Journal of Electroanalytical Chemistry 659 (2011) 128133

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Journal of Electroanalytical Chemistry

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NixFe(1x)Fe(CN)6 hybrid thin lms electrodeposited on glassy carbon: Effect of tuning of redox potentials on the electrocatalysis of hydrogen peroxide
Alam Venugopal Narendra Kumar, Srinivasan Harish, James Joseph , Kanala Lakshminarasimha Phani
Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630 006, India

a r t i c l e

i n f o

a b s t r a c t
The electrochemical deposition of mixed NixFe(1x)Fe(CN)6 thin lms on a glassy carbon (GC) electrode surface were carried out by electro-deposition under continuous potential cycling condition for the rst time. The redox potential of the low spin iron in the hybrid lm was found to depend on the ratio of metal centres. The improvement in the electrocatalytic property of the nickel hexacyanoferrate lm with incorporation of iron ions in the lm towards the electrocatalysis of hydrogen peroxide was studied in electrolytes like KNO3 and NaNO3. The stability of hybrid lm in Na+ containing supporting electrolytes was examined. Detection limit of H2O2 was about 1 lM as determined by amperometry with the sensitivity of 192 nA/lM. The chemically modied glassy carbon electrodes with NixFe(1x)HCF hybrid lms were characterized by cyclic voltammetry, impedance spectroscopy, energy dispersive X-ray analysis etc. These lms may nd extensive applications as redox mediators in biosensors which employ oxidase enzymes. 2011 Elsevier B.V. All rights reserved.

Article history: Received 8 February 2011 Received in revised form 6 May 2011 Accepted 11 May 2011 Available online 19 May 2011 Keywords: Chemically modied electrodes MHCF hybrids H2O2 sensor Electrocatalysis

1. Introduction The metal hexacyanoferrate (MHCF) is a class of compounds used for modication of electrochemical interfaces for the last 20 years due to their interesting ion transport, electrocatalytic, electrochromic and photoelectrochemical properties [1,2]. Possibility of using simple electrochemical control for preparing thin lms of these compounds from a bath containing potassium ferricyanide and corresponding metal salt is exciting. In prototype transition metal hexacyanoferrate, ferric ferrocyanide (FeHCF) the iron coordinated with N of cyanide ligand is termed as high spin iron and the other which is co-ordinated to C of the cyanide is low spin iron, established from Mossbauer and infrared studies [2]. The intense blue colour in FeHCF is due to the charge transfer from Fe(II) in a carbon hole to Fe(III) in a nitrogen hole [3]. Modication of glassy carbon substrates with metal hexacyanoferrates were reported from our laboratory recently [4,5]. The modications of the surfaces with metal hexacyanoferrates (MHCF) gain further importance owing to the fact that the interface can be modied with two MHCFs simultaneously. Electrochemical modication of electrode with NiHCF prepared in presence of Ag+ make the electrode less catalytic to Fe2+ oxidation [6]. Cataldi et al. reported that the CoHCF modied electrode on cycling in RuCl3 solution gains extra stability without alteration in the electrochemical properties [7]. Modication of electrodes with mixed analogues of
Corresponding author. Tel.: +91 4565 227550x441; fax: +91 4565 227779.
E-mail address: jameskavalam@yahoo.com (J. Joseph). 1572-6657/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jelechem.2011.05.006

metal hexacyanoferrates with combinations such as FeNi, NiPd, and NiTl were reported [810]. Dostal et al. demonstrated that the Prussian blue modied electrode can undergo lattice substitution during cycling in Cd2+ containing solutions [11]. James et al. showed that the Prussian blue (PB) modied GC electrode can be converted to CuHCF modied GC completely on cycling in Cu2+ solution [12]. Electrocatalytic hydrogen peroxide reduction on pure and mixed hexacyanoferrates of Cu, Ce and Pd were reported [13,14]. Bharathi et al. prepared mixed analogues of PB-NiHCF and PB-MnHCF mixed metal hexacyanoferrate electrodes [15]. They formed the mixed analogues of Prussian blue by potential cycling the glassy carbon electrode in a neutral medium containing metal salt and potassium ferricyanide to a very high anodic potentials where the ferricyanide decomposes to form ferric ions. The substitution of PB lattice by hetero atom is expected to alter the properties of the resulting mixed MHCF. However, there are not much systematic studies on the effect of substitution of PB lattice with another metal on the electrochemical properties. Scholz and Reddy prepared the mixed crystals of FeNiHCF with various ratios of Ni2+ and Fe3+ by chemical precipitation and incorporated these precipitate onto electrode by mechanical abrasion. Though the authors were able to show correlation between formal potential of the mixed crystal on composition, their voltammetric response show features of the existence of a small fraction of individual MHCF response also. In this work, we have demonstrated a simple electrochemical approach for the electrochemical formation of thin lms of hybrid lms of NiFehexacyanoferrate directly onto the substrates. This lm has applications in catalyzing the hydrogen

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peroxide oxidation/reduction electrochemically. Recently Karyakin et al. have demonstrated the record performance of Prussian blue modied electrodes in the detection of nanomolar level of hydrogen peroxide by electroreduction [16]. The PB type compounds are termed as articial peroxidase [17]. The redox potential of the ferro/ferricyanide couple was found to be dependent on the composition of metal ions in the hybrid lms. Tuning of redox potential can be advantageously used for creating new electrocatalytic interfaces. The ferric ferrocyanide has two electron transport channels namely high spin iron and low spin iron [18]. The introduction of heteroatoms Fe3+ on the NiHCF network is expected to open up a new electron transport channel in the hybrid lm. The ion transport properties of the hybrid lm can be altered by the incorporation of selected metal ion in the MHCFs lattice. Considerable improvement of hybrids electrochemical stability in sodium containing (Na+) electrolytes compared to that of PB is reported. Further, the effect of increasing iron content in the hybrid on the creation of electrocatalytic interface towards oxidation/reduction of hydrogen peroxide is described (Eqs. (5) and (6)). 2. Experimental The electrochemical experiments were performed in a three electrode cell using a potentiostat, Autolab Model PGSTAT 30, Netherlands. The working electrode was a glassy carbon (GC) disc electrode (Bio Analytical Systems, USA, area 0.07 cm2). The working electrode was polished with 4/0 grade alumina coated emery paper. The polished electrode was subsequently cleaned by ultra sonication in Millipore water for 23 min. A large area platinum foil fused to a glass tube served as counter electrode. All the potentials were measured with respect to 1 M calomel electrode (NCE). All the solutions were prepared fresh in Millipore water of resistivity 18.2 M X cm). The electrodes were modied by cycling the working electrode potential between 1.0 V and 0.0 V at scan rate of 0.05 V/s for 20 cycles, in 0.1 M KNO3 medium containing 0.01 M HCl, 1 mM potassium ferricyanide and 1 mM of metal chlorides (total concentrations of ferric chloride and nickel chloride in the medium is 1 mM for corresponding hybrid synthesis). The lms deposited on the electrodes were characterized for their electrocatalysis towards hydrogen peroxide by cyclic voltammetry. Energy-dispersive X-ray analysis (EDX) for the hybrids were conducted on lms electrodeposited on glassy carbon (GC) electrode embedded in Teon. AC impedance experiments for GC modied with lms of FeHCF and NixFe(1x)Fe(CN)6 were performed using an impedance analyser (Model IM6-Bio Analytical Systems, USA) in the frequency ranges from 1 mHz to 10 Hz. The amplitude was xed at 10 mV (Number of data points per decade: 4). The impedance spectra were recorded at applied bias of mid-peak potential i.e. (Epa + Epc)/2. 3. Results and discussion Fig. 1AF shows the cyclic voltammetric responses of NiHCF and FeHCF and their hybrid modied GC electrodes by the procedure described in the experimental section in 0.1 M KNO3. The origin of redox processes of the modied electrodes are elaborately discussed in the literature [1,2]. FeHCF has two Fe redox sites one coordinated with carbon and the other coordination to the nitrogen of the cyanide ligand. The high spin iron (peak-I) coordinated with N of the ligand undergo redox reaction at around 0.15 V as follows.
II fK2 FeII HS FeLS CN6 gs

The low spin iron (peak-II) coordinated with C of the ligand undergo redox reaction at higher potential is given below.
II fK2 FeII HS FeLS CN6 gs

Anodic

II fK FeIII HS FeLS CN6 gs

Prussian blue

Cathodic

Prussian blue

K e

Similarly GC electrodes can be modied with thin lms of NiHCF by electrochemical cycling of electrode potential between 0.0 and 1.0 V in the medium containing 1 mM of K3[Fe(CN)6] and 1 mM NiCl2. NiHCF modied electrode yield two sets of redox processes [19]. Fig. 1A shows the response of the NiHCF modied electrode in KNO3. The Ni2+ does not undergo redox reaction under these experimental conditions. Hence the two redox processes ferro/ferricyanide are arising due to the presence of NiHCF with two different stoichiometric ratios between Ni and Fe [7,8]. The redox potential of the ferro/ferricyanide couple showed an anodic shift as a function of the concentration of iron ion in the modication mixture as seen from Fig. 1BE. Linear variation of voltammetric peak potential of low spin iron as a function of composition of iron is observed as shown in Table 1. When the GC electrode is cycled in the modication bath containing ferricyanide ions and mixture of NiCl2 and FeCl3, we would expect the formation of NiHCF and FeHCF independently on the electrode surface. To our surprise, we observed two redox centres, one corresponding to redox process due to high spin iron and the other corresponding to low spin iron when the GC electrode was cycled in 0.1 M KNO3 medium containing 1 mM K3[Fe(CN)6] and 0.5 mM of FeCl3 and 0.5 mM NiCl2 between the potential limit of 1.00.0 V at 0.05 V/s as seen from Fig. 1C. There was no broadening or splitting of the redox process due to low spin iron centre. Occurrence of a single peak for the redox reaction corresponding to low spin iron is surprising. The redox peak potential corresponding to low spin iron in NiHCF lms is shifted to more anodic values with the amount of ferric ion in the modication mixture. The possibility of merging two redox processes of NiHCF and FeHCF is ruled out as we did not observe any splitting of redox peaks in the voltammetric response of the hybrids even at sweep rates as low as 1.0 mV/s. The full width at half maxima (FWHM) is a parameter indicating the multiplicity of redox process or the attractive or repulsive interaction present in the lm between redox sites [20]. The reversible surface redox process is expected to exhibit FWHM of 90.6/n mV. We observed FWHM of 100 130 mV for the hybrid lms which may be due to some repulsive interaction present in the hybrid lms. The chemical precipitation of hybrids containing FeHCFNiHCF hybrid is performed by Reddy et al. The X-ray diffraction studies of these hybrids clearly proved the incorporation of second metal in the lattice of the primary metal hexacyanoferrate [21]. The formation of these hybrids by electrodeposition is complex due to the fact that the MHCFs are formed on the electrode surface by electro-reduction. To rule out the possibility of the formation of MHCF deposition at the initial potential, we have started the initial potential of cycling from 1.0 V in our experiment which ensures that there is no lm formation on the electrode initially. Here we wish to state that there was no lm formation noticed on GC surface when we potentiostated the electrode at 1.0 V vs. NCE. During reductive cycling, the ferricyanide ion in the medium gets reduced to ferrocyanide ion. The solubility product of many transition metal ions with ferrocyanide ion is less than the corresponding ferricyanide ion [22]. Hence both the metal ions simultaneously get precipitated on the electrode electrochemically as follows.At potential below 0.3 V,

FeCN6 3 e ! FeCN6 4 FeCN6 4 1 xFe3 x Ni

2

3 ! Nix Fe1x FeCN6 4

Anodic

II fK FeIII HS FeLS CN6 gs

Everitt0 s salt

Cathodic

Prussian blue

K e

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20 10 0 -10 -20 -30 30 20

30 20 10 0 -10 -20

40 30 20 10 0 -10 -20 -30 -40 80 60 40 20 0 -20 -40 -60 -80

Current, A

10 0 -10 -20 -30 30 20 10 0 -10 -20 -30

0.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

0.4

0.6

0.8

1.0

Potential, V vs NCE

Potential, V vs NCE

Fig. 1. Voltammetric response of modied GC electrodes in 0.1 M KNO3 medium at the scan rate of 0.02 V/s. Modied mixture containing 1 mM of K3[Fe(CN)6] + 0.1 M KNO3 + 0.01 M HCl and (A) 1 mM NiCl2 (B) 0.7 mM NiCl2 + 0.3 mM FeCl3 (C) 0.5 mM NiCl2 + 0.5 mM FeCl3 (D) 0.3 mM NiCl2 + 0.7 mM FeCl3 (E) 0.1 mM NiCl2 + 0.9 mM FeCl3 (F) 1 mM FeCl3.

Table 1 Ep values of peak-I and peak-II and potential shift data as a function of Ni2+% in the modication mixture. Ni (%) 0 10 30 50 70 90 100

DEp (peak-I) mV
40 40 40 35

DEp (peak-II) mV
100 50 20 10 50 75 25

DEp (peak-I) mV
90 100 105 115

DEp (peak-II) mV
810 760 690 655 540 500 520

Bharathi et al. have formed the mixed PB analogues by subjecting the GC in a mixture containing NiCl2 + K3Fe(CN)6 to extreme positive potential of 1.5 V vs. NCE which decompose the ferricyanide ions to free ferric ion [15]. Decomposition of ferricyanide to free ferric ion at extreme positive potential is rst reported by Gomathi and Rao [23]. The formation of mixed analogue takes place in two steps. In this work, it is possible to observe signatures of individual M-HCFs independent of others in the work. The charge trapping effects were reported for MHCF lms formed as bilayers [12,24]. In our case the Prussian blue and NiHCF are formed as hybrids by simultaneous co-electrodeposition and the charge trapping effects were not observed for our lms. The ratio of the metal ions in the lm was assumed to be the same as that present in the modication mixture. This assumption was found to be true from EDX studies of the hybrid lms.

In most of the papers dealing with mixed MHCF modication, redox transition of ferro/ferricyanide takes place at similar potentials [810]. In the case of Ni (Fe) HCF modied electrodes, introduction of Fe2+ opens up a new electron transport channel in the lattice of the hybrid. On introducing the iron ions in the NiHCF lattice, the following changes in response of the modied electrode are noticed. (i) Anodic shift of the redox peak potential corresponding to ferro/ferricyanide redox centre to more positive direction. (ii) There exists only one redox process for the low spin iron unlike the two redox processes observed in NiHCF modied GC. (iii) Appearance of a set of new redox peak at 0.15 V corresponding to introduction of new electron transfer channel due to incorporation of high spin iron (above 30% of iron). Table 1 shows the peak to peak separation and the redox peak shift of redox processes of the modied electrode as a function of Ni2+%. When the modication mixture for NiHCF contain iron ion in it we observed a regular anodic shift in the redox potentials of ferro/ferricyanide redox centre in the hybrid MHCF (see Table 1). This kind of tuning of redox potential as a function of composition of the lm is not reported elsewhere. 3.1. Electrocatalysis of Nix-Fe(1x)Fe(CN)6 modied electrodes The Prussian blue modied electrode is known to electrocatalyze hydrogen peroxide oxidation or reduction very effectively in comparison with biocatalyst. So the Prussian blue can be used in biosensor application which indirectly acts as articial peroxidase in the detection of hydrogen peroxide [15,25]. Our group has

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Fig. 2. (A, B, C-thick lines) Response for FeHCF, NiHCF and Fe0.5Ni0.5HCF in 0.1 M KNO3 medium. (A, B, C-dotted line) shows voltammogram of FeHCF, NiHCF and Ni0.5 Fe0.5 HCF in presence of 1 mM hydrogen peroxide.

|Z| cm2

-12

14 12 10 8 6 100 1k 10k 100k 1M

Z, cm 2

-9 -6 -3 0 -12

ln f

10.3kHz

A
Fe-HCF

14
|Z| cm2

12 10 8 6 100 1k 10k 100k 1M ln f

Z, cm 2

-9 -6 -3 0

6.54kHz

B
Fe0.5-Ni0.5- HCF

4
Fig. 3. Amperometric response of hybrid Ni0.5Fe0.5 HCF modied GC electrode at applied potential of 0.09 V vs. NCE. Inset shows a linear plot of current vs. concentration of H2O2 (from amperometry).

10
Z, cm2

12

14

16

Fig. 5. Nyquist plot for (A) FeHCF and (B) Ni0.5Fe0.5HCF modied GC electrode in the frequency range 1 mHz10 Hz. Inset gure Bode plot (|Z| vs. ln f) are shown for both FeHCF and Ni0.5Fe0.5HCF modied GC electrodes .

reported an electrochemical preparation of PB-Au nanocomposite for electrocatalysis of hydrogen peroxide in the nano molar levels [26]. The application of MHCF modied electrode to catalysis is limited due to the fact that the electrochemical stability of the modied lm highly depends on the supporting electrolyte cation. Fig. 2 dotted lines depict the electrocatalytic oxidation/reduction of 1 mM H2O2 using FeHCF, NiHCF and Fe0.5 Ni0.5 HCF modied GC in KNO3 medium. From the voltammetric response, it is clear that the hydrogen peroxide can undergo either electro-oxidation or reduc-

15 10

5 0 -5 -10 -15 -20 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

tion at FeHCF modied electrode. However, the NiHCF modied electrode does not show signicant catalytic current due to hydrogen peroxide reduction nor oxidation. The Ni0.5 Fe0.5 HCF modied electrode showed almost similar hydrogen peroxide oxidation currents at slightly lower potential. The peak to peak separation for the low spin iron centre in Fe HCF is 90 mV compared to 20 mV for Fe0.5 Ni0.5 HCF which clearly indicate improved reversibility of redox process by the Ni2+ incorporation (see Table 1). From the above, it is evident that the electrocatalytic properties for the NiHCF modied electrode can be signicantly altered by the incorporation of second metal ion which shifts the redox potentials to more favourable values. Our experiments show that the hydrogen peroxide oxidation/reduction started taking place after 30% incorporation of Fe3+ in NiHCF modied electrode. The hydrogen peroxide could be electrocatalytically detected at the modied electrode at levels with a sensitivity of 192 nA/lM very easily. The electro-oxidation of H2O2 take place at potential above 0.64 V as follows:

Current, A

Potential, V Vs NCE
Fig. 4. Cyclic voltammogram of Ni0.5Fe0.5 HCF in 0.1 M NaNO3 (thick lines). Response after addition of 1 mM of hydrogen peroxide to the cell (dotted line).

1 H2 O2 ! H2 O O2 2e 2
The electro-reduction of H2O2 takes place below 0.38 V

H2 O2 2e ! 2OH

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Fig. 6. (thick lines) Voltammetric response of FeHCF, NiHCF and Ni0.5Fe0.5 HCF in 0.1 M KNO3 medium before cycling in 0.1 M NaNO3 supporting electrolyte (dotted line). Voltammetric response of FeHCF, NiHCF and Ni0.5Fe0.5 HCF in KNO3 medium after cycling in Na+ ion containing electrolyte.

Detection of hydrogen peroxide by electro-reduction enables one to avoid interference from routinely occurring oxidizable compounds in bio-uids. Fig. 3 shows the amperogram for the detection of hydrogen peroxide using the Fe0.5 Ni0.5 HCF modied electrode at applied potential of 0.09 V vs. NCE. The linear calibration plot for the detection of hydrogen peroxide (192 nA/lM) in the micromolar level is also given in Fig. 3 (inset). The response time for hydrogen peroxide reduction is very fast as seen from the response time less than 30 s. Detection of hydrogen peroxide by electro-reduction generates high hydroxyl ion concentration near the interface (Eq. (6)) which causes to destabilization of MHCF at higher analyte concentration [27]. The sensitivity of hydrogen peroxide detection can be improved by optimizing the lm characteristics like lm thickness, medium pH, etc. [28]. Detailed investigation aimed at improving the sensitivity of hydrogen peroxide detection is currently underway in our laboratory. Electroreduction of H2O2 in NaNO3 supporting electrolyte is shown in Fig. 4 which reveals the usefulness of these hybrids in sodium containing buffers. The buffers which are used to maintain the physiological pH conditions generally contain sodium ions. The increased stability of Fe0.5Ni0.5HCF hybrid lm in sodium containing electrolytes towards electrochemical cycling assume great signicance in the eld of biosensing. 3.2. Impedance spectroscopy Fig. 5 shows the impedance plane plot (imaginary component, Z00 vs. real component Z0 ) for both FeHCF and Fe0.5Ni0.5HCF in KNO3 medium. The charge transfer resistance (Rct) values derived from the Nyquist plot (Fig. 5) of FeHCF modied GC and Fe0.5 Ni0.5 HCF at bias potential of Ep = (Epa + Epc)/2 are around 9.66 X cm2 and 8.4 X cm2 respectively. The lower Rct values observed for the modied electrode with Ni2+ incorporation is consistent with the increased reversibility observed in terms of lower peak separation observed from the voltammetric response for Fe0.5Ni0.5HCF modied electrodes. From Fig. 5, Bode plot (|Z| vs. ln f) clearly show the line bend at higher frequency region. Similar line bend at higher frequency region is observed for CuHCF lms and is attributed to the porous nature of the lm [29].

the Rct values from the electrochemical impedance spectra. The j0 values for FeHCF and Fe0.5 Ni0.5 HCF are 2.657 103 A/cm2 and 3.054 103 A/cm2 respectively. Higher value of j0 is a sign of better reversibility of the redox processes. This observation is in line with the lower peak to peak separation values for the Fe0.5 Ni0.5 HCF modied lms as given in Table 1. 3.3. Electrochemical stability of Fe0.5Ni0.5HCF lm The electrochemical reversibility/stability of redox processes in MHCF lm depend on the nature of supporting electrolyte cation. The electrochemical response of Prussian blue electrodes is not stable when cycled in Na+ containing electrolytes. The effect of various supporting electrolytes on the NiHCF and FeHCF and CuHCF etc. of modied electrodes were studied in detail [31,6,7]. The stability of these modied lms in Na+ containing electrolyte is studied by examining the charge retention in KNO3 electrolyte after cycling the modied electrode in 0.1 M NaNO3 for 100 cycles in the potential range of 0.01.0 V (Fig. 6). The FeHCF modied lm show only 35% retention of charge whereas NiHCF modied electrodes exhibit more than 90% retention. The Fe0.5Ni0.5HCF modied electrode retains almost 80% of charge after cycling in sodium containing electrolytes. The improvement in the electrochemical stability in Na+ without losing the electrocatalytic properties can enlarge the scope of these hybrid modied electrodes in sensing applications in sodium ion containing buffer media.

4. Conclusions Simple electrochemical modication of GC with hybrids Nix Fe(1x)Fe(CN)6 thin lm is reported. The tuning of redox potential of FeHCF lm by controlled incorporation Ni2+ in the lattice by electrochemical means was successfully demonstrated. These hybrid lm exhibited single redox process for the redox reaction of low spin iron. Incorporation of Iron ion in the NixFe(1x)Fe(CN)6 lattice has signicantly improved the electrocatalytic properties of the interfaces towards hydrogen peroxide oxidation/reduction (192 nA/lM). The Ni2+ ions substitution has improved hybrids electrochemical cycling stability in Na+ containing supporting electrolytes. The modication of M-HCF hybrids opens up possibilities of tailoring the interfacial properties by simple electrochemical control of composition. This hybrid modied electrode possesses improved electrocatalytic properties towards hydrogen peroxide reduction/oxidation than the individual MHCF modied electrode. These modied electrodes are expected to play an important role in the development of oxidase-enzyme based amperometric biosensors which produce H2O2 as intermediate.

j0

RT nFARct

Exchange current density (j0) a kinetic parameter which have more inuence on the hydrogen peroxide oxidation and reduction process by electrochemically modied electrodes FeHCF and Fe0.5Ni0.5HCF, which can be directly calculated from Eq. (7) [30] all the constants in the equation (R, Gas constant; T, Temperature; F, Faraday; A, area of GC electrode) have its corresponding values, by using

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Acknowledgements This work was supported by Department of Science & Technology, India through a grant-in-aid project [SR/S1/PC-22/2007]. S. Harish thanks Council of Scientic and Industrial Research, New Delhi for the award of senior research fellowship.

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