Transition Metal Chemistry (2007) 32:4755 DOI 10.

1007/s11243-006-0127-9

Springer 2007

Electrocatalytic activity of binary Palladium Ruthenium anode catalyst on Ni-support for ethanol alkaline fuel cells
Joyeeta Bagchi and Swapan Kumar Bhattacharya* Physical Chemistry Section, Department of Chemistry, Jadavpur University, Kolkata 700032 India
Received 30 August 2006; accepted 6 September 2006

Abstract In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited on nickel support has been found to increase the current density and decrease the anodic overvoltage signicantly with respect to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The eect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state polarization, and conjugated scanning electron microscopyenergy dispersion X-ray spectroscopy. It has been found that electrode containing the higher amount of deposit are less aected by carbonaceous poisons.

Introduction For the development of a cost-effective direct alcohol fuel cell (DAFC), many researchers have devoted their time in search for anode catalyst which is cheaper, more efcient and abundant than Pt [1]. Palladium can be an interesting substitute for Pt, since it is less costly and 50 times more abundant than Pt [2]. Moreover Palladium can be used as an excellent catalyst for various chemical and electrochemical reactions [37]. It has been used as an elegant electrocatalyst [8] for alcohol oxidation. Palladium has the power to reduce protons, store and release hydrogen [9] and is further used to remove adsorbed CO formed from ethanol electrooxidation, thus reducing poisoning [10]. In many studies, Pt has been coupled with Ru to construct eective binary anode catalyst having eciency more than Pt [11, 12]. Pd is just above Pt in the same group of the Periodic Table. So, maintaining analogy, we have here coupled Pd with Ru on Ni-support and studied the catalytic capability of constructed binary electrocatalysts with reference to ethanol oxidation. Moreover Pd can form stronger bonds with another metals than itself [13]. So, its change in electronic character in a thin coating of deposit may be helpful in reducing poisoning. In our previous study [14] we worked with the co-deposited Pt Ru electrode and found large cathodic shifts of potential, indicating it to be a much better in performance than Pt, Ru and Ni as electrocatalyst. In the present study we have co-deposited Pd and Ru on
* Author for correspondence: E-mail: skbhatt7@yahoo.co.in

Ni foil from their binary solution. We have varied the time of deposition in order to get dierent loading on Ni-support and thus prepared four dierent electrodes in order to understand also the eect of loading of Pd Ru electrocatalyst on Ni support, with reference to ethanol oxidation. Electrochemical behaviour of Pd has been studied in acid medium by many researchers [1519]. Study of Ni anode used for ethanol oxidation in alkaline medium has also been done [20]. Here we have studied the electrocatalytic activity of four dierent PdRu electrodes of the same composition but varied loading on Ni-support for anodic oxidation of ethanol at room temperature ($25 C). Cyclic Voltammetry (CV), chronopotentiometry (CP) and steady state polarization (SP) studies have been presented in this paper. Scanning electron microscopy and energy dispersion X-ray spectroscopy of dierent parts of electrodes have been also executed and analysed.

Experimental Preparation of electrocatalysts Ni-foil (99.9+% gold level, Aldrich Chem. Com Inc) of thickness 0.0125 cm was used as a support for the electrocatalyst. The mid-portion of the foil was wrapped with Teon tape (Champion) keeping both ends bare. Co-deposition of palladium and ruthenium electrocatalyst was done on one of these ends after polishing, washing and drying and the other end of the foil was kept bare for electrical connection. A binary solution was made out of 2 weight % solutions of PdCl2

48 and RuCl3 nH2O (n$2) in 2(M) HCl by taking 0.04 wt% of the former and 0.004 wt% of the latter in a (w/v) ratio. These salts for preparation of binary solution were taken from Arora Matthey Ltd and were used as received. Four polished and dressed Ni foils were coated with the binary electrocatalyst Pd and Ru by co-deposition from the said binary solution galvanostatically at 5 mA cm)2 for 1, 5, 10 and 30 min. The deposited electrodes correspond to Ni/Pd Ru(1), Ni/Pd Ru(2), Ni/Pd Ru(3), and Ni/Pd Ru(4), respectively. These electrodes were weighed before and after deposition in order to know the amount of coating on Ni foils. All the reagents used were of AR grade and triple distilled water was used throughout the experiment. Electrochemical measurements The electrochemical measurements were executed in a two compartment glass-cell using a conventional threeelectrode assembly. The reference electrode used during all electrochemical measurements was Hg/HgO/ OH) (1 M) (MMO), whose equilibrium electrode potential was $0.1 V w.r.t standard hydrogen electrode (SHE). In all the electrochemical measurements a large Pt-foil (1 1 cm2) was used as counter electrode and potential data were recorded w.r.t MMO. Cyclic Voltammetric study was performed using a computer-aided Potentiostat/Galvanostat (AEW-2, Munistst, Sycopel Scientic Ltd, UK). Cyclic Voltammogram (CV) of each electrode immersed in 1(M) EtOH in presence of 1(M) NaOH as supporting electrolyte, was recorded at the scan rate of 50 mV s)1. Galvanostatic Polarisation (GP) and Chronopotentiometry (CP) were also performed with the help of a constant current charger (DB-300, DB-Electronics and an EC digital multimeter DM6104B) as described before [14]. Galvanostatic Polarisation was carried out by applying constant current density in the range of 0.053 mA cm)2 for a long time until steady potential was obtained. The data for GP and CP studies were recorded by an EC digital multimeter DM610B. The chronopotentiometric study was done by applying a current density of 1 mA cm)2. However, in all measurements, the surface of the working electrode was cleaned by keeping it in 1 M NaOH for 5 min at a constant potential of ) 900 mV. It is then allowed to equilibrate in a fresh 1 M NaOH solution and then in 1 M ethanol solution containing 1 M NaOH until a steady negative value of open circuit potential was obtained. Any further activation of the electrode was avoided in order to exclude any change of state of surface of the electrodes before any electrochemical measurement. Surface studies The morphology of surfaces of anodes was investigated with a JEOL-6360 scanning electron microscope (SEM), at an accelerating potential of 20 KV. Catalyst composition of the surface was analysed by energy dispersive X-ray spectroscopy (EDX) using INCA XStream Oxford instruments (UK).

Results and discussion Surface characterisation The weight of the loaded and dried electrodes has been found to increase with respect to that of bare Ni, as expected but the amount of deposit per minute has been found to decrease with the deposition time as mentioned in Table 1. The data indicate that Pd prefers to deposit more on the surface of Ni than on the layer of Pd itself, since possibly NiPd bond strength like that of NiPt (273.70 KJ mol)1), is higher than that of PdPd (100 KJ mol)1) [21]. Moreover for the same reason it seems that more time the Ni foil dipped in solution for co-deposition more is the corrosion of the electrode, which is reected by the decreasing values of average rate of deposition per unit area as presented in Table 1. Scanning electron microscopic (SEM) image of overall electrode surface of Ni/Pd Ru(4) is presented in Figure 1(a). This image shows scroll-like structure of layers of deposit with characteristic cracks, smooth layers and extra-white globules which appear mostly at the two sides of the cracks. The smooth layers can also be subdivided into two types: (i) that within the scroll like deposit and (ii) that outside the scroll like deposit, i.e., within the cracks. These dierent parts of Figure 1(a), are also separately presented in Figures 1(be) respectively. Figure 1(b) shows a large crack and several globules of ca. 20 nm diameter. Figure 1(c) shows smooth layer within the scroll like deposit, which contains some black spots. They are possibly deposit of Ru [14] and of ca. 1015 nm in diameter. White spots observed in the gure, arise possibly due to corrosion of Ni. Figure 1(d) shows globules in a magnied scale. When smooth portion outside the scrolled layer is magnied into 40,000 times, it looks like Figure 1(e), which shows patches of deposit where size of the particles, is found in the nanometer scale. The overall energy dispersion Xray spectrum (EDX) (Figure 1(f)) along with the
Table 1. Amount of co deposit per unit area and rate of co deposition of Pd Ru on Ni foil to construct Ni/Pd Ru(i) (i=14) electrodes Electrode Time of deposition (min) Amount of deposit per unit area (mg cm)2) 1.4286 2.9474 3.4290 4.2105 Amount of deposit per unit minute per unit cm)2 (mg min)1 cm)2) 1.4286 0.5895 0.3429 0.1404

Ni/Pd Ni/Pd Ni/Pd Ni/Pd

Ru(1) Ru(2) Ru(3) Ru(4)

1 5 10 30

49

Fig. 1. (a) Overall SEM image of Ni/Pd Ru(4), magnied 55 times, (b) SEM image of one of the several cracks present in overall image of one face of Ni/Pd Ru(4) as presented in Figure 1(a), (c) SEM image of a little smooth portion within the scrolled layer of Ni/Pd Ru(4), (d) SEM image of some globules present in overall image of Ni/Pd Ru(4), (e) SEM image of smooth portion outside the scrolled layer, magnied 40,000 times of Ni/Pd Ru(4), (f) overall EDX spectrum of Ni/Pd Ru(4), (g) EDX spectrum of the 40,000 times magnied smooth portion within the scrolled layer of Ni/Pd Ru(4).

corresponding column of Table 2 for the Ni/Pd Ru(4) electrode show absence of ruthenium on the surface relative to the palladium count, although the smooth part within the scroll like deposit corresponding to SEM image, Figure 1(c), contains some Ru. This is evident from the corresponding spectrum [Figure 1(g)] of the smooth part and Table 2 which summarizes composition of the dierent parts including the smooth part of the surface of the Ni/Pd Ru(4) electrode, as obtained from their corresponding EDX

spectra. These indicate that ruthenium has been deposited on the surface of Ni as a trace metal. This can also be substantiated by standard electrode potential of Ru+3/Ru (0.3519 V) and Pd+2/Pd (0.9510 V) [21] and their ionic concentrations in binary solution. From the SEM image obtained with 40,000 times magnication (Figure 1(e)), it is quite evident that the Nifoil surface is not totally covered by Pd Ru electrocatalyst even after deposition for 30 min. It indicates the future scope for better amounts of deposition of Pd

50

Fig. 1. continued

and Ru per unit area for improvement of catalytic eciency of the anode. The compositions of the dierent parts of electrode, Ni/Pd Ru(4) were presented in Table 2. They show that cracks and layers contain more Ni and less Pd whereas the globules part contains less Ni and more Pd but without any deposit of Ru. This indicates that deposit of Ru is insignicant where globules are formed, i.e., where deposition of Pd is very fast. This causes overall elemental composition of Ru insignicant with respect to other metals, although it does present within the smooth portion of the scrolled layer as evident from Figure 1(g) and Table 2. Thus conjugated SEM and EDX study reveals the presence of trace Ru on the surface of Ni/Pd Ru(4) electrode. Composition presented in Table 2 also suggests that Ni is present both as oxides and element in addition to Pd and trace Ru on the surface of the elec-

trode, since elemental oxygen cannot be present and Ni forms oxides much easily than Pd [20, 22]. Cyclic voltammetry The cyclic voltammograms of bare Ni-foil and Ni/Pd Ru(i), (i = 14), electrodes in the blank, viz, 1 M NaOH solution, have been illustrated in Figure 2(a). All these voltammograms show hydrogen evolution at the starting potential, viz, ) 0.8 V, which can be realized by simultaneous generation of high cathodic current and gas bubbles on the surface of electrodes. The smaller value of the cathodic potential for Ni/Pd Ru over bare Ni-foil electrode at a given current density, say, 1.5 mA cm)2, seems to be due to greater roughness factor and better electrocatalytic activity of Pd Ru over Ni for the said reaction. In all the proles of

Table 2. Elemental compositions of dierent parts of surface of Ni/Pd Ru(4) electrode, as obtained from their corresponding EDX spectra Elements Atom % of elements on Ni/Pd Ru(4) electrode Overall A part containing (55 times magnied) a crack

A little smooth portion within the scrolled layer

globules

Smooth portion outside the scrolled layer (40,000 times magnied) 1.25 84.96 13.79

Pd Ru Ni O

14.52 57.13 28.36

0.98 84.76 14.26

26.61 1.11 42.50 29.77

18.54 29.84 51.62

51

(a)

M 2OH M(OH)2 2e

(b)

(c)

Fig. 2. (a) Steady state cyclic voltammograms of Ni/Pd Ru(i)(i = 14) electrodes in aqueous 1 M NaOH solution(blank), (b) Cyclic voltammograms of representative cycles for ethanol oxidation in 1 M EtOH containing 1 M NaOH on Ni/Pd Ru(i)(i = 14) electrodes, (c) plots of current density versus time, indicating peak portions of cyclic voltammetric steady cycles under summits of iF and iB for Ni/Pd Ru(4) for ethanol oxidation in 1 M EtOH containing 1 M NaOH solution, which manifests the area under the summits.

Figure 2(a), a small anodic peak appears at about ) 0.5 V which possibly corresponds to oxidation of Ni and Ru [14, 20] according to the reaction

Similar oxidation on Pd is known to start at a much higher potential, 0.58 V with respect to MMO [22]. For Ni, as evident from Figure 2(a), another anodic peak appears at around 0.491 V. This peak, as mentioned elsewhere [20], arises possibly due to transformation of Ni(OH)2 to NiO(OH). For Ni/Pd Ru(i) (i = 14) electrodes, peak potentials are shifted anodically with respect to that for bare Ni on increasing loading, indicating simultaneous oxidation Ni(II) Ni(III) and Pd(0) Pd(II) in the potential range. Increased loading of Pd Ru on Ni support caused an increase in the number of layers of electrodeposit of Pd Ru on Ni support. This may be responsible for an increased order of anodic peak current density of the deposited electrodes; viz, Ni/Pd Ru(1) < Ni/Pd Ru(2) < Ni/Pd Ru(3) < Ni/Pd Ru(4) as evident from Table 3. This indicates the greater the amount of loading of electrodeposits, greater is the oxide formation. Moreover, it is observed that the anodic peak current density for Ni/Pd Ru(4) electrode is less than that of Ni/Pd Ru(3) electrode, because it seems that formation of too many layers of Pd Ru may render steric hindrances causing diculty for oxidation of inner oxidisable metals, viz, Pd, Ru and specially Ni. Diculty in oxide formation for the inner layers of deposit can also be understood from the anodic shift of potential (values in volts) of the deposited electrodes in the order: Ni/Pd Ru(1) (0.582) < Ni/Pd Ru(2) (0.590) < Ni/ Pd Ru(3) (0.666) < Ni/Pd Ru(4) (0.751) and the order of cathodic current density (values in mA cm)2) : Ni/Pd Ru(4) (3.959) < Ni/Pd Ru(3) (4.820) < Ni/ Pd Ru(1) (5.051) < Ni/Pd Ru(2) (8.320) as evident from Table 3. So these results describe some characteristics of layer structures of thin lm of metal deposits on their oxidation. Cyclic voltammetric studies on these four electrodes, Ni/PdRu(i)(i = 14), have been carried out in the range of )500420 mV at 50 mV sec)1 in 1(M) EtOH containing 1(M) NaOH, and the corresponding voltammograms have been depicted in Figure 2(b). They show typical behaviour of alcohol oxidation on Pt metals [23, 24]. At the inset of Figure 2(b), CV for oxidation of ethanol on bare Ni has been presented in order to compare it with that of the deposited electrodes. Two peaks have been obtained as usual. The current density of the rst peak (iF) at potential EF is obtained during the forward potential scan, i.e., for scanning from ) 500 mV to 420 mV and that of the second peak (iB) at potential EB is obtained in the reverse potential scan, i.e., for scanning from 420 mV to ) 500 mV. The potentials at which iF values are obtained are ) 101.26 mV for Ni/Pd Ru(i) (i = 1, 2, 3) and ) 92.51 mV for Ni/Pd Ru(4) as evident from Table 4. The iF of Ni, as obtained from its CV at a potential scan range of ) 500900 mV at 50 mV sec)1 is though more than Ni/Pd Ru(i) (i = 1, 2) and less

52
Table 3. The anodic and cathodic peak potentials and current densities obtained from cyclic voltammetric studies of Ni/Pd Ru(i) (i = 14) immersed in 1(M) NaOH solution Electrode Time of deposition (min) Anode current density (mA cm)2) 10.22 12.48 21.26 18.47 Anode peak Potential (mV) Cathode current density (mA cm)2) ) 5.051 ) 8.32 ) 4.82 ) 3.959 Cathode peak Potential (mV) ) 0.224 ) 0.302 ) 0.201 ) 0.200

Ni/Pd Ni/Pd Ni/Pd Ni/Pd

Ru(1) Ru(2) Ru(3) Ru(4)

1 5 10 30

0.582 0.590 0.666 0.751

Table 4. The peak potentials (EF and EB), peak current densities (iF and iB) and other related parameters obtained from cyclic voltammetric studies of Ni/Pd Ru(i) (i = 14) immersed in 1(M) EtOH in 1(M) NaOH solution Electrode Ni/Pd Ni/Pd Ni/Pd Ni/Pd Ni Ru(1) Ru(2) Ru(3) Ru(4) EF(mV) ) 101.26 ) 101.26 ) 101.26 ) 92.51 605.60 iF(mA/cm)2) 23.09 30.14 37.84 45.68 35.58 EB(mV) ) 240.12 ) 260.21 ) 263.48 ) 270.26 589.30 iB(mA/cm)2) 60.08 54.31 55.27 61.37 37.71 iF/ iB (mA cm)2) 0.384 0.555 0.685 0.744 0.943 EFEB (mV) 138.86 158.95 162.22 177.75 16.30

than Ni/Pd Ru(i) (i = 3, 4), EF for Ni foil is as high as 605.60 mV (Table 4) which indicates incapability of Ni foil for oxidation of ethanol at lower potential. Thus the large cathodic shift of forward peak potential observed for all the electrodes of Ni/Pd Ru(i) system with respect to that for bare Ni-foil indicates a signicant improvement in electrocatalytic activity of them over pure Pt [23] and Ni electrode [20]. Again, iBs of Ni/Pd Ru(i) (i = 1, 2, 3, 4) increase with the amount of loading of Pd Ru deposit on Ni-support, which is evident from Table 4. This is also evident from the area under the 2nd peak (Table 5) which depicts the amount of oxidation of ethanol under the summit at EB potential during reverse scan. EB s are found to shift cathodically with the amount of loading of Pd Ru electrocatalyst on Ni-support for all the four electrodes, whereas EB of Ni has been found at a very high potential, 589.30 mV, as is evident from the Table 4. So it can be stated that Ni has been modied to a better electrode by co-depositing Pd Ru on it in terms of peak potentials of ethanol oxidation in alkaline medium. The area under forward summit iF and backward summit iB have been obtained from the plots of current density versus time (sec). They have been obtained from the corresponding CV s of the

electrodes. Such a typical plot has been shown in Figure 2c. The area under iF signies the amount of charge own for oxidation during forward scan when electron transfer takes place due to dehydrogenation of EtOH and generation of species due to chemical breakdown of EtOH [2, 4]. Similarly, the area under iB reveals mainly the amount of charge own for oxidation of carbonaceous intermediates [25] during reverse scan. The small extent of electron transfer reaction under the summit iF for Ni and Ni/Pd Ru(1) electrodes, as is evident from the small area under the peak of iF, indicates the small extent of dehydrogenation in the primary steps for ethanol oxidation. On the other hand, the areas under iB for Ni/Pd Ru(1) and Ni signify mainly relatively greater oxidation of carbonaceous poisons by Ni(OH)2 and NiOOH [20]. This justies a relatively greater magnitude of area under iB than that under iF for Ni/Pd Ru(1) and Ni electrodes. But Ni/Pd Ru(i) (i = 2, 3, 4) have the reverse order of the magnitude of areas under iF and iB. For these electrodes, signicant amount of dehydrogenation of ethanol in addition to oxidation of its chemically decomposed species is being carried out in the forward scan possibly due to presence of greater amount of Pd Ru on Ni surface.

Table 5. The areas under the summit iF and iB, their conjugate values and their ratio obtained from cyclic voltammetric studies of Ni/Pd Ru(i) (i = 14) immersed in 1(M) EtOH in 1(M) NaOH solution electrode Time of deposition (min) 1 5 10 30 Area under iF (X) (mC cm)2) 95.50 98.10 178.60 252.10 321.50 Area under iB(Y) (mC cm)2) 125.70 146.00 166.70 195.70 211.70 Area under (iF+ iB) (mC cm)2) 221.20 244.10 345.30 447.80 533.20 X/Y

Ni Ni/Pd Ni/Pd Ni/Pd Ni/Pd

Ru(1) Ru(2) Ru(3) Ru(4)

0.760 0.672 1.071 1.288 1.519

53 Again, it is well known that lesser the value of tolerance power for carbonaceous species, as given by iF/iB [25], greater is the poisoning of the electrode. The order of iF/iB follows the sequence: Ni/Pd Ru(1) < Ni/Pd Ru(2) < Ni/Pd Ru(3) < Ni/Pd Ru(4) < Ni, as is evident from Table 4. This order indicates that poisoning decreases with amount of loading for the deposited electrodes. Again, although Ni has the highest value of iF/iB, it does not indicate its superiority over the other electrodes for ethanol oxidation as it occurs at a very much higher overpotential and the extent of oxidation is also very small as indicated from the composite areas under (iF + iB) summits, as evident from Table 5. Coverage of the electrode surface by the carbonaceous species generated during dehydrogenation is the prime reason of poisoning of electrodes. Here area under iB increases as Ni < Ni/Pd Ru(1) < Ni/Pd Ru(2) < Ni/ Pd Ru(3) < Ni/Pd Ru(4) which indicates greater extent of M-CO breakage by M-OH species in this sequence. Thus, this shows that, greater the formation of M-CO which is reected from the iF values, the greater is its ability to decrease the CO coverage and hence the poisoning eect as reected by iB, as found for all Ni/Pd Ru(i) (i = 2 ) 4) electrodes. Thus overall cyclic voltammetry suggests that electrode with maximum loading of Pd Ru (i.e., 30 min) is the best among the electrodes studied in electrocatalytic activity with reference to ethanol oxidation in alkaline medium. Moreover, (EFEB)value decreases in the order of Ni/Pd Ru(4) < Ni/Pd Ru(3) < Ni/Pd Ru(2) < Ni/Pd Ru(1) < Ni, indicating order of time taken to remove the passivating layer formed by mainly OH species in the reverse scan. The more the dehydrogenation, the greater is the poison formation and hence greater is the time taken to remove them. Chronopotentiometry Chronopotentiometric proles as obtained from chronopotentiometric studies by application of constant current density of 1 mA cm)2 have been depicted in Figure 3. The transition time (s) (minutes) found is of the following order: Ni$Ni/Pd Ru(1)$Ni/Pd Ru(2) (6.5) < Ni/Pd Ru(3) (108) < Ni/Pd Ru(4) (288), which reects the resistance oered by dierent electrodes towards poisoning [14]. It is believed that the composition does not vary signicantly with the amount of loading. Thus the order reveals the order of stability of the electrodes and hence in turn the catalytic activity of the electrodes at lower potentials due to increased loading. Three regions are distinctly observed for Ni/Pd Ru(3) and Ni/Pd Ru(4) in the given scale [26]. In the lower potential range, the potential increases very sluggishly with time and then in the second region, a sharp increase occurs which leads to a third and steady region at about 0.45 V. The rst region signies the region of potential where mainly dehydrogenation occurs in the process of ethanol oxidation. The second region signies fast coverage of electrode by carbonaceous species which makes the dehydrogenation step unimportant. The third steady region indicates the region of oxidation of the carbonaceous species chiey, which occur at relatively high potential range for completion of oxidation. Better the electrode, more the time it would enjoy at the lower potential, engaging itself with more dehydrogenation and relatively faster oxidation of carbonaceous species, with a result of less accumulation of poison on the surface. This suggests that Ni/Pd Ru(4) is the best among the electrodes studied. The more the availability of the rescuer intermediates M-OH (M = Ni, Pd, Ru) coming from the layered structure of these electrodes with increased loading, seems to be responsible for the experimental order of electrocatalytic activity of the electrodes. Steady state polarisation Steady state polarization studies for ethanol oxidation on the said electrodes dipped in 1(M) EtOH containing 1(M) NaOH, have been executed at relatively high potential range. The current densities applied to the electrodes have been in the range 0.053 mA cm)2. Figure 4 illustrates the tafel plots and the order of the slope given in parenthesis (in mV) is as follows: Ni/Pd Ru(4)(91.23) > Ni/Pd Ru(3)(83.89) > Ni/Pd Ru(1) (70.79) > Ni(58.21) > Ni/Pd Ru(2)(33.34).This order of electrocatalytic activity is apparently reverse of the order that has been found from CV study. Moreover, the order of intercepts (in mV) are Ni/Pd Ru(3) (481.72) > Ni/Pd Ru(4)(476.40) > Ni/Pd Ru(2) (474.19) > Ni(470.54)$Ni/Pd Ru(1)(470.31). An analysis of these data reveals that the tafel slopes for Ni and Ni/Pd Ru(1) are almost same, indicating similar type of mechanism of reactions occurring on their surface as

Fig. 3. Chronopotentiometric potential-time prole for ethanol oxidation on dierent Ni/Pd Ru(i) (i = 14) electrodes immersed in 1 M ethanolic solution of 1 M NaOH.

54 higher potential a reverse sequence of activity is revealed when extent of deposition is signicant. 4. For Ni and Ni/Pd Ru(1) electrodes, ethanol oxidation is dictated by Ni(OH)2 and NiOOH formed on the surface of Ni rather than by Pd Ru. 5. Ni/Pd Ru(4) is the most stable and less aected by poisonous intermediates among the electrodes studied, as evident from CV and CP studies. 6. Tolerance for carbonaceous species with reference to anodic oxidation of alcohol can be better understood by the ratio of areas under, rather than heights of forward and backward peaks in CV.

Acknowledgements
Fig. 4. Plot of steady state potential versus log (current density/ mA cm)2) for dierent Ni/Pd Ru(i) (i = 14) electrodes and bare Ni electrode immersed in 1 M ethanolic solution of 1 M NaOH.

observed from CV study. This arises possibly due to an insignicant amount of deposition of Pd Ru electrocatalyst on Ni surface during constructions of Ni/Pd Ru(1) electrode. The order of tafel slopes and intercepts of other three electrodes reveal that intrinsic order of electrocatalytic activity of these electrodes follow the reverse order of that of their slopes and intercepts. These results at higher potential are indeed a dierent from that obtained by CV and CP studies which reect electrocatalytic activity at lower potential. Therefore from these studies it may be concluded that for ethanol electrooxidation high amount of deposition of Pd Ru electrocatalyst on Ni-support is favoured only when the said oxidation is executed at lower potential but low amount of deposition of Pd Ru electrocatalyst on Ni-support, is favoured for electrooxidation at higher potential. This seems to be due to the involvement of oxides/hydroxides of Ni as electrocatalyst at higher potential [14, 20]. It is also quite expected that Ni/Pd Ru(4) would form the greatest extent of RuO(H)n islands [27] at higher potentials among all the electrodes because of its layered structure, causing a decrease in current density and intercept and an increase in tafel slope at higher potential. Conclusion Thus the study concludes: 1. Ni/Pd Ru can be used as a potential cost-eective anode. It can substitute Ni/Pt Ru electrode for electrochemical oxidation of ethanol. 2. The cathodic shift of peak potential for Ni/Pd Ru electrodes with respect to that for bare Ni foil electrode in CV study reveals the improvement of catalytic capability by deposition. 3. At lower potential, i.e., below peak potential of CV study, the electrocatalytic activity of electrodes increases with the amount of Pd Ru deposit. But at

We gratefully acknowledge nancial assistance from the University with Potential for Excellence of the UGC, New Delhi, Scheme (Rec/N/66/04), the help of Prof. Kaushik Das and Debasmita Das of Jadavpur University (Chemistry Department) in taking CV data from their laboratory.

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