be detected by XRD [71]. This issue means that some of un-calcined
hydroxyl carbonates have been remained in the final catalyst and this
poor ordered structure can play a pivotal role to prepare a highly active
catalyst [72]. As pointed above, at ZnO contents higher than 28%, Zn-
rich aurichalcite phase as a side product will be formed. Here we ob-
served hydrozincite at higher Zn amounts as a Zn rich specimen for
CZA-5. We believe that part of this Zn rich hydroxyl carbonates de-
composes to rich defect ZnO. This issue is seen in Fig. 7f as dislocation
in ZnO. Despite its simple chemical formula, ZnO has a very rich defect
chemistry. Oxygen vacancies formed on the surface of ZnO crystals
serve as the active sites for dissociative adsorption of H2 [73,74].
This rich defect ZnO accelerates the dissociation of H2 and conse-
quently enhances the rate of methanol production. Another point was
shown in FFT images in nano-twin area. By more attention, a spot with
d-spacing of 0.21 nm is seen in FFT. It has been supposed that residual
carbonates in final catalyst can contribute in the formation of copper
sub-oxide species [75,76]. So the spot at 0.21 nm can be ascribed to
(200) plane of Cu2O [77]. Hence, presence of two types copper species
was verified in interwoven nano-twin area indicating that different
hydroxyl carbonates decompose into different copper species appearing
in FFT images and TPR profiles.
Therefore, by adjusting the atomic ratio, formation of interwoven
nano-twin islands could be taken place wherein 4 types of different
species are incorporated into these complexes structures. To our mind,
one of the main reasons of high activity at CuO/ZnO = 1.8 ratio is re-
lated to the formation of such nano-twins. We believe that the syner-
getic effect between different species in a nano-twin particle accelerates
both dissociation and formation the atomic bonds and consequently
enhances the rate of methanol production.
The second TPR in N2O refractive frontal chromatography (N2O
chemisorption) for CZA-12 and CZA-5 are depicted in Fig. 8a and b,

45
M. Sadeghinia et al.
Fig. 7. (a–c) TEM images of CZA-12 (CuO/ZnO = 2.8) along with corresponding FFT. (d–f) TEM images if CZA-5 (CuO/ZnO = 1.8).
respectively. Two peaks in second TPR imply that more than one type of
Cu+ are present at the surface. Most active centers at the surface are
located in Cu-Zn interface. Therefore, the first peak with high intensity
can be assigned to Cu+ dissolved in ZnO. The second peak with lower
intensity is related to fine dispersed Cu particles acting as a weak
electron donor. There is a main difference between CZA-12 and CZA-5.
The second peak for CZA-5 is sharper than the peak observed in CZA-
12. We believe that this difference is due to interwoven nano-twins.
Four types of species in nano-twin area may affect the second TPR.
Furthermore, defect rich structure plus oxygen vacancies affect the N2O
chemisorption. Hence, second peak can be assigned to fine dispersed Cu
plus defects and oxygen vacancies. Higher intensity of the second peak
for CZA-5 indicates that fine dispersed Cu species, defect and oxygen
vacancies can be found in higher levels for CuO/ZnO = 1.8. Therefore,
electron donor effect is higher at this ratio. Electron donor effect can
46
Molecular Catalysis 456 (2018) 38–48
promote the dissociation and formation of atomic bonds resulting in
enhancing of methanol production rate. Some of residual hydrozincite
are decomposed into a ZnO defect rich structure which in turn boosts
the dissociative adsorption of H2 and consequently methanol produc-
tion. The Donor effect was observed in second peak as a sharper mode
and the sharper mode is seen at CuO/ZnO = 1.8.
3.7. Stability
The catalytic stability test for CZA-12, CZA-5 and commercial cat-
alyst was carried out to evaluate the catalytic activity during long time
reaction. Fig. 9 shows the stability results of the CZA-12, CZA-5 and
commercial catalysts. The decrease in methanol production has lower
rate for CZA-5.
Table 3 shows the BET area, crystallite size and Cu surface area of
M. Sadeghinia et al. Molecular Catalysis 456 (2018) 38–48

Table 3
Textural properties of the fresh and spent CZA-12, CZA-5 and commercial
catalysts.
Sample BET (m2/g) Cu crystallite size 2
Cu surface area (mCu /gcat)
(nm) (N2O chemisorption)
From XRD

fresh spent fresh spent fresh spent

CZA-12 130.6 69.9 8.7 23.4 35.56 20.34

CZA-5 102.4 61.5 10.7 18.3 26.86 18.96
Commerciala 84.2 50.8 8.8 22.8 28.63 17.37

a
MK-121 methanol synthesis catalyst.

crystallite size for CZA-5 from one hand and lower percent of CuO on its
formulation as well as high intensity of crystal defects and imperfection
in another hand, have led to a lower deactivation rate for CZA-5.

4. Conclusion

In this study, 16 set of ternary Cu/Zn/Al catalyst were synthesized

Fig. 8. Second TPR in N2O chemisorption for (a) CZA-12, (b) CZA-5.
via coprecipitation method to evaluate and understand the best opti-
mized structure. all catalysts were synthesized at the same synthetic
condition but they were different in their component ratios. The most
active catalyst was obtained at CuO/ZnO = 2.7 and CuO/Al2O3 = 9.
Another interesting point was about the samples synthesized at CuO/
ZnO = 1.8. These samples were also of the most active catalysts. At
CuO/ ZnO = 1.8 Cu surface area was lower and their Cu crystallite size
were larger than the best sample but surprisingly STY for these samples
were high and close to the best sample. Detailed characterization re-
vealed that the most active sample at CuO/ZnO = 1.8 compared to the
best synthesized sample, contains interwoven nano-twins consisting of
four different species. FFT images for CZA-5 (CuO/ZnO = 1.8) illu-
strated that some hydrozincite Zn5(CO3)2(OH)6 is present in the final
catalyst. This residual un-calcined hydroxy carbonate can decompose
into defect rich structure which can promote the methanol production.
Besides good activity, these nano-twins at CuO/ZnO = 1.8 led to rela-
tively higher stability than the best sample (CZA-12). We found that
there is no linear relationship between Cu surface area and methanol
productivity. Our study also revealed that these ternary catalysts are
structure and morphology sensitive. In a nutshell, this research showed
how to achieve high selectivity and selectivity by selecting proper ratio
of catalyst components. Also it was observed what structural change
could be happen by varying the main components.

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