Journal of Catalysis 347 (2017) 45–56

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Optimization of Au0–Cu+ synergy in Au/MgCuCr2O4 catalysts for aerobic

oxidation of ethanol to acetaldehyde
Peng Liu a,b,⇑, Tao Li a,b, Hanping Chen b, Emiel J.M. Hensen c,⇑
a
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Key Laboratory of Material Chemistry and Service Failure, School of Chemistry
and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China
c
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands

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

Article history: A ternary MgCuCr2O4 spinel-supported gold nanoparticle catalyst is optimized toward high acetaldehyde
Received 1 November 2016 productivity in gas-phase aerobic oxidation of ethanol. We investigate the structure–performance rela-
Revised 26 November 2016 tionships of Au/MgCuCr2O4 catalysts by changing support and catalyst pretreatment to gain further
Accepted 28 November 2016
insight into the Au0–Cu+ synergy. Support calcination at 700 °C and catalyst prereduction result in the
most active and stable ethanol oxidation catalyst. Extensive characterization shows this to be mainly
due to the enrichment of Cu in the surface by H2- or ethanol-induced catalyst restructuring and the sta-
Keywords:
bilization of surface Cu+ species in well-crystallized spinel without reduction to Cu0, which leads to a
Gold
Ethanol oxidation
higher surface Cu+ fraction and enhanced Au0–Cu+ interaction. Kinetic studies show that the apparent
Spinel support activation energies of prereduced catalysts are higher than those of preoxidized catalysts, suggesting that
Synergy oxygen vacancy formation via water removal from Au–H and active oxygen species is a dominant rate-
Kinetics limiting step. Molecular O2 is activated on defective Cu+ sites at the AuNP/support interface to form
peroxide-type O2 species, which serve as active sites for removing hydride from the gold surface and
breaking the O-H bond of ethanol. The reaction rate increases with space velocity and reactant concen-
tration, achieving a lower boundary estimate of space–time yield of up to 1245 galdehyde gAu1 h 1 at 250 °C
with air as oxidant.
Ó 2016 Elsevier Inc. All rights reserved.

1. Introduction nanostructured carbons [5–7], manganese oxide [8–10], molybde-

num oxide [11,12], and supported metal nanoparticles [3,13–25].
In recent years, there has been growing interest in the produc- However, these catalysts still suffer from the usual trade-off
tion of acetaldehyde (AC) by gas-phase ethanol dehydrogenation, between activity and selectivity, typically yielding small amounts
as bioethanol is becoming more abundant and its use as a renew- of AC at high ethanol conversion. This drawback arises from the
able feedstock for bulk chemicals production is increasingly nonselective activation of molecular oxygen. Therefore, the devel-
competitive [1–3]. From a practical viewpoint, oxidative opment of more efficient catalysts that can activate O2 into specific
dehydrogenation of ethanol (ODE) is preferred over nonoxidative active intermediates that can selectively oxidize ethanol to AC is
dehydrogenation of ethanol (NODE) [4], not only because the for- strongly desired.
mer reaction is exothermic but also because NODE requires a Supported gold nanoparticles (AuNP) have shown great promise
higher reaction temperature (>250 °C), which causes serious deac- for aerobic alcohol oxidation to carbonyl compounds, with the size
tivation by metal sintering and coking. Currently, many studies on of AuNP and the gold–support interaction being the key factors in
aerobic ODE are devoted to developing novel catalysts such as tuning the catalytic performance [26–30]. As gold shows low affin-
ity for oxygen and alcohols, the support often plays a more promi-
nent role than dispersing the active metal phase [31–34]. A wide
⇑ Corresponding authors at: Key Laboratory of Material Chemistry for Energy
range of supports have been investigated for AuNP-catalyzed
Conversion and Storage, Ministry of Education, Key Laboratory of Material
Chemistry and Service Failure, School of Chemistry and Chemical Engineering, ODE [16–25]. For instance, Haruta concluded that oxidation of
Huazhong University of Science and Technology, Wuhan 430074, China. Fax: +86 27 ethanol to acetic acid and CO2 takes place over AuNP deposited
87543632 (P. Liu). on n-type and p-type semiconductive oxides, respectively, whereas
E-mail addresses: pengliu@hust.edu.cn (P. Liu), e.j.m.hensen@tue.nl (E.J.M. AuNPs deposited on metal oxides with strong acidity or weak
Hensen).

http://dx.doi.org/10.1016/j.jcat.2016.11.040
0021-9517/Ó 2016 Elsevier Inc. All rights reserved.
46 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

basicity are more suitable for mild oxidation of ethanol to AC [21]. as the precipitation agent. The targeted gold loading was 1.0 wt.
Sobolev and co-workers found that Au/TiO2 shows good AC yield %. The catalysts were finally calcined in air at 350 °C for 5 h. The
(48%) at relatively low temperature (120 °C) due to facile O2 acti- Au/MgCuCr2O4 samples obtained using the different supports are
vation, but the catalyst deactivates rapidly [22–24]. Kegnœs and denoted as Au/S500, Au/S600, Au/S650, Au/S700, and Au/S750,
his group showed that the encapsulation of AuNP in zeolite pores respectively.
is effective in suppressing sintering of gold particles, but the max-
imum AC yield of such catalysts remains below 80% [18]. There- 2.3. Catalyst characterization
fore, enhancing the activity, selectivity, and stability of supported
AuNP catalysts for aerobic ODE has become a significant research X-ray diffraction (XRD) was performed on an Empyrean appara-
topic. tus using Cu Ka radiation (40 kV and 30 mA). Nitrogen physisorp-
In our recent work, we discovered a ternary MgCuCr2O4 spinel tion was done on a Tristar 3000 automated gas adsorption
oxide that acts as a suitable support for AuNP to facilitate activa- system. Scanning electron microscopy (SEM) images were taken
tion of O2 and ethanol by stable Cu+ sites and basic oxygen species using a FEI Nova NanoSEM 450 microscope. Transmission electron
at the Au–support interface, respectively [35,36]. This catalyst microscopy (TEM) images were acquired on a FEI Tecnai G2 20
achieves >95% AC yield at 250 °C with a space–time yield (STY) electron microscope at an acceleration voltage of 200 kV. The aver-
of up to 311 galdehyde gAu1 h 1. This catalyst is stable for at least age size of AuNP was calculated by measuring 200 metal particles
500 h. Its exceptional performance relates to synergy between from several images. The gold loading was determined by a Perkin
Au0 and Cu+. The Cu+ sites allow facile desorption of product water, Elmer AA-300 atomic absorption spectrometer (AAS) after extrac-
the resulting vacancy being the locus of O2 adsorption and activa- tion of the metal in aqua regia. X-ray photoelectron spectroscopic
tion [34]. The Au/MgCuCr2O4 catalyst outperforms other recently (XPS) measurements were performed using a Thermo VG Multilab
described ODE catalysts such as silica-supported bimetallic Au– 2000 spectrometer. The spectra were recorded using X-rays from
Cu [37,38], Au–Ir [39], and Au–Pd [40] alloys. Gaining more an aluminum anode (Al Ka radiation at 1486.6 eV). Energy correc-
detailed understanding of the nature of the Au0–Cu+ synergy can tions were performed using C1s (284.5 eV) as the reference.
guide the design of improved supported AuNP catalysts. Temperature-programmed reduction (TPR) experiments were
It is well known that the preparation conditions of mixed oxides performed in a flow apparatus equipped with a fixed-bed reactor,
have significant influence on their textural and chemical properties a computer-controlled oven, and a thermal conductivity detector.
[41–45]. In particular, the calcination temperature in the prepara- Typically, 10 mg of catalyst was loaded into a tubular quartz reac-
tion of copper-containing spinel phases strongly affects the surface tor. Prior to TPR, the catalyst was oxidized by exposure to a flowing
area, composition, and reducibility of copper [46–52]. Obviously, mixture of 4 vol.% O2 in He and heating to 300 °C. After cooling to
these variables also have an influence on gold dispersion and room temperature in flowing N2, the sample was reduced in 4 vol.%
gold–support interaction, viz., Au0–Cu+ synergy in Au/MgCuCr2O4 H2 in N2 at a flow rate of 8 mL/min, while it was heated from room
catalysts. The objective of this work is to clarify the influence of temperature up to 800 °C at a ramp rate of 10 °C/min. The H2 signal
the calcination temperature of the MgCuCr2O4 spinel on the struc- was calibrated using a CuO/SiO2 standard.
tural properties of Au/MgCuCr2O4 catalysts, as well as of the activa- X-ray absorption near-edge structure (XANES) spectra were
tion of the catalyst on the catalytic performance in the ODE. measured at the Dutch–Belgian Beamline (Dubble) at the European
Surface- and bulk-sensitive spectroscopy and kinetic studies Synchrotron Radiation Facility (ESRF, Grenoble, France). Data were
provide insight into structure–performance relationships for collected at the Au LIII-edge and Cr K-edge in fluorescence mode
Au/MgCuCr2O4 catalysts. The resulting optimization of the with a nine-channel solid state detector. Energy selection was done
catalytic performance allows increasing the overall activity of the by a double-crystal Si(1 1 1) monochromator. The photon energy
catalyst threefold compared with earlier results. was calibrated with standard Au and Cr metal foil. Background
removal was carried out by standard procedures. For the in situ
Au LIII-edge and Cr K-edge XANES measurements, the sample was
2. Experimental
placed in a stainless steel controlled-atmosphere cell. The cell
was heated with two firerods controlled by a temperature con-
2.1. Materials
troller via a thermocouple placed close to the catalyst sample. Typ-
ically, 100 mg of sample was pressed in a stainless steel holder and
Gold(III) chloride trihydrate (HAuCl4
3H2O) was purchased from
placed in the cell. High-purity carbon foils with a thickness of
Sigma-Aldrich. Metal nitrates (Cu(NO3)2
3H2O, Mg(NO3)2
6H2O,
150 lm were used as windows. High-purity gases (He, or 20 vol.
and Cr(NO3)3
9H2O), sodium hydroxide (NaOH), ethanol (absolute,
% O2 in He) were delivered by Bronkhorst thermal mass flow con-
>99.8%), and acetaldehyde and acetic acid were purchased from
trollers. For the in situ ethanol oxidation experiments, the catalyst
Sinopharm Chemical Reagent Co., Ltd. All chemicals were used as
was exposed to a flowing mixture of ethanol in 20 vol.% O2 in He
received.
(by introducing a 50 mL min–1 O2-in-He stream through an ethanol
saturator under room temperature) and heated to 150, 250, and
2.2. Catalyst preparation 350 °C at a rate of 10 °C min–1, maintaining each temperature for
30 min.
The Mg0.75Cu0.25Cr2O4 spinel (denoted as MgCuCr2O4) was pre-
pared by a co-precipitation method [35]. Typically, a mixed metal 2.4. Catalytic activity measurements
nitrate solution with the molar ratio Mg(NO3)2/Cu(NO3)2/Cr
(NO3)3 = 3/1/8 was prepared. To this solution 1 M NaOH solution Ethanol oxidation was carried out in a fixed-bed plug flow reac-
was added dropwise to bring the pH to 11 in order to ensure full tor system. Typically, 0.1 g of catalyst diluted with 0.3 g of a-Al2O3
precipitation. The blue precipitate was filtered, washed, and then was loaded into a quartz reactor with an internal diameter of
dried at 110 °C. The solid was grinded and divided into five parts, 6 mm. Prior to reaction, the catalyst was treated with a mixture
which were calcined at 500, 600, 650, 700, and 750 °C in air for of 10 vol.% O2 or H2 in N2 at 300 °C for 2 h. The reactant feed mix-
8 h. The resulting samples are referred as S500, S600, S650, S700, ture was obtained by evaporating ethanol in a N2 stream in a con-
and S750, respectively. Au/MgCuCr2O4 catalysts were prepared trolled evaporator mixer. The volumetric composition of the feed
by homogeneous deposition–precipitation of HAuCl4 using urea mixture was ethanol/O2/N2 = 1/3/63 and the total gas flow rate
 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56 47

was 167 mL/min. The ethanol flow rate was 2.5 mL/min (1.5 vol.%) AuNP size of all Au/MgCuCr2O4 catalysts are collected in Table 1.
and the GHSV was 100,000 mL gcat1 h 1. The reaction products were The large difference in textural properties did not affect the gold
analyzed online using a GC (Fuli GC 9070II) equipped with a 30 m loading procedure and, in all cases, the measured metal content
Rtx-Wax capillary column and a TDX-01 packed column. In all was close to the targeted value of 1.0 wt.% Au.
cases, the carbon balances closed at 100 ± 2%. The occurrence of TEM was then used to analyze the distribution and size of the
internal and external mass and heat transfer limitations was tested AuNP in the Au/MgCuCr2O4 samples (Fig. 3). The nanoparticles
by Maers and Thiele modulus criteria [36]. The results of this anal- became larger with decreasing support surface area. The average
ysis show that, at lower conversion below 200 °C, the reported rate AuNP size of Au/S500 is smallest (2.1 nm), followed by Au/S600
is nearly completely controlled by chemical kinetics. (2.5 nm), Au/S650 (2.9 nm), and Au/S700 (3.1 nm). Au/S750 con-
tained significantly larger nanoparticles (4.5 nm).
3. Results and discussion XPS was used to compare the composition and oxidation state
of the constituents in the surface. Both the (Mg + Cu)/Cr and Au/
3.1. Characterization of Au/MgCuCr2O4 catalysts Cu atomic ratios increased when the calcination temperature was
raised (Table 1). Thus, increasing the calcination temperature
We first carefully studied the influence of the calcination tem- enriches the surface in Mg and Cu relative to Cr. The increased
perature on the physicochemical properties of the MgCuCr2O4- Au/Cu ratio is mainly due to the increased number of AuNP per
spinel support. Fig. 1 shows the XRD patterns of the MgCuCr2O4 unit surface area. Despite signal overlap of the Mg2s and Au4f
supports. All MgCuCr2O4 supports have the same cubic Fd-3m spi- states hindering XPS analysis, Au4f7/2 was located at 84.0 eV in
nel structure and the lattice constant corresponds to that of MgCr2- all samples (Fig. 4A). This shows that the active phase is in the
O4 (8.33 Å, JCPDS 10-0351). The pure spinel phase was already metallic state after calcination in air. In the Cu2p3/2 XP spectra,
formed after calcination at 500 °C. Increasing the calcination tem- two contributions can be discerned at 935 and 932 eV (Fig. 4B).
perature to 750 °C leads to sharpening of the XRD peaks. The par- The higher-binding-energy (BE) peak is assigned to Cu2+ in the spi-
ticle size was evaluated by application of the Scherrer equation to nel; this feature is accompanied by the characteristic Cu2+ shakeup
the 2h = 18.4° peak corresponding to the (1 1 1) plane. The volume- satellite peaks in the 938–945 eV region. The lower BE peak at
averaged crystallite size increases from 20 nm for the S500 sam- 932 eV can be assigned to Cu+ sites, primarily due to the absence
ple to 80 nm for the S750 sample. The XRD patterns did not of Cu0 in the air-calcined catalysts [35]. The surface Cu+/Cu ratio in
change upon gold loading (Fig. S1 in the Supporting Information), these samples varied in the range 20–26%, with Au/S700 having
except for a small peak at 38.2° originating from the (1 1 1) plane the highest Cu+ fraction (Table 1). As shown in Fig. 4C, the O1s
of gold visible in some samples. XP spectra contain three contributions at 529.6, 531.5, and
SEM was used to study the morphology of Au/MgCuCr2O4 sam- 533.0 eV, which can be assigned to lattice oxygen (O2 , Olatt),
ples (Fig. 2). Clearly, the size of the spinel particles increases with surface-adsorbed oxygen such as O22 , O2 , O or OH species (Oads),
increasing calcination temperature. Calcination above 600 °C leads and surface-adsorbed H2O [53,54], respectively. The surface Olatt
to well-faceted crystals, although smaller cubic-shaped particles fraction increased from 15% for Au/S500 to 43% for Au/S700 and
are also present. The gold loading procedure did not change the then decreased to 32% for Au/S750 (Table 1). It is noteworthy that
morphology (Fig. S2 in the Supporting Information) and textural the Olatt fraction of MgCuCr2O4 supports increased with calcination
properties of the MgCuCr2O4 support. The surface area of the Au/ temperature from 30% for S500 to 51% for S750 (Fig. S3 in the Sup-
MgCuCr2O4 samples decreased with increasing calcination temper- porting Information), which is generally higher than the corre-
ature of the MgCuCr2O4 support from 37 m2/g for Au/S500 to 3 m2/g sponding gold catalysts, possibly due to the masking effect of
for Au/S750. Data about the surface area, gold loading, and average AuNPs on the spinel surface.
H2 TPR was used to follow the reduction of the Au/MgCuCr2O4
samples. As shown in Table 2, the amount of reducible species of
the spinel supports and the gold catalysts derived thereof was con-
sistent with the Cu content (1.24 mmol/gcat). In general, two
reduction peaks were observed, the first below 300 °C and the sec-
ond above 500 °C (Fig. 5). The reduction peak at lower temperature
can be attributed to the reduction of surface Cu2+/Cu+ species to
Cu+/Cu0, the one at elevated temperature to the reduction of bulk
Cu2+ in the spinel to Cu0 [35]. As calcination temperature increased
from 500 to 700 °C, the fraction of readily reduced Cu species
(below 300 °C) decreased from 48 to 7% for the supports them-
selves and from 43 to 5% for the supported gold catalysts. These
results show that a larger fraction of the surface Cu2+/Cu+ species
can be reduced in the spinel supports calcined at lower tempera-
tures. In contrast, higher stability of Cu2+/Cu+ was achieved for
the MgCuCr2O4 calcined above 650 °C. Interestingly, addition of
AuNP results in reduction of surface Cu2+/Cu+ species below
100 °C. This demonstrates that gold is involved in H2 activation
[55], enhancing the reducibility of surface copper cations.
To clarify the oxidation state changes of surface copper species
upon H2 reduction, an XPS study was conducted for several H2-
pretreated (at 300 °C) spinel supports and gold catalysts (Fig. S4).
As Cu2p3/2 XPS cannot differentiate between Cu+ and Cu0, Auger
Cu LMM spectra were obtained to confirm the presence of Cu+ at
BE 570.5 eV [36]. For the H2-pretreated S500 sample, the surface
Cu+ fraction derived from Cu2p3/2 (78%) is much higher than the
Fig. 1. XRD patterns of various MgCuCr2O4 supports. Cu+ fraction by Cu LMM (23%), pointing to a high surface Cu0
48 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

Fig. 2. SEM images for various Au/MgCuCr2O4 catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650, (d) Au/S700, and (e) Au/S750.

Table 1
Physicochemical properties of various Au/MgCuCr2O4 catalysts.

Catalyst SBET (m2/g) [Au] (wt.%)a dAu (nm) Mg/Cu/Cr atomic ratiob Au/Cu atomic ratiob Cu+/Cu (%)b Olatt/O (%)b
Au/S500 37 0.95 2.1 0.66/0.29/2.0 0.09 20 15
Au/S600 23 0.95 2.6 0.70/0.32/2.0 0.14 21 22
Au/S650 12 0.90 2.9 0.75/0.33/2.0 0.25 25 38
Au/S700 5 0.90 3.1 0.78/0.35/2.0 0.74 26 43
Au/S750 3 0.93 4.5 0.83/0.32/2.0 0.83 21 32
Au/S700c 5 0.90 3.1 0.80/0.42/2.0 0.76 63 41
S700 5 – – 0.77/0.35/2.0 – 33 49
S700c 5 – – 0.81/0.40/2.0 – 54 45
a
Determined by AAS.
b
Evaluated by XPS results.
c
Treated in H2 at 300°C.

fraction (55%) in the reduced S500 sample. This is in keeping with ture (< 650 °C) leads to a more defective spinel surface, resulting
the H2 TPR analysis of this sample. In contrast, the Cu LMM in more facile reduction of Cu2+/Cu+ species to Cu0. The well-
spectra-derived Cu+ fractions of the H2-pretreated S700 (54%), crystallized spinels obtained by higher-temperature calcination
Au/S650 (56%), Au/S700 (63%), and Au/S750 (55%) samples are con- show higher intrinsic stability of the surface Cu, in the sense that
sistent with the values derived from Cu2p3/2 XP spectra, implying reduction in H2 at 300 °C results in Cu+ but not Cu0. It is also
that no metallic Cu0 was formed in these H2-pretreated samples. observed that Au helps in the reduction of Cu2+ to Cu+. We next
Therefore, the small H2 uptake (3–8%) below 300 °C (Table 2) for study the catalytic performance of the various Au/MgCuCr2O4 sam-
the Au/S650, Au/S700, and Au/S750 samples is primarily due to ples in ODE.
the partial reduction of surface Cu2+ to Cu+ species. From the H2
TPR results and the fact that the surface Cu+ fraction of the 3.2. Catalytic performance
H2-pretreated Au/S700 sample (63%) is higher than that of the
S700 sample (54%), it is reasonable to propose that Au0 and Cu+ 3.2.1. Catalyst pretreatment
sites are located at the nanoparticle/support perimeter. Moreover, We investigated the effect of preoxidation and prereduction on
prereduction not only increased the surface Cu+ fraction of the the catalytic performance in gas-phase aerobic oxidation of etha-
S700 and Au/S700 samples, but also led to an increase in the sur- nol. Fig. 6 shows the ethanol conversion and the AC selectivity as
face (Mg + Cu)/Cr atomic ratio (Table 1), pointing to H2-induced functions of the temperature for various Au/MgCuCr2O4 catalysts.
surface reconstruction with Cu enriching the surface accompanied For preoxidized catalysts, the preferred reaction temperature range
by the formation of defective Cu+ sites. is between 150 and 250 °C, with AC selectivity higher than 98%.
The foregoing characterization results demonstrate that the cal- Below this optimum temperature range, ethyl acetate is the main
cination temperature of MgCuCr2O4 spinel and the prereduction byproduct and, above it, acetic acid and CO2. The reaction
substantially influence the structural, textural, and chemical prop- rate increased in the order Au/S750 < Au/S500 < Au/S600 <
erties of the Au/MgCuCr2O4 catalysts. Lower calcination tempera- Au/S650 < Au/S700 (Table 3). The quasi turnover frequency (qTOF)
 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56 49

Fig. 3. TEM images of various Au/MgCuCr2O4 catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650, (d) Au/S700, and (e) Au/S750.

Fig. 4. Au4f XP spectra (A), Cu2p3/2 XP spectra (B), and O1s XP spectra (C) for various Au/MgCuCr2O4 catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650, (d) Au/S700, and (e) Au/
S750.

values based on the AC yield and the gold dispersion were highest 200 °C and the highest AC yield (97%) at 250 °C. Based on the
for Au/S700 (0.65 s 1) and lowest for Au/S500 (0.27 s 1). These above results, it is reasonable to conclude that pretreatment in
qTOF values represent lower boundary estimates of the real TOF H2 is favorable for enhancing the activity and AC selectivity of
due to the relatively high ethanol conversion. When the catalysts Au/MgCuCr2O4 catalysts.
were prereduced under H2, the selectivity to AC was higher than The activity and selectivity differences between the preoxidized
99% below 200 °C. The AC selectivity strongly decreased for the and prereduced catalysts can be related primarily to changes in the
Au/S500 and Au/S600 catalysts, with acetic acid as the main bypro- surface copper speciation and the Au–Cu interaction. For the prere-
duct between 200 and 250 °C, and CO2 at higher temperatures. The duced Au/S500 and Au/S600 samples, the low activity is related to
AC selectivity of the other three catalysts decreased less strongly the presence of a large amount of surface Cu0, which will lead to
and remained above 80% even at a reaction temperature of formation of CuO under oxidative conditions. CuO is not preferred,
300 °C. Compared with preoxidation, prereduction led to higher as it slows down recombinative water removal from interfacial Cu–
activity for Au/S650, Au/S700, and Au/S750 at reaction tempera- OH and Au–H species due to the strong Cu–O binding energy in
tures above 125 °C. Evidently, prereduced Au/S700 achieved the CuO [34,56]. Above 200 °C, the Cu0 sites are more reactive than
maximum reaction rate (6.2  10 5 g s 1) and qTOF (0.70 s 1) at metallic Au0 and enable nonselective cleavage of C–H and C-C
50 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

Table 2 sizes were slightly increased (Table 4). The size of AuNP in the
Temperature-programmed reduction results for various MgCuCr2O4 supports and Au/ Au/S500 sample increased from 2.1 to 2.5 nm after 50 hours on
MgCuCr2O4 catalysts.
stream. The increase was relatively small for the Au/S700 sample
Sample H2 uptake H2/Cu2+ Cu2+ reduced (from 3.1 to 3.3 nm) after 200 h on stream. As discussed before
(mmol/gcat) below 300 °C (%) [35,36], the Au/S700 and Au/S650 catalysts showed at least 500
S500 1.27 1.02 48 and 120 h stability, respectively, with no apparent loss of activity
Au/S500 1.17 0.94 43 and selectivity. For the other three catalysts, it was observed that
S600 1.28 1.03 26
Au/S600 1.20 0.96 21
the ethanol conversion at 200 °C was slightly decreased after reac-
S650 1.28 1.03 13 tion at 300 °C. We attribute this to the slight decrease in gold
Au/S650 1.22 0.98 8 dispersion.
S700 1.26 1.01 7 The XPS data of the spent Au/MgCuCr2O4 catalysts suggest an
Au/S700 1.23 0.99 5
increase in the Cu/Cr atomic ratio and a decrease in the Au/Cu ratio
Au/S750 1.23 0.99 3
(Table 4). The surface enrichment of Cu should be associated with
H2- and ethanol-induced surface reduction. For the Au/S700 sam-
ple, the spent catalyst showed an even higher Cu/Cr atomic ratio
than the H2-pretreated sample (see Table 1), implying that further
restructuring occurs during ethanol oxidation. The decreased Au/
Cu ratio could be attributed to the somewhat decreased gold dis-
persion and the increased concentration of surface Cu species.
The Au4f7/2 peak of the spent Au/MgCuCr2O4 catalysts remains
unchanged at 84.0 eV (Fig. 8A), indicating that metallic Au is the
active phase for ethanol oxidation. Interestingly, significant
changes were observed when Cu2p3/2 XP spectra of the untreated
fresh catalysts and the spent catalysts were compared, with the
surface Cu+ fractions increasing from 20% to 50%. For the spent
Au/S650, Au/S700, and Au/S750 catalysts, the surface Cu+/Cu ratios
derived from C 2p3/2 XP spectra are consistent with the values
derived from Cu LMM spectra (see Fig. 8 and Table 4), demonstrat-
ing that Cu2+ were reduced to Cu+ in the corresponding spinel sup-
ports. For the spent Au/S500 and Au/S600 catalysts, the lower Cu+
fractions determined from the Cu LMM envelope in comparison
with the fractions derived from the Cu2p3/2 envelope are due to
the presence of Cu0. Interestingly, opposite changes in the Cu+ frac-
tion by Cu LMM were observed when the H2-pretreated Au/S500
sample (26%) is compared with the spent Au/S500 one (35%)
and the H2-pretreated Au/S700 sample (63%) with the spent
Au/S700 one (53%). This is explained by the oxidation of partial
Cu0 to Cu+ in the former case and the oxidation of partial Cu+ to
Cu2+ in the latter. From the much higher activity of the Au/S650
and Au/S700 samples in comparison with the Au/S500 and
Au/S600 samples (Fig. 6 and Table 3), we infer that Cu+ is more
effective in activating molecular oxygen than Cu0.
Bearing in mind that Au–Cr synergy between AuNPs and MgCr–
Fig. 5. Temperature-programmed reduction profiles showing H2 consumption for hydrotalcite is also efficient for O2 activation, which is related to
various Au/MgCuCr2O4 catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650, (d) Au/ Cr3+ ? Cr6+ oxidation during aerobic alcohol oxidation [25,57], it
S700, and (e) Au/S750. The dashed line represents the profile of the corresponding is necessary to clarify whether similar Au–Cr synergy occurs in
support.
Au/MgCuCr2O4-catalyzed ethanol oxidation. To this end, we
employed in situ XANES to monitor the oxidation state changes
in Au and Cr during ethanol oxidation. Fig. 9 shows in situ XANES
bonds of AC to acetic acid and CO2, in accord with the catalytic per-
spectra around the Au LIII-edge and the Cr K-edge of the optimal
formance of Cu/MgCuCr2O4 catalyst [36]. For the prereduced Au/
Au/S700 catalyst as a function of temperature in the presence of
S650, Au/S700, and Au/S750 samples, the higher activity in com-
ethanol and oxygen. For comparison, the spectra of reference sam-
parison with the preoxidized samples above 125 °C can be attribu-
ples for Au (Au foil, Au2O3) and Cr (Cr(III) acetate, K2CrO4) are
ted primarily to H2-induced surface restructuring that enriches the
included. Evidently, the oxidation state of Au remained unchanged
surface in Cu accompanied by reduction to Cu+ and enhanced Au0–
upon an increase of the reaction temperature from 150 to 350 °C.
Cu+ synergy, which facilitates O2 and ethanol activation. Hence, H2
This confirms that metallic Au is the active phase for alcohol oxida-
pretreatment of the gold-containing catalyst made from MgCuCr2-
tion. A pre-edge peak occurs in all Cr K-edge spectra because of the
O4 calcined at 70 °C displays the strongest Au0–Cu+ synergy.
1s to 3d electronic transition [58,59]. This transition is dipole for-
bidden, but the probability of the transition increases as a result
3.2.2. Stability of the catalysts of Cr3d and O2p orbital mixing and the lack of a symmetry center.
To compare the stability of different Au/MgCuCr2O4 catalysts This explains the sharp pre-edge peak at 5992 eV for K2CrO4 in
during ethanol oxidation, the spent prereduced catalysts (Fig. 6) which Cr6+ is tetrahedrally coordinated [58]. In contrast, the spec-
were characterized by TEM and XPS to reveal the changes in AuNP trum of Cr(III) acetate with Cr3+ in centrosymmetric octahedral
size, surface metal composition, and the metal oxidation state. coordination exhibits greatly reduced intensity of this pre-edge
Fig. 7 shows representative TEM images of spent Au/MgCuCr2O4 feature. The position of the edge is at a higher energy for Cr6+ than
catalysts. Compared with the fresh samples, the average AuNP for Cr3+ [59]. As shown in Fig. 9B, the in situ Cr K-edge spectra of
 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56 51

Fig. 6. Effect of pretreatment atmosphere (in O2 or in H2) on ethanol conversion (X) and acetaldehyde selectivity (S) of various catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650,
(d) Au/S700, and (e) Au/S750, and effect of H2 pretreatment on acetaldehyde yield of various catalysts. Reaction conditions: 0.1 g catalyst, ethanol/O2/N2 = 1/3/63,
GHSV = 100,000 mL gcat1 h 1.

Table 3
Effect of pretreatment on the catalytic activity of various Au/MgCuCr2O4 catalysts.

Catalyst Pretreatment atmosphere X (%)a S (%)a Rate (10 5

gs 1 a
) qTOF (s 1 b
) Ea (kJ mol 1 c
)
Au/S500 O2 45 98 3.8 0.27 50
H2 44 98 3.7 0.27 79
Au/S600 O2 54 99 4.6 0.41 47
H2 58 99 4.9 0.44 70
Au/S650 O2 65 99 5.5 0.58 39
H2 73 99 6.2 0.65 48
Au/S700 O2 68 99 5.8 0.65 31
H2 73 99 6.2 0.70 40
Au/S750 O2 43 99 3.6 0.58 36
H2 51 99 4.3 0.69 47
a
Ethanol conversion (X), acetaldehyde selectivity (S), and reaction rate under certain reaction conditions: 200 °C, 0.1 g catalyst, ethanol/O2/He = 1/3/63,
GHSV = 100,000 mL gcat1 h 1.
b 1 1
Quasi turnover frequency (qTOF) based on acetaldehyde yield and gold dispersion (D = 1.3/d) and given in molaldehyde molsurface Au h .
c
Apparent activation energy based on the Arrhenius plots.

Au/MgCuCr2O4 remain the same, with no sharp pre-edge peak and and decrease in the order Au/S500 > Au/S600 > Au/S650 >
the main edge at lower energy than for the Cr6+ reference sample. Au/S750 > Au/S700. The Ea values of preoxidized Au/S500
Evidently, Cr3+ is in octahedral coordination in the Au/MgCuCr2O4 (50 kJ/mol) and Au/S600 (47 kJ/mol) and prereduced Au/S650
catalyst, even under oxidation conditions and elevated tempera- (48 kJ/mol) and Au/S750 (47 kJ/mol) were found to be comparable
ture. This strongly points to the absence of Au–Cr synergy for etha- to the value of 49 kJ/mol for Au/SiO2 [39]. The lowest Ea was
nol oxidation, in line with the low activity of Au/MgCr2O4 [35]. observed for the preoxidized Au/S700 sample (31 kJ/mol). It is
noteworthy that the prereduced Au/S500 (79 kJ/mol) and Au/
3.3. Kinetic measurements S600 (70 kJ/mol) samples showed significantly higher Ea values
than their preoxidized counterparts and the other prereduced cat-
3.3.1. Temperature dependence alysts, demonstrating the significant influence of calcination tem-
To further understand the effect of support calcination and cat- perature and catalyst pretreatment on the mechanism of ethanol
alyst pretreatment on the mechanism of Au0–Cu+ synergy, Arrhe- oxidation.
nius plots for aerobic ethanol oxidation are shown in Fig. 10. The Generally speaking, the large differences in Ea value suggest a
corresponding apparent activation energies (Ea) are collected in change in the rate-limiting step, possibly due to different active
Table 3. Reaction data measured in the range 100–175 °C were sites. High values for the Ea of the prereduced Au/S500 and
used, which are free from mass and heat transfer limitations Au/S600 samples may be related to deep reduction of surface
[36]. Interestingly, the Ea values of the prereduced catalysts are Cu2+/Cu+ to Cu0, which will lead to formation of CuO under reaction
generally higher than those of the corresponding preoxidized ones, conditions and high oxygen vacancy formation energy [34]. For the
52 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

Fig. 7. TEM images for spent Au/MgCuCr2O4 catalysts: (a) Au/S500 after 50 h, (b) Au/S600 after 50 h, (c) Au/S650 after 100 h, (d) Au/S700 after 200 h, and (e) Au/S750 after
100 h.

Table 4
Physicochemical properties of spent Au/MgCuCr2O4 catalysts.

Spent catalyst dAu (nm) Mg/Cu/Cr atomic ratioa Au/Cu atomic ratioa Cu+/Cu (%)a
by Cu 2p3/2 by Cu LMM
Au/S500 2.5 0.63/0.38/2.0 0.04 56 35
Au/S600 2.9 0.67/0.41/2.0 0.10 51 42
Au/S650 3.1 0.70/0.45/2.0 0.18 56 53
Au/S700 3.3 0.75/0.51/2.0 0.58 55 53
Au/S750 4.8 0.78/0.43/2.0 0.67 54 52
a
Evaluated by XPS results.

Fig. 8. Au4f (A), Cu2p3/2 (B), and Cu LMM (C) XP spectra for spent Au/MgCuCr2O4 catalysts: (a) Au/S500, (b) Au/S600, (c) Au/S650, (d) Au/S700, and (e) Au/S750.
 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56 53

Fig. 9. In situ Au LIII-edge (A) and Cr K-edge (B) XANES spectra of catalyst Au/S700 under ethanol oxidation conditions.

Fig. 10. Arrhenius plots for ethanol oxidation over various preoxidized (A) and prereduced (B) Au/MgCuCr2O4 catalysts (for all fits the adjusted R2 is higher than 0.997).
Reaction conditions: 0.1 g catalyst, ethanol/O2/N2 = 1/3/63, GHSV = 100,000 mL gcat1 h 1.

preoxidized Au/S500 and Au/S600 samples, the fraction of Cu2+/Cu+ involve atomic oxygen species in ethanol oxidation [24,60]. For a
that is reduced to Cu0 by ethanol is much smaller, as indicated by mixture of O2 and H2, hydroperoxo (OOH) or hydrogen peroxide
XPS (not shown). These data suggest that oxygen vacancy forma- may be considered as active oxygen species [61–64]. Ethanol oxi-
tion would be a rate-limiting step for the Au/S500 and Au/S600 dation with N2O over the prereduced Au/S700 sample resulted in
samples. In contrast, the other three catalysts with higher support much lower conversion in comparison with the experiment using
calcination temperatures have lower oxygen vacancy formation O2 as oxidant (Fig. 11A). Despite the lower activity, the AC selectiv-
energies, presumably because Cu0/CuO formation is avoided. ity was slightly better with N2O as oxidant. Similarly to nonoxida-
Instead, structural Cu2+ and Cu+ species are stable, the latter pre- tive ethanol dehydrogenation [35], the catalyst strongly
sumably being involved in a reaction cycle that results in lower deactivated with N2O as oxidant, most likely due to buildup of
activation energy. For the prereduced Au/S650, Au/S700, and Au/ alcoholates that are not oxidized. An important aspect that
S750 samples, the higher Ea values in comparison to those for the explains the low activity with N2O as oxidant is the very slow dis-
preoxidized counterparts may be primarily attributed to the pres- sociation of N2O over gold catalysts. In an experiment with a N2O/
ence of more Au–H species and the difficulty in water formation He feed, the conversion of N2O was only 2% at 300 °C. This result is
and removal at lower reaction temperatures [34], accounting for consistent with experiments involving Au/MgCuCr2O4-catalyzed
their lower activity below 150 °C (Fig. 6). To get further insight into propylene oxidation [65] and Au/TiO2-catalyzed ethanol oxidation
the reaction mechanism, the role of O2 and the nature of the active by N2O [24].
oxygen species should be clarified. In the case of ethanol oxidation over the prereduced Au/S700
sample used in a co-feeding experiment with O2 and H2 (etha-
3.3.2. Active oxygen species nol/O2/H2 = 1/3/1, H2 feed = 2.5 vol.%), no promoting effect of H2
We compared O2 as an oxidant for ethanol conversion with N2O was observed on the conversion or the selectivity (Fig. 11B). In
and a mixture of O2 and H2. Presumably, N2O as an oxidant will contrast, H2 co-feeding led to slightly lower ethanol conversion
54 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

Fig. 11. Effect of N2O (A) and O2–H2 cofeeding (B) as oxidant on ethanol conversion (X) and acetaldehyde selectivity (S) over H2-pretreated Au/S700. Reaction conditions: 0.1 g
catalyst, ethanol/O2/N2 = 1/3/36 or ethanol/N2O/N2 = 1/3/36 or ethanol/O2/H2/N2 = 1/3/1/35, GHSV = 60,000 mL gcat1 h 1.

than with O2 only, probably due to competitive adsorption of H2 on

the surface or a side reaction of O2 with H2. The absence of a clear
promoting effect of H2 is different from the positive effect that H2
had in oxidation of propylene on titania-supported gold catalysts
[61–64]. The low conversion of H2 (<5% at 20 °C) further suggests
that O2 is not involved in the formation of OOH species with hydro-
gen over the AuNPs, but is activated molecularly on the defective
Cu+ sites at the Au–Cu+ interface. This is also consistent with cat-
alytic experiments using Au/MgCuCr2O4 catalyst in propylene oxi-
dation, which mainly yielded acrolein [65]. Based on all
experimental and computational results, a peroxide-type O2 spe-
cies is thought to be the activated oxygen species, which is located
in the oxygen vacancies of surface Cu+ species; these O2 interme-
diates act as basic sites to facilitate O-H bond cleavage.

3.3.3. Influence of reactant concentration

The influence of reactant concentration on the catalytic perfor-
mance of the prereduced Au/S700 catalyst was also investigated.
Fig. 12 shows how the catalytic performance depends on the O2
concentration at a GHSV of 100,000 mL gcat1 h 1, a temperature of Fig. 12. Effect of O2 concentration on the catalytic performance of Au/S700.
200 °C, and a constant ethanol concentration of 1.5 vol.%. Evi- Reaction conditions: 0.1 g catalyst, 1.5 vol.% ethanol, 200 °C,
dently, the reaction rate increases with O2 concentration, with GHSV = 100,000 mL gcat1 h 1.
ethanol conversion increasing from 38% (1.5 vol.% O2) to 80%
(15 vol.% O2). The AC selectivity is almost unchanged and remains increasing from 0.5 to 3%, ethanol conversion decreases from 89
higher than 98%. The Langmuir-type dependence of the rate of to 77% and AC selectivity increases slightly from 98 to 99%
ethanol oxidation on the O2 concentration indicates that the sur- (Fig. 13). Evidently, the reaction is first order with respect to
face becomes covered with active oxygen species. In the absence ethanol.
of O2, the prereduced Au/S700 sample exhibited an initial ethanol A series of experiments were carried out at different space
conversion of about 10%, which decreased gradually during the velocities. The GHSV was varied by changing the total reactant flow
first 5 h in a fashion similar to that for the preoxidized catalyst rate, while maintaining the catalyst amount (0.1 g), ethanol con-
[35]. The Ea of nonoxidative dehydrogenation over the prereduced centration (1.5 vol.%), and O2/ethanol ratio (10). Fig. 14 shows
Au/S700 sample is about 67 kJ/mol between 100 and 175 °C, which how the GHSV affects the behavior of the catalyst. In the given
is significantly higher than the activation energy of 40 kJ/mol in GHSV range the reaction is evidently first order in the reactant.
oxidative dehydrogenation. The decrease in the apparent activa- An increase of the GHSV from 50,000 to 200,000 mL gcat1 h 1 led
tion energy upon addition of oxygen points to more facile removal to a decrease of the ethanol conversion from 91 to 73%. Meanwhile,
of H atoms by activated O2 species in close proximity to AuNPs. the AC selectivity increased slightly from 97 to 99%.
The effect of ethanol concentration on catalytic performance We then used these promising results to optimize the space–
was further evaluated at GHSV = 100,000 mL gcat1 h 1, 200 °C, and time yield (STY) of AC by controlling the reaction conditions. We
a constant O2/ethanol ratio of 10. With ethanol concentration used 0.1 g of prereduced Au/S700 catalyst at a GHSV of
 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56 55

Fig. 13. Effect of ethanol concentration on the catalytic performance of Au/S700. Reaction conditions: 0.1 g catalyst, ethanol/O2 = 1/10, 200 °C, GHSV = 100,000 mL gcat1 h 1
.

200,000 mL gcat1 h 1, a constant ethanol concentration of 3 vol.%,

and an O2/ethanol ratio of 10. As the temperature increased, the
ethanol conversion increased from 25% (150 °C) to 100% (250 °C)
with AC selectivity remaining close to 100% (Fig. 15). The STY of
AC increased accordingly from 328 to 1311 gAC gAu1 h 1 with the
temperature increase. In practice, air is the preferred oxidant. Thus,
we also examined ethanol oxidation in air at 3 vol.% ethanol,
97 vol.% air, and the same GHSV (200,000 mL gcat1 h 1). The ethanol
conversion and AC selectivity reached 96 and 99% at 250 °C with a
STY of 1245 gAC gAu1 h 1. This STY value is the highest reported for
ethanol oxidation [18,36] and presents a threefold increase com-
pared with our earlier result (311 gAC gAu1 h 1) using a preoxidized
Au/S700 catalyst [35].

4. Conclusions

We have shown that the calcination temperature of the

MgCuCr2O4 support and the pretreatment atmosphere of the
Au/MgCuCr2O4 catalyst affects the support surface structure and
Fig. 14. Effect of GHSV on the catalytic performance of Au/S700 (X = conversion%). composition, and in this way the catalytic performance of the
Reaction conditions: 0.1 g catalyst, 1.5 vol.% ethanol, ethanol/O2 = 1/10, 200 °C,
active metallic gold nanoparticles in gas-phase ethanol oxidation.
GHSV = 50,000–200,000 mL gcat1 h 1.
A lower support calcination temperature (<650 °C) leads to facile

Fig. 15. Catalytic performance (A) and space–time yield of acetaldehyde (B) for ethanol oxidation over catalyst Au/S700 under optimal reaction conditions: 0.1 g catalyst,
ethanol/O2/N2 = 3/30/67, GHSV = 200,000 mL gcat1 h 1.
56 P. Liu et al. / Journal of Catalysis 347 (2017) 45–56

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