Well dispersed Pt–Pd bimetallic nanoparticles on functionalized graphene as
excellent electro-catalyst towards electro-oxidation of methanol

Xiaoyu Yan, Tao Liu, Jun Jin, Samrat Devaramani, Dongdong Qin, Xi-
aoquan Lu

PII: S1572-6657(16)30127-8
DOI: doi: 10.1016/j.jelechem.2016.03.033
Reference: JEAC 2564

To appear in: Journal of Electroanalytical Chemistry

Received date: 23 February 2016

Revised date: 21 March 2016
Accepted date: 21 March 2016

Please cite this article as: Xiaoyu Yan, Tao Liu, Jun Jin, Samrat Devaramani, Dong-
dong Qin, Xiaoquan Lu, Well dispersed Pt–Pd bimetallic nanoparticles on functionalized
graphene as excellent electro-catalyst towards electro-oxidation of methanol, Journal of
Electroanalytical Chemistry (2016), doi: 10.1016/j.jelechem.2016.03.033

This is a PDF file of an unedited manuscript that has been accepted for publication.
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Well dispersed Pt-Pd Bimetallic Nanoparticles on Functionalized Graphene as

Excellent Electro-catalyst toward Electro-oxidation of Methanol
Xiaoyu Yan, Tao Liu, Jun Jin, Samrat Devaramani, Dongdong Qin, Xiaoquan Lu*
Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province,

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College of Chemistry & Chemical Engineering, Northwest Normal University,
Lanzhou 730070, China.

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Abstract

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In this paper, an easy carbon radicals reaction procedure is put forward to
functionalized graphene-supported Pt-Pd bimetallic Nanoparticles(NPs). To begin with,

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graphene was functionalized with carboxylic sodium electro-catalyst though method of
π-π interaction, which could provide more binding sites for Pt-Pd NPs. Then a fast
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method of in-situ electrochemical reduction was developed to synthesize highly
dispersed Pt-Pd NPs on functionalized graphene. The prepared nanocomposite was
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characterized by Raman spectroscopy, thermogravimetric analysis (TGA), Fourier

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transformed infrared spectrometry (FT-IR), scanning electron microscopy (SEM),

High-angle annular dark-field scanning transmission electron microscopy
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(HAADF-STEM), and electrochemical technique. The obtained nanocomposite shows

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much high catalytic activity and long-term stability towards methanol oxidation than
that of Pt or Pd black. It was suggesting the synergetic effects of bimetallic NPs.
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Moreover, it demonstrates that the incorporation of the carbon radical reaction with
electrochemical reduction method is a novel approach to functionalize graphene. Our
study may provide a new insight into electro-oxidation of methanol on bimetallic
material.
Keywords: Graphene, radical reaction, electro-catalysts, methanol oxidation

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*Corresponding author. Tel: +86-931-7971276; Fax: +86-931 7971323.
E-mail address: luxq @nwnu .edu.cn (Xiaoquan Lu).
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These authors contributed equally to this work.

1. Introduction
Graphene is a two–dimensional flat structure formed by hexagonal honeycomb
lattice. It has fascinated the scientific community in recent years due to its remarkable

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electronic conductivity, superior mechanical properties, large surface area and thermal
properties. Because of these unique properties, graphene is showing promise in a

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diverse range of applications such as sensors [1], transistors [2], batteries [3]. Besides,

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unlike rolled structured carbon nanotube (CNT) [4] and ordered mesoporous carbons
[5] as catalyst carriers for supporting catalysts. Graphene is also expected to be a

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promising catalyst carrier with open structure which exhibits extremely high specific
surface area to provide sites for catalysts [6, 7]. It is well known that well dispersed
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catalysts on the catalyst carriers can improve their catalytic activity [8-10]. Therefore, it
is necessary to functionalize graphene for introducing surface groups to anchor metal
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ions and form highly dispersed metal particles. To introduce more surface anchoring
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groups and binding sites, surface functionalization of graphene was generally carried
out. Several strategies including non-covalent attachment of large/small
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aromatic-containing molecules through π-π stacking [11]; covalent grafting of

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molecules on the basal plane of graphene [12] and chemical reactions to modify the
functional groups on graphene [13] have been reported. However, these methods either
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lead to weak interaction between the surfaces of graphene and aromatic-containing

materials or cause some structural damage to the graphene. Recently, an easy carbon
reaction [14, 15] was reported to modify CNT efficiently and consequently, a stable
suspension of nanotube in water can be formed. Most importantly, it is found that the
procedure has little destructiveness to the structure of the CNT and no loss of their
electrical conductivity. Considering the similarity in the properties of the CNT and
graphene, this is probably a promising method to functionalize graphene as well.
Pt-Pd bimetallic electro-catalysts are widely used in fuel cells. The synergetic effect
of alloys can overcome poisoning effect of adsorbed CO and the Pt–Pd bimetallic
electrocatalysts can improve catalytic activity due to more available surface active sites
[16-18]. Therefore, several routes were developed to synthesize graphene-supported
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Pt-Pd bimetallic catalysts by reducing Pt and Pd metal ions on graphene, including the
reduction of Pt-Pd NPs in a water–ethylene glycol system [19], using NaBH4 [20] and
ascorbic acid [21, 22] as reduction agent. However, these methods are time-consuming.
To overcome these shortcomings, in-situ electrochemical reduction of precursor metal

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ions [23] is a promising method to form uniform Pt catalysts on graphene [24] and
Pt-Pd bimetallic catalysts onto TiO2 [25] with fastness. To the best of our knowledge,

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there is no report in which in-situ electrochemical reduction is employed to synthesize

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well dispersed Pt -Pd NPs on functionalized graphene.
The aim of this work is to synthesize uniform and well-ordered carboxylic

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sodium-functionalized graphene (CS-G) and further synthesize well dispersed metal
particles onto the CS-G by in-situ electrochemical reduction method. As a model, the
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catalytic activity of the Pt-Pd on CS-G as catalyst towards the electro-oxidation of
methanol is evaluated. As a comparison, Pt-Pd electro-catalysts supported on on the
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graphene (G) without functionalization by carboxylic sodium and Pt electro-catalysts

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supported on the CS-G for electro-oxidation of methanol were also investigated.

2. Experimental
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2.1. Apparatus and Characterization

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All electrochemical measurements were carried out using a CHI 660C electrochemical
workstation (Shanghai Chenhua Instrument Co. Ltd., China). A three-electrode system
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was employed for all the electrochemical studies, which comprise of the glassy carbon
electrode (GCE) (θ=3 mm diameter) or a modified electrode as a working electrode,
platinum wire as the auxiliary electrode, and an Ag/AgCl (sat. KCl ) electrode as a
reference electrode. All potentials were referred to the reference electrode.
The surface morphologies of the prepared electrodes were observed through
scanning electron microscopy (SEM) on Zeiss Ultra plus field emission scanning
electron microscope. The distribution of each element in the NPs was observed
through high-angle annular dark-field scanning transmission electron microscopy
(HAADF-STEM) on JEM-3010 transmission electron microscope. Raman spectra
were obtained on a J-Y Labram HR800 Raman spectrometer. Fourier transformed
infrared spectroscopy 3000 was used to record the FTIR spectra.
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2.2. Synthesis of carboxylic sodium -functionalized graphene and Pd-Pt /CS-G

modified GCE
GO nanosheets were synthesized from graphite flakes by a modified Hummers’ method
[26]. Concentrated H2SO4 (34.5 mL) was added to a mixture of graphite flakes (1.5 g)

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and NaNO3 (0.75 g), and the mixture was cooled to 0 ℃. Then KMnO4 (4.5 g) was

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added to the mixture slowly and reaction temperature was kept below 20 ℃. The

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reaction mixture was warmed to 35 ℃ and stirred for 30 min, then water (69 mL) was

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added and the mixture was producing a large exotherm to 98 ℃ for 15 min. After the
removal of heat, water (210 mL) and 30% H2O2 (1.5 mL) were added. The exfoliation

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of graphene oxide was performed by ultrasonication.
The reduced graphene oxide (rGO) was prepared according to the previously
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reported method starting with GO solution [27]. Briefly, GO (100 mg) was dispersed
into the water (100 mL), then hydrazine hydrate (1.00mL) was added and the solution
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heated in an oil bath at 100 ℃ under a water-cooled condenser for 24 h over which the
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rGO was obtained.

Carboxylic sodium-functionalized graphene was prepared following the reported
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protocol with some modifications [15]. In brief, 100 mg graphene was dispersed in
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100mL of toluene by sonication. Subsequently, 20mL of toluene solution containing

6.40 g azodiisobutyronitrile (AIBN) was added to the dispersion under strong stirring.
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The resulting dispersion was heated at 75 ℃ for 4 h in Ar atmosphere, after the

graphene-cyano (graphene-CN) was produced. 50 mg graphene-CN was dispersed in a
mixture of methanol (VCH3OH:VH2O=1:5) and 10 M sodium hydroxide, the resultant
dispersion was subjected to refluxing at 60 ℃ for 48 h, and finally the CS-G was
obtained.
As-synthesized CS-G was ultrasonically dispersed in 0.05 % Nafion solution to form
a homogenous suspension (1 g/L). The CS-G modified GCE was prepared by casting 5
μL of CS-G suspension on the electrode surface and drying at room temperature. The
CS-G modified GCE was dipped into 0.1 M KCl solution containing 3.75 mM PdCl2
and electrochemically grafted by applying a constant potential of -0.2 V (vs. Ag/AgCl)
for 100 s. Subsequently, the resulted Pd/CS-G modified GCE (Pd/CS-G/GCE) was
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used to direct the growth of Pt at a constant potential of -0.35 V (vs. Ag/AgCl) in 0.1 M
NaClO4 solution containing 3.75 mM H2PtCl6 for 300 s. Then Pt-Pd co-loaded
electro-catalysts on carboxylic sodium-functionalized graphene (Pt-Pd/CS-G/GCE)
were obtained. As a control, the Pt-Pd/G/GCE was obtained on the graphene by the

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same conditions of electro-deposition that of Pt-Pd/CS-G/GCE. The Pt/CS-G/GCE was
obtained by only electro-deposition of Pt at -0.35 V in 0.1 M NaClO4 solution

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containing 3.75 mM H2PtCl6 for 300 s and Pd/CS-G/GCE was obtained by only

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electro-deposition of Pd at -0.2 V in 0.1 M KCl. solution containing 3.75 mM PdCl2
for 100 s.

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3. Results and discussion
The schematic design of synthesis of uniform carboxylic sodium-functionalized
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graphene and the fabrication of well dispersed Pt-Pd co-loaded on CS-G are presented
in scheme 1. As shown in scheme.1, graphene is functionalized with carboxylic sodium
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groups by the thermal decomposition of AIBN. The corresponding Raman spectra of

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CS-G (a) and graphene (b) are shown in Fig 1. As can be seen, the CS-G (a) shows the
D (where the D peak is a defect peak due to intervalley electron scattering [28].) and G
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bands (G refers to the graphene G peak) at 1323 cm-1 and 1567cm-1.respectively. The
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intensity ratio of D/G is found to be 0.5157.which is slightly higher than that of

graphene (b, the D/G intensity ratio is 0.45), suggesting that the carbon radicals
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reaction is a little reduced to of the average size of graphene (determining the electrical
conductivity of graphene sheets). The result demonstrates that the carbon radical
reaction is an effective method to modify the graphene with ignorable destructiveness.
The thermogravimetric analysis (TGA) of graphene and CS-G are shown in Fig. 2
Graphene (Fig. 2a) exhibits high thermal stability, the weight loss of 0.958 wt% below
150 ℃ illustrates negligible water loss in graphene given its hydrophobic nature. The
onset of weight loss occurs at 600 ℃ relative to the thermal decomposition of graphene,
and a 11.41 wt% weight losses is observed up to 800 ℃. As a comparison, the TGA of
the CS-G has also been investigated in Fig. 2b. It is found that the weight loss of 4.4
wt% below 150 ℃ indicate a little water loss in CS-G given its hydrophilic nature. The
sharper decomposition rates in the temperature range 250-450 ℃ indicate that the
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graphene structure acts as acceptor of carboxylic sodium groups during the oxidative
degradation of carboxylic sodium groups. It suggests that carboxylic sodium groups are
efficiently grafted onto graphene.
The Fourier transform infrared spectroscopy (FT-IR) of graphite, graphene, GO,

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graphene-CN and CS-G are shown in Fig. 3. The spectrum of graphene oxide
illustrates O–H (ν (carboxyl)) at ~1400 cm-1, O–H (broad coupling ν (O–H)) at ~3200

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cm-1 originated from carboxylic acid, while the band at ca. 3450 cm-1 could be due to

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the O–H stretching mode of the intercalated water [29]. The characteristic peaks of
C–O (ν (epoxy or alkoxy)) at ~1050 cm-1, and C=O in carboxylic acid and carbonyl

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moieties (ν (carbonyl)) at ~1750 cm-1 respectively. Compared with the spectrum of
graphene (Fig. 3c), graphene-CN (Fig. 3d) exerts a characteristic peak of cyano groups
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at ca. 2235 cm-1, which suggests that carbon radicals originated from AIBN are
efficiently grafted onto graphene. As shown in (Fig. 3e), the disappearance of the peak
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of cyano groups and the appearance of peak at 1570 cm-1 and 1398 cm-1 confirmed that
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carboxylic sodium groups are produced by hydrolysis of cyano groups on

graphene-CN.
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The carboxylic sodium-functionalized graphene is further modified with metal

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particles by the in-situ electrochemical reduction of Pd and Pt ions to form Pt-Pd/CS-G

onto GCE. The SEM image of the resultant Pt-Pd/CS-G/GCE is shown in Fig. 4B. It
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can be seen that spherical Pt-Pd co-loaded catalysts are obtained on the CS-G/GCE and
the size of the Pt-Pd co-loaded catalysts is in the range of 40 to 90 nm. Compared with
the Pt-Pd catalysts on G/GCE in Fig. 4C, the Pt-Pd catalysts on CS-G/GCE are
smaller in size. This suggests that smaller size on the surface of graphene could provide
binding sites for anchoring precursor palladium ions by coordination reaction, which is
beneficial to the metal NPs loading with controllable feature size [21]. For a
comparison, Pt spherical catalysts onto CS-G/GCE were obtained by the same
procedure but in the absence of Pd. As seen from SEM images in Fig. 4A, the size of
the Pt spherical catalysts ranges from 40 nm to 200 nm. Besides, the Pt spherical
catalysts show significant aggregation, as compared with Pt-Pd catalysts on CS-G/GCE.
It means that well dispersed Pd catalysts may serve as dispersants for co-deposition of
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Pt and Pd NPs [25]. The corresponding Energy Dispersed X-ray (EDX) spectrum of
Pt-Pd co-loaded catalysts on CS-G/GCE in Fig. 4D shows the signals of C, O, Pd, and
Pt elements, confirming the existence of Pt-Pd on the surface of carboxylic
sodium-functionalized graphene.

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To gain further insight into the distribution of each element in NPs, the
HAADF-STEM-energy-dispersed X-ray spectroscopy (EDS) images of

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Pt-Pd/CS-G/GCE were obtained .In addition, the measuring area of HAADF-STEM is

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arbitrarily selected and from EDS elemental mapping images (Fig. 5a) the following
conclusions can be obtained: CS-G is modified on the GCE as basal of

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electro-deposition, therefore, C, Na and O element can be seen in the whole area. The
2D-projected elemental maps for the Pd and Pt elements are shown in Fig. 5e-g. The
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presence of large amounts of Pd element, less Pt element in the selected area can be
seen from Fig. 5e-h. Afterwards, we can conclude that the both Pd and Pt NPs have
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been successfully loaded and obviously, the former is the major component in the
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mixed metal NPs.

To investigate the electro-catalytic activity of the Pt-Pd/CS-G/GCE towards the
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electro-oxidation of methanol, cyclic voltammogram (CV) of Pt-Pd/CS-G/GCE, Pt-Pd

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/G/GCE and Pt/CS-G/GCE are carried out in N2-saturated 1 M H2SO4 solution

containing 1 M CH3OH. As seen from Fig. 6, the peak current density of Pt-Pd
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/CS-G/GCE for the electro-oxidation of methanol is 15.7 mA/cm2, which is about 4

times larger than that of Pt-Pd/G/GCE (3.91 mA/cm2) and is nearly 2.5 times larger
than that of Pt/CS-G/GCE (6.34 mA/cm2). The quantity of Pd NPs loaded on the
electrode is too little, so catalytic performance was too low to be seen in the CV curve.
This clearly shows that the Pt-Pd/CS-G/GCE exhibits superior electro-catalytic activity
towards the oxidation of methanol. Compared with that of Pt-Pd/G/GCE, high activity
of the Pt-Pd/CS-G/GCE could be due to better dispersion of Pt-Pd on the CS-G/GCE
than that on the G/GCE. The higher electro-catalytic activity of Pt-Pd/CS-G/GCE than
the Pt/CS-G/GCE is most likely due to the synergetic effects of Pt and Pd catalysts. In
addition, much higher If/Ib value (2.27, If and Ib denote the peak currents for forward
and backward potential scans, respectively) on Pt-Pd/CS-G/GCE than that on Pt
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/CS-G/GCE (1.53) was observed, which demonstrates that more effective oxidation of
methanol occurs on Pt-Pd/CS-G/GCE in the forward potential scan, representing less
accumulation of CO ads-like species on the catalyst surface due to the synergetic effect
of bimetallic and resulting a better CO-poisoning tolerance of Pt-Pd/CS-G catalysts.

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Electrochemical impedance spectroscopy (EIS) is an efficient tool for studying the
interface properties of the surface-modified electrodes [30]. The semicircle diameter

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equals the electron transfer resistance, Rct [31]. The resistance showed that the

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electronic transmission power of the modified layer. Fig.7 is the impedance spectra of
frequency range of 100 kHz to 0.1 Hz in the solution of 5 mM Fe(CN)6)4-/3-,According

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to the fitting of data it can be known, in the high frequency region, the sequence of Rct
for the four electrodes can be inferred as Pt-Pd/CS-G﹤ Pt-Pd/G﹤Pt/CS-G﹤GCE.
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This result means that Pt-Pd/CS-G has the lowest charge-transfer resistance value due
to the synergy of metals i.e. Pd NPs and Pt NPs. Durability is one of the major concerns
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in direct methanol fuel cell (DMFC), the stability of Pt-Pd/CS-G/GCE is further

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examined by the time-dependent current density curve. Fig. 8 shows that the
steady-state polarization curve for Pt-Pd /CS-G/GCE is about 2.0 times higher than that
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for Pt-Pd/G/GCE and is nearly 24 times higher than that for Pt/CS-G/GCE, further
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indicating that the Pt-Pd/CS-G/GCE composites has superior electro-catalytic activity

towards the electro-oxidation of methanol. In addition, the current density of the Pt-Pd
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/CS-G/GCE shows long-term stability, indicating that the Pt-Pd/CS-G/GCE possesses

good poisoning-tolerant towards reaction intermediates and favors long-term
application as the anode materials in DMFC.
4. Conclusions
We proposed an easy carbon radicals reaction procedure to synthesize the CS-G and
a fast method of electrochemical reduction to fabricate well dispersed Pt-Pd
electro-catalyst on the CS-G. The carbon radicals reaction procedure is employed to
synthesize the CS-G which possess uniform and well-ordered carboxylic sodium
groups on the surface of graphene, these groups could provide binding sites for Pt-Pd
NPs, which introduce with uniform distribution to grow metal particles by the in-situ
electrochemical reduction method. Most importantly, the resultant Pt-Pd /CS-G/GCE
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shows much higher synergistic catalytic activity and more long-term stability towards
the electro-oxidation of methanol than that of Pt-Pd/G/GCE and Pt/CS-G/GCE,
demonstrating a new approach for the development of high-performance Pt-Pd
co-loaded electro-catalysts on graphene. The present approach can be extended to

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control the morphology of their particles on graphene for electro-catalytic or
electrochemical sensors.

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Acknowledgments

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This work was supported by National Natural Science Foundation of China (Grant Nos.
21327005, 21175108); the Program for Chang Jiang Scholars and Innovative Research
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Team, Ministry of Education, China (No. IRT1283); and the Program for Innovative
Research Group of Gansu Province, China (Grant No.1210RJIA001). The Program of
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Innovation and Entrepreneurial for Talent, LanZhou, Gansu Province, China (Grant No.
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2014-RC-39)
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[30] P. Xi, Y. Cao, F. Yang, C. Ma, F. Chen, S. Yu, S. Wang, Z. Zeng, X. Zhang, Facile
synthesis of Pd-based bimetallic nanocrystals and their application as catalysts for
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catalyst for methanol fuel cell, Electrochem. Commun. 8 (2006) 129-132.

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Figure Captions
Scheme.1 The scheme of synthesis of carboxylic sodium - functionalized graphene and
the fabrication of well dispersed Pt-Pd on CS-G.

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Fig.1 The Raman spectra of the CS-G (a), graphene (b).
Fig. 2 TGA of graphene(a), CS-G (b).

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Fig.3 FT-IR spectra of graphite (a), graphene oxide(GO) (b), graphene (c),

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graphene-CN (d), CS-G (e).
Fig.4 SEM images of Pt/CS-G/GCE (a), Pt-Pd/CS-G/GCE (b), Pt-Pd/G/GCE (c), and

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EDX of Pt-Pd/CS-G (d).
Fig.5 HAADF-STEM images of Pd-Pt/CS-G. (a) HAADF-STEM image. (b – g)
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STEM-EDS elemental maps of the Pd-Pt/CS-G.
Fig.6 CV of Pt-Pd/CS-G/GCE (1,black), Pt/CS-G/GCE(2,red), Pt-Pd/G/GCE(3,bule)
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and Pd/CS-G/GCE (4,pink) in N2-saturated 1 M H2SO4 solution containing 1 M

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CH3OH at a scan rate of 50 mV/s.

Fig.7 EIS results of GCE, Pt/CS-G/GCE, Pt-Pd/G/GCE and Pt-Pd/CS-G/GCE
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electrodes in 0.1 M KCl electrolyte solution containing 0.005 M [Fe(CN)6]4–/3–.

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Fig.8 Time-dependent current density curve of these working electrodes at 0.4 V (vs
Ag/AgCl ) in N2 saturated 1 M H2SO4 solution containing 1 M CH3OH
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Scheme.1

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Fig.1

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Fig.8

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Graphical Abstract

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An easy carbon radicals reaction procedure is proposed to functionalized

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graphene-supported Pt-Pd bimetallic Nanoparticles(NPs). graphene was functionalized

with carboxylic sodium electro-catalyst though method of π-π interaction, which could
provide more binding sites for Pt-Pd NPs. Then a fast method of in-situ electrochemical
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reduction was developed to synthesize highly dispersed Pt-Pd NPs on functionalized

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graphene. The obtain nanocomposite shows much high catalytic activity and long-term
stability towards electro-oxidation of methanol.
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Highlights:
1. An easy carbon radicals reaction procedure was firstly put forward to synthesize

CS-G.

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2. Functionalized graphene could provide more binding sites for Pt and Pd NPs.

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3. A fast method of electrochemical reduction synthesized highly dispersed Pt-Pd NPs

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on CS-G

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4. The nanocomposite shows much higher catalytic activity and more long-term

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stability.
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