Au-based catalysts: Electrochemical characterization for structural insights

Article abstract of DOI:10.3390/molecules21030261

Au-based catalysts are widely used in important processes because of their peculiar characteristics. The catalyst performance depends strongly on the nature and structure of the metal nanoparticles, especially in the case of bimetallic catalysts where synergistic effects between the two metals can be occasionally seen. In this paper, it is shown that electrochemical characterisation (cyclovoltammetry CV and electrochemical impedance spectroscopy EIS) of AuPd systems can be used to determine the presence of an electronic interaction between the two metals, thus providing a strong support in the determination of the nature of the synergy between Au and Pd in the liquid phase oxidation of alcohols. However, it seems likely that the strong difference in the catalytic behavior between the single metals and the bimetallic system is connected not only to the redox behaviour, but also to the energetic balance between the different elementary steps of the reaction.

Full text of DOI:10.3390/molecules21030261

molecules
Article
Au-Based Catalysts: Electrochemical Characterization
for Structural Insights
Valentina Pifferi, Carine E. Chan-Thaw, Sebastiano Campisi, Anna Testolin, Alberto Villa,
Luigi Falciola and Laura Prati *
Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano, Italy;
valentina.pifferi@unimi.it (V.P.); carine.chanthaw@unimi.it (C.E.C.-T.); sebastiano.campisi@unimi.it (S.C.);
anna.testolin@studenti.unimi.it (A.T.); alberto.villa@unimi.it (A.V.); luigi.falciola@unimi.it (L.F.)
* Correspondence: Laura.Prati@unimi.it; Tel.: +39-02503-14357
Academic Editor: Sonia A. C. Carabineiro
Received: 29 January 2016 ; Accepted: 22 February 2016 ; Published: 25 February 2016
Abstract: Au-based catalysts are widely used in important processes because of their peculiar
characteristics. The catalyst performance depends strongly on the nature and structure of the metal
nanoparticles, especially in the case of bimetallic catalysts where synergistic effects between the
two metals can be occasionally seen. In this paper, it is shown that electrochemical characterisation
(cyclovoltammetry CV and electrochemical impedance spectroscopy EIS) of AuPd systems can be
used to determine the presence of an electronic interaction between the two metals, thus providing a
strong support in the determination of the nature of the synergy between Au and Pd in the liquid
phase oxidation of alcohols. However, it seems likely that the strong difference in the catalytic
behavior between the single metals and the bimetallic system is connected not only to the redox
behaviour, but also to the energetic balance between the different elementary steps of the reaction.
Keywords: bimetallic catalyst characterization; cyclovoltammetry; electrochemical impedance
spectroscopy; AuPd catalysts; synergistic effect
1. Introduction
Gold nanoparticles have attracted more and more interest due to their special activity in catalytic
reactions such as low-temperature oxidation of CO, hydrochlorination of alkyne, liquid phase oxidation
of alcohols and polyols, etc. [1]. However, concerning selective liquid phase oxidation, despite the
peculiar selectivity shown, gold catalysts suffer from a severe limitation consisting in the use of a
basic environment. This drawback has a strong impact on the use of gold catalysts and promoted
the evolution of monometallic into bimetallic systems. Indeed, Au in recent years has been used
as a modifier of more active metals, even in homogeneous catalysis (Pd [2–7]; Pt [8,9]; Ru [10–12];
Ag [13 14]; Cu [15], etc.). In particular, the addition of Au to Pd or Pt catalysts in the liquid phase
,
˝
oxidation of polyols (sorbitol and glycerol) in the presence of O2 under mild conditions (<60 C
and <4 atm) not only improves catalytic activity and selectivity to the desired product, but also
enhances the resistance to poisoning [16]. The presence of a synergistic effect has been connected to an
intimate contact between the two metals and possibly to an isolation of the effective active sites [17,18].
However, the full understanding of Au-metal synergistic effects still remains uncertain because of
two different reasons. The first one lies in the difficulties encountered in synthesizing bimetallic
systems showing a homogeneous structure (alloy, core-shell, decorated nanoparticles) and composition
throughout the whole sample. Indeed, segregation of metals and/or different ratio of metals present in
the nanoparticles are the problems that often affect the preparation of these systems [19,20]. The second
Molecules 2016, 21, 261; doi:10.3390/molecules21030261
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reason, even sometimes connected with the first one, is the lack of full characterization of a significative
sample. HRTEM connected with EDX analyses and sometimes correlated with cross sectional analysis
can be helpful in determining the structure and composition of nanoparticles [1,21,22], but are often
performed on a few nanoparticles with the risk of not being representative of the whole sample.
The electrochemical behavior of the nanoparticles have been recently introduced as an important
tool to determine the structure of nanoparticles [23,24] with the advantages of being practical and
providing an overlook of a significative amount of sample. Therefore, we used Cyclic Voltammetry
(CV) and Electrochemical Impedance Spectroscopy (EIS) techniques to characterize AuPd bimetallic
nanoparticles and to establish a correlation between their electrochemical behavior and catalytic
performances in the selective oxidation of glycerol. AuPd bimetallic nanoparticles prepared by
coreduction allowed us to have alloyed samples which present an evident synergistic effect between
Au and Pd, as already reported [25]. CV and EIS clearly pointed out that the electronic behavior of
both metals are profoundly modified when alloyed, showing a lower potential of oxide reduction with
respect to single Pd and higher than Au. This finding states that the electron transfer resistance is Pd
> AuPd > Au. For explaining the higher catalytic activity of the AuPd alloyed particles compared
to the ones of Pd and Au in catalytic oxidations, all the elemental steps have to be considered.
In particular, according to experimental evidences [26,27] and kinetic models [28,29] that exclude a
radical mechanism, the metal-catalyzed liquid phase oxidation of alcohols follows the dehydrogenation
mechanism, which consists in a first step of hydride abstraction with formation of a metal hydride and
in a second step of oxidation [30]. It is well-known that hydride species formation is favored in the case
of Pd, while it constitutes a high energy demanding step in the case of Au [31]. We therefore concluded
that in the AuPd catalyzed reaction the presence of alloyed nanoparticles allow a balance between
the first step (Pd-favorite) and the second step (Au-favorite). Our findings are in agreement with the
hypothesis of the presence of isolated Pd sites [32] with different catalytic properties with respect to
bulk Pd and with high activity of Au in oxygen transfer reaction [33]. CV and EIS evaluations are
moreover simple tools for evaluating the presence of an electronic interaction between the two metals.
2. Results
Metallic sols of single Pd, Au and bimetallic AuPd were prepared accordingly to a well-known
procedure [25] that provides a narrow size distribution within the 2.5–3.5 nm range (Table 1).
In particular, the bimetallic samples deriving from coprecipitation/reduction of Au(III) and Pd(II)
precursors have been confirmed to be fully reduced (UV-Vis spectrum, Figure 1) and did not show any
Au segregation evident from the absence of the typical plasmonic resonance band of Au nanoparticle
centered at 530 nm (Figure 1). TEM-EDX analyses confirmed the presence of the alloy.
Figure 1. UV-vis spectra in H2O of AuPVA, PdPVA and AuPdPVA nanoparticles.

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Table 1. Catalytic results in liquid phase oxidation of glycerol.
Selectivity (%) c
Tartronic Formic
Mean Particle
Size (nm)
Catalyst a
Activity b
Glyceric
Acid
Glycolic
Acid
Lactic
Acid
Oxalic
Acid
Acid
Acid
AuPVA
PdPVA
AuPdPVA
a
2.6
2.8
3.4
1065
299
4264
64
85 d
83
23
2 d
3
1
4 d
7
5
3 d
4
3
4 d
1
4
2 d
2
Glycerol 0.3 M in water; 4eq of NaOH; metal/alcohol = 1/1000 mol/mol; 300 kPa O2; T = 50 ˝C; b Calculated
as mol of glycerol converted per hour per mol of metal, calculated after 15 min reaction; c selectivity at 80% of
conversion; d selectivity at 20% of conversion.
The monometallic and the bimetallic sols were tested in the liquid phase of glycerol. The results
are shown in Table 1. As expected from the literature [34] the bimetallic nanoparticles showed the
highest activity compared with the monometallic counterparts and a selectivity very close to that of
Pd (Table 1). Moreover, the alloyed nanoparticles allow the conversion to proceed, reaching >90%
conversion in only one hour (Figure 2). Conversely, monometallic Pd activity declined very rapidly
with conversion stopping around 20%. Monometallic Au catalyst appears very stable (Figure 2).
Moreover, AuPd system showed a selectivity more similar to Pd than to Au, the latter promoting the
C–C bond cleavage and the subsequent higher selectivity to C2 (glycolic acid, 23%, and oxalic acid,
4%) and C1 (formic acid, 5%) products. The supposed reason for the extraordinary behavior of alloyed
particle lies on the possible formation of Pd isolated sites, the chemistry of which differs from the one
of Pd nanoparticles [32]. The detection of electronic effect on the single metals in the alloyed sample is
complicated by the partial overlapping of Au and Pd XPS signals.
Figure 2. Reaction profiles for AuPVA, PdPVA and AuPdPVA nanoparticles.
We then characterized the three catalysts by CV and EIS in order to highlight any significative
differences in redox properties. Figure 3 shows the voltammetric patterns, recorded in 0.1 M sulphuric
acid at 0.5 V s
´1, of the AuPd nanoparticles casted on a glassy carbon inert electrode. The voltammetric
¨
features of palladium and the gold nanoparticles are also reported for comparison.
Gold and palladium nanoparticles present the characteristic oxidation (OxPd and OxAu) and
reduction (RedAu and RedPd) peaks related to the formation and reduction of the surface metal
oxides [24,35–37]. Palladium voltammogram is shifted in the cathodic region, indicating the higher
stability of the palladium oxide with respect to the gold one. The voltammetry of the nanoalloy
presents a larger oxidation peak due to the oxidation of the alloy, which comprises the two oxidation
peaks of the single metals. On the other hand, the reduction voltammetric peak at 0.63 V, indicates
that the oxide formed on the alloy is more stable with respect to the gold one, but really less stable in

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comparison with palladium oxide. In particular, it is worthwhile noticing that the nanoalloy metallic
nature is restored at a lower energy with respect to palladium. It should be also noted that in the
nanoalloy reduction scan, the presence of the two reduction peaks (RedAu and RedPd) related to
partially segregated metals is still visible even if in a very low amount. This is in agreement with the
observation made by Schiffrin for alloys containing a Pd percentage > 15% [24].
Figure 3. Cyclic Voltammetry of GC electrode modified with AuNP (1), PdNP (2) and Au-Pd alloy (3),
registered in 0.1 M sulphuric acid at a sweep rate of 0.5 V¨ s´1
.
Figure 4 shows the voltammetric curves (4A) and the impedance Nyquist plots (4B, taken at
0.25 V) of the conventional Fe(CN)63´{2´ redox probe registered in aqueous 0.1 M KCl at 0.1 V
for the three electrodes modified with Au, Pd and Au-Pd alloy.
¨
s´1
,
(A)
(B)
Figure 4. Cyclic voltammetry at 0.1 V
electrode modified with AuNP (1), PdNP (2) and Au-Pd alloy (3), in the presence of 3 mM K4[Fe(CN)6]
in 0.1 M KCl.
¨
s´1
(
A
) and impedance Nyquist plots taken at 0.25 V (B) of GC
Palladium nanoparticles present an electrochemical irreversible behavior, i.e., very slow electrode
kinetics with respect to the analyte mass transfer. On the other hand, gold nanoparticles show

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a faster electron transfer, as demonstrated by the electrochemical quasi-reversible CV feature
´1
(Ep-Ep/2 = 72 mV¨ s
;
∆
Ep = 128 mV s
´1). The Au-Pd alloy behaves intermediately, shifting the Pd
¨
irreversibility towards quasi-reversibility, thanks to the Au-Pd interaction. Analogues considerations
can be driven considering the impedance spectra (Figure 4B), fitted with an equivalent circuit composed
by the solution resistance in series with the charge transfer resistance and the double layer capacitance
in parallel, in the case of Pd and the Au+Pd alloy, with the addition of a Warburg element in the
Au case. The values of the charge transfer resistance RCT (derived from the amplitude of the plot
semicircles and accounting for the kinetics of the electronic transfer) are in the order Pd > Alloy >> Au,
confirming the intermediate behavior shown in the voltammetric characterization.
3. Discussion
The electrochemical characterization of AuPd nanoparticles compared to that of single Pd or Au
nanoparticles highlighted an intermediate behavior of the bimetallic nanoparticles both in terms of
electron transfer resistance (CV and EIS) or in the stability of oxides (CV). The cyclic voltammetry
and the impedance plots for AuPd are both able to clearly distinguish the presence of the alloyed
species pointing out a net electronic interaction between the two metals. This electronic modification
that involves both metals could be the base for the extraordinary synergetic effect detected during
the use of the bimetallic systems as catalyst in the liquid phase oxidation of glycerol. In fact, Friend
and coworkers [33] established that Au covered by oxygen atoms readily reacts with alcohols and
accordingly, CV establishes that the oxide is not very stable compared to the Pd one. On the other hand,
Pd oxide appears more stable than the AuPd one and this is in accordance with the study of Goodman
and coworkers [32] that addressed the higher activity of AuPd with respect to Pd to a diluting effect of
Au which is able to create catalytic single sites of Pd with a different reactivity.
Our study, however, pointed out that just on the basis of the relative stability of the metal oxides
established by CV and the electronic transfer determined by CV and EIS it would be possible to
conclude that Au is expected to be more active than Pd, but also than AuPd. Catalytic data showed
that AuPd are by far more active than Pd, but also than Au.
Looking at the reaction profile (Figure 2) we can address the deactivation of Pd catalyst to a
progressively covering of Pd surface by the oxide. In fact, CV shows that the PdO is highly stable
(Figure 3). Conversely the Au reaction profile (Figure 2) did not show any deactivation and this
behavior can be addressed to the poor stability of the oxide. AuPd reaction profile presented the
highest activity together with a high stability (Figure 2) but an intermediate stability of oxide that is
formed at more or less the same potential as the one on Au (Figure 3), but it is reduced at a lower
potential than Au.
Therefore, to explain the catalytic behavior of the AuPd system one should consider the whole
catalytic cycle. The metal catalyzed oxidation mechanism follows a dehydrogenation path (Scheme 1)
where the rate determining step for gold catalyst is the hydride abstraction from alcohol [26–29]. This
step is more readily carried out by Pd, being the Pd-hydride species more stable than Au-hydride [38]:
Scheme 1. Alcohol oxidation mechanism.
The quite high stability of PdO which can be formed during the reaction can be invoked as the
main cause of deactivation, normally observed with Pd catalyst. In the case of AuPd, the electronic
modification to the Pd catalyst made by Au, decreases the stability of the oxide thus increasing the

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stability of the catalyst. On the other hand, the presence of Pd in AuPd bimetallic system allows the
intermediate hydride to form, thus improving the overall reactivity.
Also from a selectivity point of view the AuPd system is more similar to Pd (Table 1), showing a
lower selectivity towards C1 and C2 products (deriving from the C
monometallic Au catalyst. This might be correlated to the enhanced accumulation of H2O2, responsible
for C C cleavage [39], in the case of Au, according to experimental observations [40] and to the higher
´C bond cleavage) compared to
´
calculated barrier for the peroxide decomposition on Au as compared to Pd. [41]. These considerations
let us suppose that the most important effect to be considered is the modification that Au imparts
to Pd.
4. Materials and Methods
4.1. Monometallic Nanoparticles
4.1.1. Au nanoparticles Preparation.
Solid NaAuCl4 2H2O (Aldrich, Milan, Italy, 99.99% purity; 0.043 mmol) and polyvinylalcohol
‚
solution (PVA, MWPVA = 13,000–23,000, 87%–89% hydrolysed, Aldrich; 1% w/w; Au/PVA 1:1,
w/w) were added to 100 mL of H2O. After 3 min, NaBH4 (Fluka, Milan, Italy >96%; Au/NaBH4
1/4 mol/mol) solution was added to the solution under vigorous magnetic stirring. A ruby red
Au(0) sol was immediately formed. An UV–visible spectrum of the Au sol was recorded to check the
´
complete AuCl4 reduction and the formation of the plasmon peak, of Au(0) nanoparticles.
4.1.2. Pd nanoparticles Preparation.
Solid Na2PdCl4 (Aldrich, 99.99% purity; Pd 0.043 mol) and PVA solution (1% w/w) (Pd/PVA
1:1 w/w) were added to 100 mL of H2O. After 3 min, NaBH4 (Pd/NaBH4 = 1/8 mol/mol) solution
was added to the yellow-brown solution under vigorous magnetic stirring. The brown Pd(0) sol was
immediately formed. An UV–visible spectrum of the Pd sol was recorded to check the complete
2´
PdCl4 reduction.
4.2. Bimetallic AuPd Nanoparticles
Solid NaAuCl4 2H2O (0.0258 mol) and Na2PdCl4 (0.0172 mol) (Au/Pd ratio 6:4 mol/mol) and
‚
PVA solution (1% w/w) (Pd/PVA 1:1 w/w) were added to 100 mL of H2O. After 3 min, NaBH4
(Pd/NaBH4 = 1/8 mol/mol) solution was added to the yellow-brown solution under vigorous
magnetic stirring. The brown AuPd(0) sol was immediately formed. An UV–visible spectrum of
sols were recorded on a HP8453 spectrophotometer (Hewlett-Packard, Milan, Italy) in H2O between
200 and 800 nm, in a quartz cuvette to check the complete metal reduction.
4.3. Electrochemical Characterization
Electrochemical characterizations were carried out in a conventional three electrodes cell, by
using a saturated calomel, a Pt wire and a modified glassy carbon (GC, 3 mm diameter, AMEL, Milan,
Italy) as reference, counter and working electrodes, respectively. The modified glassy carbon was
prepared depositing 20
Milan, Italy)automatic pipette. The GC electrode was previously polished with diamond synthetic
monocrystalline nanopowder (Aldrich, 1 m, 99.9%) on a DP-Nap wet cloth (Struers, Arese-Milan,
cm´1, Millipore, Billerica, MA, USA) was used for
µL of nanoparticles sol on the top of the electrode by a Kartell (Noviglio,
µ
Italy) and rinsed in water. Milli-Q water (18 M
the preparation of all the solutions.
Ω
Cyclovoltammetric investigations were performed using an Autolab PGSTAT 30 (EcoChemie,
Utrecht, The Netherlands) equipped with NOVA (Advance Electrochemical Software, Utrecht,
The Netherlands), in 0.1 M KCl or 0.1 M H2SO4 as supporting electrolytes, at a scan rate of 100 or
500 mV s
´1. Electrochemical Impedance Spectroscopy (EIS) measurements were carried out in 0.1 M
¨

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KCl in the presence of the redox probe K4[Fe(CN)6] (3 mM, Sigma Aldrich Analytical Grade) using
the PGSTAT 30 (Autolab, Utrecht, The Netherlands) equipped with a Frequency Response Analyzer
(FRA). Range of frequencies was fixed between 0.1 Hz and 65,000 Hz with an amplitude of 10 mV.
Impedance spectra were fitted using electrical equivalent circuits generated with ZView 3.2 software
(Scribner Associates Inc., Southern Pines, CA, USA).
4.4. Catalytic Tests
Glycerol oxidation was carried out in a 30 mL glass reactor equipped with a thermostat and
an electronically controlled magnetic stirrer connected to a 5000 mL reservoir charged with oxygen
(3 atm.). The oxygen uptake was followed by a mass-flow controller connected to a PC through an
A/D board, plotting a flow time diagram.
Glycerol 0.3 M, the sol (substrate/total metal = 1000 mol/mol) and 4 equivalent of NaOH were
mixed in distilled water (total volume 10 mL). The reactor was pressurized at 3 atm of oxygen and
set to 50 ˝C. Once this temperature was reached, the reaction was initiated by stirring. Samples were
removed periodically and analyzed by high-performance liquid chromatography (HPLC) using a
column (OA-10308, 300 mm–7.8 mm, Alltech, Milan, Italy) with UV and refractive index (RI) detection
to analyze the mixture of the samples. Aqueous H3PO4 solution (0.1 wt %) was used as the eluent.
Products were identified by comparison with the original samples.
5. Conclusions
CV and EIS characterisations of AuPd nanoparticles and the comparison with those of single
metals established that there is a net electronic effect between the two metals. These characterization
techniques can be easily used for establishing the nature of the bimetallic systems. Moreover, combining
the catalytic results with the electrochemical characterization we concluded that the higher activity of
the AuPd bimetallic system in the liquid phase oxidation of glycerol is due to a compromise between
the stability of the oxidic species (decreased with respect to Pd) and the facility of hydride formation
(increased with respect to Au). This balance creates the observed synergistic effect between Au and Pd.
Author Contributions: V. Pifferi and A. Testolin: drafting of the manuscript and electrochemical characterizations;
C.E. Chan-Thaw: synthesis and characterizion by UV spectroscopy of metal nanoparticles; S. Campisi: catalytic
tests; A. Villa, L. Falciola, L. Prati: supervising the analysis and the interpretation of data and final editing of
the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.
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Sample Availability: Samples of the metallic sol are available from the authors under request.
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