Rev. Adv. Mater.

Synthesis, Sci. 30 (2012)

characterization and133-149
applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 133

SYNTHESIS, CHARACTERIZATION AND APPLICATIONS

OF BIMETALLIC (Au-Ag, Au-Pt, Au-Ru)
ALLOY NANOPARTICLES

Afzal Shah, Latif-ur-Rahman, Rumana Qureshi and Zia-ur-Rehman

Department of Chemistry, Quaid-i-Azam University, 45320, Islamabad, Pakistan
Received: December 29, 2011

Abstract. This review article describes the preparation and characterization of bimetallic alloy
nanoparticles of Au-Ag, Au-Pt, and Au-Ru. The synthetic details of monometallic nanoparticles of
Au, Ag, Ru, and Pt have been given for comparison. The main objective of this review is to clearly,
quantitatively, and comprehensively describe the synthesis of bimetallic alloy nanoparticles and
their characterization. A number of synthetic methods have been discussed in detail to provide
the reader with an extensive knowledge of controlling the nanoparticle physical characteristics
(size, size distribution, morphology). For getting valuable surface information, CO adsorption
studies of all the three samples have also been presented. The application of bimetallic alloy
nanoparticles as electrocatalysts for direct methanol fuel cell and their ability to oxidize methyl
alcohol with 60% more efficiency than multi walled carbon nanotubes supported on monometallic
Pt nanoparticle catalyst has also been discussed.

1. INTRODUCTION cluster-in-cluster type forms nanoclusters and the

other acts as binder. In bulk metals, two kinds of
Alloying of metals is a way of developing new
metal elements often provide an alloy structure.
materials that have better technological usefulness
Elements with similar atomic sizes form a random
than their starting substances. Alloy nanoparticles
alloy while intermetallic alloy is formed by elements
show different structural and physical properties than
of different atomic sizes.
bulk samples [1,2]. Increase in solid solubility of
The oxygen reduction reaction (ORR) plays a
alloy components with decreasing particle size is
major role in several electrochemical systems, such
one of the prominent effects. Bimetallic nanoparticles
as fuel cells, batteries, corrosion, and biological
(BMNP) have excelled monometallic nanocrystals
processes [5]. Therefore, considerable attention has
owing to their improved electronic, optical and
been focused on this reaction. Platinum is usually
catalytic performances [3,4]. BMNP often improve
employed as ORR catalyst because measurable
the selectivity of metal catalyzed reactions.
current density is obtained only in this metal due to
Moreover, the change in composition of metals
low exchange current density and high potential.
provides another dimension in tailoring the properties
The search for more active and less expensive ORR
of BMNP besides the usual size and shape
catalysts, with greater stability than Pt has resulted
manipulation.
in the development of several Pt alloys. In this
BMNP may have random, cluster-in-cluster, core
context, it has been reported that alloying platinum
shell and alloy structures. In random structure,
with transition metals such as Fe, Ru, Co, Pt, Ag,
atoms are arranged haphazardly. One element in
Corresponding author: Afzal Shah, e-mail: [email protected]

q( (5Ug
R_TVUGe
fUj7V_e
Vc7 @e
U
134 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

etc., enhances the electro-catalytic activity of ORR borohydride, sodium citrate, ethanol, toluene, and
by reducing Pt-O formation [6,7]. However, such an de-ionized water are used for the synthesis of Au,
improvement has also been attributed to various Ag, and Pt nanoparticles [12]. 0.8 mL of 4 mM
structural and electronic changes caused by alloying. aqueous sodium citrate solution is added to 10 mL
Japan and Taylor have documented that shortening of 1 mM aqueous AuCl3 solution. Under vigorous
of Pt-Pt inter-atomic distance after alloying results stirring, 0.75 mL of 112 mM aqueous NaBH4 solution
in activity enhancement [8]. Beard and Ross related is introduced drop wise to prepare Au hydrosol in
the increase in activity to the exposure of a more which sodium citrate acts as a stabilizer. The molar
active vicinal plane on dispersed platinum particle ratio of NaBH4 to AuCl3 is kept constant to ensure
[9]. Several researchers have explained the the reduction of Au to zero valence state. The Ru
enhanced ORR activity on the basis of interplay hydrosol is also left to stand for 4 hours to complete
between the decrease of electronic Pt d-vacancy the reduction reaction. The hydrosol is then mixed
and coordination number [9-11]. Toda and coworkers with 10 mL of ethanol containing 100 L of
suggested that increased d-electron vacancy at a dodecylamine and the mixture is stirred for 2
thin Pt surface layer by underlying alloy is minutes. 5 mL of toluene is added with stirring
responsible for ORR enhancing mechanism [11]. A continued for 3 more minutes. Dodecylamine-
part of the current review is devoted to the activity of stabilized Au nanoparticles are rapidly extracted from
Au-Ag, Au-Ru and Au-Pt, for the kinetics of ORR in toluene layer, leaving behind a colorless aqueous
acidic medium. The aim of the kinetic data analysis solution. The same procedure is followed for the
is to correlate the catalytic activity with electronic preparation of dodecylamine-stabilized Ag, Pt and
and structural properties of the nanoparticles [12]. Ru nanoparticles, except AuCl3 being replaced by
Hydrogenation rate of simple olefins is increased in AgNO3, H2PtCl6 and RuCl3.
the presence of palladium catalysts containing 20%
gold, when compared with monometallic palladium 2.1.1. Preparation of gold
catalysis [13]. The nanoparticles are stabilized with nanoparticles
polymers but high molecular mass polymers can
reduce the catalytic properties of such particles. Generally, gold nanoparticles are produced in a liquid
Hence, citrate, being relatively small in size is more v]ZbfZ U TYV Z TR] Ve Y Udw  Sjc VUfTe Z_ W
likely to stabilize nanoparticles without causing chloroauric acid (H[AuCl4]), although more advanced
hindrance during catalysis. and precise methods do exist. After dissolving
BMNP have wide range of applications in H[AuCl4], the solution is rapidly stirred along with
technologies due to additional degrees of freedom the addition of a reducing agent that converts Au3+
as compared to monometallic nanoparticles [14-16]. to Au0. With the formation of more and more gold
However, in spite of intensive research in size and atoms, the solution becomes supersaturated, that
shape manipulation of BMNP, it is still a significant leads to precipitation in the form of sub-nanometer
challenge to control their internal structures and particles. The rest of the gold atoms that form stick
chemical order with sizes smaller than 5 nm [16]. to the existing particles and if the solution is stirred
The current review is mainly focused on the controlled vigorously, the particles will be fairly uniform in size.
synthesis of Au-Ag, Au-Pt, and Au-Ru nanoparticles To prevent the particles from aggregation, a
via a chemical reduction route using citrate and thiol- stabilizing agent that could stick to the nanoparticle
stabilised gold nanoparticle seeds as a starting surface is usually added. The prepared nanoparticles
material. An important aspect of the article is the are functionalized with various organic ligands to
characterization of the particles, without which the create organic-inorganic hybrids with advanced
size, monodispersity and shape characteristics functionality [17]. Santanu Bhattacharya
could not be determined. synthesized gold nanoparticles by dissolving 5 mg
of HAuCl4.3H2O in methanol followed by the addi-
tion of 5 mg NaBH4. The mixture was then bath-
2. SYNTHESIS
sonicated for 5 min to ensure proper mixing of Au
and NaBH4. The reduction of Au3+ to Au0 was achieved
2.1. Synthesis of monometallic by using 15-fold excess of NaBH4. Immediate colour
nanoparticles change from bright yellow to red was observed. Red
precipitation was noticed within a minute after the
H 2 PtCl 6 .6H 2 O, HAuCl 4 .33H 2 O, AgNO 3 , addition of reducing agent. The supernatant was
Dodecylamine, 1-dodecanethiol, sodium removed and the precipitate was washed twice with
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 135

water and MeOH each to remove the impurities. The method is preferred over other processes because
nanoparticles were designated as Au-1. Bhandari of fewer chances of impurities and role of ethylene
and Sharma used preparation of simultaneous TBP glycol as a solvent as will as a reducing agent.
self assembled threads and TBP-capped gold
nanoparticles for which 0.6 mL of cold freshly 2.1.2. Preparation of silver
prepared 0.1 M NaBH4 aqueous solution was added nanoparticles
to 20 mL 0.25 mM HAuCl4 aqueous solution and
the solution was kept under stirring condition for at For the preparation of silver nanoparticles 300 mg
least 12 hours at 30 p C. The temperature was of AgNO3 is added to 180 cm3 of ethanol at a
precisely maintained by circulating thermostated temperature of 60 pC with constant stirring. Different
hRe VchZ eYZ_e YVf_TVc eRZ_eZVd Wt pC. The aminosilanes are dissolved in ethylene glycol
solution was then transferred to 10 mL tightly capped followed by dispersion in alcohol-AgNO3 solution
sample tubes and kept for aging in dark for 1 month. previously prepared under stirring to obtain AgNO3
Similar reactions were carried out at 40, 50, and 60 aminosilanes in various ratios. Maribel and
pC. In each case, a light pink color appeared initially coworkers synthesized silver nanoparticles using
with different color intensities at different two stabilizing agents, sodium dodecyl sulphate
temperatures. The color slowly disappeared on aging (SDS) and sodium citrate [23]. Silver nitrate solution
within 4-5 days leading to the appearance of black u, A hRdfdVURd Ve R]dR] eac VTfc dc
threads floating at the bottom of the sample tube. Hydrazine hydrate solution with a concentration of
Afterwards the nature of the solution remained 2.0 - 12 mM and sodium citrate solution (1.0 - 2.0
essentially the same for several months. Zhao and mM) were used as reducing agents. Sodium citrate
Xu chose gold as a core for Au-Pt core-shell was also used as stabilizing agent at room
nanoparticles because its surface favors deposition temperature. The transparent colorless solution was
of platinum and shows inertness in acid electrolytes converted to the characteristic pale yellow color
[18,19]. Brown and coworkers synthesized gold which indicated the formation of silver nanoparticles.
nanoparticles of diameter ranging from 2.6 to 100 These were then purified by centrifugation. For the
nm, using a seeding technique. They compared the removal of excess silver ions, the silver colloids were
use of citrate and hydroxylamine as reductant. The washed thrice with deionized water under nitrogen
citrate seeded particles were highly uniform in size; stream. A dried powder of the nanosize silver was
however, the hydroxylamine seeded gold colloids obtained by freeze-drying. The most convenient
produced two distinct populations of large spheres method of synthesizing Ag nanoparticles is polyol
and small rods [20]. It was found that the 2.6 nm process in which the mixture of 3 mL each of 1.0
diameter seeds had a standard deviation of ~1 nm. mM AgNO3 solution (prepared in ethylene glycol)
The citrate method which is one of the best-known and PVP is kept for 45 minutes in oven at 175 p C.
methods for producing gold nanoparticles that The appearance of blackish brown color shows the
involves reduction of HAuCl4 by sodium citrate was formation of Ag nanoparticles.
first developed by Turkevich et al. [17]. Brust
synthesized thiol-derivatized gold nanoparticles of 2.1.3. Preparation of platinum
1-3 nm diameter in a two-phase liquid-liquid system. nanoparticles
Sodium borohydride was used for the reduction of
Stable aqueous colloidal platinum nanoparticles are
AuCl4 in the presence of alkanethiol [21]. Yang and
prepared by citrate reduction. The method was first
coworkers used a combination of seeding growth
used by Furlong who prepared platinum
and digestive ripening for achieving precise control
nanoparticles as small as 4 nm [17]. It was found
of monodispersed gold nanoparticles. Alkyl amines
that increasing heat during the reaction causes an
were used for the stabilization and thermal reduction
increase in particle size. Henglein et al. produced
of HAuCl4. Gold nanoparticles of various diameters
different Pt colloidal sols by utilizing radiolysis,
(2.1-8.8 nm) were produced. A change in color of
hydrogen and citrate reduction [24]. Particles with
the sol was noticed. The sol was brown for particles
average diameter of 1.8, 2.5, and 7.0 nm are obtained
of 2.1 nm and red for 3.1 nm [22]. In polyol method
by Radiolysis, citrate and hydrogen reduction. The
AuNP-PEG-A solution is prepared by mixing 0.2 mM
citrate acts not only as a reductant, but also as a
aqueous solution of thiolated poly ethylene-glycol
stabiliser for Pt colloidal sols [19]. Lin et al. shaped
(PEG) with AuNP-H2O system. A solution of AuNP-
citrate-stabilised platinum nanoparticles of 2-3 nm
PEG-B is prepared by mixing 0.2 mM aqueous
Rg VcRXVd ZkVhZ eYRaaci ZRe V]
jt(_ UZ d ecZ
SfeZ_
solution of PEG with AuNP-citrate solution. The
136 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

Fig. 1. Different structures of bimetallic nanoparticles.

via methanol reduction. Luo and Sum devised a Supriya Devarajan used N,N-[3-
single-step heat-treatment method for the produc- (trimethoxysilyl)propyl]diethylenetriamine (TPDT),
tion of poly(vinylalcohol) (PVA) stabilised platinum tetraethoxysilane (TEOS), chloroauric acid,
nanoparticles with diameters of 2-7 nm. The PVA palladium chloride, silver nitrate, chloroplatinic acid,
acted as reductant and stabiliser [20]. sodium borohydride, and methanol for the
preparation of different structures of bimetallic
2.1.4. Preparation of ruthenium nanoparticles [26]. Double-distilled water was used
nanoparticles in Brust process. Ethylene glycol was used as a
solvent in case of polyol process.
Vladimir and his team synthesized 20 wt.% Ru/C
under argon using dry solvents [25]. In a 2-L two-
2.2.1. Preparation of bimetallic
neck flask fitted with a dropping funnel and a vacuum
nanoparticles
adapter, maintained under a steady flow of argon,
2.868 g of anhydrous ruthenium chloride and 1 L of Burst et al. added 130 l of N,N_-[3
dry THF were introduced and sonicated for 15 min (trimethoxysilyl)propyl]diethylenetriamine (TPDT) to
to generate a uniform suspension of the salt. 5.6 g 3.8 ml of methanol followed by 50 l H2O and 50 l
of vulcan XC 72 was added to the suspension, and 0.1 M HCl. [26] The mixture was shaken well for a
the mixture was stirred vigorously for 2 h at room couple of minutes. Different volumes of 0.01 M AuCl3,
temperature. The flask was then placed in an oil AgNO3, H2PtCl6, and RuCl3 were added to the silica
bath maintained at 50 p C. 27.0 mL of 1.5 M LiBet3H/ sol and mixed well until the solution became
THF solution was dripped over 2 h, and the resulting homogeneous. Sodium borohydride (2.5 mg) was
mass was allowed to stir vigorously for 24 h at 50 then added with vigorous stirring. Instantaneous color
pC. After stopping the stirring the flask was allowed change ranging from deep violet of Au colloid to brown
to cool to room temperature. Colorless and clear color of Ru and Pt or yellowish brown in case of Ag
supernatant was pressed off and the precipitate was colloid, depending on the composition, was
washed twice with 150 mL portions of THF and dried. observed. Various molar compositions of the two
The residue was conditioned at 200 p C using argon metal components such as 0.25:0.75, 0.43:0.57,
(5 min) followed by hydrogen (30 min) and argon (5 0.5:0.5, 0.57:0.43, 0.75:0.25, and 0.9:0.1 were
min) again. The sample tube was allowed to cool to prepared using the same protocol. The sols and the
room temperature. This enabled the formation of resulting solid monoliths of all the compositions were
stable, 20 wt.% Ru/C catalyst. very stable over extended periods of several months.
Films of different thickness ranging from 0.1 to
2.2. Bimetallic nanoparticles (BMNP) 10 m were cast on glass slides by a coating
process. Gels and monoliths of any desired shape
BMNP are the combination of two metals in the were obtained by allowing the solvent to evaporate.
nanoscale size range. This area of nanoscience is The dried material was found to shrink considerably
gaining mounting attention in the field of catalysis but slow evaporation of the solvent led to crack the
due to synergistic effects. BMNP have four types of free monoliths.
mixing patterns: core-shell nanoparticles, sub-
cluster nanoparticles, mixed (alloy) nanoparticles
2.2.2. Preparation of Au-Ag bimetallic
and multishell nanoparticles. Core-shell
nanoparticles consist of a shell of one type of atom alloy nanoparticles
surrounding a core of another type of atom as shown Sang W. Han prepared nanoparticles via the two-
in Fig. 1 [26]. phase method [21]. Initially, aqueous solutions of
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 137

potassium tetrachloroaurate (KAuCl4), potassium complete solubility of Ag+ in the presence of Cl- the
dicyanoargentate (KAg(CN)2) and their mixtures in solutions used in Au and Ag seed preparation were
various molar ratios of AuCl4 /AgCN were prepared; diluted by a factor of 50 in order to lower the reaction
the total solute concentration was chosen to be the quotient (Q e (+z -11 [28]. Flasks were cleaned
same in all solutions, i.e., 40 mM. Into a beaker, 30 with aqua regia and deionized water and then filled
mL of one of these aqueous solutions and 50 mL of with 100 mL of deionized water and 50 L of 0.01 M
50 mM tetraoctylammonium bromide in toluene were sodium citrate. Varying mole fractions of 0.01 M
added together, and the resulting immiscible mixture HAuCl4 and 0.01 M AgNO3 were added to each
was stirred vigorously until all of the AuCl4 and AgCN solution for a total metal salt concentration of 10 M.
species in aqueous phase were transferred into the The solution was allowed to stir for an additional 30
organic layer. 0.2 mL of neat dodecanethiol was s. A faint color change occurred almost immediately.
added to the organic phase and subsequently a The color change caused by the reduction of metal
freshly prepared aqueous solution of 0.4 M sodium salts was found to be dependent on the
borohydride (25 mL) was added with vigorous stirring. concentrations of AgNO3 and HAuCl4 in solution.
After the mixture was stirred further for 12 h, the The pure Ag solution turned from colorless to light
organic phase was separated and evaporated to 10- yellow upon addition of NaBH4. In contrast, the
20 mL in a rotary evaporator. The resulting solution 75%Ag/25%Au solution turned yellowish red. As the
was mixed with 300 mL of ethanol to remove excess Au/Ag molar ratio increased, the intensity of the
thiol and then kept in a refrigerator at 218 p C for 6 h. reddish color increased. In the first method AgCN
Thereafter, the dark brown precipitate was filtered used is poisonous so it should be replaced by
and washed with ethanol and acetone. The AgNO3. PVP can also be used because it is the
synthesized particles were characterized by UV-Vis best solvent as will as reducing agent.
and Infrared spectroscopy. Supriya Devarajan and
coworkers used tetraoctylammonium bromide 2.2.3. Preparation of the Au-Pt
(TOABr) and sodium mercaptopropionate (Na-MPA). bimetallic nanoparticles
Solutions of Na-MPA were aged for 3-5 days before
the experiment [27]. Initially, water (95 mL) Hau and Shu prepared Au-Pt nanoparticles by adding
containing desired mole fractions of Au and Ag (total the reductant into the solution containing 0.2 mM
Ve R]T _TV_e cReZ_hRd RZ _e RZ_VURe (/ z -4 AuCl4 and varying concentration of PtCl6-2 (0.2-0.8
M) was refluxed and a required amount of Na- MPA mM). The reductant was a solution of 4 mL tannic
(147 @ W A c Vdf]eZ
_XZ _ -z -4 M) and 5 acid (2%) and 1 mL citric acid (1%). The reaction
mL of 1% aqueous trisodium citrate solution were mixture was stirred for 15 min at 100 p C, followed
added simultaneously. The color of the solution by 10 min of stirring without heating [28]. Schrinner
changed from turbid yellow to varying shades of and his team used cationic spherical polyelectrolyte
reddish-brown depending on the alloy composition. brushes carrying chains of poly(2-
The sol was boiled for another hour and then cooled aminoethylmethacrylate hydrochloride) [29]. The
to room temperature. Various compositions with radius of the core particles was 45 nm and the
different mole fractions of Au and Ag were prepared. average contour length of the grafted chains was
In phase-transfer experiments two immiscible 165 nm. The entire number of charged groups in the
layers were obtained by mixing 50 ml toluene polyelectrolyte layer was determined precisely by
T _e RZ_Z_X)..z -4 M TOABr with 50 ml of hydro- conductometric titration [29]. Another research team
sol containing alloy nanoparticles. Initially, the aque- successfully deposited platinum onto gold
ous layer at the bottom was colored and the or- nanoparticles by reducing K2[PtCl6] with hydrogen
ganic phase was colorless. This biphasic mixture in a colloidal solution of gold nanoparticles with a
was vigorously stirred and a transfer of the alloy _Rc ch dZ kVUZ de cZ
SfeZ_ _ t (_  Z _eYV
nanoparticles from aqueous to toluene phase was presence of PVP as stabilizer [30]. Kumar and Zou
observed by the movement of color across the prepared colloidal gold of 3 nm diameter using 3-
interface. The organic phase was collected and the aminopropyltrimethoxysilane for the attachment of
solvent was rotary-evaporated to yield a brown colloidal gold to ITO glass slides via surface
colored powder which was washed thoroughly with derivatization. Platinum films were deposited on to
ethanol to remove the uncoordinated TOABr. the colloidal gold by means of the galvanic
Au-Ag alloy nanoparticles were also synthesized replacement technique [31,32]. Henglein produced
by the reduction of HAuCl4 and AgNO3 with NaBH4 Au(core)-Pt(shell) and Pt(core)-Au(shell) bimetallic
in the presence of sodium citrate [27]. For ensuring nanoparticles using hydrogen reduction and
radiolysis techniques.
138 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

2.2.4. Production of Au-Ru bimetallic

nanoparticles
The research group of Akita shaped Au(core)-
Ru(shell) bimetallic nanoparticles with a diameter
W )t)(_ g Z
RRd _ TYV Z TR]eVTY_Z bfVO ))P
The product nanoparticles were recovered by
centrifugation and washed with ethanol several times
to remove nonspecifically bound dodecylamine. The
nanoparticles were then dried at room temperature
in vacuum.
The synthesis of Au-Ru core-shell nanoparticles
by sequential polyol process involves the reduction Fig. 2. UV-visible spectra of Au-Ag nanoparticles.
of Ru(acac)3 (acac = acetylacetonate) in refluxing
glycol using PVP stabilizer. The resulting Ru
the individual colloids, however, shows two surface
nanoparticles (mean particle size = 3.0 nm) are
plasmon peaks corresponding to the monometallic
subsequently coated with Au by adding AuCl3 to
counterparts. The stability of the silver colloids in
the Ru/glycol colloid and slowly heating to 200 p C.
the silicate matrix, however, is very low. This could
The Au-Ru alloy nanoparticles can also be
be attributed in part to the low stability constant of
synthesized via co-reduction of the [Ru(CO)3Cl2]2
the Ag-amine complex [39,40]. This is subsequently
dimer and Au(acac) 3 with glycol at 200 p C.
revealed in the relative instability of Au-Ag alloys
Monometallic Au and Ru nanoparticles are prepared
where the Ag content is higher than 50%. The
from AuCl3 and Ru(acac)3, respectively, using slight
formation of bimetallic dispersions depends on the
modifications of published procedures [34].
kinetics and thermodynamics of reduction of
individual components. The complete reduction of
3. CHARACTERIZATION Au(III) and Ag(I), under the present conditions
The sol-gel derived silicates containing nanoparticles requires 5 and 10 min, respectively. The stability
are very stable in both liquid and solid phases. The value for Au is expected to be close to that of silver
stability is checked by following the absorbance based on the ease of reduction as observed in the
spectra over extended periods of several months. time required for complete formation of the metallic
The amino groups present in the silicate stabilize colloid. Hence, it is expected that Pd and Pt may
the BMNP as proposed by Lev and co-workers form a shell, while Au may occupy the core of the
[35,36]. The use of sodium borohydride results in bimetal in case of Au-Pd and Au-Pt bimetallic
fast reduction of metal ions. But ethylene glycol is structures. However, from CO adsorption
the best reducing agent and stabilizer that also acts measurements, it is observed that both the metals
as a solvent. A variety of techniques such as UV- are present with an enrichment of Pt and Pd on the
Visible spectroscopy, TEM, XRD, FTIR, and CV are surface. In the case of Au-Ag bimetal, silver
used for the characterization of nanoparticles. enrichment is observed. It is reported that planar
Au-Ag alloys formed by high-temperature method
3.1. Au-Ag Bimetallic alloy exhibit an enrichment of Ag on the surface, due to
nanoparticles
3.1.1. UV-visible studies
Fig. 2 shows the absorption spectra of different
compositions of Au and Ag (0.57:0.43, 0.43:0.57,
and 0.25:0.75 molar ratios). Alloy formation is
evidenced by the appearance of a single peak with
max
depending strongly on composition. The
plasmon band is blue-shifted with increasing amount
of silver [37,38]. The absorption spectra of Au, Ag,
and Au-Ag alloy nanoparticles of varying mole
fractions show a linear relationship between the max
and Au mole fraction (Fig. 2). A physical mixture of Fig. 3. TEM images of Au-Ag Alloy nanoparticles.
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 139

Wc e YV<FH9AZ d() t m HYVc

VZd_ ] Re
tice mismatch observed since the Au and Ag have
very similar lattice parameters.

3.1.3. XRD studies

As mentioned in the introduction, Au and Ag have
very similar lattice constants and hence their d and
2 values lie very close to each other. Fig. 4 shows
the XRD spectra corresponding to the Au-Ag alloy.
Fig. 4. XRD spectra of Au-Ag nanoparticles.
The molar ratio of silane to metal salt is maintained
at 100:5, using 1:1 Au to Ag ratio. As for the
diffractogram of Ag, the strongest band is observed
lower heat of sublimation of Ag than Au [41,42]. at 38.14p(2 ) that corresponds to the (111) plane. A
However, in case of nanoparticles preparation under broad band is observed at 44.15p(2 ) that can be
ambient conditions, the borohydride reduction and attributed to the (200) crystallographic plane. Two
the metal atom deposition chemistry may play a broad reflections are observed at 64.55pand 77.48p
role in determining the surface enrichment. It is found (2 ) that correspond to the (220) and (311) planes
that the use of only tetraethoxysilane or O-P= _eYVTRdV We YV5fu5XR] ]jR] ]cVW
]VTeZ_d
methyltrimethoxysilane or trimethylamine as the are similar to monometallic Au and Ag. The particle
stabilizer results in the precipitation of the particles. d Z
k VZdTR] Tf]ReVUeSV+t _ SRd VU _e YV  
This suggests a dual role for the aminosilanes as peak, which corroborates well with the data obtained
stabilizers of nanobimetallic particles. It is possible from TEM.
that the amino groups stabilize the nanobimetallic
aRc e
ZT]VdhYZ ]Ve YVuGZ uCuGZ uR_UGZ uC< Wc R
3.1.4. CO adsorption studies
network surrounding the metallic particles.
Additionally, the use of long-alkyl-chain-contain- Gold and silver have fully occupied d-orbitals and
ing matrices is expected to help in the stabilization exhibit weak coordination ability toward CO [47,48].
of nanoparticles by keeping them far apart and It is reported that only weak Raman and IR bands
thereby preventing coagulation. Mulvaney and co- are observed for CO on gold and silver surfaces to
workers [43,44] have reported the formation of silica be adsorbed [48].
shells around gold nanoparticles prepared using si-
lanes. Lev and his team [45,46] postulated that si- 3.2. Au-Pt Bimetallic alloy
lanes form a network around the nanometallic par- nanoparticles
ticles of gold, silver, platinum, and palladium. The
stability of the mono- as well as the bimetallic 3.2.1. UV-visible spectroscopy
colloidal dispersions is found to be very good and The UV-Vis spectra of Au-Pt sol are very similar to
the particle size does not change with time. those of Au-Ru sol. Fig. 5 shows comparison
Absorbance of the sol as well as the dry gel is found between the UV-Vis spectra of different compositions
to be indistinguishable immediately after preparation of Au and Pt (0.75:0.25, 0.5:0.5, and 0.25:0.75 molar
and after several months of storage. The particle ratios of HAuCl4:H2PtCl6) and the monometals. The
size distribution is retained in both solid and liquid molar ratio of silane to metal ion is 100:0.25. This is
phases. It is observed that the absorbance spectra less than the corresponding ratios used for other
of a silicate film (3- m thickness) containing bime- systems. It is known that Au and Pt tend to
tallic nanoparticles of composition 1:1 molar ratio precipitate when mixed together at high
of the salts is nearly the same as that of the sol. In concentrations of Pt [11]. The Pt sol is brown and
this case, the film is formed from a mixture of TPDT shows a broad absorption band. The absence of
and TEOS. The addition of TEOS to the sol de- peaks at 378 and 460 nm indicates the reduction of
creases the cross-linking time but does not change Pt(IV). In case of physical mixtures, the plasmon
the absorbance spectra. remains visible for all ratios of Au and Pt.

3.1.2. TEM studies 3.2.2. TEM studies of Au-Pt alloy

Au-Ag alloy particle size ranges from 1 to 6 nm with nanoparticles
the maximum close to 2.5 nm as can be seen from The size of Au-Pt bimetallic particle varies between
the histogram in Fig. 3. The lattice spacing obtained 1 and 6 nm. Fig. 6 shows the HRTEM of the
140 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

even a small variation in the measurement of the

lattice spacing could lead to a large error in the final
composition.

3.2.3. XRD studies

The molar ratio of silane to metal salt and Au to Pt
is maintained at 100:5 and 5:1 in order to avoid
precipitation. Pt, like Pd is more crystalline than
gold nanoclusters in silicate matrices. Fig. 7
indicates that the (200) band observed at 45.44p
(2 ) is very sharp. A strong band at 56.47p(2 ) may
be due to the (102) reflection of PtO2. Bands are
also observed at 65.94p(2 ) and 75.22p(2 ) that
correspond to the (111) and (201) planes of PtO2,
respectively. The XPS data of the bimetal also shows
Fig. 5. UV-visible spectroscopy of Au-Pt alloy Pt in oxidized states [50].
nanoparticles at various concentrations. The Au-Pt bimetal exhibits a broad band at 38.35p
(2 ) that matches with the (111) plane A broad peak
at 44.58p(2 ) is attributed to the (200) plane. Two
bimetallic particles. The lattice is quite well-resolved additional bands are observed at 65pand 77.73p(2 )
and equally spaced showing the single crystalline that correspond to PtO2 (JCPDS 38-1355). The
nature of the nanoparticle. The lattice spacing is particle size calculated on the base of (111) peak is
() t m 6f]De YRdR] ReeZTVdaRTZ _X W ((- -t _ hYZ TYZdT]dVe e YVg R]fV SdVc g VUSj
m 5ddf Z _XJVXRc Ux
d] Rh e YV SdVc gVU] ReeZ
TV TEM measurements.
spacing will yield a nominal composition of 1:2 Au/
Pt for a starting composition of 5:1 Au/Pt [49]. This 3.2.4. CO adsorption Studies
value should be treated with some caution since
The IR spectrum of CO adsorbed on TPDT-stabilized
Au-Pt particles show a strong band at 2030 cm-1
and is assigned to the linearly adsorbed CO on the
Pt surface [51]. Hence, in both Au-Pd and Au-Pt
bimetallic particles, an enrichment of Pd and Pt is
observed on the surface.

3.3. Au-Ru bimetallic alloy

nanoparticles
3.3.1. TEM studies
The Au-Ru nanoparticles show a mean particle size
of 4.1 nm (Fig. 8a), which is larger than that of
monometallic Ru nanoparticles (3.0 nm) and smaller
than that of monometallic Ru nanoparticles (6.1 nm)
[52,53]. The high-resolution transmission electron
microscopy (HRTEM) image in the inset shows a
typical Au-Ru nanoparticle with (111) lattice fringes.
The TEM image (Fig. 8c) of the assembled system
indeed shows large extended aggregate structures
consisting of two different types of particles (core-
shell Ag-Pt and core-shell Au-Ru nanoparticles) with
good repeatability, of which, the core-shell Ag-Pt
nanoparticles can be easily identified by the strong
image contrast between the core and shell
Fig. 6. TEM images of Au-Pt Alloy nanoparticles. components. The core-shell Au-Ru nanoparticles
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 141

Fig. 9. XRD studies of Au-Ru alloy nanoparticles.

Fig. 7. XRD patterns of Pt, PtAu(1:1), and AuRu(1:1) become well-defined and sharp due to increased
nanoparticles (from bottom to top) deposited on crystallinity as shown in Fig. 9. On heat treatment
AKBHu= @W
Z] the particle size increases threefold for all bimetal-
lic combinations [56-58].
The XRD spectra of the monometals as well as
the bimetal of different compositions have been
recorded for the as-prepared samples in the form of
dry powders. The molar ratio of silane to metal salt
is maintained at 100:5 [59]. As for the monometals,
it is observed that Ru is more crystalline than the
gold nanoclusters in silicate matrices. The peak that
appears at around 38p(2 ) corresponds to the (111)
crystallographic plane and the peak at around 45p
Fig. 8. TEM image of Au-Ru alloy nanoparticles.
(2 ) corresponds to the (200) plane (JCPDS 4-0784,
5-0681). The diffractograms show that (111) crystal-
lographic surface is marked for gold clusters (2 =
were nearly alternating with each other in the as-
38.46p ) and is broad, while the (200) plane is less
sembly, and forming three dimensional structures
distinct (2 = 44.41p ). Two additional broad bands
on the TEM grid. On the contrary no isolated
are observed at 64.48% (2 ) and 77.71p(2 ) and
particles were found on the TEM grid.
they correspond to the (220) and (311) planes of
TEM image of mixture of core-shell Ag-Pt and
Au, respectively.
Au-Ru nanoparticles functionalized by non-
In the case of Ru, there is a strong band at 56.33p
complementary thiolated oligonucleotides.
(2 ), which closely matches the (222) plane. This is
not surprising since it is known that Ru gets oxidized
3.2.2. XRD studies fairly fast when under ambient conditions [60-62].
The diffractograms of the bimetallic combinations Another strong band is seen at 45.37p(2 ), which
generally show broad bands while their monometallic corresponds to the (200) plane of Ru. The observed
counterparts exhibit fairly sharp bands [54,55]. The reflections for the bimetal clusters are slightly
particle sizes of the bimetallic combinations different from that of the monometallic components.
determined from the XRD spectra correlate well with The (111) plane is observed at 38.62p(2 ) and the
the sizes obtained from TEM measurements. The (200) plane occurs at a value of 45.25p(2 ) for the
particle size is calculated on the base of Debye bimetal of Au-Ru molar ratio 1:1 Fig. 9. These values
Scherrer equation: lie in between the values reported for monometallic
clusters. The particle size has been calculated
Dp 0.9 / cos , (1) fdZ _X9b    e SV t _ SRdVU _e YV  
peak. These values are close to the values deduced
where Dp T c cVda _Ude e YVaRc eZT]
VdZ kVZ _m is from TEM measurements. A fairly strong band is
the Xray wavelength, is the Bragg angle, and seen at 66.2p(2 ), which lies close to the (400)
corresponds to the full width at half maximum (fwhm, reflection of RuO [63]. Two sharp bands are seen at
in radians) of the peak under consideration. When 75.34p(2 ) and 75.15p(2  Z _5fuFfSZ Ve R]R_U
the samples are heated to 200 p C for 3 h, the peaks Ru, respectively.
142 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

nanoparticle. On gold nanoparticles, however, CO

is known to be very weakly and reversibly adsorbed.
The adsorbed CO is generally observed only at low
temperatures for Au-Ru [65].

3.3. Electrochemical studies

The electrocatalytic activity of the nanoparticles
stabilized in silicate matrices has been followed by
carrying out preliminary studies on Au-Ag, Au-Pt
and Au-Ru alloy nanoparticles. A glassy carbon
electrode coated with silicate stabilized
nanoparticles has been used. Oxygen reduction is
taken as the demonstrative case. Use of TEOS
along with TPDT to stabilize the particles facilitates
cross-linking and the resulting films are found to be
very sturdy and adherent to the substrate. Cyclic
voltammetric experiments have been performed on
the modified electrode in phosphate buffer pH 7.2.
Fig. 10 shows the cyclic voltammograms on the
bare as well as nanometal modified electrodes. It is
Fig. 10. Cyclic voltammograms and AFM image of clear that the oxygen reduction potential shifts to
DeFf 0  %
;79 De Ff 0 uAKBH%;79 R_U more positive values in presence of the metallic
DeFf 0  uAKBHu= @%
;79Z_ +A<2SO4 solutions. particles. A potential shift of about 200 mV in the
case of Au-Ru modified classy carbon electrode Fig.
11 shows the catalytic nature of the immobilized
3.3.3. CO adsorption studies metallic particles [66-68].

Infrared spectroscopy has been widely used to study

the surface chemistry of small, adsorbed molecules
3.4. FT-IR studies
[64]. The vibrational frequency of adsorbed CO FT-IR studies have been carried out to follow the
changes with the metal substrate and binding evolution of silicate matrix during the stabilization
structure. Hence, IR spectroscopy of CO on the of the metallic particles. The spectra have been taken
surface of bimetallic nanoparticles is expected to for the dried material and they represent the
give information about the surface of the completely polymerized silicate network

Fig. 11. 7J WRDe Ff 0  uAKBHu= @%

;79Z _D6G a<-  T _e RZ_Z
_X AX]fT dV Af] e
Za]VR_ UZ T
peaks attributed to the oxidation of glucose and resulting intermediates are observed for the positive scan.
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 143

encapsulating the nanoparticles. The IR peaks agree for the low cost manufacturing and fine pitch appli-
well with the reported literature values [66] for silicate cations. Bimetallic alloy nanoparticles properties are
matrices. The band at 1117 cm-1 confirms the pres- influenced by both metals and show more advan-
ence of siloxane groups [ GZ uCuGZ  PZ_e YVa ] j tages over ordinary metallic NPs [74,75]. They offer
merized material while the band at around 1659 tunability in the sense that the metal composition
cm-1 corresponds to the primary amine [ (NH2)] of and structures of nanoparticles can be varied to
the silane. The position of this band shifts to higher optimize the nanostructure properties. Bimetallic
values as the silane is cross-linked and polymer- alloy nanoparticles have shown activities as cata-
ZkVUHYVBu<d e
cVeTYZ _XSR_URcf_U)+ T -1 is lysts in chemical reactions and in environmental
broadened in the cross-linked material as compared remediation. The interest in bimetallic nanoparticles
to that of neat silane. This is attributed to the as MEMS switch lubricants includes controlled
complexation of the amine groups of the silicate Nanotexturing and the ability to tailor contact be-
with the metal particles [66]. havior using desirable properties of each metal in-
volved. Microelectromechanical systems (MEMS)
4. APPLICATIONS OF BIMETALLIC (also written as Micro Electro Mechanical or micro-
ALLOY NANOPARTICLES electronic and Microelectromechanical systems) is
the technology of very small mechanical devices
4.1. Electrical conductivity driven by electricity; it merges at the nano-scale
Among metal fillers, Ag flakes are most widely used into Nanoelectromechanical systems (NEMS) and
because Ag has the highest electrical conductivity nanotechnology. Nanotexturing was proved to be
and, unlike many other metals, their oxides have beneficial for MEMS switch contacts using bime-
relatively better conductivity [69-71]. However, there tallic nanoparticles [76,77]. Metal alloys of Au with
have been some concerns on the electromigration Ag, Cu, Pt, or Pd were found to have decreased
of Ag ions in the Ag filled adhesives in the presence wear as compared to pure Au contacts at the
of high humidity and electrical bias. Thus, other low expense of higher cost [78-80]. Bimetallic
cost metal i.e., copper has been proposed as nanoparticles allow more than one metal to be used
alternate conductive filler in electrically conductive in the contact without the expense and complexity
polymer composites for the next generation, due to of integrating and Au alloy into the MEMS switch
its high electrical conductivity, low electrical fabrication process.
migration, and high compatibility with the next
generation of Cu interconnect technology. However, 4.3. Reduction in electromigration and
due to its facile oxidation, the existence of pure electronics behaviors
copper is difficult and its generation from Cu-salt
Among the variety of bimetallic nanoparticles, Ag-
requires complete inertness. A thin layer of silver
Au Nanoparticles have been investigated as a
coating on copper particles has been an approach
candidate material for electrode or interconnection
to improve the electrical and physical performance
lines in flexible electronics, since Ag films have a
of copper fillers. Conductive polymer composites
lower resistivity (1.63 ) and melting point (961.80C)
filled with these silver coated copper fillers (~5 m)
than other metal films. Nevertheless, pure Ag lines
have shown considerably high electrical conductivity
are liable to induce system failure resulting from
[72]. Another solution is the formation of Ag-Cu alloy.
the electromigration of ions, which is one of the main
A similar approach (i.e., alloying of Au with Ag) can
reliability issues in modern integrated circuits. It is
improve the use of Au as an electrode material by
reported in refs. [81-83] that the alloying of Cu into
decreasing its inertness [73].
Ag reduces the electromigration. Interconnection
]Z_VdT a d VU W 5X_R_ aRc eZ
T]
Vd c 5Xu7fR] ]j
4.2. Electroplating and fabrication nanoparticles fabricated on poly (ether sulfone)
For fabricating the silver coated gold particles, Ag (PES) substrates have been prepared. Moreover,
coating process such as electroplating is required. their electrical characteristics have been
Moreover, current commercial silver-gold particles investigated with and without optical heating [84].
have micron-size, which are larger than the required Nano sized Au/Ru alloy particles synthesized in the
size, will not be suitable for ultra-fine pitch (<100 polymer matrix have overcome the fine pitch
nm) assembly. Thus, a simpler fabricating method interconnection and simplified surface mounting
and finer particles i.e., in nanosize are necessary technology [85,86].
144 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

4.4. Plasmonic and electromagnetic

enhancement
An important application of bimetallic nanoparticles
is their development as substrates (hosts) capable
of providing large electromagnetic enhancements for
surface enhanced spectroscopy [86,87]. Such
enhanced local field properties originates as a result
of surface plasmon resonance (SPR) due to
collaborative oscillations of the free conduction band
electrons on the metal surface on resonant
excitation with electromagnetic radiation [88,89]. The
surface plasmon enhanced luminescence observed
in bimetallic nanoparticles have currently captured
exponential attention due to their relevance as color Fig. 12. Typical cyclic voltammograms of the
displays, optical amplifiers as well as optical methanol oxidation with different bimetallic
sensors [90,91]. nanoparticle catalysts in 2 M CH3OH and 1 M H2SO4
under deoxygenated conditions. The scan rate was
4.5. Unusual optical and electrical 60 mV/s.
properties
The unusual optical and electrical properties of This is a problem that affects such diverse facets of
bimetallic nanoparticles arise due to several factors industry as ventilation systems, automotives, cooling
like modification of the electronic structure of towers, and chemical process plants. It has been
bimetallic nanoparticles like Au-Pt, interplay between demonstrated that nanofluids consisting of Ag-Au
volume and surface properties, chemical reactions in water enhances the thermal conductivity of the
between the nanoclusters and interparticle fluids [96,97]. Additionally, thermal conductivity of
interactions [90,92]. However, fabrication of nano nanofluids has been associated with strong
scale monometallic and particularly inter-metallic temperature dependence [98,99] and a significantly
particles encapsulated within dielectric (glasses) higher critical heat flux than that of the pure fluid
matrices are not simple and encounter several [100].
difficulties like different chemical reactivity of two Electron transport in nanostructures, particularly
metals with the matrix, which can promote in bimetallic nanoparticles and their arrays is not
separation (via oxidation, for instance) instead of only of academic interest, but also holds promise
alloying of the species. in nanoelectronics [101,102]. Synthesis of bimetallic
alloy nanoparticles and nanowires of desired
4.6. Potential applications properties, therefore, assumes countless
significance for the developing world.
Bimetallic alloy nanoparticles embedded in surfaces
regions of glass are of great interest because of
their potential application [93,94]. Specific linear and
4.8. Electrocatalytic activities
nonlinear optical properties have been achieved for Among the platinum based catalysts, Pt-Ru is
Ag-Au alloy nanoparticles in silica glasses [95]. The currently the most promising anode catalyst for the
resulting macroscopic properties are based on a oxidation of methanol in low temperature direct
surface plasmon resonance (SPR), the frequency methanol fuel cells, Bimetallic systems prepared
of which depends strongly on the materials (types by the assembly method linking the Pt and Ru
of metals) and their composition. nanoparticles by a biomolecule (e.g. DNA), have
been explored for applications in catalysis [103].
4.7. Thermal conductivity The catalytic performance of these bimetallic Pt-Ru
aggregates (actually core-shell Ag-Pt and Au-Ru
Nanofluids, consisting of bimetallic nanoparticles
aggregates) in methanol electro-oxidation has been
suspended in a heat-transfer liquid, may offer
evaluated by cyclic voltammetry. The results were
significant enhancement of thermal conductivity,
intended to provide interesting insights into the
which is technologically important for cooling
difference between alloy nanoparticle catalysts and
applications that rely on the efficient transfer of heat.
Synthesis, characterization and applications of bimetallic (Au-Ag, Au-Pt, Au-Ru) alloy nanoparticles 145

Table 1. Comparison of the electrochemical activities of the catalysts.

Nanoparticles onset potential forwardpeak potential forwardpeak current If /Ib current ratio
(mV versus NHE) (mVversus NHE) (A/mgofPt) (efficiency)

Au-Ag 411 913 0.68 2.95

Pt-Au 409 892 0.052 2.34
Ru-Au 431 887 0.10 2.50
Au 351 898 0.033 2.33
Ag 424 899 0.031 2.30

the ensemble of constituent monometallic catalysts. Previous investigators have conducted a

nanoparticles [104]. chronoamperometric along with a CV studies and
Electrocatalytic activities of the MWCNT- demonstrated that catalysts with a higher If/Ib ratio
supported bimetallic nanoparticles for the oxidation are correlated with catalyst longevity [109,110] The
of methanol were examined using CV (Fig. 12). The MWCNT-supported bimetallic nanoparticle catalysts
voltammograms consist of two oxidation peaks: one all exhibit at least 60% higher If/Ib ratio relative to
in the forward scan (arrow left to right) and the other that of Au and Ag monometallic nanoparticles (If/Ib
in the backward scan. It was observed that the = 1.4). It is interesting to note that the Au-Ru
oxidation of the Aurium and bimetallic surfaces bimetallic system has a high If/Ib ratio (2.50) next to
occurred during the forward scan when the switching that of the Pt-Au system [111,112]. Table 1
potential exceeded 1.1 V versus NHE, and during summarizes the onset potentials, the forward peak
the backward scan, the reduction peak was potentials, the forward peak current, and the current
observed at around 0.7-0.8 V versus NHE. Hence, ratio (If/Ib) of each bimetallic electrocatalyst. The
the CV was conducted within the potential range of onset potential suggests the apparent activation
1.1 and 0.3 V versus NHE. As seen in Fig. 12, energy of methanol oxidation. All of the Pt-based
backward scans do not contain the oxidation/ bimetallic catalysts have a lower onset potential than
reduction peak of platinum or the secondary metals. that of the Pt monometallic catalyst, with the onset
The forward scan is attributable to methanol potential of Au being the lowest.
oxidation, forming Au-adsorbed carbonaceous Gold nanoparticles are of high interest as a
intermediates, including carbon monoxide (reaction potential core for bimetallic core-shell nanoparticles,
2) and CO2 (reaction 3). This adsorbed carbon as they are easy to synthesize and more
monoxide (COads) causes the loss of activity of the economically viable than the metals that are
electrocatalyst. [105,106]. generally used for catalysis. Platinum nanoparticles
have been extensively studied for their catalytic
+ -
Pt+ CH3 OH Pt-CO ads + 4 H + 4 e , (2) properties [113] as Pt is a highly useful industrial
catalyst for reducing automobile pollutant gases,
+ - for producing hydrogen from methane and in the
CH3 OH+ H2 O CO 2 + 6 H + 6 e , (3)
direct methanol fuel cell electrochemistry,
The backward oxidation peak, shown as reaction electrocatalysis, and fuel cells.
(4), is attributed to the additional oxidation of the
adsorbed carbonaceous species to carbon dioxide 5. CONCLUSIONS
[56].
The preparation of various bimetallic nanoparticles
+ - in organically modified silicates has been
Pt-CO ads + H2 O Pt+ CO 2 + 2 H + 2 e . (4)
demonstrated. The citrate-stabilized gold
Therefore, the current ratio of the forward scan peak nanoparticle seeds acted as better starting material
current (If) over the backward scan peak current (Ib) for the bimetallic core-shell nanoparticles; but
shows the amount of methanol oxidized to carbon suffered problems with aggregation and morphology.
dioxide relative to carbon monoxide [107,108]. A The thiol-stabilised gold nanoparticles were of
higher If/Ib value suggests that the catalysts are more improved morphology, but that made coating of gold
efficient at lowering the adsorbed carbon monoxide. nanoparticles difficult. Stabilization by PVP was
The current ratio is a useful way of comparing the preferred as it was free of the above disadvantages.
long-term catalytic activity between the different The detailed discussion on Au-Ru and Au-Pt
146 A. Shah, Latif-ur-Rahman, R. Qureshi and Zia-ur-Rehman

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