Res Chem Intermed (2012) 38:383391 DOI 10.

1007/s11164-011-0354-3

Electro-catalytic performance of Pt-supported poly (o-phenylenediamine) microrods for methanol oxidation reaction
T. Maiyalagan C. Mahendiran K. Chaitanya Richa Tyagi F. Nawaz Khan

Received: 16 May 2011 / Accepted: 22 July 2011 / Published online: 4 August 2011 Springer Science+Business Media B.V. 2011

Abstract Poly (o-phenylenediamine) (PoPD) microrods were obtained by interfacial polymerization using ferric chloride as oxidant and without any template or functional dopant. Pt/PoPD nanocatalysts were prepared by the reduction of chloroplatinic acid with sodium borohydride, and the composite catalysts formed were characterized by X-ray diffraction and electrochemical methods. The nanocomposite of Pt/PoPD microrods has been explored for their electro-catalytic performance towards oxidation of methanol. The electro-catalytic activity of Pt/PoPD was found to be much higher (current density 1.96 mA/cm2 at 0.70 V) in comparison to Pt/Vulcan electrodes (the current density values of 1.56 mA/cm2 at 0.71 V) which may be attributed to the microrod morphology of PoPD that facilitate the effective dispersion of Pt particles and easier access of methanol towards the catalytic sites. Keywords Methanol oxidation Pt supported poly (o-phenylenediamine) Nanostructured materials Electro-catalyst

T. Maiyalagan (&) School of Chemical and Biomedical Engineering, Nanyang Technological University, 50 Nanyang Drive, Singapore 639798, Singapore e-mail: maiyalagan@gmail.com C. Mahendiran Department of Chemistry, Anna University of Technology Tirunelveli, Nagercoil 629004, India K. Chaitanya F. Nawaz Khan Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632014, India e-mail: nawaz_f@yahoo.co.in R. Tyagi Department of Chemistry, Deshbandhu College, Delhi University, Delhi 110007, India

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Introduction Though fuel cells are considered as potent energy conversion devices, they have not been evolved as an economically viable, socially acceptable, easily manipulative tool for energy conversion [18]. A fuel cell essentially consists of three components: the two electrodes and an electrolyte. Pt and Pt-based noble metals have been employed as electro-catalysts in both the anode and cathode, and nowadays there are attempts to reduce the amount of noble metal loading in the electrodes by dispersing the noble metals on suitable electronically conducting supports with low metal loadings. To decrease the platinum loading as well as to improve the oxidation rate and electrode stability, considerable efforts have been applied to study the electrode materials for the direct electrochemical oxidation of methanol [917]. Carbon is the most common catalyst support material that conducts only electrons in the electro-oxidation reaction. An alternative is to develop a catalyst support that conducts both protons and electrons efciently [18 20] by employing conducting polymers possessing both protonic and electronic conductivity. Recently, conducting polymer matrices are being employed as catalyst support materials for the oxidation, and metal nanoparticles dispersed on conducting polymer support provide access to a large number of catalytic sites with the possibilities of the recovery of spent catalyst. Catalytic particles dispersed on conducting polymers, mainly polypyrrole (PPY) and polyaniline (PANI), have received considerable attention as the electrode material for methanol oxidation [2123]. The conducting and electroactive polymers, such as poly(o-phenylenediamine) (PoPD), have a greater potential in various elds of technology due to their interesting properties, different from those of the usual conducting polymers, like PANI or PPY, which make them promising for applications in electro- and bioelectro-chemical sensors. One of these properties relates to an unusual dependence of the electric conductivity on the redox state of the PoPD polymer. Different from PANI or PPY, PoPD shows high conductivity in its reduced state, whereas the oxidized state is insulating. This determines the electrochemical properties of PoPD, since many electrode redox processes have been shown to take place within a relatively narrow potential window, corresponding to the reduced (conducting) form of this polymer. Within this potential window, electro-catalytic oxidation of some species takes place, making it possible to use PoPD for electro-catalytic applications, such as the electro-oxidation of coenzyme NADH, electro-oxidation of methanol [2427] and oxygen reduction [2830]. PoPD is usually obtained through electrochemical polymerization. In this polymerization method, the PoPD obtained usually exhibits an irregular morphology. 1D nano-structured PoPD is obtained by mixing aqueous solutions of HAuCl4 and OPD without any surfactants or templates [30]. However, the materials obtained were not pure. Hence in this article, we describe an efcient method for the preparation of PoPD microrods with different lengths using ferric chloride as oxidant, which takes advantage of the easy removal of FeCl2 by simple washing with water; the PoPDs so obtained were of high purity [31]. In the present investigation, the composite material based on Pt-supported PoPD microrods has been compared with that of the Pt/C electrodes for electro-oxidation

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of methanol. These materials were characterized using X-ray diffraction (XRD) and cyclic voltammetry (CV). The Pt-supported PoPD microrods electrode exhibited better catalytic activity and stability compared to the 20 wt% Pt supported on the Vulcan carbon electrode.

Experimental Materials The present study was carried out in aqueous solutions. Puried water obtained by passing distilled water through a milli Q (Millipore) water purication system was used. The reagents o-Phenylenediamine (oPD), ferric chloride (FeCl3), chloroplatinic acid (H2PtCl6), ruthenium chloride (RuCl3), sodium borohydride (NaBH4), sodium hydroxide (NaOH) were purchased from Aldrich (India) and used as received. Methanol and sulphuric acid were obtained from Fischer Chemicals (India). Naon 5 wt% solution was obtained from Dupont (USA) and was used as received. Synthesis of POPD microrods The PoPD microrods were obtained by chemical oxidation of oPD using ferric chloride as an oxidant. In a typical procedure, different contents of oPD monomer were dissolved in 30 mL distilled water at room temperature. Then, 10 mL aqueous solutions of ferric chloride (the molar ratio of ferric chloride to oPD is 1:1) were added to the above mixtures under vigorous stirring at room temperature for 5 h. The resulting precipitates were washed with water twice and ltered. Finally, the products were dried in vacuum at 50 C for 24 h. Synthesis of Pt supported PoPD microrods Amounts of 0.1 gm of PoPD and 2 mL of 50 mM H2PtCl6 were mixed with 100 mL of distilled water. Then, 2 mL NaBH4 solution (50 mg mL-1) was added drop-wise to the above solution with vigorous stirring at room temperature. Stirring was continued overnight before the solid phase was recovered by ltration and then washed copiously with water. The recovered solid was dried overnight under vacuum at room temperature. An aqueous solution of H2PtCl6 was prepared, and the pH of the solution was adjusted to 6.8 by adding NaOH. A freshly prepared aqueous solution of NaBH4 was added to this solution under stirring at room temperature. After the addition of NaBH4, the color of the solution changed to brown, indicating the formation of nanoparticles. The solution was stirred overnight. Characterization The morphologies of the microrods were observed by an optical microscope (Olympus BX-100).The phases and lattice parameters of the catalyst were

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characterized by X-ray diffraction (XRD) patterns employing a Shimadzu XD-D1 diffractometer using Cu Ka radiation (k = 1.5418 A) operating at 40 kV and 48 mA. XRD samples were obtained by depositing composite-supported nanoparticles on a glass slide and drying the latter in a vacuum overnight. Electrochemical measurements All electrochemical measurements were performed in a conventional threeelectrode cell at room temperature. A Pt wire was used as a counter electrode. All electrochemical potentials in the present study are given versus an Ag/AgCl (saturated KCl) reference electrode. Glassy Carbon (GC) (electrode area = 0.196 cm2) was polished to a mirror nish with 0.05-lm alumina suspensions before each experiment which served as an underlying substrate of the working electrode. In order to prepare the composite electrode, the catalysts were dispersed ultrasonically in water at a concentration of 1.0 mg mL-1 and a 20-lL aliquot was transferred on to a polished glassy carbon substrate. After the evaporation of the water, the resulting thin catalyst lm was covered with 5 wt% Naon solution. Then, the electrode was dried at 353 K and used as the working electrode. A solution of 1.0 M CH3OH in 0.5 M H2SO4 was used to study the methanol oxidation activity.

Results and discussion The PoPD microrods were obtained by interfacial polymerization and Fig. 1 shows the optical micrograph of uniform PoPD microrods of several micrometers in length and with diameters of approximately 13 lm, which suggested that they were fabricated successfully by the interfacial polymerization method. The XRD pattern of the catalyst (Pt/PoPD) is shown in Fig. 2. The peaks consistent with facecentered cubic (fcc) as expected for Pt were clearly observed for the Pt/PoPD catalyst. The XRD patterns were used to estimate the average particle size using the Scherrer equation: dA kk=b cosh where k is a coefcient (0.9), k the wavelength of X-ray used (1.54056 A), b the full-width half maximum and h is the angle at position of peak maximum. The mean particle size obtained from the XRD patterns were 4.48 nm for Pt/PoPD and 2.8 nm for Pt/C. To further identify the composition of these Pt/PoPD materials, the EDX analysis (Fig. 2b) was used to analyze the content of Pt in the Pt/PoPD composite which revealed a satisfactorily result close to the theoretical value (i.e., 20%) calculated based on the fact that Pt precursors being reduced completely and the entire reduced Pt particles are incorporated into the Pt/PoPD composite. The cyclic voltammograms of Pt nanoparticles-supported PopD microrods exhibiting hydrogen adsorptiondesorption peaks corresponding to platinum oxidationreduction in 0.5 M H2SO4 at a scan rate of 50 mV/s are shown in

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Fig. 1 Optical micrographs of poly (o-phenylenediamine) microrods

Fig. 3. The appropriate cyclic voltammogram pattern of Pt nanoparticles-supported PopD microrods was attained within ve cycles in the background electrolyte. The electrochemical surface areas (ECSA) calculated using the hydrogen desorption peak and used to evaluate the surface area of the Pt-based catalysts are given in Table 1. The surface area of Pt-supported PopD microrods was found to be higher than the surface area of Pt/C [14]. The electrochemical surface area of various polymer electrodes area is reported and the electrochemical surface area of Pt/C electrode consistent with the previously reported electrodes is given in Table 1. The electro-catalytic activity of the particulate composite electrodes for methanol oxidation was studied by cyclic voltammetry. Figure 4 shows the cyclic voltammograms (CVs) of the electrodes in 1.0 M MeOH ? 0.5 M H2SO4 at 25 C with a

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Pt (111)

(a)
C (002)

(b)
(a) 20% Pt/C (b) 20% Pt/PoPD
Pt (200)

Intensity (a.u)

(b)

20

30

40

50

60

Pt (220) 70

(a)

80

2 (degrees)
Fig. 2 a X-ray diffraction patterns and b EDX patterns of 20% Pt Pt/PoPd electro-catalysts prepared by sodium borohydride reduction

2 (mA/cm Pt )

1.0 0.5 0.0 -0.5 -1.0 -1.5

-200 0 200 400 600

(a) (b)

Current density

800

1000

1200

Potential (V) vs Ag/AgCl

Fig. 3 Cyclic voltammograms of a 20% Pt/PoPD and b 20% Pt/C in nitrogen-saturated 0.5 M H2SO4 at a scan rate of 50 mV/s

scan rate of 50 mV s-1. The specic activity of the catalysts normalized to Pt surface area is shown in Table 1. The oxidation current of Pt/PoPD electrode (If = 1.96 mA/cm2) was also higher than that of Pt/C (1.56 mA/cm2). During the reverse scan, the oxidation peak at 0.50 V was obtained with a peak current of Ib = 1.45 mA/cm2. This peak is attributed to the release of adsorbed CO or CO-like species, which can be generated via incomplete oxidation of methanol in the forward scan [33]. These carbonaceous species are mostly in the form of linearly bonded Pt=C=O, which are oxidized in the reaction of the backward scan peak [33]. Thus, the ratio of the forward anodic peak current density (If) to the reverse anodic peak current density (Ib), i.e., If/Ib, suggests a tolerance to carbonaceous species accumulation on catalysts during methanol electro-oxidation. The low If/Ib

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Electro-catalytic performance of Pt Table 1 Electrochemical properties of PoPD microrods-supported Pt and carbon-supported Pt Electrode Electrochemical surface area (m2 g-1) 78.4 84 96 117 114

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Current density (mA/cm2) 1.56 1.39 1.96 2.60 3.56 14.1 7

Pt/C Pt/C [38] Pt/PoPD microrods Pt/poly(N-acetylaniline) nanorods [39] Pt/poly(o-anisidine) nanober [40] Pt/polypyrrole [41] Pt/CNx [41]

2.0

(a) (b)

Current density (mA/cm )

1.5

1.0

0.5

0.0

-0.5 -0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Potential (V) vs Ag/AgCl

Fig. 4 Cyclic voltammograms of a 20% Pt/PoPD and b 20% Pt/C electrode in 0.5 M H2SO4/1 M CH3OH at 50 mV/s

indicates poor oxidation of methanol to carbon dioxide during the forward anodic scan and excessive accumulation of carbonaceous residues on the catalyst surface. On the other hand, the high If/Ib indicates excellent oxidation of methanol during the reverse anodic scan and less accumulation of residues on the catalyst. The reported If/Ib value for the commercial E-TEK catalyst is *1 [34, 35]. The ratio observed for PtRu after vigorous heat treatment is *1.30 [36]. In the present study, the ratio is observed to be 1.34 for Pt/PoPD catalysts, larger than the ratio of 1.1 [37] which was calculated for the Pt/C (E-TEK) sample. Therefore, the higher tolerance of the catalysts to incompletely oxidized species is another important reason for the higher efciency of Pt/PoPD catalysts. The stability of Pt/PoPD and Pt/C was tested by chronoamperometric curves for methanol oxidation as shown in Fig. 5.The current density has been normalized to Pt surface area for the evaluation of the catalytic activity of the electrodes. In the curves of all composite catalysts there was a sharp initial current drop, followed by a

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Current density (mA/cm )

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 500 1000 1500 2000 2500 3000 3500

(a) (b)

Time (seconds)
Fig. 5 Chronoamperometric curves for the catalysts a 20% Pt/PoPD and b 20% Pt/C recorded at the 0.7 V versus Ag/AgCl for 3,600 s in nitrogen-saturated 0.5 M H2SO4 and 1 M methanol at 25 C

slow decay. A possible reason for the slow decay of current density is the poisoning effect by COads intermediates [32]. As observed from Fig. 5, methanol oxidation on Pt/PoPD gives a higher oxidation current than that on Pt/C during the process. This indicated that the direct oxidation of methanol on Pt/PoPD was enhanced. Therefore, Pt/PoPD had better poisoning-tolerance ability than Pt/C. At the same time, the Pt/PoPD maintained the highest current density compared to Pt/C electrodes. This was mainly due to the more facilitative methanol oxidation on Pt/ PoPD, which was in agreement with the aforementioned CV results. The more facile diffusion of both liquid fuel and products of the microrods-supported catalyst structure interpenetrated with the electrolyte network. Therefore, the utilization efciency of catalysts becomes higher. The microrods arrays may have a great potential in the application of direct methanol fuel cells.

Conclusions Synthesis and characterization of conducting PoPD microrods-incorporated Pt nanoparticles are reported here. Good catalytic activity was observed for the electrooxidation of methanol at the metalpolymer microrods composite electrode. The Ptloaded PoPD microrods not only increase the electronic-ionic contact but also provide an easier electronic pathway between the electrode and the electrolyte, which increases the reactant accessibility to the catalytic sites. The electro-catalytic activity of the microrods-based electrode was compared with those of 20 wt% Pt supported on the Vulcan carbon electrode, using cyclic voltammetry. The Pt-loaded PoPD microrods electrode exhibited better catalytic activity and stability than the 20 wt% Pt supported on the Vulcan carbon electrode.

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