materials

Article
Bimetallic Nanoparticles as Efficient Catalysts:
Facile and Green Microwave Synthesis
Magda Blosi 1 , Simona Ortelli 1 , Anna Luisa Costa 1 , Michele Dondi 1 , Alice Lolli 2 ,
Sara Andreoli 2 , Patricia Benito 2 and Stefania Albonetti 2, *
1 ISTEC-CNR, Institute of Science and Technology for Ceramics, National Research Council, Via Granarolo 64,
Faenza 48018, Italy; magda.blosi@istec.cnr.it (M.B.); simona.ortelli@istec.cnr.it (S.O.);
anna.costa@istec.cnr.it (A.L.C.); michele.dondi@istec.cnr.it (M.D.)
2 Department Industrial Chemistry Toso Montanari, Bologna University, Viale Risorgimento 4,
Bologna 40136, Italy; alice.lolli4@unibo.it (A.L.); sara-189-@hotmail.it (S.A.); patricia.benito3@unibo.it (P.B.)
* Correspondence: stefania.albonetti@unibo.it; Tel.: +39-051-2093681

Academic Editor: Nikolaos Dimitratos

Received: 13 June 2016; Accepted: 4 July 2016; Published: 8 July 2016

Abstract: This work deals with the development of a green and versatile synthesis of stable mono-
and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water
as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the
chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were
achieved with this method of preparation. All of the materials were tested as effective catalysts in the
reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive
effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter
showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to
prepare TiO2 - and CeO2 -supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural
(HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts
led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated
into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the
hydrodechlorination of CF3 OCFClCF2 Cl to CF3 OCF=CF2 . The effect of Cu on the hydrogenating
properties of Pd was demonstrated.

Keywords: Au/Cu; Pd/Au; Pd/Cu; nanosols; microwave-assisted synthesis; supported catalysts;

HMF; hydrodechlorination

1. Introduction
In recent years, noble metal nanoparticles have attracted much attention owing to their potential
application in many different fields due to their optical, electrical, mechanical and catalytic properties.
Bimetallic nanoparticles, composed of two different metal elements, are of a great interest from both the
scientific and technological points of view. The structure of bimetallic nanoparticles is defined by the
distribution modes of the two elements and can be oriented in random alloy, alloy with an intermetallic
compound, cluster-in-cluster and core-shell structures, leading to enhanced applications, compared to
monometallic nanoparticles [14].
In this context, bimetallic nanostructures show remarkably improved optical, catalytic and
electronic properties with respect to monometallic counterparts [5]. In fact, it is expected that bimetallic
nanoparticles could show not only the combination of the properties related to the presence of two
individual metals, but also new properties due to a synergy between the two metals. The shape and
size of mono- and bi-metallic nanoparticles are strictly dependent on the preparation methods and
conditions and affect the physicochemical properties of the final nanomaterial. The combination of two

Materials 2016, 9, 550; doi:10.3390/ma9070550 www.mdpi.com/journal/materials

Materials 2016, 9, 550 2 of 25

metals results in much more possibilities in shape and structure due to the miscellaneous distribution
of each metal within a particle and their various organization [6].
Pre-formed metal nanoparticles can be used in catalysis in a wide range of reactions.
The deposition of these particles onto different supports is fundamental to guarantee particles stability,
mechanical resistance and easier work-up procedure at the end of the process. Thus, a synthetic
approach, which allows a homogeneous nanoparticle suspension, is of crucial importance for catalytic
applications, in order to exploit the real effect of the active phase on the activity. This effect is even
more significant when it comes from the comparison of bimetallic and monometallic nanoparticles.
In particular, the development of a colloidal synthesis that can guarantee precise composition,
morphology and particle size is of crucial relevance for bimetallic nanoparticles [7].
In this study, we report the development of bimetallic nanostructures (Au/Cu, Pd/Au, Pd/Cu) by
means of a patented environment-friendly approach [8], easily transferable to large-scale production
and allowing the achievement of stable nanosols, even at high solid loading. Water is the benign
solvent; glucose serves as a mild, renewable and non-toxic reducing agent; and polyvinylpyrrolidone
(PVP) as a water-soluble, inexpensive and non-toxic chelating additive. The uses of inexpensive and
nontoxic chemicals, environmentally-benign solvents and renewable materials are some of the essential
issues in the nanomaterials science field in light of the green synthetic strategy for industrial-scale
manufacturing [9]. Most of the synthetic routes reported in the literature, even if scalable to large
production, are based on organic solvents, thus implying a complex environmental path to the
industrial production [1014]. So far, some expensive and/or toxic chelating agents (thiols, oleic acid,
hexadecylamine, trioctylphosphine oxide) [1517] are employed to prepare metal nanoparticles in
organic solvents, making these synthesis processes less promising for a subsequent industrial scale
up. Moreover, concerning the reducing agents, a large body of literature [1820] proposed strong and
hazardous reducing agents, such as hydrazine, sodium borohydride (NaBH4 ) and dimethyl formamide
(DMF), which are highly reactive and present potential environmental and biological risks.
From the process intensification viewpoint, microwave irradiation was exploited as the heating
source [2123], so enabling rapid achievement of the desired temperatures and the homogenous
heating of the treated volumes.
On all of the prepared bimetallic nanosols, the catalytic performances were assessed and compared
exploiting the probe reaction of 4-nitrophenole (4-NP) hydrogenation [24]. Then, on the supported
catalysts, a deeper catalytic characterization was carried out.
Gold-supported nanoparticles have been widely used as catalysts in the field of alcohol oxidation
reactions [25,26]. More recently, these catalysts have been tested in 5-hydroxymethylfurfural (HMF)
oxidation to produce 2,5-furandicarboxyic acid (FDCA) [27,28], a monomer used for the synthesis
of a new class of polymers made from renewables [29,30]. In fact, HMF is derived from sugars
dehydration, and it can be transformed into a series of interesting building blocks, both exploited
in the pharmaceutical and in the chemical industries [31]. In order to improve catalyst performance
in terms of activity and stability, researchers have focused their attention on the development of
bimetallic nanoparticles with controlled size, composition and morphology and the use of different
supports [7]. For example, Au/Pd-supported catalysts are considered to be efficient for alcohols
oxidation reactions [32].
The goal of this paper was thus to describe the synthetic approach developed in our group.
This microwave (MW)-assisted method allows the formation of colloidal monometallic and bimetallic
nanoparticles with controlled size, composition and different morphologies (alloy and core-shell)
to be used as is and for the preparation of supported catalysts. In particular, supported Au/Cu
and Au/Pd nanoparticles were used in HMF oxidation, while Pd/Cu-MCM-41 catalysts were
tested in the hydrodechlorination of CF3 OCFClCF2 Cl to produce trifluoromethyl trifluorovinyl
ether (CF3 OCF=CF2 ).
Materials 2016, 9, 550 3 of 25

2. Results and Discussion

2.1. Preparation and Characterization of Metallic Sols

All of the prepared bimetallic sols exploited the green glucose as the reducing agent, which
maximizes its reducing performance in alkaline conditions [33,34]. A simple, microwave-assisted
strategy was developed for the preparation of different metal nanoparticles stabilized by
polyvinylpyrrolidone (PVP), with various morphologies (alloy and core-shell). For lack of space,
in this work, we will just discuss the results obtained using metallic alloys; nevertheless, recent works
report our results obtained utilizing core-shell systems [35,36]. As a general observation, microwave
heating has been shown to provide homogeneous particle nucleation and shorter synthesis time than
traditional heating, and the developed synthesis route showed several advantages with respect to
other methods (Figure S1). Indeed, it is simple, eco-friendly, carried out at low temperature and easily
transferable to large-scale production [8]. Particle size-control, total reaction yield and long-term
stability of colloids were achieved thanks to an accurate reaction optimization and the combination
with microwave heating, promoting the intensification of the process even for large-scale production.
The characteristics of the synthesized bimetallic samples are listed in Table 1.

Table 1. Particle size distribution of the synthesized nanoparticles by means of different techniques:
dynamic light scattering (DLS), transmission electron microscopy (TEM), X-ray diffraction (XRD).

Sample 1 d-DLS (nm) PDI 3 d-TEM(nm) d-XRD (nm)

Au 17 0.2 4 2 [37] 4 [38]
Cu 350, 80 2 0.4 31 70
Pd 23 0.3 2 1 [35] 6
Au3 Cu1 17 [38] 0.2 - 4.0 [38]
Au1 Cu1 23 0.3 32 3.5 [38]
Au1 Cu3 61 0.3 - 3.0 [38]
Au1 Cu6 80 0.5 - n.d. [38]
Pd3 Au1 - - 3 1 [35] 3
Pd1 Au0.5 36 - - 5
Pd1 Au1 25 0.4 3 1 [35] 3
Pd1 Au2 71 - - 3
Pd1 Au3 35 0.3 42 4
Pd1 Au6 34 0.2 3 2 [35] 5
Pd1 Au9 - - 4 [35] 5
Pd1 Cu0.5 73 0.3 - 5
Pd1 Cu1 79 0.4 - 3
Pd1 Cu2 88 0.4 - 4
Pd1 Cu3 99 0.2 - 5
Pd1 Cu6 133, 40 2 0.5 - 6
1The nominal molar distribution of the bimetallic structure is reported; 2 the DLS diameter refers to the bimodal
distribution; 3 polydispersion index.

2.1.1. Au/Cu System

Au and Cu nanosols showed very different colloidal stability. In fact, the Au sample showed
an optimal time stability of almost 12 months, while Cu nanosol was affected by strong aggregation
phenomena that involved precipitation within 24 h.
In detail, Au nanoparticles had a mean hydrodynamic diameter by Dynamic Light Scattering
(DLS) of 17 nm, with a low polydispersity index (PDI) value typical of a narrow size distribution.
On the contrary, Cu nanoparticles showed a bimodal distribution with the major peak set at 350 nm.
This marked difference was not reflected by TEM analysis, which is reliable for the detection
of Cu primary nanoparticles with an average dimension of 3 nm, so neglecting the coarser and
sedimented particles.
Materials 2016, 9, 550 4 of 25

The co-syntheses performed for achieving the alloy compounds, Au/Cu, showed a very good
colloidal stability (several months), despite the aggregation tendency observed for Cu nanoparticles
alone. Probably, the presence of Au seed acted with a sort of stabilizing effect, preventing the rapid
aggregation of the newly-formed bimetallic particles. Anyway, the influence of the copper presence was
observed by DLS. For gold and gold/copper suspensions, up to a Au:Cu atomic ratio 1:1, a relatively
monodispersed signal, with an average diameter of 1720 nm, was detected. Increasing the copper
content led to polydispersed particles with a larger mean DLS diameter. Moreover, as indicated
by the PDI, the size distribution was closely related to the average particle diameter: the larger the
particle diameter, the broader the particle size distribution. Actually, these results seems to indicate
that aqueous sols, up to a Au:Cu atomic ratio 1:1, are predominantly constituted by homogeneous
bimetallic nanoparticles with a unimodal particle size distribution, while increasing the copper content
in the sol causes the formation of nanoclusters with inhomogeneous size and/or composition, as shown
by XRD analysis discussed in the following. Furthermore, a deepened study on the influence of PVP
concentration over the hydrodynamic diameter was performed and reported in the Supplementary
Materials (Table S1 and Figure S2).
XRD analyses with different Au:Cu molar ratios showed the peak broadening typical of nanosized
crystallites. The patterns are consistent with the single-phase face centered cubic structure (fcc) of gold
and copper (space group Fm-3m), with no observable impurities of CuOx of the phase-segregated
metals up to the Au1 Cu3 sample. Increasing the copper amount, a shift of the main gold peak was
progressively observed; this behavior is consistent with the formation of the alloy compounds [39].
For higher Cu content (Au1 Cu3 , Au1 Cu6 ), the presence of a reflection at 43.1 2 suggests the
segregation of copper with the formation of copper oxide (Cu2 O).
The interplanar distances assessed for the different samples are reported in Table 2. Probably in
the presence of an excess of copper, only part of the Cu forms the alloy, while the remaining part
could be oxidized by gold, forming a redox couple Cu/Au. The decreasing of the interplanar distance
for a high copper amount would be caused by Cu-Au isomorphous substitution with copper atoms
characterized by a lower atomic radius.

Table 2. Interplanar distances (100) detected for Au, Cu and Au/Cu compounds.

Sample d ()
Au 2.352
Au1 Cu1 2.314
Au1 Cu3 2.291
Au1 Cu6 2.278
Cu 2.080

Moreover, the bimetallic materials give broader XRD peaks, suggesting that the Au/Cu system
has a smaller crystallite size than the monometallic one. In effect, crystal size values, estimated using
the Scherrer equation, indicated ~4 nm for gold and ~33.5 nm for Au/Cu sols, confirming the coarser
size of the monometallic system. These results were also confirmed by TEM analysis that evidenced for
Au1 Cu1 a particle size lower than the monometal Au, supporting the formation of the alloy Au1 Cu1
(Figure 1). As well as the gold nanoparticles [40], also the bimetallic structure (Au1 Cu1 ) showed
a spherical morphology. The irregular shape observed for the larger particles probably results from the
aggregation during the permanence for 40 min at 90 C.
The selected area electron diffraction analysis (SAED) supported the formation of the Au/Cu
alloy, corresponding to crystallites with a face centered cubic structure. The collected signals evidenced
interplanar distances of 0.22, 0.20 and 0.14 nm, corresponding respectively to the plans (111), (200) and
(220) and consistent both with the XRD results and with the values reported in the literature for the
Au1 Cu1 alloy (JCPDS Card No. 65-0937) (Table 3).
Materials 2016, 9, 550 5 of 25
Materials 2016, 9, 550 5 of 25

Figure 1. HRTEM images of sample Au1Cu1 at different magnifications (a,b). The inset shows the FFT
of the observed nanoparticle (distances at 0.22 and 0.20 nm are circled); (c) selected area electron
diffraction analysis (SAED) analysis performed on several nanoparticles.

The selected area electron diffraction analysis (SAED) supported the formation of the Au/Cu
alloy, corresponding to crystallites with a face centered cubic structure. The collected signals
evidenced
Figure 1.interplanar distances
HRTEM images of 0.22,
of sample Au1Cu0.20 and 0.14magnifications
1 at different nm, corresponding
(a,b). Therespectively toFFT
inset shows the the plans
Figure 1. HRTEM images of sample Au1 Cu1 at different magnifications (a,b). The inset shows the
(111),of(200) and (220)
the observed and consistent
nanoparticle bothatwith
(distances the XRD
0.22 and 0.20 nmresults and with
are circled); the values
(c) selected areareported
electron in the
FFT of the observed nanoparticle (distances at 0.22 and 0.20 nm are circled); (c) selected area electron
literature for the
diffraction Au1Cu
analysis 1 alloy
(SAED) (JCPDS
analysis Card No.on65-0937)
performed (Table 3).
several nanoparticles.
diffraction analysis (SAED) analysis performed on several nanoparticles.

The selected
Table area electron
3. Interplanar diffraction
distances of the Auanalysis (SAED)
1Cu1 sample. The supported the formation
values collected of the
by TEM and XRDAu/Cu
are
Table 3. Interplanar distances of the Au1 Cu1 sample. The values collected by TEM and XRD are
alloy,compared
corresponding
to the to crystallites
tabulated data. with a face centered cubic structure. The collected signals
compared to the tabulated data.
evidenced interplanar distances of 0.22, 0.20 and 0.14 nm, corresponding respectively to the plans
Interplanar Distance d () TEM d () XRD d () Literature
(111), (200) and (220) and consistent
Interplanar Distancebothdwith the XRDd results
()2.27
TEM () XRD
and with the values reported in the
d () Literature
d (111) 2.31
literature for the Au1Cu1 alloy (JCPDS Card No. 65-0937) (Table 3). 2.23
dd(111)
(200) 2.27
1.97 2.31
2.03 2.23
1.98
dd(200) 1.97
1.41 2.03
1.42 1.98
1.40TEM and XRD are
Table 3. Interplanar distances of the Au1Cu1 sample. The values collected by
(220)
d (220) 1.41 1.42 1.40
d (311)
compared to the tabulated
d data.
1.20
1.20
1.22
1.22
1.19
1.19
(311)

Interplanar
The evolution Distance
of the surface plasmond () TEM d
resonance () XRD
bands d ()
(SPR) for theLiterature
Au/Cu samples is shown in
The evolution of thedsurface
(111) plasmon resonance
2.27 bands (SPR) for the 2.23
2.31 Au/Cu samples is shown in
Figure 2. By adding Cu, the SPR maximum peak absorption shifted from the Au characteristic value
Figure 2. By adding Cu, the SPR maximum 1.97
d (200) peak absorption shifted from the Au characteristic value
(525 nm) towards the Cu typical value, becoming even2.03
in shape more 1.98similar to the Cu resonance
d (220) value, becoming
(525 nm) towards the Cu typical 1.41 even in shape
1.42 more similar 1.40to the Cu resonance band
band characterized by a non-sharp profile [40].
d (311)profile [40]. 1.20
characterized by a non-sharp 1.22 1.19

The evolution of the surface plasmon resonance bands (SPR) for the Au/Cu samples is shown in
Figure 2. By adding Cu, the SPR maximum peak absorption shifted from the Au characteristic value
(525 nm) towards the Cu typical value, becoming even in shape more similar to the Cu resonance
band characterized by a non-sharp profile [40].

Figure2.2.UV-VIS
Figure UV-VISspectra
spectracollected
collectedfor
forAu/Cu
Au/Cu alloy
alloy samples.
samples.

The reaction yield for these samples was calculated by estimation of the unreacted ions assessed
by ICP analysis on the ultrafiltered samples. The results showed a total reaction yield for all of the
considered samples.
Figure 2. UV-VIS spectra collected for Au/Cu alloy samples.
Materials 2016, 9, 550 6 of 25

The reaction yield for these samples was calculated by estimation of the unreacted ions assessed
by ICP analysis on the ultrafiltered samples. The results showed a total reaction yield for all of the
considered samples.
Materials 2016, 9, 550 6 of 25

2.1.2. Pd/Au and Pd/Cu Systems

2.1.2.Exploiting
Pd/Au and thePd/Cu Systems
same green reaction, both Pd/Au and Pd/Cu compounds were synthesized in the
formExploiting
of alloys. the
As same
observed for Au/Cuboth
green reaction, sols,Pd/Au
despiteandthePd/Cu
aggregation tendency
compounds wereofsynthesized
the only Cu in
nanoparticles, the coupling
the form of alloys. with for
As observed Pd Au/Cu
produced highly
sols, stable
despite thesols, evidencing
aggregation a positive
tendency synergistic
of the only Cu
effect on the colloidal
nanoparticles, stability.
the coupling with Pd produced highly stable sols, evidencing a positive synergistic
Figure 3 shows some of the prepared sols for both Pd/Au and Pd/Cu series. The addition of
effect on the colloidal stability.
palladium,
Figuredue to its some
3 shows typical
ofdark color, with
the prepared a very
sols broad
for both absorbance
Pd/Au in the visible
and Pd/Cu series. range, enhanced
The addition of
the darkness of the suspensions, making very difficult the collection of UV-VIS spectra
palladium, due to its typical dark color, with a very broad absorbance in the visible range, enhanced the for
these nanosols.
darkness of the suspensions, making very difficult the collection of UV-VIS spectra for these nanosols.

Figure3.3. Images
Figure Imagesof
of(a)
(a)the
thePd/Au
Pd/Au series;
series; and
and (b)
(b) the
the Pd/Cu
Pd/Cuseries.
series.

The hydrodynamic diameters evaluated by DLS are listed in Table 1. For the Pd/Au sols, the
The hydrodynamic
resulting diameters with
curves were monomodal evaluated
mean by DLS arecomparable
diameters listed in Table each1. other
For the Pd/Au
(from 24 tosols, the
35 nm)
resulting
and curves
slightly werethan
larger monomodal
the singlewith meanones
metal diameters
(17 nm comparable
for Au and each23other
nm for(from 24 to
Pd). 35 nm)
Only Pd1Auand2
slightly larger than the single metal ones (17 nm for Au and 23 nm
evidenced a larger dimeter, 71 nm, probably due to some aggregation phenomena. 1 2 for Pd). Only Pd Au evidenced
a larger dimeter, behavior
A different 71 nm, probably due to some
was observed for theaggregation
Pd/Cu series,phenomena.
as already shown in Au/Cu samples;
A different behavior was observed for the Pd/Cu
the higher is the Cu amount, the larger is the detected hydrodynamic series, as already shown(from
diameter in Au/Cu73 to samples;
133 nm)
the higher is the Cu amount, the larger is the detected hydrodynamic
with an increased polydispersion well evidenced by the PDI values. The size distribution diameter (from 73 to 133 nm)
curves
with
(Figure an 4a,b)
increased polydispersion
showed the markedwell evidenced
influence by the PDI
produced values.
by the copper Theaddition,
size distribution
which forcurves
the
(Figure 4a,b) showed the marked influence produced by the copper
composition Pd1Cu6 evidenced the bimodal size distribution typical of copper sols. addition, which for the composition
Pd1 CuWe 6 evidenced
hypothesizedthe bimodal
that the size distribution
smaller peak could typical of copper sols.
corresponded to a different phase, for example
Cu2O; We hypothesized
probably, with a that
largethe smaller
excess peak could
of copper the totalcorresponded
reduction of to thea precursor
different phase, for example
is too difficult to be
Cu 2 O;
completed,probably,
and an oxidized part remained in the sample. This hypothesis was strengthened bytothe
with a large excess of copper the total reduction of the precursor is too difficult be
completed,
XRD resultsandthatan oxidized the
evidenced partformation
remainedof inCu
the2Osample. This hypothesis
in the sample containing wasthestrengthened
highest amountby theof
XRD results
Cu (Figure 5). that evidenced the formation of Cu 2 O in the sample containing the highest amount of Cu
(Figure 5).
In Figure 5, both the diffraction pattern collected for the Pd/Cu samples (a) and the table listing
the shifts detected for the principal peak that supports the formation of the alloys (b) are reported.
Materials 2016, 9, 550 7 of 25
Materials 2016, 9, 550 7 of 25
Materials 2016, 9, 550 7 of 25

(a) (b)
(a) (b)

Figure 4. Particle size distribution assessed for Pd/Cu bimetallic nanosols: (a) samples from Pd1Cu0.5
Figure
Figure 4. Particle
4. Particle size
size distribution
distribution assessed
assessed for for Pd/Cu
Pd/Cu bimetallic
bimetallic nanosols:
nanosols: (a) (a) samples
samples fromfrom
Pd1Pd Cu0.5
Cu10.5
to Pd1Cu3 compared with Pd and Cu; (b) Pd1Cu6 sample compared to Pd and Cu.
to Pd Cu compared with Pd and Cu; (b) Pd Cu sample compared to
to Pd1 Cu3 compared with Pd and Cu; (b) Pd1 Cu6 sample compared to Pd and Cu.
1 3 1 6 Pd and Cu.

(a) (b)
(a) (b)

Figure 5. (a) Focusing of the XRD spectra on the principal peak for the Pd/Cu series; (b) List of the
Figure 5. (a) Focusing
progressive shift of theof the XRD
principal spectrapeaks.
detected on the principal shift
Progressive peakoffor
thethe Pd/Cudetected
principal series; peak.
(b) List of the
progressive
Figure 5. shift of the principal
(a) Focusing detected
of the XRD peaks.
spectra Progressive
on the principalshift
peakoffor
thethe
principal
Pd/Cu detected
series; (b)peak.
List of the
In Figure 5, both
progressive shift the
of thediffraction
principalpattern
detectedcollected for the Pd/Cu
peaks. Progressive shiftsamples (a) and the
of the principal table peak.
detected listing
theAnyhow,
shifts detected for the
the peak principal
shift was wellpeakappreciated
that supportstill thethe
formation
Pd1 Cuof 2
the alloys
sample, (b)
but are
for reported.
a copper molar
Anyhow,
In Figure the
5, peak
both shift
the was
diffractionwell appreciated
pattern till
collected the Pd
for 1CuPd/Cu
the 2 sample,
concentration higher than 67%, the data suggested that the added copper does not enter the lattice but
samples for a
(a) copper
and the molar
table listing
concentration
the shifts higher
detected than
for the 67%, the
principal data suggested
peak that that
supports the added
the copper
formation
structure, but contributes to the segregation phenomenon of Cu2 O. On sample Pd1 Cu6 , the analysis of does
of the not enter
alloys (b)the lattice
are reported.
structure, but contributes to the wassegregation phenomenon ofthe
Cu2PdO. 1On 2sample Pd1Cu6,for the analysis
the dataAnyhow,
confirmed thethepeak shift
presence of two well appreciated
different phases;tillin fact, theCu main sample,
peak atbut 36.5 2a corresponds
copper molar
of the data
concentration confirmed
higher the
than presence
67%, the of two
data different
suggested phases;
that the in fact,
added the main
copper peak
does notat enter
36.5 the
2 lattice
to the Cu2 O oxide phase (JCPDS Card No. 65-3288), while at 41.524 2, the detected peak corresponds
corresponds to the Cu2O oxide phase (JCPDS Card No. 65-3288), while at 41.524 2, the detected
to structure,
the PdCu but alloycontributes
(JCPDS Card to theNo.segregation
48-1551). phenomenon of Cu2O. On sample Pd1Cu6, the analysis
peak corresponds to the PdCu alloy (JCPDS Card No. 48-1551).
of By
themeans
data of
confirmed
thetheScherrer the presence
equation, of mean
the two different
crystallite phases;
size was in fact, theand
calculated main peak in
reported at Table
36.5 1.2
By means of Scherrer equation, the mean crystallite size was calculated and reported in
corresponds
Except to the Cu O oxide phase (JCPDS Card No. 65-3288), while at 41.524 2, the detected
Table for Pd1 Cufor0.5 , Pd
the1Curesults are coherent with the trend observed by DLS data; indeed, the higher
2
1. Except 0.5, the results are coherent with the trend observed by DLS data; indeed,
waspeak
the corresponds
copper amount, to thethe PdCu
larger alloy
was (JCPDS Card No. 48-1551).
the higher was the copper amount, thethe mean
larger wascrystallite
the mean size. The peak
crystallite shift
size. Thewaspeakdetected
shift wasalso for
the By
Pd/Aualso
detected means
series, of
for and the Scherrer
for thisseries,
the Pd/Au equation,
sample,andno the mean
forsegregated
this sample, crystallite
phases size was
were detected;
no segregated calculated
phases thewere and
progressive reported
detected; the shift is in
Table
consistent 1.
progressive Except
with for Pd
theisformation
shift 1 Cu 0.5
consistent with , the
of PdAu results are coherent
alloy (Figure
the formation with the trend
6). alloy (Figure 6).
of PdAu observed by DLS data; indeed,
the higher was the copper amount, the larger was the mean crystallite size. The peak shift was
detected also for the Pd/Au series, and for this sample, no segregated phases were detected; the
progressive shift is consistent with the formation of PdAu alloy (Figure 6).
Materials
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(a)
(a) (b)
(b)

Figure
Figure 6.(a)
Figure6.6. (a)Focusing
(a) Focusingof
Focusing ofthe
of theXRD
the XRDspectra
XRD spectraon
spectra onthe
on theprincipal
the principalpeak
principal peakfor
peak forthe
for thePd/Au
the Pd/Au series;
Pd/Au series; (b)
series; (b) List
(b) Listof
List ofthe
of the
the
progressive
progressive shift
shiftof
ofthe
theprincipal
principaldetected
detectedpeaks.
peaks.
progressive shift of the principal detected peaks.

2.2.
2.2. Catalytic
2.2. Catalytic Activity
CatalyticActivity
Activity

2.2.1.
2.2.1. Catalytic Test of Pristine Nanoparticles in the Hydrogenation of 4-Nitrophenol
2.2.1. Catalytic
Catalytic Test
Test of
of Pristine
Pristine Nanoparticles
Nanoparticles inin the
the Hydrogenation
Hydrogenation of of 4-Nitrophenol
4-Nitrophenol
The
The catalytic performance of the synthesized nanoparticles was tested in the reduction of
The catalytic
catalytic performance
performance of of the
the synthesized
synthesized nanoparticles
nanoparticles waswas tested
tested in in the
the reduction
reduction of
of
4-nitrophenol
4-nitrophenol (4-NP)
(4-NP) to
to 4-aminophenol
4-aminophenol (4-AP)
(4-AP) with
with an
an excess
excess of
of NaBH
NaBH 44, as the model reaction
, as the model reaction
4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with an excess of NaBH4, as the model reaction
(Scheme
(Scheme 1). Accordingly, the reduction rates can be regarded as being independent of the concentration
(Scheme 1).1). Accordingly,
Accordingly, the the reduction
reduction rates
rates can
can be
be regarded
regarded as as being
being independent
independent of of the
the
of the reducing
concentration agent, NaBH [41].
concentration ofof the
the reducing
reducing 4 agent,
agent, NaBH
NaBH44 [41].
[41].

NO
NO22 NH
NH22

+
+ NaBH
NaBH44 +
+ H
H22O
O

OH
OH OH
OH
4-Nitrophenol
4-Nitrophenol 4-Aminophenol
4-Aminophenol
Scheme
Scheme1.1.
Scheme 4-Nitrophenol
1.4-Nitrophenol reduction
4-Nitrophenolreduction with
reductionwith NaBH
NaBH444...
withNaBH

This
This reaction
This reaction
reaction is is particularly
particularly easyeasy to
easy to follow
to followbecause
follow becauseonly
because onlythe
only theproduct
the product4-aminophenol
product 4-aminophenol
4-aminophenol (4-AP)
(4-AP)
(4-AP) is
is
formed,
formed, and
and the
the extent
extent of
of the
the reaction
reaction can
can
is formed, and the extent of the reaction can be determined by be
be determined
determined by
by measuring
measuring the
the change
change in
in UV-VIS
UV-VIS
in UV-VIS
absorbance
absorbanceat
absorbance at the
atthe 400-nm
the400-nm wavelength
400-nmwavelength
wavelengthtypicaltypical
typicalof of 4-NP
of4-NP
4-NPin in alkaline
inalkaline condition.
alkalinecondition.
condition.
Preliminary
Preliminarytests
Preliminary tests without
testswithout
without the the
the catalyst
catalyst
catalyst indicatedindicated
that nothat
indicated that no
no reaction
reaction occurs inoccurs
reaction occurs in
in the
the studied the studied
studied
conditions,
conditions,
conditions, confirming
confirming the
the absence,
absence, during
during our
our tests,
tests, of
of non-catalytic
non-catalytic
confirming the absence, during our tests, of non-catalytic phenomena. On the contrary, all of the phenomena.
phenomena. On
On the
the contrary,
contrary,
all
all of
of the
the nanoparticles
nanoparticles nanoparticles acted
acted as
acted as effective as effective
for catalyst
effective
catalyst catalyst for
for the
the hydrogenation the hydrogenation
hydrogenation of
of 4-nitrophenol
of 4-nitrophenol 4-nitrophenol
in the presence in
in the
the
of
presence
presence
NaBH . of
of NaBH
NaBH
Indeed, the4. Indeed, the addition of metallic sols to the reaction mixture causes a gradual
4. addition
Indeed, the
of addition
metallic of
sols metallic
to the sols
reaction to the
mixturereaction
causesmixture
a causes
gradual a gradual
decoloration
4
decoloration
of the solutionof
decoloration the
ofand solution
solution and
theultimately and ultimately
ultimately
a bleaching of aathe
bleaching
bleaching of
of the
yellow color, thedueyellow
yellow
to thecolor,
color, due
due to
formation toofthe
the formation
formation
4-AP, showing of
of
4-AP,
a4-AP, showing
weakshowing
absorption a weak
a weak absorption
absorption
of violet wavelength of violet
of violet wavelength
wavelength
stemming from itsstemming
stemming
peak at 300 from its
fromnm. peak at 300
its peak at 300 nm. nm.
In
In Figure
Figure 7,
7, typical
typical degradation
degradation spectra
spectra of
of 4-nitrophenolate
4-nitrophenolate
In Figure 7, typical degradation spectra of 4-nitrophenolate are reported. On are
are reported.
reported. On the
On the basis
the basis
basis ofof the
of the
the
collected
collected UV-VIS
UV-VIS spectra,
spectra, the
the plot
plot of
of ln
ln (A/Ao)
(A/Ao) versus
versus time
time was
was obtained
obtained
collected UV-VIS spectra, the plot of ln (A/Ao) versus time was obtained and the kinetic constants and
and the
the kinetic
kinetic constants
constants
calculated.
calculated.The
calculated. The resulting
Theresulting kinetic
resultingkinetic constants
kineticconstants
constantsfor for
forallall
allofof the
ofthe bimetallic
thebimetallic nanosols
bimetallicnanosols
nanosolsareare listed
arelisted
listedinin Table
Table4.44
inTable
Materials 2016, 9, 550 9 of 25
Materials 2016, 9, 550 9 of 25

Figure 7. Typical evolution of UV-VIS spectra as a function of time during the hydrogenation of
Figure 7. Typical evolution of UV-VIS spectra as a function of time during the hydrogenation of
4-nitrophenole (4-NP) in the presence of catalyst.
4-nitrophenole (4-NP) in the presence of catalyst.

As reported
As reported elsewhere
elsewhere [42],
[42], thethereaction
reactiondoesdoesnotnot start
start immediately
immediately after
afterthe
theaddition
additionofofthethe
catalyst,
catalyst, butbut
onlyonly after
after a noticeable
a noticeable timelag,
time lag,i.e.,
i.e.,the
theinduction
induction time.
time. This
This may
maybebeascribed
ascribedtotoseveral
several
reasons:
reasons: the the presence
presence of of oxygen
oxygen dissolvedininwater
dissolved wateror oraa thin
thin nanoxide
nanoxide coating
coatingon
onthe
theparticle
particlesurface.
surface.
In order
In order to reduce
to reduce thethe induction
induction time,
time, severalstrategies
several strategieshave
have been
been investigated
investigated[40,43,44],
[40,43,44],observing
observing
that it was significantly reduced for all of the prepared samples only by bubblingnitrogen
that it was significantly reduced for all of the prepared samples only by bubbling nitrogenfor 1 min
for 1 min
before the addition of NaBH4 and adding the reagents in this order: catalyst, 4-NP and, finally,
before the addition of NaBH4 and adding the reagents in this order: catalyst, 4-NP and, finally,
NaBH4. Probably, this procedure allows the removal of oxygen dissolved in the solution, which
NaBH4 . Probably, this procedure allows the removal of oxygen dissolved in the solution, which
would involve NaBH4 in a competitive reaction with 4-NP. The results, referring to data collected
would involve NaBH4 in a competitive reaction with 4-NP. The results, referring to data collected
after the pre-treatment with bubbling nitrogen, are summarized in Table 4 in terms of kinetic
after the pre-treatment with bubbling nitrogen, are summarized in Table 4 in terms of kinetic constant,
constant, conversion and turn over frequency (TOF, defined as the number of moles of reduced 4-NP
conversion
per moleand turn over
of catalyst perfrequency
second). (TOF, defined as the number of moles of reduced 4-NP per mole
of catalyst per second).
Table 4. Catalytic performances of the prepared bimetallic nanosols. TOF, turn over frequency.
Table 4. Catalytic performances of the prepared bimetallic nanosols. TOF, turn over frequency.
Sample Catalyst Concentration 105 (M) K 102 (s1) TOF 102 (s1)
Au 1.1 1.70 5.3
Sample Catalyst Concentration 105 (M) K 102 (s1 ) TOF 102 (s1 )
Cu 1.1 0.20 0.4
Au Pd 1.1 0.11 1.70
1.95 34.1 5.3
Cu Au1Cu1 1.1 1.1 0.20
2.70 5.8 0.4
Pd Au1Cu3 0.11 1.1 1.95
1.70 4.9 34.1
Au1 Cu1 Au1Cu6 1.1 1.1 0.70
2.70 1.2 5.8
Au1 Cu3 Pd1Cu0.5 1.1 0.11 1.14
1.70 32.2 4.9
Au1 Cu6 Pd1Cu1 1.1 0.11 0.80
0.70 15.7 1.2
Pd1Cu2 0.11 0.26 7.8
Pd1 Cu0.5 0.11 1.14 32.2
Pd1Cu3
Pd1 Cu1 0.11 0.11 0.19
0.80 5.5
15.7
Pd1 Cu2 Pd1Cu6 0.11 0.11 0.07
0.26 3.1 7.8
Pd1 Cu3 Pd1Au0.5 0.11 0.11 2.10
0.19 40.7 5.5
Pd1 Cu6 Pd1Au1 0.11 0.11 2.29
0.07 49.5 3.1
Pd1Au2 0.11 1.35 37.5
Pd1 Au0.5 Pd1Au3
0.11 0.11 2.10
0.59 30.3
40.7
Pd1 Au1 0.11 2.29 49.5
Pd1Au6 0.11 0.35 10.3
Pd1 Au2 0.11 1.35 37.5
Data
Pd1refer
Au3 to the following concentrations:
0.11 4-NP 9 105 M and NaBH
0.59 4 0.715 M. For all 30.3
of the samples,
TOF values
Pd1 Au6 are calculated considering
0.11 the first 60 s of the reaction.
0.35 10.3
Data refer to the following concentrations: 4-NP 9 105 M and NaBH4 0.715 M. For all of the samples,
TOF values are calculated considering the first 60 s of the reaction.
Materials 2016, 9, 550 10 of 25
Materials 2016, 9, 550 10 of 25

All of the prepared nanoparticles act as catalysts in the hydrogenation of 4-NP; among the
single
Allmetals
of theAu, Cu andnanoparticles
prepared Pd, the best performances
act as catalysts werein observed for Pd, followed
the hydrogenation of 4-NP;by Au
amongand the
Cu.
As evidenced
single metals Au,in the
Culiterature
and Pd, the [45,46],
best bimetallic
performances nanoparticles
were observedcouldforshow
Pd,not only the
followed bycombination
Au and Cu.
of the properties related to the presence of two individual metals, but also new
As evidenced in the literature [45,46], bimetallic nanoparticles could show not only the combination properties due to the
so-called
of synergistic
the properties effect
related between
to the presencethe of
twotwo metals. A marked
individual synergistic
metals, effect
but also new on the catalytic
properties due to
performances
the for this probe
so-called synergistic reaction the
effect between wastwoevidenced
metals. A formarked
Au/Cusynergistic
and Pd/Au nanostructures.
effect on the catalytic In
Au/Cu, despite the poor catalytic performance assessed for the Cu monometal,
performances for this probe reaction was evidenced for Au/Cu and Pd/Au nanostructures. In Au/Cu, the addition of Cu to
Au produced
despite the pooran enhancement of the activity
catalytic performance for the
assessed forcomposition of Au1Cuthe
the Cu monometal, 1. Aaddition
further increase
of Cu to ofAu
Cu
content produced, instead, a detrimental effect. The latter was justified by the
produced an enhancement of the activity for the composition of Au1 Cu1 . A further increase of Cu marked increment of
the hydrodynamic diameter and the formation of Cu O segregated phases. Similarly,
content produced, instead, a detrimental effect. The latter was justified by the marked increment of the
2 in Pd/Au
series, the synergic
hydrodynamic effect
diameter and was
theassessed
formationtill ofthe
Cu2composition
O segregatedPd 1Au1, Similarly,
phases. which reached
in Pd/Authe maximum
series, the
performance (Figure 8a). Again, a further increase of added Au metal decreases
synergic effect was assessed till the composition Pd1 Au1 , which reached the maximum performance progressively the
catalytic activity, despite the similar nanoparticle dimension, hydrodynamic
(Figure 8a). Again, a further increase of added Au metal decreases progressively the catalytic activity, diameter and
homogeneity
despite of the
the similar bimetallic phase
nanoparticle (Tablehydrodynamic
dimension, 1). diameter and homogeneity of the bimetallic
On the
phase (Table 1).other hand, the Pd/Cu compounds did not show any kind of catalytic improvement with
respect to the
On the othersingle
hand,Pd the metal.
Pd/CuIndeed,
compounds a constant decreasing
did not show trend
any kind was observed
of catalytic addingwith
improvement Cu
(Figure 8b) combined with structural variation, such as the hydrodynamic diameter
respect to the single Pd metal. Indeed, a constant decreasing trend was observed adding Cu (Figure 8b) increase and the
occurrencewith
combined of structural
the segregation phenomena
variation, such as the(Table 1), whichdiameter
hydrodynamic probablyincrease
prevailed
and on
the any potential
occurrence of
synergistic
the outcome.
segregation phenomena (Table 1), which probably prevailed on any potential synergistic outcome.

(a) (b)
Figure 8.8. Evolution
Figure Evolution ofof the
the kinetic
kinetic constant
constant for
for the
the 4-NP
4-NP hydrogenation
hydrogenation reaction
reaction for
for Pd
Pd bimetallic
bimetallic
compounds with different amounts of Au and Cu added: (a) the Pd/Au system
compounds with different amounts of Au and Cu added: (a) the Pd/Au system and (b) the Pd/Cu and (b) the Pd/Cu
system. Data
system. Datarefer to the
refer following
to the concentration:
following concentration: 10 9M,catalyst
4-NP 94-NP 5 1.1 catalyst
105 M, 10 M, NaBH
6
1.1 4100.715 M.
6 M,

NaBH4 0.715 M.
It is well know that the synergistic effect on the catalytic activity depends on the surface
electronic structure that can be modified by the interactions between the two kinds of atoms in the
It is well know that the synergistic effect on the catalytic activity depends on the surface electronic
bimetallic alloy owing to the strain and ligand effects. The strain effect involves the average bond
structure that can be modified by the interactions between the two kinds of atoms in the bimetallic
length of metal atoms, which is typically different from those in the monometals, while the so-called
alloy owing to the strain and ligand effects. The strain effect involves the average bond length of
ligand effect involves the hetero-metallic bonding interactions of atoms in the surface of
metal atoms, which is typically different from those in the monometals, while the so-called ligand
nanoparticles, which modifies their surface electronic structure [6]. Even if the mechanism is still
effect involves the hetero-metallic bonding interactions of atoms in the surface of nanoparticles, which
under debate, both effects result in changes in the width and average energy of the d-band that may
modifies their surface electronic structure [6]. Even if the mechanism is still under debate, both effects
account for the enhancement in catalytic activity.
result in changes in the width and average energy of the d-band that may account for the enhancement
The hydrogenation reaction involving 4-NP can be divided into two main parts: firstly, the
in catalytic activity.
decomposition of NaBH4 on the surface of nanoparticles, producing H-atoms, which turn to be
The hydrogenation reaction involving 4-NP can be divided into two main parts: firstly, the
available to 4-NP molecules, and, finally, the addition of protons to the 4-NP and the simultaneous
decomposition of NaBH4 on the surface of nanoparticles, producing H-atoms, which turn to be
removal of its oxygen, following one of the typical mechanisms of heterogeneous reactions, like the
available to 4-NP molecules, and, finally, the addition of protons to the 4-NP and the simultaneous
EleyRideal or the Langmuir Hinshelwood [42]. An overall comparison among the catalysts can be
Materials 2016, 9, 550 11 of 25

removal
Materials of its9,oxygen,
2016, 550 following one of the typical mechanisms of heterogeneous reactions, 11 like the
of 25
EleyRideal or the Langmuir Hinshelwood [42]. An overall comparison among the catalysts can be
carried
carried outouton on
thethe basis
basis of TOF
of the the TOF value,
value, whichwhich evidenced
evidenced for theforPd-based
the Pd-based catalysts
catalysts the bestthe best
catalytic
catalytic performances,
performances, probably due probably
to thedue to the Pdcharacteristic
Pd intrinsic intrinsic characteristic of efficient
of efficient hydrogen hydrogen
relay. relay.
Instead,comparing
Instead, comparing the the catalytic
catalytic performances
performances forfor the
the Pd-based
Pd-based catalysts,
catalysts,thethemost
mostactive
active
compound resulted in being Pd 1Au1. As hypothesized for Au/Pt alloys [46], also for the Au/Pd
compound resulted in being Pd1 Au1 . As hypothesized for Au/Pt alloys [46], also for the Au/Pd
nanostructure,
nanostructure, a synergic
a synergic effect
effect between
between neighboring
neighboring PdPdandandAuAu sites
sites could
could be be triggered.
triggered. Indeed,
Indeed, it
it was
was proposed
proposed that, during
that, during the hydrogenation
the hydrogenation of nitroaromatic
of nitroaromatic compounds,
compounds, the Pd clusters
the Pd clusters adsorb BHadsorb
4 -/H2
BH4-/H2 dissociatively with a much lower activation barrier than Au. Thus, activated H atoms can
dissociatively with a much lower activation barrier than Au. Thus, activated H atoms can migrate to Au
migrate to Au or mixed Pd/Au sites located in the neighborhood. The same co-operative effect could
or mixed Pd/Au sites located in the neighborhood. The same co-operative effect could act also between
act also between Au and Cu, supporting the synergistic behavior shown for the Au1Cu1 alloy [47].
Au and Cu, supporting the synergistic behavior shown for the Au1 Cu1 alloy [47]. Furthermore, some
Furthermore, some structural features described in the literature for the Au/Cu bimetallic
structural features described in the literature for the Au/Cu bimetallic nanoparticles [48] ascribe to the
nanoparticles [48] ascribe to the composition Au1Cu1 the formation of the most ordered and packed
composition Au1 Cu1 the formation of the most ordered and packed structure at the nanoscale, with
structure at the nanoscale, with the smallest crystallite size.
the smallest crystallite size.
2.2.2. Catalytic Tests of Supported Catalysts in the Oxidation of 5-Hydroxymethylfurfural
2.2.2. Catalytic Tests of Supported Catalysts in the Oxidation of 5-Hydroxymethylfurfural
5-hydroxymethyfurfural (HMF) can be used to prepare different intermediates, and
5-hydroxymethyfurfural (HMF) can be used to prepare different intermediates, and
2,5-furandicarboxylic acid (FDCA) is considered to be one of the most interesting derivatives from
2,5-furandicarboxylic acid (FDCA) is considered to be one of the most interesting derivatives from
the chemical point of view. In Scheme 2, a general reaction scheme for HMF oxidation is reported.
the chemicalusing
Generally, pointgold-based
of view. Innanoparticles,
Scheme 2, a the general reaction scheme
first transformation thatfor HMFisoxidation
occurs is reported.
the oxidation of the
Generally, using gold-based nanoparticles, the first transformation that occurs
aldehydic group, generating the first intermediate 5-hydroxymethyl-2-furancarboxylic acid is the oxidation of the
aldehydic group, generating the first intermediate 5-hydroxymethyl-2-furancarboxylic
(HMFCA). Most of the time, the rate-limiting step for this process is the oxidation of the alcoholic acid (HMFCA).
Most of the
group; time, the
however, rate-limiting
when step for this process
5-formyl-2-furancarboxylic acidis (FFCA)
the oxidation of the
is formed, it alcoholic
suddenly group;
reacts tohowever,
form
when 5-formyl-2-furancarboxylic
the desired acid (FFCA)
product 2,5-furandicaboxylic is (FDCA)
acid formed, [28,35,49,50].
it suddenly reacts to form the desired
2,5-diformylfuran (DFF) product
is not
2,5-furandicaboxylic
observed in the most acid (FDCA) [28,35,49,50].
commonly-used oxidation2,5-diformylfuran
conditions, since it (DFF) is not observed
is converted very fastininto
the the
most
commonly-used oxidation
second intermediate FFCA.conditions, since it is converted very fast into the second intermediate FFCA.

Scheme2.2.General
Scheme Generalreaction
reaction scheme
scheme for
for 5-hydroxymethylfufural
5-hydroxymethylfufural(HMF)
(HMF)oxidation.
oxidation.

Preformed mono- and bi-metallic nanoparticles were supported onto TiO2 and CeO2 and used
as Preformed
heterogeneous mono- and bi-metallic
catalysts nanoparticles were (HMF)
for 5-hydroxymethylfufural supported onto TiO
oxidation and CeO2 and used as
to2 2,5-furandicarboxylic
heterogeneous
acid (FDCA) catalysts
in water.for 5-hydroxymethylfufural
The synthetic approach reported (HMF) oxidation to 2,5-furandicarboxylic
in the previous section allowed the acid
(FDCA)
preparation of reproducible and stable colloids with a controlled particle size, and the influence ofof
in water. The synthetic approach reported in the previous section allowed the preparation
reproducible and phase
the metal active stable on
colloids with aactivity
the catalytic controlled
wasparticle
studied,size,
sinceandthe the influence
catalyst of the metal
preparation active
procedure
phase on the
did not catalytic
affect activity
the catalyst was studied, since the catalyst preparation procedure did not affect the
performance.
catalystMonometallic
performance.Au-, Cu- and Pd-supported catalysts were used in HMF oxidation, and their
Monometallic
catalytic Au-,
activity was Cu- andtoPd-supported
compared that typical ofcatalysts
bimetallicwere
systemsused(Au/Cu,
in HMF oxidation,
Au/Pd). and their
The obtained
catalytic
results activity
confirm was compared
that catalyst to that
activity andtypical of bimetallic
product selectivity systems
is affected(Au/Cu, Au/Pd).of
by the presence The obtained
bimetallic
results confirm that
nanoparticles catalyst
as the activeactivity
phase.and product
Indeed, ourselectivity
recent worksis affected by the presence
demonstrated that theofability
bimetallic
of
synthesizing bimetallic systems with a different metal molar ratio can be
nanoparticles as the active phase. Indeed, our recent works demonstrated that the ability of the key to tune catalyst
selectivity towards
synthesizing a specific
bimetallic systems compound. Moreover,
with a different metalthemolar
presence of can
ratio an alloy
be thecan improve
key to tunecatalyst
catalyst
activity. The
selectivity HMF oxidation
towards a specific reaction
compound.can beMoreover,
exactly thethecase where the
presence of presence
an alloy of animprove
can alloy improves
catalyst
greatly the catalytic performance. As a matter of fact, Au/Cu- and Au/Pd-based
activity. The HMF oxidation reaction can be exactly the case where the presence of an alloy improves catalysts are even
three-times more active than the monometallic counterparts. The graph reported in Figure 9
underlines the effect of alloyed nanoparticles on the catalytic activity. As far as monometallic
 Materials 2016, 9, 550 12 of 25

greatly the catalytic performance. As a matter of fact, Au/Cu- and Au/Pd-based catalysts are even
three-times
Materials more active than the monometallic counterparts. The graph reported in Figure 9 underlines
2016, 9, 550 12 of 25
the effect of alloyed nanoparticles on the catalytic activity. As far as monometallic catalysts are
catalysts are concerned,
concerned, both Au and bothPdAuareand Pd in
active areHMF
active in HMF while
oxidation, oxidation, while Cu-supported
Cu-supported material didmaterial
not allow
didsubstrate
not allowtransformation,
substrate transformation,
leading to theleading to the of
formation formation
by-productsof by-products
derived from derived
HMFfrom HMF
degradation.
degradation.
However, the However,
additiontheof addition
very low of very low
amounts amounts
of copper andof palladium
copper andinpalladium
the systeministhe
ablesystem is
to increase
able to increase
FDCA productionFDCA production
under under conditions.
mild reaction mild reaction conditions.
It can It can
be noticed thatbe noticedmetal
a specific that amolar
specificratio
metal
mustmolar ratio must
be employed be employed
to achieve to achieve
the highest FDCA yield:the highest
the Au/Cu FDCA yield:
sample the Au/Cu by
characterized sample
a metal
characterized
molar ratio by 3:1 agave
metal molarthe
actually ratio 3:1performance.
best gave actuallyThe theselectivity
best performance.
towards the Thedesired
selectivity
producttowards
(FDCA)
theincreased
desired product (FDCA)
significantly increased
for Au 3 Cu1 and significantly for Au
Au1 Cu1 , which 3Cu1 and Au
emphasizes the1Cu 1, which emphasizes
importance of the Au:Cuthe ratio
importance of the Au:Cu ratio to achieve copper promotion on gold. Our
to achieve copper promotion on gold. Our data suggest that Cu acts as a gold promoter and/or data suggest that Cu acts
as adispersing
gold promoteragent and/or
only if dispersing
present in aagent
Au:Cu only if present
ratio higher thanin a Au:Cu
1:1, andratio higher than
the highest FDCA 1:1,yield
and can
the be
highest FDCA
obtained yield
using can be
a ratio of obtained
Au:Cu ofusing a ratio of Au:Cu of 3:1 [38].
3:1 [38].

Figure 9. Product selectivity achieved using different metal active phases under mild reaction
Figure 9. Product selectivity achieved using different metal active phases under mild reaction
conditions (70 C, 10 bar O2 , H2 O as solvent, NaOH, HMF:metal 1:0.01, 4 h); results are given at total
conditions (70 C, 10 bar O2, H2O as solvent, NaOH, HMF:metal 1:0.01, 4 h); results are given at total
conversion of HMF. Data report catalysts performance in their best condition (Au- and Cu-containing
conversion of HMF. Data report catalysts performance in their best condition (Au- and
samples have been tested using four equivalents of NaOH, while Pd-containing samples required only
Cu-containing samples have been tested using four equivalents of NaOH, while Pd-containing
two equivalents of the base).
samples required only two equivalents of the base).

Products
Products distribution
distribution was was
alsoalso strongly
strongly affected
affected by bythethe Au:Pd
Au:Pd atomic
atomic ratio
ratio (Figures
(Figures 10 and
10 and 11).11).
In In particular,
particular, thethe resultsclearly
results clearlyshowed
showedthe thepresence
presence of of aa synergic
synergic effect
effect due
dueto tothe
thepresence
presenceofofthe thetwo
metals with increased FDCA selectivity due to the increase in Au content,
two metals with increased FDCA selectivity due to the increase in Au content, until the Au:Pd until the Au:Pd atomic ratio
was equal to 1:6 (Figure 10). The further increase of Au content resulted
atomic ratio was equal to 1:6 (Figure 10). The further increase of Au content resulted in lower FDCA in lower FDCA selectivity,
althoughalthough
selectivity, all catalystsall with high with
catalysts Au content
high Au (Aucontent
3 Pd1 , Au 6 Pd
(Au 1 and
3Pd 1, AuAu 9 Pd
6Pd ) were
and
1 1 Aumore
9Pd1) efficient
were more in the
formation of this product [35]. These results confirm the recent data reported
efficient in the formation of this product [35]. These results confirm the recent data reported by Prati by Prati and co-workers
andwho used Pd/Au
co-workers whonanoparticles supported on supported
used Pd/Au nanoparticles activated carbon [50] forcarbon
on activated glycerol[50]andfor
alcohol oxidation.
glycerol and
Therefore, a small quantity of Pd seems to be adequate to significantly change
alcohol oxidation. Therefore, a small quantity of Pd seems to be adequate to significantly change the the electronic properties
of Au and
electronic enhanceofthe
properties Aucatalytic activity
and enhance theincatalytic
alcohol oxidation.
activity in alcohol oxidation.
C scarcely affected FDCA selectivity (Figure 10).
TheThe temperature
temperature increase
increase fromfrom70 70
to to90 90C scarcely affected FDCA selectivity (Figure 10).
Indeed, for the reported Au/Pd systems, the
Indeed, for the reported Au/Pd systems, the tuning of the metaltuning of the metal molar
molar ratio
ratio seems
seems to significantly
to be be significantly
more important than the increase in reaction temperature. Furthermore, even the distribution
more important than the increase in reaction temperature. Furthermore, even the product product
was slightly
distribution was affected
slightlybyaffected
temperature. Indeed, theIndeed,
by temperature. 20 degree thetemperature increase led only
20 degree temperature to a led
increase slight
increase of FDCA formation with a simultaneously decrease of the
only to a slight increase of FDCA formation with a simultaneously decrease of the amount of amount of HMFCA in the final
HMFCA in the final reaction mixture (Figure 11). The oxidation of the primary alcohol side-chain,
necessary to form the FDCA, is a more demanding process and proceeds with a significant rate at
temperatures higher than 80 C. Therefore, this step is favored by the use of Au/Pd-supported
catalyst with high gold content, confirming once again the importance of synthesizing the
bimetallic active phase with a specific metal molar ratio.
Materials 2016, 9, 550 13 of 25

reaction mixture (Figure 11). The oxidation of the primary alcohol side-chain, necessary to form the
FDCA, is a more demanding process and proceeds with a significant rate at temperatures higher than
80 C. Therefore, this step is favored by the use of Au/Pd-supported catalyst with high gold content,
confirming
Materials 2016,once
9, 550 again the importance of synthesizing the bimetallic active phase with a specific13
metal
of 25
Materials 2016, 9, 550 13 of 25
molar ratio.

Figure 10. FDCA

Figure 10. FDCA selectivity
selectivity for
for TiO
TiO2-supported
-supported Au/Pd
Au/Pdcatalysts
catalystsat
atdifferent
different reaction
reaction temperatures.
temperatures.
Figure 10. FDCA selectivity for TiO22-supported Au/Pd catalysts at different reaction temperatures.
Reaction
Reaction conditions:
conditions: 10
10 bar O22,, H
H22O
Oas
as solvent,
solvent, HMF:NaOH:metal
HMF:NaOH:metal 1:2:0.01,
1:2:0.01, 44 h.
h. Results
Results are
are given
given at
Reaction conditions: 10 bar O2, H2O as solvent, HMF:NaOH:metal 1:2:0.01, 4 h. Results are given at
total conversion of HMF.
total conversion of HMF.

Figure 11. Products selectivity for TiO2 -supported Au/Pd-based catalysts. Reaction conditions: 90 C,
Figure
10 bar O11. Products selectivity for TiO2-supported Au/Pd-based
4 h. Resultscatalysts.
are givenReaction conditions:
of90 C,
Figure 2, H
11. 2 O as solvent,
Products HMF:NaOH:metal
selectivity 1:2:0.01,
for TiO2-supported Au/Pd-based catalysts. at total conversion
Reaction conditions: HMF.
90 C,
10 bar O2, H2O as solvent, HMF:NaOH:metal 1:2:0.01, 4 h. Results are given at total conversion of HMF.
10 bar O2, H2O as solvent, HMF:NaOH:metal 1:2:0.01, 4 h. Results are given at total conversion of HMF.
Although the type of metal site played a pivotal role, it must be noticed that even the support can
Although the type of metal site played a pivotal role, it must be noticed that even the support
Although
strongly the the
influence typecatalytic
of metalactivity
site played
in HMF a pivotal role,As
oxidation. it must be noticed
an example, thatofeven
the use the oxide
cerium supportto
can strongly influence the catalytic activity in HMF oxidation. As an example, the use of cerium
can strongly
support influence
bimetallic the catalytic
nanoparticles hadactivity in HMF
a detrimental oxidation.
effect on FDCA As production
an example,with the respect
use of tocerium
TiO
oxide to support bimetallic nanoparticles had a detrimental effect on FDCA production with respect2
oxide
samplesto support bimetallic
(Figure 12). Indeed,nanoparticles
in the case ofhad a detrimental
cerium oxide, theeffect on FDCA
presence production
of a second metal with
in therespect
active
to TiO2 samples (Figure 12). Indeed, in the case of cerium oxide, the presence of a second metal in the
to TiOseems
phase 2 samples (Figurethe
to prevent 12).interaction
Indeed, inbetween
the case gold
of cerium oxide,
and ceria the presence
support, which ofwasa second metal intothe
demonstrated be
active phase seems to prevent the interaction between gold and ceria support, which was
active
the keyphase seems
factor for HMFtooxidation
prevent over
the this
interaction between
system [51]. gold these
However, and differences
ceria support,can be which was
overcome
demonstrated to be the key factor for HMF oxidation over this system [51]. However, these
demonstrated to be the
increasing the reaction key factoratfor
temperature: 95 HMF
C, theoxidation
FDCA yield over this system
is around [51].
100% for bothHowever,
systems. these
differences can be overcome increasing the reaction temperature: at 95 C, the FDCA yield is around
differences
These can databehighlighted
overcome increasing the reaction temperature:
that the rate-limiting at 95 C,(alcohol
step of the reaction the FDCA yield is around
oxidation) can be
100% for both systems.
100% for both
promoted systems.
either by the use of the appropriate metal phase or by the increase in temperature. The right
These data highlighted that the rate-limiting step of the reaction (alcohol oxidation) can be
These
active phasedatathathighlighted
has to be usedthatdepends
the rate-limiting step support.
on the chosen of the reaction (alcohol
Generally, using oxidation) can be
titania to support
promoted either by the use of the appropriate metal phase or by the increase in temperature. The
promoted
bimetallic either by the use
nanoparticles, an of the appropriate
enhancement in themetal phase
catalytic or by can
activity the increase
be achievedin temperature.
especially whenThe
right active phase that has to be used depends on the chosen support. Generally, using titania to
right active phase that has to be used depends on the chosen support. Generally, using titania to
support bimetallic nanoparticles, an enhancement in the catalytic activity can be achieved especially
support bimetallic nanoparticles, an enhancement in the catalytic activity can be achieved especially
when metals are alloyed in the ratio Au:Cu 3:1. On the other hand, it seems not to be worth using
when metals are alloyed in the ratio Au:Cu 3:1. On the other hand, it seems not to be worth using
bimetallic nanoparticles when ceria is used as the support. Au/Ce is the best catalyst, and the
bimetallic nanoparticles when ceria is used as the support. Au/Ce is the best catalyst, and the
addition of copper in different amounts worsens the activity (Figure 13). Using cerium
addition of copper in different amounts worsens the activity (Figure 13). Using cerium
Materials 2016, 9, 550 14 of 25

metals are alloyed in the ratio Au:Cu 3:1. On the other hand, it seems not to be worth using bimetallic
nanoparticles when ceria is used as the support. Au/Ce is the best catalyst, and the addition of
Materials 2016, 9, 550 14 of 25
copper in
Materials different
2016, 9, 550 amounts worsens the activity (Figure 13). Using cerium oxide-supported catalysts, 14 of 25
a proper interaction between gold and the support must be guaranteed to strength the catalytic
production, the support effect must be taken into consideration and the choice of the best active activity.
production,
This means the in
that, support
order effect
to designmust be taken
a catalyst withinto consideration
improved and the choice
FDCA production, of the best
the support effectactive
must
phase depends on the selected support.
phase depends on the selected support.
be taken into consideration and the choice of the best active phase depends on the selected support.

Figure
Figure 12.
12. FDCA
FDCA selectivity
selectivity achieved
achieved using
using the
the Au/Cu
Au/Cucatalyst
catalystin
inthe
the ratio
ratio of
of 3:1
3:1 supported
supported on
on TiO
TiO2
Figure 12. FDCA selectivity achieved using the Au/Cu catalyst in the ratio of 3:1 supported on TiO22
and
and CeOCeO at different
2at different temperatures.
temperatures. Reaction Reaction conditions:
conditions:
2 2 at different temperatures. Reaction conditions: 10 bar O , H
2 10
10O bar
as O 2, H
solvent, 2O as solvent,
HMF:NaOH:metal
2 bar O2, H2O as solvent,
and CeO
HMF:NaOH:metal
1:4:0.01, 4 h. Results1:4:0.01, 4 h.atResults
are given are given of
total conversion at total
HMF.conversion of HMF.
HMF:NaOH:metal 1:4:0.01, 4 h. Results are given at total conversion of HMF.

13. FDCA
Figure 13.
Figure FDCA selectivity
selectivityasasa afunction of of
function copper
copper content in bimetallic
content catalyst
in bimetallic whenwhen
catalyst TiO2 and
TiO2CeO
and2
Figure
are used 13.asFDCA
the selectivity
support. as a function
Reaction of copper
conditions: 70 content
C, 10 bar O in, bimetallic
H O as catalyst
solvent, when TiO2 and
HMF:NaOH:metal
CeO2 are used as the support. Reaction conditions: 70 C, 10 bar O2, H2O as solvent,
2 2
CeO2 are
1:4:0.01, 4 h.used as are
Results thegiven
support.totalReaction conditions: 70 C, 10 bar O2, H2O as solvent,
HMF:NaOH:metal 1:4:0.01, 4 h.atResults
conversion
are given of HMF.conversion
at total of HMF.
HMF:NaOH:metal 1:4:0.01, 4 h. Results are given at total conversion of HMF.

With theaim
With the aimofof increasing
increasing FDCAFDCA production,
production, the prepared
the prepared catalysts
catalysts have
have been been calcined
calcined at
at different
With the aim of increasing FDCA production, the prepared catalysts have been calcined at
different temperatures.
temperatures. Our recent Our recent
data [51] data [51] demonstrated
demonstrated that both that
withboth with
Au-Ce Au-Ce
and and
for Au 3 Cufor Ausamples,
1 -Ce 3Cu1-Ce
different temperatures. Our recent data [51] demonstrated that both with Au-Ce and for Au3Cu1-Ce
samples, catalyticcan
catalytic activity activity can bebyincreased
be increased removingby removing polyvinylpyrrolidone
polyvinylpyrrolidone (PVP) from the(PVP) from
catalyst the
surface.
samples, catalytic activity can be increased by removing polyvinylpyrrolidone (PVP) from the
catalyst surface.
In fact, metal In fact, metal
nanoparticles, nanoparticles,
deposited onto the deposited
support, areonto the support,
surrounded are surrounded by
by polyvinylpyrrolidone,
catalyst surface. In fact, metal nanoparticles, deposited onto the support, are surrounded by
polyvinylpyrrolidone,
the stabilizing agent usedtheduring
stabilizing agent used
the synthetic during(as
procedure thereported
synthetic procedure
in Table (asMaterials
5 in the reportedandin
polyvinylpyrrolidone, the stabilizing agent used during the synthetic procedure (as reported in
Table 5 in the Materials and Method section), which can actually prevent a proper interaction
Table 5 in the Materials and Method section), which can actually prevent a proper interaction
between the substrate and the metal active site and the deep contact between the metal and the
between the substrate and the metal active site and the deep contact between the metal and the
support. TGA curves reported in Figure 14 show an increase in catalyst weight loss due to PVP
support. TGA curves reported in Figure 14 show an increase in catalyst weight loss due to PVP
combustion with the copper content. This is due to the presence of a higher amount of PVP on
combustion with the copper content. This is due to the presence of a higher amount of PVP on
Au/Cu samples.
Materials 2016, 9, 550 15 of 25

Method section), which can actually prevent a proper interaction between the substrate and the metal
active site and the deep contact between the metal and the support. TGA curves reported in Figure 14
show an increase in catalyst weight loss due to PVP combustion with the copper content. This is due
to Materials
the presence
2016, 9, of
550a higher amount of PVP on Au/Cu samples. 15 of 25

Figure14.
14.TGA
TGAcurves
curves for
for Au/Cu-CeO
Au/Cu-CeO2 catalysts.
Figure 2 catalysts.

Due to the enhanced interaction of metal nanoparticles with reactants and support, once PVP
was Due to the by
removed enhanced interaction
combustion, Au-Ce of andmetal nanoparticles
AuCu-Ce with reactants
catalysts were calcined inand support,
static once PVP
air at different
wastemperatures, and their catalytic results are reported in Figure 15. Calcination at 300 C led different
removed by combustion, Au-Ce and AuCu-Ce catalysts were calcined in static air at to the
temperatures, and theiryield
catalytic resultsevery
are reported in Figure led to the
increase of the FDCA for almost sample, because this15. Calcination
temperature at 300
allows theCcomplete
increase of the FDCA
PVP combustion, yield for
as shown almost
in TGA every sample,
analysis. because
The beneficial thisoftemperature
effect the improvedallows the complete
interaction of the
PVP combustion,
substrate with theas metal
shownis in TGA analysis.
particularly evident The
forbeneficial
the Au-Ceeffect of the
catalyst. improved
Moreover, thisinteraction
catalyst is of
thecharacterized
substrate with by the metal
presence is particularly
of a smaller evident
amount for the Au-Ce
of residual PVPcatalyst.
from theMoreover, this catalyst
gold synthesis, and
consequently, itbyisthe
is characterized lesspresence
affected byof particle
a smaller growth.
amount Asof a matter
residualof PVP
fact, particle
from the sintering is fostered
gold synthesis, and
by the local exothermicity generated during PVP combustion, and it is directly
consequently, it is less affected by particle growth. As a matter of fact, particle sintering is fostered by correlated to PVP
thecontent. The calcination
local exothermicity of the during
generated catalystPVPat combustion,
200 C did not andpromote
it is directlyHMF oxidation,
correlated sincecontent.
to PVP this
Thetemperature
calcinationisof not high
the enough
catalyst at to remove
200 C didthe stabilizing
not promoteagent.HMF On the contrary,
oxidation, sincethe thisincrease in the is
temperature
notcalcination
high enough temperature
to remove uptheto stabilizing
400 C worsenedagent. the
On catalytic performance,
the contrary, the increasebasically
in thebecause of
calcination
particles growth. Moreover,
in bimetallic systems, some segregation effects
temperature up to 400 C worsened the catalytic performance, basically because of particles growth. must be taken into
account, which can modify the catalytic properties. However, from the data reported in Figure 15, it
Moreover, in bimetallic systems, some segregation effects must be taken into account, which can
is evident that even bigger particles are active in HMF oxidation; this could be due to the presence of
modify the catalytic properties. However, from the data reported in Figure 15, it is evident that even
OH in water solution that promotes alcohol oxidation even with 20-nm particles [52]. In fact, the
bigger particles are active in HMF oxidation; this could be due to the presence of OH in water solution
hydroxyl absorption on the Au surface is considered to be fundamental to increase the activity of
that promotes alcohol oxidation even with 20-nm particles [52]. In fact, the hydroxyl absorption on the
Au-supported catalysts [5355].
Au surface is considered to be fundamental to increase the activity of Au-supported catalysts [5355].
Thus, the catalytic activity is influenced by PVP removal (which brings an enhanced interaction
Thus, the catalytic activity
active phase-support), particle is influenced
growth, phasebysegregation
PVP removal (which
(which brings
actually an enhanced
modifies the metalinteraction
active
active
phase)phase-support), particle growth,
and OH concentration in aqueous phase segregation (which actually modifies the metal active
phase.
phase) In OH concentration
andFigure 16, the comparison in aqueous
of thephase.
catalytic activity between Au-Ce and Au-Ti calcined
In Figure
catalysts 16, the comparison
is reported. Even if FDCA of theselectivity
catalytic activity
increases between
for theAu-Ce
catalyst and Au-Ti calcined
calcined at 300 C,catalysts
the
is reported. Even if FDCA selectivity increases C, the improvement
improvement due to thermal treatment is not asfor the catalyst
evident as it iscalcined
for Au-Ce, at 300
highlighting once again
duethetodifferences
thermal treatment
between theis not as evident
support used. as it is for Au-Ce, highlighting once again the differences
between the support used.
Materials 2016, 9, 550 16 of 25
Materials 2016, 9, 550 16 of 25
Materials 2016, 9, 550 16 of 25

Figure
15. 15.FDCAFDCA selectivityand
selectivity and particle size
size distribution
distribution(from XRD analysis) as aas
function of
FigureFigure 15. FDCA selectivity andparticle
particle size distribution (from
(from XRD
XRD analysis)
analysis) a function
as a function of of
calcination
calcination temperature.
temperature. Reaction
Reaction conditions: 70 C,
10 bar O , H O as solvent, HMF:NaOH:metal
Reactionconditions:
conditions: 70 C, 10
10bar
barOO2,2H,H O as solvent, HMF:NaOH:metal
2 2
calcination temperature. 70 C, 2O2 as solvent, HMF:NaOH:metal
1:4:0.01,
1:4:0.01, 4 h. 44Results
h. Results
areare given
given atat totalconversion
total conversion of HMF.
1:4:0.01, h. Results are given at total conversion of HMF.
of HMF.

Figure 16. FDCA selectivity as a function of calcination temperature. Reaction conditions: 70 C, 10 C, 10 bar
Figure 16. FDCA
Figure selectivity
16. FDCA as aasfunction
selectivity of of
a function calcination
calcinationtemperature.
temperature.Reaction
Reaction conditions: 70C,
conditions: 70 10
bar O2, H2O as solvent, HMF:NaOH:metal 1:4:0.01, 4 h. Results are given at total conversion of HMF.
O2 , Hbar
2 OOas solvent,
2, H HMF:NaOH:metal
2O as solvent, HMF:NaOH:metal 1:4:0.01, 4 h.4Results
1:4:0.01, are
h. Results given
are givenatattotal
total conversion
conversion ofofHMF.
HMF.
2.2.3. Catalytic Tests in the Hydrodechlorination of CF3OCFClCF2Cl
2.2.3.2.2.3. Catalytic Tests in the Hydrodechlorination of CF3OCFClCF2Cl
Catalytic Tests in the Hydrodechlorination of CF3 OCFClCF2 Cl
Today, the commercial production of trifluoromethyl trifluorovinyl ether (CF3OCF=CF2) is
Today, the commercial production of trifluoromethyl trifluorovinyl ether (CF3OCF=CF2) is
Today, on
based the CF
commercial
3OCFClCF2production
Cl precursor of trifluoromethyl
dechlorination [56] trifluorovinyl
and produces ether large
(CF OCF=CF
quantities2 ) isof
based
based on CF3OCFClCF2Cl precursor dechlorination [56] and produces large3 quantities of
on CFby-products,
3 OCFClCF such
2 Cl as ZnCl2. Adechlorination
precursor new approach, based [56] on Hproduces
and 2-assisted gas-phase
large dechlorination
quantities of over
by-products,
by-products, such as ZnCl2. A new approach, based on H2-assisted gas-phase dechlorination over
such metal-supported
as ZnCl2 . A newcatalysts,
metal-supported approach,
catalysts,
maybased
lead to
may lead to onaa H
new sustainable
2 -assisted
new
process dechlorination
gas-phase
sustainable
[57,58].
process [57,58]. over metal-supported
Hydrogen-assisted
catalysts, Hydrogen-assisted dechlorination
may lead to a newdechlorination
sustainable process(elimination
[57,58].of halogen atoms to form unsaturated
of halogen atoms to form
(elimination unsaturated
compounds) and hydrodechlorination (replacement of selected halogen atoms with hydrogen) have
Hydrogen-assisted dechlorination (elimination
compounds) and hydrodechlorination (replacementofofhalogen
selectedatoms
halogen toatoms
form unsaturated
with hydrogen) compounds)
have
received much attention in the literature as an option for the safe disposal of chlorofluorocarbon and
received much attention(replacement
and hydrodechlorination in the literatureof as selected
an option halogen
for the safe disposal
atoms of chlorofluorocarbon
with hydrogen) have receivedand
to produce valuable chemicals. Monometallic Pd, Ru or Pt materials were reported to be effective for
to produce
muchtheattention valuable chemicals.
in the literature Monometallic Pd, Ru
as an optiontoforethylene,or Pt materials
the safebut were
disposal reported to be effective
of chlorofluorocarbon for
and to
hydrodechlorination of dichloroethane this useful product was readily
the
produce hydrodechlorination of dichloroethane to ethylene, but this useful product was readily
converted into ethane over these catalysts [59]. Conversely, group IB-based monometallic Sn or Cu for
valuable chemicals. Monometallic Pd, Ru or Pt materials were reported to be effective
converted into ethane over these catalysts [59]. Conversely, group IB-based monometallic Sn or Cu
the hydrodechlorination of dichloroethane
catalysts are effective for to ethylene,
the full dechlorination but thishydrocarbons
of chlorinated useful product withwas readily
higher converted
selectivity
catalysts are effective for the full dechlorination of chlorinated hydrocarbons with higher selectivity
into ethane
toward over thesehowever,
ethylene; catalystssuch
[59].catalysts
Conversely, group
are less activeIB-based
under mildmonometallic
conditions Sn
andorcan
Cubecatalysts
easily are
toward ethylene; however, such catalysts are less active under mild conditions and can be easily
deactivated
effective [60].dechlorination
for the full For this reaction,of bimetallic
chlorinated catalysts, such as with
hydrocarbons Pt/Cu, Pt/Sn, selectivity
Pd/Cu and Pd/Ru [61],
deactivated [60]. For this reaction, bimetallic catalysts, such as Pt/Cu,higher
Pt/Sn, Pd/Cu andtoward ethylene;
Pd/Ru [61],
have
however, been proven to be much more selective toward ethylene than the monometallic noble metals.
have such
been catalysts
proven toare less active
be much more under
selectivemild conditions
toward ethylene and can
than thebemonometallic
easily deactivated [60]. For this
noble metals.
reaction, bimetallic catalysts, such as Pt/Cu, Pt/Sn, Pd/Cu and Pd/Ru [61], have been proven to be
much more selective toward ethylene than the monometallic noble metals.
Materials 2016, 9, 550 17 of 25
Materials 2016, 9, 550 17 of 25

Based ononthisthis
information, in ourinrecent
information, our work,
recentwework,
investigated the production
we investigated theof trifluoromethyl
production of
trifluorovinyl ether by the hydrogen-assisted dechlorination of
trifluoromethyl trifluorovinyl ether by the hydrogen-assisted dechlorination CF 3 OCFClCF
of CF Cl using
2 3OCFClCF bimetallic
2Cl using

Pd/Cu catalysts
bimetallic Pd/Cusupported
catalysts over mesostructured
supported silica. Since the
over mesostructured hydrodechlorinating
silica. performances
Since the hydrodechlorinating
were demonstrated
performances were to be strongly related
demonstrated to the Pd/Cu
to be strongly relatedinteraction
to the Pd/Cuand the size of metallic
interaction and the particles,
size of
metallic particles, Pd/Cu-MCM-41 catalysts were prepared from pre-formed Pd/Cu nanoparticles,the
Pd/Cu-MCM-41 catalysts were prepared from pre-formed Pd/Cu nanoparticles, to verify to
possibility of reactionof
verify the possibility optimization [62].
reaction optimization [62].
Scheme 3 reports the main productsproducts detected
detected during
during the
the catalytic
catalytic tests. The main
tests. The main product,
product,
OCF=CF2 2(MVE),
CF33OCF=CF (MVE), Cl/H
Cl/H substitution
substitution by-products
by-products like
like CF CF3 OCFHCF
3OCFHCF 2Cl and2 Cl
CFand CF3 OCFClCF
3OCFClCF 2H (AMH),2H
(AMH), de-fluorinated
de-fluorinated by-products
by-products like CFlike CF3 OCCl=CF
3OCCl=CF 2 (AMH*)
2 (AMH*) andand productssuch
products suchas as CF
CF33OCFHCF2H
(AMH2)) were
were formed in different quantities depending on the catalytic systems used.

Scheme 3.
Scheme 3. General
General reaction
reaction scheme
scheme for
for CF
CF33OCFClCF
OCFClCF22Cl
Cl hydrodechlorination.
hydrodechlorination.

PdCu-MCM-41 catalysts were demonstrated to be able to activate H2 and to anchor the

PdCu-MCM-41 catalysts were demonstrated to be able to activate H2 and to anchor the
chlorofluorinated reagents. Moreover, the presence of Cu decreases the Pd hydrogenating activity,
chlorofluorinated reagents. Moreover, the presence of Cu decreases the Pd hydrogenating
increasing the selectivity in the desired product [62,63]. However, catalytic performances were
activity, increasing the selectivity in the desired product [62,63]. However, catalytic performances
demonstrated to depend on the synthesis procedure, silica source and template removal procedure.
were demonstrated to depend on the synthesis procedure, silica source and template removal
Indeed, catalyst preparation determined the size and composition of metallic particles and
procedure. Indeed, catalyst preparation determined the size and composition of metallic particles and
Pd/Cu interaction.
Pd/Cu interaction.
The hexagonal structure of MCM-41 (Figure 17a), the large specific surface area (1035 m 2g1)
The hexagonal structure of MCM-41 (Figure 17a), the large specific surface area (1035 m2 g1 )
and the pore volume (1.275 cm g3 )
3 1 were preserved after the inclusion of active species using Pd/Cu
and the pore volume (1.275 cm g 1 ) were preserved after the inclusion of active species using
preformed nanoparticles and led to small and well-dispersed bimetallic species in the MCM-41
Pd/Cu preformed nanoparticles and led to small and well-dispersed bimetallic species in the MCM-41
structure. However, template removal by calcination caused both the increase of the particle size
structure. However, template removal by calcination caused both the increase of the particle size and
and the oxidation of the metal. As a consequence, most of the investigated materials contained
the oxidation of the metal. As a consequence, most of the investigated materials contained different
different species: (i) Pd/Cu mixed species; (ii) well-dispersed copper oxide; and (iii) segregated Pd
species: (i) Pd/Cu mixed species; (ii) well-dispersed copper oxide; and (iii) segregated Pd species.
species.
Pd/Cu species were demonstrated to be mainly responsible for the formation of the desired
Pd/Cu species were demonstrated to be mainly responsible for the formation of the desired
product (CF3 OCF=CF2 ), while the segregated Pd and Cu species caused different selectivity in side
product (CF3OCF=CF2), while the segregated Pd and Cu species caused different selectivity in side
reactions (Figure 17b). Indeed, a high amount of palladium led to the formation of hydrogenated
reactions (Figure 17b). Indeed, a high amount of palladium led to the formation of hydrogenated
molecules, such as CF OCFHCF H, while particles enriched in palladium promoted the formation of
molecules, such as CF33OCFHCF22H, while particles enriched in palladium promoted the formation of
CF OCH=CF . In addition, Pd/Cu nanoparticles with a low content of Pd induce F/Cl substitution
CF33OCH=CF2.2 In addition, Pd/Cu nanoparticles with a low content of Pd induce F/Cl substitution
with the production of a significant amount of CF3 OCCl=CF2 .
with the production of a significant amount of CF3OCCl=CF2.
To avoid the segregation of the oxides during template removal, ionic exchange [64] was
To avoid the segregation of the oxides during template removal, ionic exchange [64] was used
used rather than calcination, demonstrating the possibility to control the properties of bimetallic
rather than calcination, demonstrating the possibility to control the properties of bimetallic
Pd/Cu-MCM-41 through the careful choice of the template elimination treatment.
Pd/Cu-MCM-41 through the careful choice of the template elimination treatment.
Materials 2016, 9, 550 18 of 25
Materials 2016, 9, 550 18 of 25

FigureFigure 17.TEM
17. (a) (a) TEM images
images of the
of the Pd/Cu-MCM-41 sample
Pd/Cu-MCM-41 sample before
beforethe
thetemplate removal
template (1), (1),
removal afterafter
the the
ionic exchange (2) and the calcination (3); (b) selectivity in the desired product (CF3OCF=CF2) as a
ionic exchange (2) and the calcination (3); (b) selectivity in the desired product (CF3 OCF=CF2 ) as
function
a function of time.
of time.

3. Materials and Methods

3. Materials and Methods
The following analytical grade reagents were used for sols and supported catalysts
The following
preparation: analytical
HAuCl 43H2O, grade
CuSOreagents were used
45H2O, NaOH, AgNO for sols 2and
3, PdCl supported catalysts
, polyvinylpyrrolidone PVPpreparation:
(Mwa
HAuCl 3H
29,000),
4 2 O,
all CuSO
from 5H O,
Sigma-Aldrich
4 2 NaOH, AgNO
(Sigma-Aldrich,3 , PdCl
St. , polyvinylpyrrolidone
Louis,
2 MO, USA), and PVP
D(+)glucose (Mwa 29,000),
(Merck,
all from Sigma-Aldrich (Sigma-Aldrich, St. Louis, MO, USA), and D(+)glucose (Merck, Darmstadt,
Darmstadt, Germany), TiO 2 anatase (DT51 Millennium Chemicals, Baltimore MD, USA), CeO 2

(Evonik VP AdNano 90, Essen, Germany). Metallic nanoparticles

Germany), TiO2 anatase (DT51 Millennium Chemicals, Baltimore, MD, USA), CeO2 (Evonik VP were prepared following a
AdNanopatented90, procedure [8], which provides
Essen, Germany). Metallicstable nanosols by using
nanoparticles werea microwave-assisted
prepared following eco-friendly
a patented
procedure [8], which provides stable nanosols by using a microwave-assisted eco-friendly and
method. MCM-41-supported catalyst were prepared by using sodium silicate as the silica source method.
cetyltrimethylammonium bromide (99%, Sigma-Aldrich, CTAB) as the structure-directing template.
MCM-41-supported catalyst were prepared by using sodium silicate as the silica source and
The synthetic procedures involved the preparation of the gel, hydrothermal treatment and
cetyltrimethylammonium bromide (99%, Sigma-Aldrich, CTAB) as the structure-directing template.
calcination, as reported in a previous paper [65]. The following reagents were used for catalytic
The synthetic
reactions:procedures
4-nitrophenolinvolved
(Sigma the preparation
Aldrich), NaBH4of the gel,
(Sigma hydrothermal
Aldrich), treatment and calcination,
5-hydroxymethylfurfural (Alfa
as reported in a previous
Aesar, Karlsruhe, Germany). paper [65]. The following reagents were used for catalytic reactions:
4-nitrophenol (Sigma Aldrich), NaBH4 (Sigma Aldrich), 5-hydroxymethylfurfural (Alfa Aesar,
3.1. Nanoparticles
Karlsruhe, Germany).Synthesis
Metal nanoparticles were prepared using microwave heating. The microwave system used was
3.1. Nanoparticles Synthesis
a MicroSYNTHplus (Milestone, Bergamo, Italy), whose reaction chamber is provided with magnetic
stirring,
Metal a reflux system
nanoparticles wereand an optical
prepared usingfiber temperature
microwave controller.
heating. The microwave
The microwave power
system usedis was
generated by 2 800-W magnetrons with a frequency of 2.45 GHz. In order to follow
a MicroSYNTHplus (Milestone, Bergamo, Italy), whose reaction chamber is provided with magnetic the scheduled
heating ramp, the power is continuously supplied and automatically modulated by software; for
stirring, a reflux system and an optical fiber temperature controller. The microwave power is generated
each ramp, only the maximum deliverable power can be imposed.
by 2 800-W magnetrons with a frequency of 2.45 GHz. In order to follow the scheduled heating ramp,

the power Au colloids: In asupplied
is continuously typical reaction, PVP (0.35modulated
and automatically g) and glucose (0.40 g)for
by software; were
eachmixed
ramp,inonly
a the
round-bottomed flask containing
maximum deliverable power can be imposed. water (80 mL), and the solution was heated at ambient
pressure using microwave stimulation to 90 C (heating rate 30 Cmin1). At this temperature,
aqueous NaOH
Au colloids: In a (10 mL, 0.88
typical M) and PVP
reaction, HAuCl 4 (10 mL,
(0.35 0.11 M)
g) and were added
glucose to the
(0.40 g) flaskmixed
were and in
stirred for 2.5 min.
a round-bottomed flaskAfter the reaction,
containing watera red,
(80 stable
mL), suspension of gold was
and the solution nanoparticles
heated atwith a
ambient
concentration of 0.011 M (0.2 wt %) was obtained.
1
pressure using microwave stimulation to 90 C (heating rate 30 C min ). At this temperature,
Cu colloids were obtained through the reduction of CuSO45H2O. In a typical experiment, PVP
aqueous NaOH (10 mL, 0.88 M) and HAuCl4 (10 mL, 0.11 M) were added to the flask and stirred
(5.66 g), glucose (7.2 g) and NaOH (1.2 or 2.4 g) were mixed in a round-bottomed flask
for 2.5 min. After the reaction, a red, stable suspension of gold nanoparticles with a concentration
containing water (180 mL), and then, the solution was microwave heated at ambient pressure
of 0.011 M (0.2
to 100 wt %) was
C (heating rateobtained.
30 Cmin1). At this temperature, the CuSO45H2O solution (20 mL,
Cu colloids
0.165 M)were
was obtained
added, and through the reduction
the temperature of CuSO4for
was maintained 5Ha2time
O. Inranging
a typical experiment,
from 1040 min. PVP
(5.66 g), glucose (7.2 g) and NaOH (1.2 or 2.4 g) were mixed in a round-bottomed flask containing
water (180 mL), and then, the solution was microwave heated at ambient pressure to 100 C
(heating rate 30 C min1 ). At this temperature, the CuSO4 5H2 O solution (20 mL, 0.165 M)
was added, and the temperature was maintained for a time ranging from 1040 min. In order
to achieve the pure metallic phase, both the NaOH/metal molar ratio and reaction time were
Materials 2016, 9, 550 19 of 25

set as reported in Table 5. A red sol with a solid loading of 0.1 wt % and a time stability of 24 h
was obtained.
Au/Cu colloids: The bimetallic colloids, Au/Cu, were obtained through the microwave
(MW)-assisted co-reduction of HAuCl4 and CuSO4 5H2 O. Au/Cu were prepared on the basis of
the experimental set up used for the monometal particles, in order to work with the conditions the
most useful for both metals. For this reason PVP, glucose and NaOH contents were optimized for
each sample depending on the Au/Cu ratio and with the purpose to ensure the total formation of
the copper metallic phase, the reaction time was set to 40 min. However, in order to decrease the
nanoparticle size, some syntheses were performed with a reaction time of 2.5 min. In a typical
reaction for preparing Au1 Cu1 sol, PVP (1 g), NaOH (0.52 g) and glucose (1.27 g) were mixed in
a round-bottomed flask containing water (180 mL), and the solution was heated at ambient
pressure to 90 C (heating velocity 30 C min1 ) using microwaves. At this temperature,
a solution containing both HAuCl4 (20 mL, 0.025 M) and CuSO4 (0.025 M) with a Au/Cu molar
ratio of 1 was added to the flask with stirring, and the temperature was maintained for 40 or
2.5 min. The samples were prepared with Au/Cu molar ratios of 3/1, 1/1, 1/3, 1/6 (Table 5) and
a total solid concentration of 0.005 M. After the reaction, a brown, stable suspension of bimetallic
nanoparticles was obtained.
Pd colloids were synthesized through the reduction of PdCl2 . The dissolution of PdCl2 was
facilitated by adding 3 drops of concentrated HCl (37%) and by keeping the solution at 90 C till
complete dissolution. The experiments were performed following the same procedure used for
gold colloids, but with a different metal concentration.
Pd/Cu and Pd/Au colloids: In a typical preparation of the Pd/Cu system, 0.062 g of CuSO4 5H2 O
were dissolved in 5 mL of water and 0.044 g of PdCl2 in 10 mL of H2 O. The so-obtained precursor
solutions were mixed together and then added under stirring to 85 mL of the microwave heated
(90 C) solution containing 0.51 g of PVP, 0.64 g of glucose and 0.26 g of NaOH. The reaction was
performed for 2.5 min, and the synthesized samples were produced by keeping the total metal
concentration at 0.005 M and respecting the molar ratio listed in Table 5. The same procedure was
followed for the Pd/Au colloids.

Table 5. The composition and the concentration of prepared bimetallic nanoparticles and the molar
ratio with reagents used during the synthesis.

%Au %Cu Cu/Au PVP/[Metal] Glucose/[Metal] NaOH/[Metal] [Metal]

Sample
(mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/L)
Au 100 0 - 3 2 8 0.011
Au3 Cu1 75 25 0.3 6 5 11 0.005
Au1 Cu1 50 50 1 9 7 13 0.005
Au1 Cu3 25 75 3 12 10 16 0.005
Au1 Cu6 16 84 6 13 10 17 0.005
Cu 0 100 - 15 12 18 0.017
%Pd %Au Pd/Au PVP/[Metal] Glucose/[Metal] NaOH/[Metal] [Metal]
Sample
(mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/L)
Pd 100 0 - 2.75 2.00 8.00 0.005
Pd3 Au1 75 25 3 2.75 2.00 8.00 0.005
Pd1 Au0.5 67 33 2 2.75 2.00 8.00 0.005
Pd1 Au1 50 50 1 2.75 2.00 8.00 0.005
Pd1 Au2 33 67 0.5 2.75 2.00 8.00 0.005
Pd1 Au3 25 75 0.33 2.75 2.00 8.00 0.005
Pd1 Au6 14 86 0.16 2.75 2.00 8.00 0.005
Pd1 Au9 10 90 0.11 2.75 2.00 8.00 0.005
%Pd %Au Pd/Au PVP/[Metal] Glucose/[Metal] NaOH/[Metal] [Metal]
Sample
(mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/L)
Pd1 Cu0.5 100 0 2 6.83 2.00 11.33 0.005
Pd1 Cu1 67 33 1 8.88 5.37 13.00 0.005
Pd1 Cu2 50 50 0.5 10.92 7.05 14.67 0.005
Pd1 Cu3 33 67 0.33 11.94 8.74 15.50 0.005
Pd1 Cu6 25 75 0.16 13.25 9.58 16.57 0.005
Materials 2016, 9, 550 20 of 25

3.2. Supported Catalysts Preparation

Monometallic and bimetallic catalysts supported on TiO2 and CeO2 were prepared by
immobilization on the support surface of the preformed colloids. Before use, the as-prepared sols
were concentrated and washed with distilled water using 50-KDa Amicon Ultra filters (Millipore) to
eliminate the excess PVP and other reagents dissolved in the aqueous media, and then, the colloids
were impregnated onto the supports with the incipient wetness impregnation method. For all samples,
the solvent was evaporated by thermal treatment at 120 C. The total metal loading of the catalyst was
always 1.5 wt %. The catalyst samples are denoted as Au-Ti, Cu-Ti, Pd-Ti and Aux Cuy -Ti, Pdx Auy -Ti,
Aux Cuy -Ce, where x and y refer to the Au:Cu or Pd:Au molar ratio and Ti and Ce refer to the TiO2 and
CeO2 supports (i.e., Au1 Cu1 -Ti indicates a TiO2 -supported sample synthesized with a Au:Cu molar
ratio of 1).
Pre-formed Pd/Cu colloids were included in the MCM-41 structure in the course of the synthesis
of the mesoporous material by a microwave-assisted synthesis. In particular, CTAB was solubilized in
the nanoparticle solution prepared by the reduction of CuSO4 and PdCl2 with D(+)glucose as reported
above; then, sodium silicate was added [62]. Slurries were microwave-hydrothermally treated at
125 C for 7 h. The template was removed by calcination at 540 C or with ionic exchange using
an ethanolic solution of NH4 NO3 .

3.3. Characterization of Metallic Sols

Metallic nanosols were characterized by optical spectroscopy (UV-VIS), dynamic light scattering
(DLS), X-ray diffraction (XRD), inductively-coupled plasma-atomic emission spectrometry (ICP-AES)
and transmission electron microscopy (TEM). UV-VIS extinction spectra were measured with a Lambda
35 spectrophotometer (Perkin Elmer, Waltham, MA, USA), using a quartz cuvette as the sample-holder.
Samples for UV-VIS spectroscopy were prepared by diluting the as-prepared colloidal suspension with
water in order to get into the cuvette the same metal concentration for every sample.
Dynamic light scattering (DLS) was used to monitor the hydrodynamic diameter and the particle
size distribution of the suspensions. Measurements were carried out by Nano S (Malvern, Malvern,
UK) working at the fixed angle of 173 . Samples were properly diluted with water and poured in
a polystyrene cuvette before measurement. The hydrodynamic diameter includes the coordination
sphere and the species adsorbed on the particle surface, such as stabilizers, surfactants and so forth.
DLS analysis provides also a polydispersion index parameter (PDI), ranging from 0 to 1, quantifying
the colloidal dispersion degree; for PDI below 0.2, a sol can be considered monodispersed.
Diffraction patterns were collected on the synthesized samples dripped on a glass slide and dried
at 100 C for 15 min. Analyses were performed by the Bruker D8 Advance diffractometer (Bruker,
Karlsruhe, Germany) operating in /2 configuration, with a LynxEye detector (20 80 2 range,
0.02 step size, 16 s time-per-step equivalent). The quantitative phase composition was performed by
using the Reference Intensity Ratio method RIR.
In order to calculate the reaction yield, the ionic fraction was separated from the sample and
analyzed by chemical analysis (ICP). Fifteen milliliters of suspension were typically centrifuged using
the ultra-centrifugal filter (UCF) unit (Amicon Ultra-15, 10 kDa, Millipore, Billerica, MA, USA), with
a centrifugal force of 5000 rpm and a spin time of 30 min. The UCF unit allows retaining NPs and
filtrating away the unreacted ions; this way, 10 mL of filtered solvent, which contains the dissolved
metal ions, were subjected to elemental analysis using inductively coupled plasma-optical emission
spectrometry (ICP-OES) (Liberty 200, Varian, Santa Clara, CA, USA).
The observation of the particle size distribution and morphology was performed using
a transmission electron microscope (TEM, Tecnai F20, FEI, Hillsboro, OR, USA). Nanoparticles were
dispersed on a standard copper grid for TEM by dripping the prepared solutions, which were dried in
air then treated at 100 C for 5 min.
Materials 2016, 9, 550 21 of 25

3.4. Characterization of Supported Catalysts

To verify the behavior of different catalysts under thermogravimetric analysis, TGA was obtained
using a Rheometric Scientific STA1500 analyzer while heating the sample in air from 25 C600 C.

3.5. Catalytic Tests

Probe reaction with 4-Nitrophenol: The catalytic reduction of 4-nitrophenol by NaBH4 was studied
at room temperature (25 C) in a standard quartz cuvette with a 1-cm path length and about a 3-mL
volume. The prepared samples were properly diluted with distilled water in order to achieve
a metal concentration of 1.1 102 mM. Thus, 10 mL of diluted suspensions were mixed with
5 mL of a 4-nitrophenol solution (9.0 102 mM) and with 1 mL of a NaBH4 aqueous solution
(0.72 M). An aliquot of the solution was poured into the quartz cuvette, and the absorption spectra
were collected by a Lambda 35 spectrophotometer (Perkin Elmer, Waltham, MA, USA) in the
range between 250 and 500 nm. The rate constants of the reduction process were determined
by measuring the change in absorbance at 400 nm, corresponding to the 4-nitrophenolate ion,
as a function of time. Although the 4-NP solution absorbs at 317 nm, a second peak appears at
400 nm after the addition of the NaBH4 solution, forming the 4-nitrophenolate ion. The reaction
is of second order (1), but as the concentration of NaBH4 is in large excess with respect to the
reagent (4-NP) one, the reduction rate can be regarded as independent from NaBH4, changing
the system in a pseudo first order reaction (2). Therefore, the rate constants of the reaction can be
determined by measuring the change in absorbance at 400 nm, the wavelength typical of 4-NP in
alkaline condition, as a function of time.
5-hydroxymehtyfurfural (HMF) oxidation: HMF oxidation was carried out in a 100-mL autoclave
reactor (Parr Instrument) equipped with a mechanical stirrer (0600 rpm) and tools for the
measurement of temperature and pressure. The reactor was charged with 25 mL of distilled
water, the appropriate amount of 5-hydroxymethylfufural, NaOH and catalyst (HMF/metal
molar ratio = 100). The autoclave was purged 3 times with O2 (5 bar) and then pressurized at
10 bar. If not differently indicated, the temperature was set at 70 C, and the reaction mixture
was stirred at 400 rpm for 4 h. At the end of the reaction, the reactor was cooled down to room
temperature, and the solution was filtered, diluted 5 times and analyzed with an Agilent Infinity
1200 liquid chromatograph equipped with a Aminex HPX 87-H 300 mm 7.8 mm column using
a 0.005 M H2 SO4 solution as the mobile phase. The identification of compounds was achieved by
calibration using reference commercial samples.
Catalytic hydrodechlorination of CF3 OCFClCF2 Cl: The hydrogen-assisted dechlorination of
CF3 OCFClCF2 Cl to CF3 OCF=CF2 was performed in a 10 mm diameter down-flow Hastelloy
tubular reactor. The catalysts were pelletized and reduced before catalytic tests. A mixture of
CF3 OCFClCF2 Cl (19% v/v), H2 (19% v/v) and N2 was fed to the reactor for 20 h of time-on-stream
with a contact time of 10 s at 250 C and 1 atm. The obtained products were sampled before
a water scrubber and analyzed with a TCD-equipped gas chromatograph.

4. Conclusions
A green and versatile approach was developed to produce stable mono- and bi-metallic colloids
(Au/Cu, Pd/Au, Pd/Cu) with a total reaction yield. The method was optimized by means of
microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild
and non-toxic reducer and PVP as the chelating agent. Compositional and particle size-control were
achieved and widely supported by UV-VIS, DLS, TEM and XRD analyses; moreover, the so-prepared
systems exhibited long-term stability.
All of the prepared particles acted as effective catalysts in the reduction of 4-NP to 4-AP, exploited
as the probe reaction. The catalytic activity observed in the first probe test showed significant
differences among the samples, evidencing for the Pd-based catalysts the best performances and
noticeable synergistic effects for AuCu and PdAu alloys at intermediate composition.
Materials 2016, 9, 550 22 of 25

Furthermore, the obtained mono- and bi-metallic colloids, employed to prepare TiO2 - and
CeO2 -supported catalysts, were tested for the liquid phase oxidation of 5-hydroxymethylfufural
(HMF) to 2,5-furandicarboxylic acid (FDCA). Au/Cu and Au/Pd bimetallic catalysts led to an increase
in FDCA selectivity, demonstrated for specific metal molar ratios. Even the choice of support was
important to enhance the catalytic properties of the metal active phase.
Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41 silica.
The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3 OCFClCF2 Cl to
CF3 OCF=CF2 , evidencing that the presence of Cu decreases the Pd hydrogenating activity, so increasing
the selectivity in the desired product.
The preparation of supported bimetallic catalysts using size-controlled preformed nanoparticles,
whose particle size is established before the deposition and/or incorporation on the metal oxide
support, was demonstrated to be a very efficient synthetic procedure. Nevertheless, the optimized
temperature of the thermal treatment must be carefully chosen in order to preserve particle size and
morphology, avoiding sintering and phase segregation effects.

Supplementary Materials: The following are available online at www.mdpi.com/1996-1944/9/7/550/s1.

Author Contributions: Magda Blosi, Alice Lolli, Patricia Benito and Stefania Albonetti designed the experiment
and wrote the paper. Simona Ortelli, Sara Andreoli and Alice Lolli performed the experiments. Stefania Albonetti,
Magda Blosi, Anna Luisa Costa, Michele Dondi and Patricia Benito analyzed the data.
Conflicts of Interest: The authors declare no conflict of interest.

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