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Article history:
Received 3 September 2014
Received in revised form 28 October 2014
Accepted 30 October 2014
Available online 23 December 2014
Keywords:
Nb2 O5
Nb/MCF
AuCu system
Glycerol and methanol oxidation
a b s t r a c t
Nb2 O5 and Nb/MCF were used as supports for gold and copper (AuCu system). The activity of these
catalysts in the oxidation of glycerol in the liquid phase and methanol in the gas phase was compared
with that of monometallic gold catalysts. The oxidation states of metals in the samples prepared were
characterised by XRD, TEM, UVVis, XPS and H2 -TPR. It was found that gold was present in metallic form,
whereas copper in the form of CuO, oligonuclear [Cu+ O Cu+ ]n clusters and isolated cations. The
introduction of copper changed the electronic state of gold in AuNb2 O5 and AuNb/MCF and the reduction of copper was found easier in bimetallic AuCu catalysts, which was interpreted as a result of the
interaction between gold and copper. Nb2 O5 supported catalysts were active in the glycerol oxidation.
Monometallic catalysts show high selectivity to glyceric acid, whereas an increase in the selectivity to
glycolic acid was found over bimetallic samples due to the presence of copper species active in the oxidative dehydrogenation of glyceric acid. AuCu catalysts exhibit very high activity in methanol oxidation
towards CO2 as a result of the presence of basic oxygen from CuO-like species on the catalyst surface.
Superior performance of bimetallic catalysts in oxidation reactions is due to the synergy between gold
and copper.
2014 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, in the eld of heterogeneous catalysis increasing
attention has been paid to noble metal-supported catalysts because
of their potential applications in industrially important chemical
reactions [13]. Gold and bimetallic systems containing gold are
nowadays the focus of attention [1,2,4,5]. Among different bimetallic nanoparticle catalysts (like AuPt, AuPd, AuAg, AuCu systems),
AuCu modied catalysts have recently been tested in catalytic oxidation reactions [2,4]. In the AuCu bimetallic catalysts, copper is
much more prone to oxidation than gold and phase segregation
tends to occur upon treatment in oxidising atmosphere (in either
reaction or pretreatment) [2]. As a consequence, copper is enriched
on the surface and may form copperoxygen species and therefore
it can act as a promoter to provide reactive oxygen in a variety of
gold catalysed oxidation reactions. Supported goldcopper catalysts have shown promising catalytic performance in oxidation of
CO [6,7], propene [8,9] and alcohols [10,11].
Selective oxidation of alcohols to the corresponding aldehydes,
ketones and acids involving the use of molecular oxygen as an
73
74
heated according to the following programme: 5 min at 358 K, temperature increase to 408 K (heating rate 5 K min1 ), 4 min at 408 K,
cooling down to 358 K (for the automatic injection on the column
with 5A), 10 min at 358 K, heated to 408 K (heating rate 10 K min1 ),
11 min at 408 K. Argon was applied as a carrier gas. The outlet
stream line from the reactor to the gas chromatograph was heated
at about 373 K to avoid condensation of the reaction products.
3. Results and discussion
3.1. Catalysts characterisation
3.1.1. Chemical composition of Nb2 O5 and Nb/MCF samples
modied with Au and Cu
Two series of catalysts were prepared: (i) supported on Nb2 O5
amorphous bulk oxide and (ii) supported on Nb/MCF material prepared by the impregnation of MCF with niobium source. In both
bimetallic samples (AuCuNb2 O5 , AuCuNb/MCF), the assumed
loading of gold and copper was the same, 2 wt% of Au and 1 wt%
of Cu. For monometallic catalysts (CuNb2 O5 , CuNb/MCF and
AuNb2 O5 , AuNb/MCF) the excess of copper was applied (3 wt%),
whereas the initial content of Au was 2 wt%.
Table 1 shows the real metals (Au and Cu) loading in all the
catalysts studied. Gold loading in mono- and bimetallic samples modied by grafting with organosilanes is very close to the
assumed value (1.9 wt%). It shows that the interaction of gold (in
the form of AuCl4 ions [24]) with NH2 groups (in the form of
NH3 + ions [24]) is effective for gold incorporation. Contrary, the
real content of copper is lower than assumed, especially in the copper monometallic samples. It is due to the electrostatic repulsion
between Cu2+ and NH3 + ions. The deposition of gold onto the support in the rst step facilitates the loading of Cu2+ cations [7,24].
The atomic Au:Cu ratio in the nal materials is 0.9 for AuCuNb2 O5
and 0.7 for AuCuNb/MCF (Table 1).
3.1.2. Textural properties of the supports
The texture parameters of Nb2 O5 and Nb/MCF materials used
as supports for gold and copper, calculated from N2 adsorption/desorption measurements, are shown in Table 2. The BET
surface area of Nb/MCF mesoporous sieve is much higher than
that of Nb2 O5 . This value signicantly decreases for the samples
modied with gold and copper. Simultaneously, a decrease in pore
volumes is also observed. The decrease in surface areas and pore
volumes in Au and AuCu modied catalysts suggests the pore
blocking as a result of metals incorporation into the pores of Nb2 O5
and Nb/MCF. The average pore size in Nb/MCF support is 16.7 and
27.7 nm for windows and cells, respectively. Nb2 O5 exhibits much
smaller average pore size (ca. 5 nm). Pore sizes do not change significantly after modications with Au and Cu in both cases. However,
it is worthy of notice that Nb/MCF is mesoporous material with
narrow pore size distribution (SD1), whereas Nb2 O5 shows mesomacroporosity as deduced from its N2 adsorption isotherm (the
hysteresis loop is observed in the p/po close to the saturation pressure (p/po = 0.91.0) indicating a presence of macroporosity) and
pore size distribution (SD1).
3.1.3. The state, coordination and location of Nb in the supports
UVVis spectroscopy was used to verify the coordination and
location of Nb in the supports. The UVVis spectrum of Nb2 O5
(Fig. 1) is typical of amorphous niobia [26,27] and exhibits an
intense wide band in the range 250350 nm (with a maximum at
around 280 nm) and a lower intensity band at 222 nm. These bands
are characteristic of octahedral and tetrahedral Nb species, respectively [28]. They are attributed to the charge transfer transitions
O2 to Nb5+ , which can be associated to the energy gap between
the O 2p-valence band and the Nb4d-conductance band [28]. The
75
Table 1
Metals loadings and average size of gold particles in the catalysts.
Catalyst
AuNb2 O5
AuCuNb2 O5
CuNb2 O5
AuNb/MCF
AuCuNb/MCF
CuNb/MCF
2
2
2
2
1.9
1.9
1.9
1.9
1
3
1
3
0.9
0.7
0.7
1.4
1/0
0.7/1
0/1
1/0
0.9/1
0/1
4.9
5.7
4.3
3.6
2.2
2.2
1.3
1.0
Table 2
Texture parameters of the catalysts.
Sample
Nb2 O5
AuCuNb2 O5
Nb/MCF
AuCuNb/MCF
85
67
607
395
0.11
0.10
2.40
1.90
5.1a
5.0a
16.7b
16.8b
Catalyst
Au4f [eV]
Cu2p [eV]
Nb3d [eV]
AuNb2 O5
AuCuNb2 O5
83.2
84.0
207.1
207.2
AuNb/MCF
AuCuNb/MCF
83.1
83.9
932.6
934.6
933.2
935.3
208.1
207.9
3.1.4. The state of copper and gold and the size of gold crystallites
The state of gold and copper in the catalysts prepared was studied by XRD, TEM, UVVis, XPS and H2 -TPR techniques. XRD, TEM
and UVVis results clearly indicate that metallic gold crystallites
are formed on both Nb2 O5 and Nb/MCF materials. In XRD patterns
(SD2) of the calcined Nb2 O5 and Nb/MCF samples containing Au the
reections characteristic of metallic gold (at 2 = 38.2 and 44.4 )
[33,34] are well visible. The metallic state of gold is conrmed by
UVVis spectra (Fig. 1). The observed intense ultravioletvisible
(UVVis) band at ca. 500 nm is typical of metallic gold [35]. TEM
images of the catalysts and gold particle size distributions are
shown in Fig. 2 and the average gold particle sizes of mono and
bimetallic catalysts are listed in Table 1. The results obtained clearly
258
283
506
Au-Nb/MCF
512
AuCu-Nb/MCF
Cu-Nb/MCF
0.25
Cu-Nb2O 5
222
253
Kubelka-Munk
Kubelka-Munk
261
Kubelka-Munk
220
220
AuCu-Nb2O5
272
2
*20
540
0.25
Au-Nb2O5
Wavelengh t, nm
Nb2O5
200
300
400
500
600
Wavelength, nm
700
800
Kubelka-Munk
a
b
27.7c
27.9c
200
300
400
500
600
700
800
Fig. 1. UVVis spectra of Nb/MCF and Nb2 O5 catalysts modied with Au and AuCu.
Wave lengh t, nm
76
Fig. 2. TEM images of catalysts containing gold and Au particles size distributions.
indicate that the particle size is determined by the chemical composition of the active phase and the type of support. Among the
catalysts containing gold supported on Nb/MCF, the smallest average metal particles size is noted for AuCuNb/MCF. The analysis
of the particle size distributions of AuNb/MCF and AuCuNb/MCF
materials shows that the introduction of copper increases the number of gold particles with diameters in the range 13 nm (this
fraction increases from 19 to 46%) and decreases the number of
particles with the size above 5 nm (this fraction decreases from 81
to 54%). It indicates the stabilising effect of Cu on gold nanoparticles
during calcination. A similar effect of copper was observed earlier
for AuCuSiO2 catalysts [6,15]. A coreshell model to interpret the
key role of Cu in limiting the aggregation of gold particles has been
proposed [6]. The typical coreshell structure was not formed in
the case of MCF samples studied. Copper oxide identied by H2 -TPR
measurement (described below) deposited on the gold nanoparticles in the form of some patches on the surface of gold core inhibits
the aggregation of gold particles during high-temperature calcination. The above effect of copper species, deposited in the same way,
on the gold particles size is not observed for Nb2 O5 based catalysts.
In this case the introduction of copper into Au/Nb2 O5 increases the
fraction of nanoparticles with the size above 6 nm (from 32 to 50%)
indicating the agglomeration of gold. Most probably it results from
much lower surface area (and as a consequence a lower dispersion of metal) of Nb2 O5 than Nb/MCF. Another reason may be the
presence of macropores in the structure of Nb2 O5 , which do not
limit the growth of the particles sizes promoting their agglomeration (in both AuNb2 O5 and AuCuNb2 O5 ). It is in agreement with
the results reported in [36] documenting that the nal gold particle size in porous materials increases with the pore size. Moreover,
one cannot exclude that the larger fraction of smaller gold crystallites (in the range 15 nm Fig. 2) on the surface of mono- and
bimetallic catalysts based on Nb/MCF than Nb2 O5 is also a result of
the interaction of highly dispersed niobium species on MCF surface
with gold.
Copper species on the surface of Nb2 O5 and Nb/MCF supports
were identied by XRD, UVVis and H2 -TPR techniques. In XRD
patterns of copper containing samples the small intensive reection assigned to CuO at 2 = 38 [JCPDS 45-0937] [37] is present
only for Cu/NbMCF material (SD2). However, one should remember about the XRD analysis limitations. This method gives reliable
results for relatively large crystals and high enough concentration
of species (the loading of copper is the highest on Cu/NbMCF
1.4 wt%). Moreover, the reection from CuO could be hidden in XRD
patterns of AuCu samples (due to similar position of the reexions characteristic of metallic gold and copper oxide). Therefore,
UVVis spectroscopy was applied as a complementary technique.
77
Table 4
The results of 2-propanol decomposition reaction.
Catalyst
Nb/MCF
AuNb/MCF
AuCuNb/MCF
Nb2 O5
AuNb2 O5
AuCuNb2 O5
Acetone
100
96
71
100
97
50
0
4
29
0
3
50
dispersed Nb2 O5 and Nb+ species in the framework are the source
of Lewis acidity which comes from the Nb/MCF support. On the
other hand, Brnsted and Lewis acid centres are present on amorphous Nb2 O5 support [27]. The modication with gold decreases
the acidity of catalysts (a decrease in activity is observed). However, the introduction of Cu species into Au-monometallic materials
enhances the activity by generating basic/redox centres as deduced
from an increase in the selectivity to acetone. The acetone formation indicates the dehydrogenating properties of bimetallic
catalysts. The oxygen from CuO is a source of basicity, whereas
copper ions are responsible for redox activity.
3.2. Glycerol oxidation with oxygen in the liquid phase
Catalytic oxidation of glycerol with oxygen allows the production of a number of new derivatives, among them glyceric, tartronic
and glycolic acids that have attracted recently signicant interest
[3,15,16,58,59]. The crucial research target is to control selectivity
for the desired product. It is known that the chemical composition
of the active phase, the temperature of the reaction, the pH of the
reaction mixture and the particle size of the metal are crucial for
the formation of a desired product.
3.2.1. Effect of gold and copper
The prepared mono and bimetallic AuCu catalysts based on
Nb2 O5 were tested in glycerol oxidation processes. The catalyst
activity was estimated by glycerol conversion at 333 and 363 K and
the results are given in Table 5 and Fig. 4.
For the reactions on AuNb2 O5 , CuNb2 O5 and AuCuNb2 O5
under identical reaction conditions (333 K), an increase in glycerol
conversion is observed for bimetallic catalyst indicating the synergetic effect between Au and Cu species (Fig. 4 A). A similar effect
of bimetallic active phase on the activity in glycerol oxidation has
been found earlier for AuPt, AuPd, PtCu catalysts supported on
carbon [e.g. 17, 19, 20]. Although negatively charged gold particles in monometallic Au catalysts (present also on Au/Nb2 O5 ) have
been found active in aerobic oxidation of alcohols [6062], the synergetic effect between Au0 and Cu species on Nb2 O5 seems to be
more important factor to obtain high performance of Nb2 O5 catalysts in glycerol oxidation. Moreover, it has been reported [15]
that the size effect i.e., the small particle size is responsible for
the improved activity of AuCu/SiO2 (a decrease in gold particles
size for bimetallic catalysts was observed) in the benzyl alcohol
oxidation. The theoretical calculations have also revealed that the
activity for the alcohol oxidation increases with decreasing Au coordination number [63]. Taking into account that the average size of
gold crystallites in AuCuNb2 O5 is larger than in AuNb2 O5 , no
correlation can be made between the increase in the activity of
bimetallic sample studied in this work with the size of gold particles.
Depending on the type of active phase (Au vs AuCu) a different distribution of products is observed for each catalyst (Table 5,
Fig. 4 B). AuNb2 O5 activates the reaction mainly towards glyceric
78
Table 5
Catalytic activity and selectivity of Au and AuCu-supported catalysts in liquid phase oxidation of glycerol.
Catalyst
Temp., K
Glycerol conv. %
AuNb2 O5
AuNb2 O5
AuCuNb2 O5
AuCuNb2 O5
CuNb2 O5
AuCuNb2 O5 a
AuCuNb/MCFa
333
363
333
363
363
363
363
54
93
65
90
51
23
15
Selectivity, %
Glyceric acid
Tartronic acid
Glycolic acid
Formic acid
Oxalic acid
Glyoxylic acid
44
45
24
13
10
traces
1
traces
1
traces
1
11
14
27
25
3
1
traces
1
7
16
13
traces
traces
1
1
1
1
traces
8
Reaction conditions: glycerol 100 mmol/kg, NaOH/glycerol molar ratio = 2, pO2 = 6 bar.
a
Reaction mixture without NaOH.
1158
50
1255
H2 consumption. a.u.
H2 consumption, a.u.
250
694
Cu-Nb2O5
683
AuCu-Nb2O5
400
935
600
800
1000
734
1162
597
448
Cu-Nb/MCF
704
583
AuCu-Nb/MCF
453
400
1200
600
800
1000
1200
1400
Temperature, K
Temperature, K
acid (44% of selectivity at 54% of glycerol conversion). The selectivity to other products of oxidation, including tartronic, glycolic
and formic acids is very low. It indicates that at low (333 K) reaction temperature the over-oxidation of glyceric acid is limited. The
Fig. 4. The effect of copper species and the reaction temperature on the activity (A) and selectivity (B) of AuNb2 O5 catalysts in glycerol oxidation. GLYCEA = glyceric acid,
GLYCOA = glycolic acid, FORA = formic acid.
OH
O
OH
glyceraldehyde
[O]
[O]
[O]
OH
HO
OH
glycerol
[-H2]
OH
HO
OH
O
glyceric
acid
[O]
[-H2]
OH
HO
OH
O
O
tartronic
acid
[-CO2]
HO
[O]
O
OH
glycolic
acid
[ - H2]
[-CO2] formaldehyde
O
H
OH
formic
acid
towards glyceraldehyde is proposed as the rst step in the oxidation process [64]. The presence of OH is essential to observe
any glycerol oxidation when using gold containing catalysts. In the
presence of NaOH, the proton is readily abstracted from one of
the primary hydroxyl groups of glycerol. The formation of AuCusystem increases the dehydrogenating properties of AuNb2 O5
catalysts, in line with the results of 2-propanol decomposition reaction. Moreover, the copper-containing catalysts are known to be
active in dehydrogenation of alcohols [6567]. The formation of
glycolic acid on AuCuNb2 O5 suggests that copper species catalyse the dehydrogenation of glyceric acid towards tartronic acid
which is next transformed to glycolic acid (via decarboxylation)
and subsequently to formic acid (via degradation of glycolic acid
to formaldehyde and CO2 and next oxidation of formaldehyde)
(Scheme 1). Copper species can also be involved in generation of
active oxygen on the catalyst surface. It has been shown that in
CO oxidation reaction Cu played an important role in activating
oxygen [6,7]. The presence of copper in contact with gold contributes much to the activation of oxygen.
The oxidation of glycerol is a typical consecutive reaction
proceeding according to the rake model [18]. In such a process the
selectivity is strongly determined by the adsorption and desorption
rate of each product. Thus, the relation between the rate of desorption of glyceric acid and the rate of its transformation to tartronic
and glycolic acids determines the selectivity to one or the other
product. The faster the desorption of glyceric acid, the lower the
selectivity to tartronic and glycolic acids. Therefore, it cannot be
excluded that copper species in AuCuNb2 O5 catalyst strengthen
the chemisorption of glyceric acid and thanks to it the selectivity
to glycolic acid via formation of tartronic acid increases.
As shown in Fig. 4 A, the increase in the reaction temperature
from 333 K to 363 K causes a signicant increase in the glycerol conversion, for both, AuNb2 O5 and AuCuNb2 O5 catalysts. Along with
increasing activity caused by growing temperature, an increase in
glyceric acid yield on AuNb2 O5 (from 24 to 42%) and glycolic acid
yield on AuCuNb2 O5 (from 9% to 25%) is observed (Fig. 4B). Similarly as at 333 K, glyceric acid is the main product of the reaction
at 363 K on AuNb2 O5 . The increase in temperature promotes the
formation of glycolic acid (an increase in selectivity observed on
Au/Nb2 O5 ) but a comparison of the selectivity of AuNb2 O5 and
AuCuNb2 O5 obtained for similar glycerol conversion (93 and 90%,
respectively) conrms that copper species are active in glycolic acid
formation on AuCuNb2 O5 (an increase in selectivity from 11 up
to 27% when copper is present on the catalyst surface). Moreover,
glycolic acid is also the main reaction product on Cu/Nb2 O5 . However, it is worth noting that when using AuCuNb2 O5 , the yield to
glycolic acid is higher than when using CuNb2 O5 (25% and 13%,
respectively) (Fig. 4B).
The sum of the selectivities towards products of glycerol oxidation is lower than 100%. It could be due to the polymerisation
of the reaction products to compounds not detected by the HPLC,
MeOH conversion, %
473 K
16
37
Au-Nb/MCF
With NaOH
Without NaOH
90
AuCu-Nb/MCF
23
15
AuCu-Nb2O5
AuCu-Nb/MCF
oxidation of the reaction products to CO2 or the adsorption of products on the supports surface as suggested in [68].
3.2.2. Effect of pH of the reaction mixture
As proved in the literature [64,69], glycerol oxidation on gold
catalysts is favoured by high-pH conditions, since the hydroxide
species adsorbed on gold are necessary to activate both C H and
O H bonds of glycerol (also adsorbed on the surface). However,
Prati et al. [70] and Hutchings et al. [71] have reported the basefree oxidation of glycerol to glyceric acid with good conversion
and selectivity obtained using AuPt catalysts supported on carbon, mordenite and MgO. High activity and selectivity to glyceric
acid have been also obtained over a PtCu/C [17]. In all cases the
improved performance of bimetallic catalysts in oxidation of glycerol under base-free conditions was attributed to the formation of
AuPt or PtCu alloyed phases.
In this study, the glycerol conversion was examined using
the reaction mixture without NaOH (pH 8) in the presence of
AuCuNb2 O5 and AuCuNb/MCF catalysts. Mesoporous silica based
catalysts were not studied in the presence of NaOH because of
solubility of silica in basic solutions. The results are shown in
Fig. 5. It can be clearly observed that the activity of AuCuNb2 O5
signicantly decreases when the reaction is performed without
NaOH. It indicates that the formation of alloy is necessary to obtain
high activity of catalysts in this reaction conditions. When copper species exist separately, in the neighbourhood of gold, NaOH
is necessary for the initiation of glycerol oxidation reaction, similarly as for monometallic gold catalysts. The observed selectivity to
tartronic and glycolic acid conrms that copper species are active in
oxidative dehydrogenation of glycerol to tartronic acid. The activity of AuCuNb/MCF catalyst is lower than that of AuCuNb2 O5 . It
indicates the role of AuNb interactions when bulk Nb2 O5 is used
as a support (SMSI between gold and niobium). The AuNb interaction in bulk Nb2 O5 is stronger than when niobium is dispersed
on the mesoporous MCF support.
99
79
Fig. 5. The effect of the base in the reaction mixture on the activity of AuCuNb2 O5
and AuCuNb/MCF catalysts in glycerol oxidation at 363 K.
523 K
98
100
90
80
70
60
50
40
30
20
10
0
AuCu-Nb2O5
100
90
80
70
60
50
40
30
20
10
0
MeOH conversion, %
A
100
90
80
70
60
50
40
30
20
10
0
Glycerol conversion, %
373 K
423 K
97
22
99
37
Au-Nb2O5
AuCu-Nb2O5
Fig. 6. The effect of copper species on the activity of Au-catalysts in methanol oxidation: Nb/MCF supported catalysts (A), Nb2 O5 supported catalysts (B).
MeOH molecues*min-1*nm-2
80
373 K
45
40
35
30
25
20
15
10
5
0
25
423 K
473 K
41
40
34
25
10
Fig. 7. The effect of the support on the activity of Au- and AuCu-containing catalysts in methanol oxidation (activity as the number of MeOH molecules reacted per
minute per nm2 of the surface area of gold crystallites).
81
Table 6
Catalytic activity and selectivity in MeOH oxidation reaction carried out at different temperatures on Nb/MCF and Nb2 O5 supported catalysts.
Catalyst
Temp. [K]
MeOH conv.
rate 102
[mmol/g/min]
HCHO
HCOOCH3
CH3 OCH3
C2 H4
CO2
AuNb/MCF
AuNb/MCF
AuCuNb/MCF
AuCuNb/MCF
AuCuNb/MCF
AuCuNb/MCF
CuNb/MCF
CuNb/MCF
AuNb2 O5
AuNb2 O5
AuNb2 O5
AuCuNb2 O5
AuCuNb2 O5
CuNb2 O5
CuNb2 O5
473
523
373
423
473
523
473
523
373
423
523
373
423
473
523
16
37
8
19
98
99
1
5
22
37
99
97
99
20
38
57
132
29
68
350
353
4
18
16
26
71
69
71
14
27
17
27
traces
31
traces
60
2
40
28
22
77
61
100
98
18
5
11
57
67
25
2
8
5
traces
traces
2
traces
traces
24
1
1
4
23
traces
traces
11
traces
traces
traces
traces
traces
1
1
3
traces
6
12
traces
2
82
64
traces
27
42
31
25
74
97
57
50
16
FA 17
Au-Nb/MCF
473 K
MF
98
19
AuCu-Nb/MCF
423 K
99
CO2
64
FA
31
AuCu-Nb/MCF
523 K
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
conversion
selectivity
EN 11
DME
24
99
FA
40
99
CO2
97
CO2
25
Au-Nb2O5
523 K
AuCu-Nb2O5
423 K
100
90
80
70
60
50
40
30
20
10
0
Selectivity, %
MF
77
selectivity
MeOH conversion, %
conversion
Selectivity, %
MeOH conversion, %
A
100
90
80
70
60
50
40
30
20
10
0
Selectivity [%]
Fig. 8. Effect of copper species on the selectivity of AuCuNb/MCF (A) and AuCuNb2 O5 (B) catalysts in methanol oxidation. FA = formaldehyde, MF = methyl formate,
EN = ethene, DME = dimethyl ether.
82
this work. Thanks are also due to Johnson Matthey (UK-USA) and
CBMM (Brazil) for the kind gifts of HAuCl4 and Nb2 O5 , respectively.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.cattod.
2014.10.051.
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