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CATTOD-10171; No. of Pages 10 ARTICLE IN PRESS

Catalysis Today xxx (2016) xxxxxx

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

On the nature of the active sites in the selective oxidative

esterication of furfural on Au/ZrO2 catalysts
C. Ampelli a , K. Barbera a , G. Centi a , C. Genovese a , G. Papanikolaou a , S. Perathoner a, ,
K.J. Schouten b , J.K. van der Waal b
a
Universit di Messina, ERIC aisbl and CASPE/INSTM, Sect. Industrial Chemistry, V.le F. Stagno DAlcontres 31, 98166 Messina, Italy
b
Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands

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

Article history: Two catalysts, based on gold on zirconia and prepared in the same way, except for the different thermal
Received 30 December 2015 treatment in air after the addition of gold (0.4% wt), show a quite different behavior in furfural oxidative
Received in revised form 25 March 2016 esterication, particularly in the selectivity to 2-MF (methyl 2-furoate). The analysis of their catalytic
Accepted 19 April 2016
behavior, in comparison with the ZrO2 support and a reference Au/TiO2 catalyst (AUROliteTM ), provides
Available online xxx
a series of indications on the reaction mechanism and the nature of the sites. It is evidenced in particular
that i) the addition of gold enhances the activity of the support in furfural conversion by a factor of
Keywords:
about ten, ii) the creation of active sites for the further conversion of the acetal intermediate to 2-MF
Selective oxidative esterication
Furfural
increases the reaction rate of furfural conversion, mainly by shifting the equilibrium of the furfural to
Methyl 2-furoate acetal reaction to right, iii) the precursor sites for the acetal to 2-MF oxidative conversion form during the
Gold supported catalysts thermal treatment in air from 200 C to 400 C, due to a reduction of gold occurring during this treatment
Zirconia with partial redispersion of gold and formation of very small Au NPs (nanoparticles) with average size of
0.7 nm, iv) the active sites for the acetal to 2-MF oxidative conversion are associated likely to these small
Au NPs, but they form in-situ at the initial stage of reaction.
2016 Elsevier B.V. All rights reserved.

1. Introduction to high-added-value products. For example, the oxidative esteri-

Sugar chemistry is at the core of biorenery/biofactories [14],
because sugars are the units of polysaccharides (among which cel-
lulose and hemi-cellulose, starch, glycogen), besides to be present
as mono-, di- or oligo-saccharides in many biomass varieties. While
the manufacture of energy vectors may rise various objections, the
production of chemicals and especially high-added-value products
is, and will be in the future, an important element of the bioren-
ery/biofactories scenario [46]. Monosaccharides can be classied
in two main classes: aldoses, where an aldeidic group is present
or ketoses, where a ketonic group is present. Isomerization or
dehydration of the latter may also lead to aldehydes, for example
HMF (5-hydroxymethyl furfural) can be produced by dehydration
of fructose and furfural by dehydration of xylose. Moreover, the
conversion of the aldehydic group to an ester via oxidative esteri-
cation is a relevant possibility for the conversion of these chemicals
Corresponding author
E-mail address: perathon@unime.it (S. Perathoner).
cation of furfural
forms methyl 2-furoate, which is a specialty fragrance, but it is
also used for different purposes in ne chemical industry. On the
other hand, HMF can be converted to the dimethyl ester of FDCA
(2,5-furandicarboxylic acid), a suitable replacement for tereph-
thalic acid (TPA) and isophthalic acid [7,8].
Oxidative esterication is realized currently using mostly
transition-metal or organo homogeneous catalysts [9,10], but the
use of heterogeneous catalysts is preferable to intensify the process
and reduce costs as well as the environmental impact. Christensen
and coworkers [11] rst introduced the use of supported gold cata-
lysts for the furfural and HMF oxidative conversion. Later, Casanova
et al. [12] reported the superior performances of gold on ceria for
the conversion of HMF in methanol. Pinna and coworkers [1318]
used catalysts based on gold supported on various oxides (ceria,
titania, zirconia) for both furfural and HMF oxidative esterica-
tion. Li et al. [19] used gold supported on Ce-Zr in the oxidative
esterication of different benzylic aldehydes, indicating that the

http://dx.doi.org/10.1016/j.cattod.2016.04.023
0920-5861/ 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
G Model
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incorporation of Zr4+ into the ceria lattice improves the activa-
tion of methanol (to form methoxy species) and facilitates the -H
elimination of hemiacetal, an intermediate in the reaction. Gold-
graphene nanocomposite catalysts were also reported recently to
be highly efcient in the oxidative esterication [20], although in
contrast with the role of the support indicated by Li et al. [19].
The optimal type of support in the reaction is also unclear.
Menegazzo et al. [15] indicated zirconia as the best support for
gold nanoparticles by comparing the performances of ceria, tita-
nia and zirconia based catalysts. However, later the same authors
[16] remarked the use of Au-CeO2 catalysts and Au supported on
sulphated ZrO2 catalysts [17]. Au nanoparticles supported on ceria-
alumina mixed oxides were instead suggested recently as active
catalysts by Smolentseva et al. [21], indicating that the oxygen stor-
age capacity of the support (possible only in ceria-based catalysts)
is the key element for the catalytic performances. In contrast with
this conclusion, Wang et al. [22] showed that a support like MgO for
gold nanoparticles, thus without oxygen storage capacity and acid
sites, has also excellent performances in the oxidative esterication
of aldehydes. Suzuki et al. [23] showed that supported gold-nickel
oxide nanoparticles have excellent performances in the oxidative
esterication. In this case, a core-shell structure is present, with
the Au nanoparticles at the core and the surface covered by highly
oxidized NiOx. This result may thus question the idea proposed by
many authors [24] that sites at the gold nanoparticle-support inter-
face are those active in selective oxidation reactions. Mononuclear
gold species present in the solution, deriving from the dissolution
of gold nanoparticles, are instead proposed by Hashmi et al. [25] as
the active species in the oxidative esterication.
There is thus a relevant interest on this reaction, although still
aspects are under discussion related to the exact nature of the active
sites and the reaction mechanism. In a high-throughput study on
this reaction [26] we observed that gold on zirconia is effectively
the catalyst giving the best performances under diluted conditions,
but with the performances strongly depending on the modalities
of preparation of the zirconia support. In addition, tests using a
much higher furfural to methanol ratio (no solvent and bases), as
necessary for the industrial development of the process, resulted
in a quite different ranking of the catalysts.
The aim of this work is to investigate in detail two Au-ZrO2 cat-
alysts, with the second derived from the rst, calcined at 400 C
rather than at 200 C. Giving these two catalysts a quite different
behavior in the oxidative esterication of furfural, the comparison
of their physico-chemical properties provides an excellent basis to
derive indications on the nature of the active sites in this reaction,
and about the possible role of the support as well as of the reac-
tion conditions. In order to allow a more reliable comparison of
the catalytic performances of these samples, the reactivity of the
reference AUROliteTM Au/TiO2 catalyst (a commercially available
standard reference gold-based catalyst) is also reported.
2. Experimental
2.1. Preparation of the catalysts
AUROliteTM Au/TiO2 (1 wt.% Au) was a commercial sample pro-
vided by Strem Chemicals Inc. in the form of small extrudates.
Before testing the catalytic activity, the pellets were crushed in
a mortar until a very ne powder was obtained and then sieved
to particle size distribution of 120250 mesh, i.e. 0.0630.125 mm.
This particle size distribution was used also for the other catalysts.
All the reagents were of analytical grade and bought from Sigma
Aldrich. ZrO2 was prepared by chemical precipitation method.
Zirconium(IV) oxychloride octahydrate (ZrOCl2 8H2 O), used as zir-
conia source, was dissolved in distilled water, then a diluted
Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
ammonia solution was added under vigorous stirring until a pH
of 8.6 was reached. After the complete precipitation, the hydroxide
suspension was aged for 20 h at 90 C. The aged hydroxide was l-
tered and washed with warm water until removal of chloride ions
(conrmed by AgNO3 test). The solid was dried at 110 C overnight
and calcined at 650 C for 3 h.
About 0.4 wt.% of gold was added by deposition-precipitation
(DP) at pH = 8.6. In a typical DP technique, the oxide support (2 g)
was suspended in 80 mL of an aqueous solution containing the gold
precursor (HAuCl4 3H2 O, in a concentration corresponding to a the-
oretical Au loading of 1% wt) for 3 h and the pH was adjusted by the
addition of aqueous NaOH (0.5 M). After deposition of gold onto the
support (in the form of gold-hydroxide), the solid was washed, l-
tered and dried at room temperature for 12 h and nally annealed
at two different temperatures (200 C, 400 C) in air. These catalysts
are indicated hereafter as AuZ200 and AZ400, respectively.
2.2. Characterization of the catalysts
Atomic absorption spectroscopy (AAnalyst 200 Perkin Elmer)
was used to determine the gold amount after dispersion of the sam-
ples in HF by ultrasounds. The phase composition and the degree
of crystallinity were analysed by X-ray diffraction analysis with a
ADP 2000 diffractometer using a Cu-K radiation. Data were col-
lected at a scanning rate of 0.025 s1 in a 2 range from 15 to 80 .
Diffraction peak identication was made on the basis of the JCPDS
database of reference compounds.
Transmission electron microscopy (TEM) images were acquired
by using a Philips CM12 microscope (resolution 0.2 nm) with
an accelerating voltage of 120 kV, while the elemental analysis
was investigated by using a Philips XL-30-FEG scanning electron
microscope equipped with an energy dispersive X-ray analyser.
Ultraviolet visible diffuse reectance spectra were recorded by a
Jasco V570 spectrometer equipped with an integrating sphere for
solid samples using BaSO4 as reference. BET surface area and pore
size distributions were determined using N2 adsorption/desorption
isotherm at 77 K with an Autosorb iQ (Quantachrome Instruments)
system.
XPS measurements were performed on a PHI Quantera (Physical
Electronics). The survey and high resolution spectra were taken
using the large area analysis which is a 100 W 100 m diameter
X-ray beam scanned over a 1300 100 m area at high speed. High
resolution spectra were obtained with a pass energy of 26 eV. The
energy scale for all samples were adjusted by placing the C 1 s peak
from adventitious carbon at 284.8 eV. The spectra were tted by
software and the resulting peak position, FWHM and percentage of
the total area are given.
FTIR measurements were carried out on self-supporting wafers
and the spectra were collected at a resolution of 4 cm1 with a
Bruker IF55 FTIR spectrophotometer equipped with a MCT detec-
tor. The self-supporting wafers were prepared and activated under
vacuum (104 Torr) for 2 h at 200 C in an IR cell allowing in situ
thermal treatments, and pyridine dosage. Lewis and Brnsted acidic
sites quantication was performed by integrating the area under-
neath the bands at 1450 and 1545 cm1 . The integrated molar
extinction coefcients (IMEC) were calculated, according to the
Beers law, by dosing pyridine (Py) at increasing concentrations
over each sample under study, after evacuation at rt under high
vacuum: A = cD, where A = absorbance, = molar extinction coef-
cient, c = concentration and D = path length. The value was
obtained by plotting A vs c (mol Py), assuming a constant D (since
the sample is in a pellet form and the thickness is always constant).
Hence, Brnsted and Lewis acid sites were quantied using the
following equation:
CPy onXsites = (AreapelletIA(X))/(IMEC(X)Weightpellet) (1)
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Table 1
Reaction conditions used for tests in oxidative esterication reaction in a 250 mL
Parr stainless steel autoclave (teon-lined).
Solvent 150 mL MeOH
Catalyst loading 100 mg
Gas 6 bar O2
Temperature 120 C
Furfural concentrations 0.02 M
Time of reaction 06 h
where C = mol gcat 1 and IA(X) = integrated absorbance of the
peak of the species X.
2.3. Testing of the catalysts
The catalytic tests were performed in a 250 mL Parr stain-
less steel autoclave (Teon-lined). As a typical procedure, furfural
(0.02 M) was dissolved in 150 mL methanol under 6 bar of O2 , at
120 C and with 1000 rpm of stirring. The progress of the reaction
was monitored for 6 h by collecting samples as a function of the
time of reaction. Reaction conditions used for tests in oxidative
esterication reaction in this lab-scale apparatus are summarized
in Table 1. Analysis was performed by a GC-FID (Finningan Trace
GC Ultra, with a Restek Rx-i-5 column) and by a GCMS (Thermo
Scientic GC Trace 1310 ISQ MS with a Restek Stabilwax column).
3. Results
As part of a broader study on the development of an industrial
process for the synthesis of methyl 2-furoate from furfural, some
results of which were reported elsewhere [26], we found that the
two Au/ZrO2 catalysts, prepared in the same way, except for a nal
stage of calcination at 200 C or 400 C after the addition of gold
(about 0.4% wt.), resulted in a quite different catalytic behavior.
These two samples (AZ200 and AZ400) thus offer a unique oppor-
tunity to understand the possible nature of the active sites, with
respect to other studies where samples with quite different char-
acteristics, composition, and preparation method are compared.
In addition, we report here the catalytic behavior of a standard
reference gold-based catalyst (AUROliteTM ). In fact, the catalytic
performances of gold-based catalysts depend signicantly on the
experimental conditions and reproducibility of the results may be
sometimes difcult. This AUROliteTM reference (and commercially
available) sample allow to check the performances and understand
eventual deviations related to the use of different reaction condi-
tions.
3.1. Catalytic performances
The catalytic tests were made in a well-stirred autoclave under
reaction conditions reported in Table 1, which are close to those
typically used in literature [1119], in order to have comparable
indications. Table 2 instead reports the results in the oxidative
esterication of furfural in terms of conversion (after 6 h of reac-
tion) and selectivity to 2-MF (methyl 2-furoate) for AuZ200 and
Table 2
Catalytic performances of catalysts in the oxidative esterication of furfural. Reactions conditions as in Table 1, time of reaction 6 h.
Catalyst Thermal treatment, C (a )
ZrO2
AuZ200 200
AuZ400 400
AUROliteTM 250
a
In air, after addition of gold. For AUROliteTM refers to the calcination before to the catalytic tests.
Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
3
AuZ400 catalysts, in comparison with the AUROliteTM reference
catalyst and zirconia alone (i.e. without gold) support.
Zirconia alone shows some activity, although low and with low
selectivity to 2-MF. Nearly zero selectivity was instead observed
without the catalyst, thus indicating that 2-MF does not derive
from auto-oxidation reactions, always possible in oxidation reac-
tions with aldehydes. The AuZ200 catalyst shows a signicantly
higher conversion of furfural, although a similar low selectivity to
2-MF. The main side product observed is the acetal (2-furaldehyde-
dimethyl-acetal). The pseudo-rst order rate constant of furfural
conversion is about 10 times higher for AuZ200 with respect to
ZrO2 . AuZ400 is more active than AuZ200, with the pseudo-rst
order rate constant of furfural depletion about ve times higher,
and about fty times higher than that of ZrO2 . However, the most
relevant difference is that the selectivity to 2-MF is denitively
higher, with a correspondent decrease in the acetal formation. Ref-
erence AUROliteTM catalyst shows a furfural conversion in between
that shown by AuZ200 and AuZ400 catalysts, but the selectivity
to 2-MF is only slightly higher than that of AuZ200. Note that the
amount of gold in AUROliteTM is about 2.5 times higher than in our
gold on zirconia samples, the latter having an Au loading three-four
times lower than that used typically in literature. Acetal is also the
main product observed for AUROliteTM .
Acetal (geminal-diether derivative) stems from the addition of
a methoxy group to C O group in furfural converting thus the alde-
hyde (-CHO) group in furfural to an acetal group ((OCH3 )2 ). This
is an acid-catalyzed reaction, which can occur when the C O in the
aldehyde is activated, for example by coordination with Lewis acid
sites. The carbon atom in the activated C O bond is then susceptible
for nucleophilic attack by the alcohol, followed by deprotonation
to form a hemiacetal, protonation of the alcohol, dehydration and
further nucleophilic attack by the alcohol and deprotonation. It is
thus reasonable that zirconia alone is able to form the acetal, but
when gold nanoparticles are present, Lewis acid sites likely at the
gold-support interface (metallic gold nanoparticles may attract OH
groups from Zr-OH sites at the interface, thus creating a Lewis acid
site), can activate the C O bond and thus promote the furfural con-
version. The main difference of the AuZ400 sample with respect
to the other catalysts is the presence of additional sites able to
catalyse the oxidation of acetal to 2-MF. These sites are not related
to the generic presence of gold NPs (nanoparticles), present also
in AuZ200 and AUROliteTM (2.5 times higher in the latter), but to
unique sites which generate in AuZ400 during thermal treatment
from 200 C to 400 C.
The TON (turnover number, in h1 ) which can be estimated,
assuming all atoms in gold nanoparticles active in the conversion,
is reported in Table 3. Considering the Au nanoparticles spherical,
and the average particles size determined by TEM (transmission
electron microscopy, see later), it is possible to determine the aver-
age surface to volume ratio (S/V) and circumference to volume ratio
(C/V). These corrective factors may be considered when only sur-
face sites (S/V) or at the perimetral edge between Au nanoparticles
and the support (C/V) are active in the reaction. However, being
likely only a fraction of the gold atoms active in the reaction, these
TON estimations may be relevant only for comparison with other
catalysts, while effective TON values will be certainly higher. Data
Au loading, wt.% Conversion of furfural, % Selectivity to 2-MF, %
5 10
0.4 0.1 63 10
0.4 0.1 99 95
1.0 0.1 73 31
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Table 3
Turnover number (TON) in gold catalysts, determined considering all atoms in gold
nanoparticles active in the conversion (reactions conditions as in Table 1). The
100
AuZ200
AuZ400
a
average surface to volume ratio (S/V) and circumference to volume ratio (C/V) AUROlite
of gold particles (supposed spherical, and with average diameter given by TEM 80
measurements).

conversion, %
Catalyst TON in furfural TON in 2-MF S/V, nm1 C/V, nm2
60
conversion, h1 formation, h1

AuZ200 155.1 15.5 1.25 0.26

AuZ400 243.7 231.6 2.73 1.24 40
AUROliteTM 71.9 22.3 1.30 0.28

20
25

0
20 0 100 200 300 400
2-MF time, min
concentration, [mM]

100
15 AZ200
AZ400 b
AUROlite
80
10

yield 2-MF, %
60
5
furfural
40

0
0 50 100 150 200 250 300
20
time, min

Fig. 1. Concentration of furfural (2-FA) and methyl-2-furoate (2-MF) vs time of 0

reaction during the catalytic test of AuZ400. Reaction conditions as in Table 1. 0 100 200 300 400

in Table 3 evidence that catalysts based on zirconia supports are
more active in furfural conversion than the AUROliteTM reference
per g of Au, but especially AuZ400 shows about one order of mag-
nitude higher TON in 2-MF formation. This higher activity remains
when surface or perimetral edge sites are considered.
The change in the concentration of furfural and 2-MF with the
time of reaction for the AuZ400 catalyst is reported in Fig. 1. There
is a progressive conversion of furfural, with a parallel increase in
2-MF formation. To note that the formation of acetal or other inter-
mediates is not observed, if not in minimal part, and the selectivity
to 2-MF does not change signicantly with time on stream. This
indicates that the conversion of acetal to 2-MF is faster than acetal
formation, which is the rate limiting step. The higher rate of con-
version of furfural on AuZ400 with respect to AuZ200 could be
explained considering reversible the acetal formation. By catalysing
its further conversion to 2-MF the equilibrium is thus shifted to the
right and this explains the higher rate of furfural conversion on
AuZ400.
In Fig. 1 it should be noted the presence of an apparent initial
induction time at the start of the reaction, particularly evident for
2-MF formation. In batch-type reactors, an initial induction time
(necessary to establish a well-mixing in the system) is typically
observed. In our reactor, this induction times should be less than
about 5 min, thus shorter than the effect observed in Fig. 1. It is
thus likely that the induction time observed in Fig. 1 is related to
an in-situ (during the reaction) modication to generate the active
sites for 2-MF formation.
This interpretation is supported from the comparison of the
curves of conversion of furfural versus the time of reaction on
AuZ200, AuZ400 and AUROliteTM catalysts (Fig. 2a). It is evident
that the rates of furfural conversion are nearly the same on the
three catalysts during about the rst hour of reaction, and then a
time, min
Fig. 2. Conversion (a) and yield to 2-MF (b) vs time of reaction in the oxidative esteri-
cation of furfural on AuZ200, AuZ400 and AUROliteTM catalysts. Reaction conditions
as in Table 1.
drastic increase in the rate of conversion of furfural is observed
particularly for the AuZ400 catalyst. This indication well supports
the idea that the sites responsible for the conversion of furfural to
the intermediate acetal are nearly the same on the three catalysts,
but during reaction a unique type of site (able to convert acetal to
2-MF) generates only on AuZ400 catalyst. The generation of these
sites accelerate the rate of reaction by shifting the furfural-acetal
equilibrium to the right. The results in terms of yield of 2-MF versus
time of reaction (Fig. 2b) are in good agreement with the above
interpretation.
3.2. Characterization
The ZrO2 sample prepared by precipitation shows relatively
high surface area (BET, 95.6 m2 g1 ) with a pore volume of
0.25 cm3 g1 . No signicant changes in the textural aspects were
present after addition of gold and further thermal treatment
(AuZ200 and AuZ400 samples). For comparison, the AUROliteTM
Au-TiO2 sample has a surface area of about 50 m2 g1 .
The phase composition of AuZ samples was investigated by X-
ray diffraction and the obtained patterns are shown in Fig. 3 in the
2 region between 15 and 80 .
The spectra are very similar corresponding to tetragonal zir-
conia, without apparent presence of Au (expected at about 38.0
and 44.3 for most intense (111) and (200) planes of metallic gold
respectively). The absence of detection of Au is likely due to the very
small amount of gold (0.4% wt) and presence of small nanocrys-

Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
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Fig. 3. XRD patterns of Au/ZrO2 samples thermally treated at 200 and 400 C.
tals. The peaks observed at 2 = 30.4 , 35.3 , 50.6 , 60.5 , 63.0 and
74.8 can be assigned to (011), (110), (112), (202), (121) and (220)
planes, respectively, of tetragonal ZrO2 (JCPDS le No. 50-1089).
Normally, the monoclinic zirconia phase is obtained by calcina-
tion of the tetragonal phase at high temperatures, with complete
transformation above about 700 C [27]. In our case (calcination at
650 C for 3 h) we do not observe monoclinic phases, as evidenced
by XRD data (Fig. 3). Pinna and co-workers [14,15,17,18] reported
only in the more recent papers [18] indications about the differ-
ent zirconia phases present in their samples. They indicated that
both tetragonal and monocline phases are present, with the ratio
tetragonal/monocline phases of zirconia increasing with a sulpha-
tion treatment, being the presence of sulphate ions on the support
favouring the stabilization of the metastable tetragonal phase of
zirconia during the calcination step. We could thus indicate that
Fig. 4. Selected TEM images of AuZ200 sample (a and b) and AuZ400 sample (c and d). Fig. 4d shows the (111) lattice planes of a crystalline Au particle.
Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
5
our zirconia preparation, giving only tetragonal phase, is different
from that earlier reported in literature.
TEM (transmission electron microscopy) analysis was used to
investigate the morphology of AuZ samples and to analyse the effect
of the calcination temperature after the gold deposition. Selected
results are reported in Fig. 4.
Round-like shaped gold nanoparticles (NPs) are present in both
AuZ200 (see Fig. 4a and b) and AuZ400 (see Fig. 4c and d) samples,
but most of the Au NPs are slightly larger in AuZ200 with respect
to AuZ400. Higher magnication images of a Au NP in AuZ400 well
evidence the lattice planes (111) of a crystalline gold particle (dia.
6 nm), with a lattice spacing of 2.35 (see Fig. 4d) [28]. There
are no evidences of a specic modication by interaction with the
support for Au NPs above about 23 nm in both AuZ200 and Au400
samples, neither specic evidences of a difference in these Au NPs
(i.e. larger than 23 nm) between these two samples, except for
slightly larger sizes in those in AuZ200 sample.
However, a more careful analysis of the TEM images reveals
the presence of smaller Au particles (in the range 0.31.5 nm, as
shown in Fig. 5) in the AuZ400 samples. The distribution of gold
particle sizes is relatively narrow and the average diameter was
estimated to be 0.7 nm. These small Au nanoparticles have a sim-
ilar size distribution in AuZ200 sample (see Fig. 1S), but they are
in a much smaller amount than for AuZ400. The average gold crys-
tallite size in AUROliteTM is instead 23 nm, as also reported by
Strem Chemicals. These high-resolution TEM images instead do not
reveal differences in the zirconia support showing in both cases
well-crystallized particles without relevant presence of amorphous
phases and crystal sizes of about 1020 nanometers, in agreement
with XRD indications.
Fig. 6 reports the visible diffuse reectance spectra of ZrO2 ,
AuZ200 and AuZ400 samples. ZrO2 , as expected, does not show
bands in the visible region, only the tail end (below about 350 nm)
of the metal-to-oxygen charge transfer (CT) bands present in UV
region. An intense absorption is instead present in both AuZ200
and AuZ400 samples, centred at 549 and 541 nm, respectively. It is
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Fig. 5. Selected TEM images of AuZ200 and AuZ400 samples, the latter evidencing the presence of Au NPs below 2 nm. The estimated particle distribution of these Au NPs is
reported on the right.

2,0 is expected for Au NPs with smaller sizes [29,30]. The SPR band near
540550 nm is consistent with particles of around 24 nm [32], as
indicated by TEM data. The slight blue shift in AuZ400 with respect
to AuZ200 is consistent with the indication of slightly smaller par-
1,5
ticles in the latter and/or a slight change in the interaction of Au
absorbance, a. u.

541 nm NPs with the zirconia support. AuZ400 shows, in addition, a band
400 nm centred near 400 nm, not well resolved due to the tails of the CT
1,0 bands of the support and the SPR band. However, the presence of
AuZ400 this band can be clearly evidenced from the comparison between
549 nm AuZ200 and AuZ400 spectra. The presence of this further band in
0,5 AuZ400 with respect to AuZ200 is in agreement with the additional
AuZ200 presence of very small Au NPs in the former.
X-ray photoelectron spectroscopy (XPS) measurements were
ZrO2
0,0 made in order to analyse the surface characteristics of the AuZ200
and AuZ400 samples. The results for Au 4f spectral region are
300 400 500 600 700 800
reported in Fig. 7. While AuZ samples shows the typical bands at
wavelenght, nm 83.6 and 87.3 eV for Au04 f7/2 and 4 f5/2 core levels, additional relative
intense components at 85.0 and 88.7 eV could be observed in the
Fig. 6. Visible absorption diffuse reectance spectra of ZrO2 , AuZ200 and AuZ400 deconvoluted spectra of AuZ200 sample. Intensity of these compo-
samples.
nents is around half of that of Au0 species, and they are indicative
of a Au+ type of species [33,34].
The XPS spectra in the Zr 3 d and O 1 s region for AuZ200 and
well-known that Au NPs on a dieletric support give rise to surface
AuZ400 samples are shown in Fig. 8, together with their deconvo-
plasmon resonance (SPR) in the visible region [29]. Au NPs strongly
lution. The two samples are nearly indistinguishable both in Zr 3 d
interact with the incident light, owing to the localised surface
and in O 1 s regions. The position of Zr 3 d5/2 and 3 d3/2 bands are well
plasmon resonance (LSPR) effect, which represents the strong oscil-
in agreement with those expected for Zr4+ and there is no indication
lation of the metals free electrons in phase with the varying electric
of the presence of Zr3+ or other species. The spectra in O 1 s region,
eld of the incident light. The optical absorption properties in the
evidences the presence of OH species at 531.5 eV together with
visible range for Au nanoparticles are represented by intraband
the main ZrO2 lattice oxygen at 530.1 eV. The small peak at 532.7 eV
LSPR (Localized Surface Plasmon Resonance) due to the interband
is related to oxygen in some contaminating organic species. It may
d sp transition. The LSPR band intensity and wavelength depends
be noted that relative intensities of lattice to hydroxyl O 1 s bands
on the factors affecting the electron charge density on the particle
are the same in AuZ200 and AuZ400 samples, and similar to that
surface such as the metal type, particle size, shape, structure, com-
present in ZrO2 alone (not reported here). This indicates that the
position and the dielectric constant of the surrounding medium
addition of Au and the subsequent thermal treatment does not
[30]. Au NPs in the 515 nm range on zirconia (prepared by a similar
induce changes in the surface acidity, neither the formation of
method of that used in our case) give rise to a SPR band moving from
reduced zirconia species, at least detectable by XPS.
about 570595 nm on increasing the Au loading [31], but a blue shift

Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
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Fig. 7. XPS spectra of AuZ200 (a) and AuZ400 (b) samples in the Au 4 f region, with indication of the deconvoluted spectra.

Fig. 8. XPS spectra of AuZ200 and AuZ400 samples in the Zr 3 d and oxygen 1 s regions, with indication of the deconvoluted spectra.

Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
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Table 4
Amount of Lewis and Brnsted acid sites of ZrO2 prepared by precipitation, after
recording the adsorption of pyridine and subsequent evacuation at room tempera-
ture and 150 C.
Evaluation at Lewis acid sites (mol/gcat ) Brnsted acid sites (mol/gcat )
RT 254 126
150 C 202 133
1.8
1.5
1445
Adsorbance (a.u.)
1.2
1613 1425
1445
0.9 1545
1575
AZ200
0.6
ZrO2
1700 1650 1600 1550 1500 1450
-1
Wavenumber (cm )
Fig. 9. FT-IR spectra of ZrO2 , AuZ200 and AuZ400 in the 13501700 cm1 spectral
region.
The acid properties were studied by Fourier-Transformed
InfraRed (FTIR) spectroscopy using pyridine as probe molecule.
Table 4 reports the quantication of the amount of Lewis and
Brnsted acid sites of ZrO2 , after recording the adsorption of pyri-
dine and subsequent evacuation at room temperature and 150 C.
Quantication was performed by integrating the areas underneath
bands at 1545 and 1455 cm1 , assigned to the pyridinium ion
(PyH+ ) formed on the Brnsted acid site and pyridine coordinated
to Lewis acid sites, respectively. The normalization has been per-
formed according to the density of the pellet (dimension/weight).
The FTIR background spectrum of ZrO2 (Fig. 9) is characterized
by a sharp band at 1613 cm1 (O H bending vibration of absorbed
water molecules), a sharp peak at 1445 cm1 rising from a broad
peak in the 14251375 cm1 region and a broad peak centred at
1555 cm1 . The latter peaks cannot be attributed to contamination
by organic species, being the sample calcined at 650 C, but can
be assigned tentatively to overtones and combination bands of the
fundamental vibration modes of ZrO2 [3537], even if not stud-
ied in detail. When gold nanoparticles are added to ZrO2 (samples
AuZ200 and AuZ400), the intensity of these bands increases, with
intensication also of components at 1425, 1460 and 1575 cm1
(Fig. 9). This is likely due to the plasmonic enhancement of vibra-
tional excitations in the infrared [38]. This effect, however, prevents
to quantify the acidity by pyridine adsorption, due to the overlap
of these bands. The effect is indicative of the coupling between Au
NPs and the support. The similar effect in both AuZ200 and AuZ400
samples indicates that this coupling is not signicantly different in
the two samples.
While pyridine adsorption cannot be monitored in the
14001600 cm1 region for AuZ200 and AuZ400 samples, as com-
mented above, new weak bands can be observed between 2100
and 1800 cm1 (Fig. 10), but only for AuZ200. This is not a spec-
tral region typically analysed for pyridine adsorption, but pyridine
shows a triplet of weak bands in this region due to a combination of
Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
1.25
AZ_200
AZ_400
1922
1.20
Adsorbance (a.u.)
1870
1983
1960
AZ_400
ZrO2
AZ-200 1.15
AZ200
2130
AZ400
1.10
2150 2100 2050 2000 1950 1900 1850 1800
-1
AZ400 Wavenumber (cm )
Fig. 10. FT-IR spectra of AuZ200 and AuZ400 in the 21501800 cm1 spectral region.
fundamental vibrations [39], which may be enhanced in the pres-
ence of -back bonding between pyridine and Au+ ions [40,41].
It is thus reasonable that their detection only in AuZ200 may be
1400 1350
related to the presence of cationic gold species, evidenced also to
be present by XPS only in AuZ200.
4. Discussion
The catalytic results of ZrO2 , AuZ200, AuZ400 and Au/TiO2
(AUROliteTM ) catalysts evidence that the presence of gold nanopar-
ticles enhances the rate of furfural conversion to the acetal
intermediate with respect to zirconia alone. The acetal derives from
the addition of methanol to carbon atoms in the C O aldehydic
group, activated by interaction likely with surface Lewis acid sites.
These sites are present also in ZrO2 , as shown by IR data with
pyridine chemisorption (Table 4), but their amount is increased
after addition of gold nanoparticles, and thus likely at the bound-
ary between Au NPs and the support, due to effect of metallic gold
NPs (related to Fermi level) in attracting OH groups in nearlying
Zr-OH sites.
While general characteristics of AuZ200 and AuZ400 samples
are quite similar, only AuZ400 shows the presence of additional
active sites, likely formed in-situ at the beginning of the catalytic
reaction, able to oxidize acetal to 2-MF. By shifting the furfural
to acetal equilibrium, AuZ400 catalysts results also more active,
besides to be largely more selective to 2-MF than AuZ200 and
AUROliteTM reference catalyst.
To note that various authors [12,14] reported that the ester-
ication reaction passes through the formation of a hemiacetal
intermediate, and then, the reaction can follow two different
routes: a direct conversion to 2-MF, or the rst transformation
of hemiacetal in the corresponding 2-furaldehyde-dimethyl-acetal
(acetal) with the further conversion to 2-MF. We do not observe the
presence of hemiacetal, but only of the acetal, thus in agreement
with the second pathway, but with the indication that the rst step
to acetal is reversible.
There are discording indications on the nature of the active
sites responsible for these steps in the reaction mechanism. Pinna
and co-workers [1318] reported that gold is necessary for the
formation of 2-MF, but indicating that gold nanoparticles below
1.52.0 nm are necessary for both activity and selectivity [13,14].
Later the same authors showed that i) larger particles (58 nm)
are instead more active on Au/ceria catalysts, but giving similar
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C. Ampelli et al. / Catalysis Today xxx (2016) xxxxxx
selectivity [16], or ii) roundish nanoparticles with average size of
2.5 nm are preferable [17], while irregular plate-like nanoparticles
with diameter above 3 nm have similar activity, but rather lower
selectivity (on Au/sulphated ZrO2 ).
It is clear that the identication of the possible active sites is
rather difcult and it is not simple the identication when samples
having different characteristics are compared. For this reason, we
have selected two samples giving quite different activity and selec-
tivity, but having quite similar characteristics, being different only
for the temperature of calcination after addition of gold. They can be
thus considered a good model system to understand the nature of
the active sites, although limited to the comparison of two samples.
The rst observation is that the presence of gold nanoparticles
enhances the rate of furfural conversion with respect to that shown
by the pure support. However, the intermediate acetal is converted
only when a specic type of gold species is present. It may be argued
that cationic gold may be implied in the selective oxidation step
(from acetal to 2-MF), but XPS data indicate that this species is
abundant in the less active catalyst (AuZ200) rather than in the
most selective (AuZ400) where cationic gold is virtual absent. The
calcination at 400 C (AuZ400) rather than a 200 C (AuZ200) after
gold addition by precipitation-deposition induces a reduction of
the Au, as shown by XPS, and the generation of rather small (below
1.0 nm, average diameter 0.7 nm) gold NPs. These species are much
less in AuZ200. As commented above, however, the active sites
for the oxidation form during the catalytic reaction, as shown by
the presence of an initial induction time. It is thus possible that
perimetral sites at the edge between very small Au NPs and zir-
conia may become partially oxidized during this induction time.
However, these sites are different from the Au+ sites present in
the AuZ200 sample. Although not characterized here, also refer-
ence AUROliteTM sample presents in minimal amount these Au NPs
sites, in agreement with its relatively poor performances. Even if we
do not know the thermal history of AUROliteTM (as it is a trademark
product), we tried to calcine the AUROliteTM sample under the same
conditions as AuZ400. Results (reported in the Supporting infor-
mation, see Fig. 2S), showed a comparable conversion prole with
respect to the not-thermally treated AUROliteTM , but an increase in
the yield to 2-MF from about 2040% was observed, conrming that
calcination at 400 C leads to the formation of more active species
(reduced and very small Au NPs).
Infrared and visible diffuse reectance data further support the
presence of these very small gold particles in AuZ400, and the pres-
ence of cationic gold species in AuZ200, while these and other
experimental results (XPS, TEM, XRD) do not evidence a difference
in the characteristics of the zirconia support in the two samples.
Although the support may have a role in the rst step of furfural
conversion, the presence of gold induces an enhancement of the
activity by one order of magnitude. It is likely that the true rate con-
stant of furfural conversion is similar between AuZ200 and AuZ400,
being the apparent higher rate of AuZ400 due to the shifting of
the equilibrium in furfural to acetal reaction associated to the con-
version of the latter to 2-MF. The main role of the support is thus
in inducing the formation of very small gold nanoparticles (below
about 1 nm) during the thermal treatment after gold deposition.
Likely the characteristics of the support, in addition to the specic
procedure of catalyst activation after gold deposition, determine
the dispersion of gold and the possibility to have active and selec-
tive catalysts.
5. Conclusions
Two catalysts, based on gold on zirconia prepared by precipita-
tion and prepared in the same way, except for the different thermal
treatment in air after the addition of gold (0.4% wt), show a quite
Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023
9
different behaviour in furfural oxidative esterication, particularly
in the selectivity to 2-MF. The analysis of their catalytic behaviour,
in comparison with that shown by the ZrO2 support and a reference
Au/TiO2 catalyst (AUROliteTM ), evidences the following aspects:
i) the ZrO2 support alone is active in furfural conversion, but to
form only the acetal intermediate (selectivity to 2-MF about
10%);
ii) the addition of gold enhances the activity in furfural conversion
by a factor about ten, although without an apparent change in
other properties.
iii) the creation of active sites for the further conversion of the acetal
intermediate to 2-MF increases the reaction rate of furfural con-
version, mainly by shifting the equilibrium to right of the furfural
to acetal reaction.
iv) the precursor sites for the acetal to 2-MF oxidative conversion
forms during the thermal treatment in air from 200 C to 400 C;
characterization data evidences that a reduction of gold occurs
during this treatment and partial redispersion of gold, with for-
mation of very small Au NPs with average size of 0.7 nm
v) the active sites for the acetal to 2-MF oxidative conversion are
associated likely to these small Au NPs, but they form in-situ at
the initial stage of reaction.
It is possible that during this initial in-situ activation, the par-
tial oxidation of gold sites at the interface with the support occurs.
However, it should be remarked that the characteristics of these
eventually oxidized sites are different from the cationic gold sites
present in large amount in the catalyst treated at 200 C (AuZ200),
which lack, however, of activity in the acetal to 2-MF oxidative
conversion.
The comparison of these two catalysts thus provide useful indi-
cations on the nature of the active catalysts for furfural oxidative
esterication, although it must be commented that these indi-
cations should be supported further by more detailed studies
extending the analysis to a broader range of supported gold cata-
lysts and to in-situ or operando studies. These results should be thus
considered an indication (going beyond literature) on the possible
nature of the active sites in this interesting reaction of relevance
for the future of bioreneries rather than a denitive proof of the
mechanism requiring further studies.
The results, however, provide some clue to understand the two
questions raised in the introduction, regarding the role of the sup-
port and of the reaction conditions. The results presented here
evidence that the key steps in the formation of the active sites for
oxidative conversion of the acetal intermediate are associated to i)
the mechanism of self-reduction of Au NPs during thermal treat-
ment in air and the formation of very small (below 1 nm) Au NPs
during this process and ii) the in-situ transformation of these very
small Au NPs during the initial stage of the catalytic reaction. It is
very likely that the rst process is largely depending on the specic
characteristics of the support, while the second to the feed compo-
sition and reaction conditions. As comment above, further studies
are necessary to understand better these aspects, but present data
provide an indication on the aspects to investigate and a tentative
hypothesis to explain the rather large differences in the behaviour
of this class of supported Au catalysts.
Acknowledgements
This work was realized in the frame of the EU project
Eco-friendly biorenery ne chemicals from CO2 photocat-
alytic reduction (Eco2 CO2 ) (Project 309701), which is gratefully
acknowledged. The EU Marie Curie IAPP (Industry-Academia Part-
nerships and Pathways) project Biopolymers and Biofuels from
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10 C. Ampelli et al. / Catalysis Today xxx (2016) xxxxxx

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Please cite this article in press as: C. Ampelli, et al., On the nature of the active sites in the selective oxidative esterication of furfural
on Au/ZrO2 catalysts, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.04.023