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Bimetallic PtPd nanoparticles on Naongraphene lm as catalyst for ethanol electro-oxidation

Xia Yang,a Qingdan Yang,b Jun Xua and Chun-Sing Lee*a
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Received 30th December 2011, Accepted 12th February 2012 DOI: 10.1039/c2jm16916a A simple electrochemical method is employed to synthesize nanoparticles of bimetallic PtPd alloy on Naongraphene lm. The alloy nanoparticles exhibit efcient electrocatalytic activity and stability toward ethanol oxidation in alkaline media. With the synergetic effects of the PtPd nanoparticles and the enhanced electron transfer stem from graphene, this anode catalyst has higher current density than the monometallic Pt or Pd catalyst. Moreover, this anode catalyst has a low onset potential at 0.73 V (vs. Ag/AgCl) and a high ratio of forward peak current density to backward peak current density (If/Ib) of 5.45. The results indicate that the catalyst has good tolerance against poisoning by intermediates generated during ethanol electro-oxidation and is effective in cleaving the CC bond to achieve oxidation of ethanol to CO2.

Introduction
The direct alcohol fuel cell (DAFC) has been considered as a promising power source for portable electronic devices and fuel-cell vehicles.1,2 Much research has been carried out on methanol oxidation to supply energy for replacing fossil fuels. However, the toxicity of methanol hinders the development of DAFCs. Recently, the direct ethanol fuel cell (DEFC) has attracted a lot of attention as ethanol is non-toxic, abundant, inexpensive and has a higher energy density than methanol. Development of a new anodic catalyst for ethanol oxidation is thus important work for improving the cell performance.3 Platinum is the most common catalyst in DEFCs, however, it is too expensive. As palladium is 50 times more abundant on earth and cheaper than Pt, a Pd-based catalyst is considered an excellent substitute for Pt in DEFCs.4 Nowadays, bimetallic or trimetallic materials with synergistically enhanced performance have been used for electrocatalytic, electronic and magnetic applications.5 Some new anode alloy catalysts like PdAu,6,7 Ru@PtPd/C,8 PdAg,9 PdNi,10 PtPdAu,11 PdRh12 have been applied in DEFCs. Graphene, as an atomic-layer-thick two-dimensional material, is a good supporting substrate for active species because of its good conductivity, high chemical stability and large surface area.13,14 Loading of metal nanoparticles on graphene can lead to nanocomposites with larger active surface areas and improved electron transport for enhancing electrocatalytic reactions.15 Moreover, graphene sheets are hydrophobic and form
a Center of Super-Diamond and Advanced Films (COSDAF) & Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR, Peoples Republic of China. E-mail: apcslee@cityu.edu.hk; Tel: +852-34427826 b COSDAF & Department of Biology and Chemistry, City University of Hong Kong, Hong Kong SAR, Peoples Republic of China

agglomerates easily and irreversibly in aqueous solution in the absence of dispersing reagents. So many efforts have been made to stabilize graphene sheets by covalent or non-covalent modication or by dispersing graphene into aromatic molecules, surfactants, and polymers.16 In this study, Naon (Nf), a negatively charged ion-exchange membrane, one kind of peruorinated polymer, is used to disperse graphene and immobilize graphene onto the electrode. The Nfgraphene composite is then used as a matrix for hosting PtPd alloy catalyst. The composite PtPd/Nfgraphene catalyst shows efcient electrocatalytic activity and good stability toward ethanol oxidation in alkaline media. This anode catalyst has a low onset potential at 0.73 V (compared with the Ag/AgCl reference electrode) and a high ratio of forward peak current density to backward peak current density (If/Ib) of 5.45, indicating a strong resistance against poisoning from intermediates generated during the electrooxidation of ethanol.

Experimental section
Synthesis of graphene Graphene used here was prepared with the modied Hummer method.17,18 Firstly, 1 g of graphite, 0.5 g of NaNO3 and 30 mL of H2SO4 (98 wt%) were added into a ask with stirring in an ice bath. Then 3.0 g of KMnO4 was added gradually in one hour. After cooling, the mixture was continually stirred at room temperature for 3 days. The mixture was then slowly added into 100 mL of 5 wt% H2SO4 in one hour under stirring. After another two hours of stirring, 2.7 mL of 30 wt% H2O2 was added into the mixture and stirred again for two more hours. The mixture was then ltered and washed with a solution of 0.5 wt% H2O2 and 3 wt% H2SO4 for several times. Finally, the mixture
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was washed with distilled water to remove residual metal ions and acid. The product graphene oxide (GO) was dried in air. The GO sample was then dispersed in distilled water (0.05 wt%) and exfoliated in an ultrasonic bath. 25 mL of the dispersion was then mixed with 44 mL of distilled water, 154 mL of ammonia and 22 mL of hydrazine. The mixture was reuxed in a water bath at 95  C for 1 hour to obtain a homogeneous graphene dispersion. Preparation of Naongraphene modied electrode
Downloaded by Korea Institute of Science and Technology / KIST on 28 March 2012 Published on 14 March 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16916A

The Naongraphene composite (Nfgraphene) was prepared by adding 40 mL of the graphene dispersion into 100 mL of 0.7 wt% Naonethanol dispersion under ultrasonication. A glassy carbon electrode (GCE, F 3 mm) was consecutively polished with 0.3 and 0.05 mm alumina powder to obtain a mirror-like surface. It was rinsed with deionized water and ethanol in an ultrasonic bath and then dried in air. The GCE was then dipped into the Nfgraphene dispersion and nally dried in air. Preparation of bimetallic PtPd alloy, Pt nanoparticles, Pd nanoparticles Electrochemical measurements were carried out on a CHI 660D electrochemistry workstation (CH Instruments, Inc, USA). A conventional three-electrode system was used with an Ag/AgCl reference electrode, a platinum wire auxiliary electrode and the modied GCE as the working electrode. Bimetallic PtPd alloy nanoparticles were deposited onto the Nfgraphene modied electrode at 0.2 V for 60 seconds in a solution of PdCl2 (20 mM) and H2PtCl6 (20 mM). Monometallic Pt or Pd particles were similarly deposited on an Nfgraphene modied electrode by using solution with only the Pt or the Pd salts for 60 seconds (20 mM each). All the electrodes (PtPd/Nfgraphene, Pt/Nf graphene and Pd/Nfgraphene modied) were nally rinsed with deionized water and dried in air before use. For comparison, electrodes with only PtPd/Nf (i.e. without graphene) modications were also prepared.

Fig. 2 TEM image of (a) Naongraphene lm and (b) bimetallic PtPd particles on the Naongraphene lm.

Results and discussion

Fig. 1 shows scanning electron microscopy (SEM) images of the PtPd particles on the Nfgraphene lm. Aggregated graphene sheets can be seen in the background of Fig. 1a. From Fig. 1b, we can see that the PtPd particles have sizes of about 200300 nm and are surrounded by graphene nanosheets. Fig. 2 shows transmission electron microscopy (TEM) images of the Nfgraphene lm (Fig. 2a) and PtPd particles on the

Nfgraphene lm (Fig. 2b). The inset of Fig. 2b shows that each PtPd particle is actually composed of many small nanoparticles. X-Ray diffraction (XRD) measurements of the samples were carried out to determine whether the nanoparticles consist of a mixture of elemental Pt and Pd or of PtPd alloy. XRD patterns of Pt, Pd, PtPd nanoparticles on Nfgraphene lms on indium tin oxide (ITO) glass substrates were shown in Fig. 3a. Pt and Pd nanoparticles show peaks that match well to those of fcc Pt (JCPDF 04-0802) and Pd (JCPDF 46-1043). The PtPd nanoparticles show peaks similar to those of the elemental nanoparticles. Fig. 3b is an expanded view of the (111) peaks of the three samples. It can be clearly seen that the position of the (111) peak of PtPd (40.18 ) is in between those of Pt (39.96 ) and Pd (40.32 ). This has been considered as an indication of the formation of PtPd alloys.19,20 Composition of the PtPd particles on the Nfgraphene lm was analyzed via energy-dispersive X-ray spectroscopy (EDS) carried out in a TEM running in a scanning transmission electron microscope (STEM) mode with a probe spot size of 0.7 nm. Fig. 4 shows an STEM image (top left) and a corresponding high-resolution TEM (HRTEM, bottom left) image of the several isolated PtPd particles of about 5 nm size. The lattice fringes show interplanar spacing of 0.221 and 0.191 nm in the particles, which match well respectively with those of the (111) and the (200) planes of fcc PtPd alloy. EDS spectra from ve particles (marked as 1 to 5) were measured. The gure on the right shows the EDS spectrum measured from particle 1. The copper signal in the EDS spectrum is due to the TEM sample grid. Atomic compositions are summarized in the table in Fig. 4. The results show that the particles have a homogeneous composition of Pd : Pt in roughly a ratio of 9 : 1. The higher

Fig. 1 SEM images of bimetallic PtPd particles on the Naongraphene lm.

Fig. 3 (a) XRD patterns of Pt, Pd, PtPd nanoparticles on Naongraphene lm on ITO coated glass substrates. Peaks marked with * originated from the ITO substrate. (b) An expanded view of the (111) peaks.

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Fig. 4 Top left: STEM of bimetallic PtPd alloy on the Naongraphene lm and ve position EDS sampling points (spot size: 0.7 nm). Bottom left: HRTEM of the STEM position. Top right: EDS of PtPd nanoparticles on Naongraphene lm. Bottom right: composition analysis at the ve positions.

concentration of Pd can be attributed to the electrostatic interactions from the negative charged Naon. The positively charged Pd2+ ions would be preferentially attracted to the surface of the electrode compared with the negatively charged PtCl62 ions. These ions would then be reduced to form the PtPd nanoparticles. That is why there is more Pd than Pt in the particles. X-Ray photoelectron spectroscopy (XPS) has also been carried out to study the composition of the PtPd alloy on the Nf graphene lm. Pt 4f and Pd 3d spectra of the sample are shown in Fig. 5. It has two peaks (4f7/2, 4f5/2) with binding energies at 70.85 and 74.3 eV for Pt 4f in Fig. 5a, respectively. Pd (3d5/2, 3d3/2) peaks are also observed at 335.25 and 340.45 eV in Fig. 5b. The results agree well with ref. 21 and 22, which further conrm that the PtPd alloy has been successfully deposited on the Nfgraphene lm. Cyclic voltammogram (CV) behavior of the PtPd/Nfgraphene/GCE sample was studied preliminarily in 0.5 M H2SO4 (Fig. 6a). In the gure, the current peaks between 0.35 and 0 V are attributed to hydrogen adsorption and desorption.23 The rst peak at 0.3 V is due to oxidation of adsorbed hydrogen (Hads); whereas the subsequent peak at 0.1 V corresponds to the

oxidation of the absorbed hydrogen (Habs) by absorption on the PtPd surface.24 The cathodic peak at 0.4 V is caused by the reduction of metal oxide.25 The effective catalytic surface area (ECSA) is evaluated by the total electric charge of hydrogen adsorption and desorption (QH) on the PtPd nanoparticles, which is obtained by integrating the area under the anodic peaks in the hydrogen region. By assuming the charge per actual active area of the catalyst is 210 mC cm2, the ECSA can be calculated by QH/210 mC cm2. Accordingly, ECSA for the PtPd/Nfgraphene, Pt/Nfgraphene and Pd/Nfgraphene electrodes were estimated to be 0.75 cm2, 0.56 cm2 and 1.06 cm2 respectively. Fig. 6b shows a CV curve of the PtPd/Nfgraphene/GCE sample in 0.5 M NaOH aqueous solution. It shows an obvious cathodic peak at 0.5 V, which is caused by the oxygen desorption at PtPd alloy nanoparticles.26 The electro-catalytic activities to ethanol oxidation by the PtPd/Nfgraphene/GCE, Pt/Nfgraphene/GCE and Pd/Nfgraphene/GCE catalysts were evaluated by CV tests, as shown in Fig. 7a. The current densities are normalized with respect to the ECSA. All the catalysts show characteristic well-separated anodic peaks in the forward and reverse sweeps due to ethanol oxidation. It can be obviously seen that the PtPd/Nfgraphene/ GCE catalyst shows higher electrocatalytic activity than the monometallic Pt/Nfgraphene/GCE and Pd/Nfgraphene/GCE catalysts. The maximum current density is 7.69 mA cm2, 2.28 mA cm2 and 0.56 mA cm2 for the PtPd/Nfgraphene/ GCE, the Pt/Nfgraphene/GCE and the Pd/Nfgraphene/GCE catalysts, respectively. The onset potential is a key parameter for evaluating the activity of catalyst. Fig. 7b is an enlarged view of Fig. 7a in the low potential region for comparing the onset potential of the three catalysts. The onset potential of the PtPd/ Nfgraphene/GCE catalyst was found to be around 0.73 V (vs. Ag/AgCl) which is considerably lower than those of the other two mono-metallic catalysts. Tolerance to poisoning species was reected by the ratio of the forward peak current density to the backward reverse peak current (If/Ib). The If/Ib ratio of the PtPd/ Nfgraphene/GCE catalyst (5.45) is 5.2 and 1.4 times higher than those of Pt/Nfgraphene/GCE (1.05) and Pd/Nfgraphene/GCE catalysts (4.00), suggesting that the alloy catalyst possesses a much better poison tolerance. The enhanced catalytic activity of bimetallic over pure metals is usually ascribed to several effects.27,28 It is considered that the alloying component tends to leach out under electrochemical conditions and results in a surface rich in noble metal. Therefore, it yields a surface which

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Fig. 5 XPS spectra of the PtPd alloy on Naongraphene lm.

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Fig. 6 CV curves of a PtPd alloy on Naongraphene lm in (a) 0.5 M H2SO4 and (b) 0.5 M NaOH (scan rate: 50 mV s1).

Fig. 7 (a) Cyclic voltammetry (CV) and (b) zoom portion of CV of different modied electrodes for ethanol oxidation in 0.5 M NaOH + 1 M ethanol.

is more active than monometallic alone. The alloy also has changed the geometrical ligand (e.g. decrease in PtPt bond distance) or electronic effect (e.g. increase of Pt d-electron vacancy), so one of the elements alters the electronic properties of the other to yield a more active catalytic surface. Key performance parameters in this work and some metal catalysts in references under the same test conditions are listed in Table 1. It can be seen that the PtPd/Nfgraphene/GCE catalyst

has good electro-catalytic activity among these metal catalysts. This may due to the synergetic effects of the PtPd nanoparticles, which are more effective at breaking the CC bond of ethanol and enhance the total oxidation of ethanol to CO2. To understand the function of graphene in the catalytic reaction, CV characteristics of the PtPd/Nfgraphene/GCE and the PtPd/Nf/GCE samples were shown in Fig. 8a. It can be seen that the maximum current density of the PtPd/Nfgraphene/GCE is

Table 1 Comparison of electrocatalytic activity with different catalysts Catalysts PtPd/Nfgraphene Pt/Nfgraphene Pd/Nfgraphene Pd nanowire PdMWCNTNi Pd80Au20 Pd/Ni foam Pd nanowire array Pd/3,4-polyethylenedioxythiophene Pdpolyaniline nanober PdNi/C PdNi PdAg Ru@PtPd/C Tetrahexahedral Pd nanocrystals PdAu/graphene
a

Onset potential/V 0.73 (vs. Ag/AgCl) 0.62 (vs. Ag/AgCl) 0.60 (vs. Ag/AgCl) 0.664 (vs. SCE) 0.635 (vs. SCE) 0.68 (vs. SCE) 0.63 (vs. SCE) 0.62 (vs. SCE) 0.56 (vs. SCE) 0.7 (vs. SCE) 0.65 (vs. MMO)a 0.81 (vs. MMO) 0.80 (vs. SCE) 0.786 (vs. SCE)

If/Ib 5.45 1.05 4.00 1.38 1.15 1.05 1.5 0.48 7.37

Supported solution Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/KOH Ethanol/NaOH Ethanol/KOH Ethanol/NaOH Ethanol/NaOH Ethanol/KOH Ethanol/NaOH Ethanol/KOH

Ref. This work This work This work 2 29 4 30 31 24 32 33 34 35 8 23 36

MMO: 0.098 V vs. SHE.

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Fig. 8 (a) Comparison of electrodes with (black) and without graphene (red) for ethanol oxidation in 0.5 M NaOH + 1 M ethanol. (b) Chronoamperometric curves for ethanol electro-oxidation at 0.43 V (vs. Ag/AgCl) in 0.5 M NaOH + 1 M ethanol.

present a better catalytic activity towards ethanol than Pt and Pd monometallic catalysts. Moreover, the Nfgraphene lm is an effective catalyst support for promoting the electron transfer, and the bimetallic PtPd/Nfgraphene catalyst as an anode catalyst has potential applications in direct alcohol fuel cells.

Acknowledgements
This project has been nancially supported by Research Grants Council of HKSAR (no. CityU 101910). The authors thank Mr T. F. Hung for TEM and STEM characterization.

References
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larger than that of the PtPd/Nf/GCE catalyst. Fig. 8b shows chronoamperometric experiments on the PtPd/Nfgraphene/ GCE and the PtPd/Nf/GCE at 0.43 V for 1200 s. We can see that the current density of the PtPd/Nfgraphene/GCE is larger than that of the PtPd/Nf/GCE. The result indicates that graphene can effectively promote the oxidation of ethanol to CO2 by PtPd nanoparticles, which is attributed to the good charge transfer characteristic of graphene. The long-term stability of the PtPd/Nfgraphene/GCE catalyst toward ethanol oxidation was assessed via a CV test for 25 cycles (Fig. 9). The current density retained about 90% of the original one, suggesting that the catalyst exhibits a good stability to ethanol oxidation. This shows that activity of the catalyst has good tolerance against poisoning species generated during the reaction process of ethanol.

Conclusions
In this work, a bimetallic PtPd alloy on the Nfgraphene lm is successfully prepared by a simple electrochemical method. This composite can be used as an anode catalyst for ethanol oxidation. It has low onset potential at 0.73 V (vs. Ag/AgCl) and the ratio of If/Ib reaches 5.45, indicating high catalytic activity to ethanol and high poisoning tolerance in the ethanol electrooxidation process. It was demonstrated that PtPd alloys can
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