Carbon 42 (2004) 191197 www.elsevier.

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High dispersion and electrocatalytic properties of platinum on well-aligned carbon nanotube arrays
H. Tang a, J.H. Chen a,*, Z.P. Huang b, D.Z. Wang b, Z.F. Ren b, L.H. Nie a, Y.F. Kuang a, S.Z. Yao a
a

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Yuelu Southern Road, Changsha 410082, PR China b Department of Physics, Boston College, Chestnut Hill, MA 02467, USA Received 11 August 2003; accepted 15 October 2003

Abstract Platinum (Pt) electrocatalyst was electrochemically dispersed on well-aligned carbon nanotube (CNT) arrays by a potential-step method. The structure and elemental composition of the resulting Pt/CNT electrode were characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic properties of the Pt/ CNT electrode for oxygen reduction reaction have been investigated by linear sweep voltammetry. Compared with a Pt/graphite electrode, higher electrocatalytic activity of the Pt/CNT electrode can be observed. This may be attributed to the high dispersion of platinum catalysts and the particular properties of CNT supports. The results imply that the Pt/CNT has good potential applications in proton exchange membrane fuel cells. 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Carbon nanotubes, electrodes; B. Chemical vapor deposition; D. Electrochemical properties

1. Introduction Proton exchange membrane fuel cells (PEMFC) are attractive electrical power sources without environmental pollution. However, one of the serious problems for PEMFC is the low rate of the oxygen reduction reaction (ORR) at cathode [1]. Platinum (Pt) seems to be the best choice of the catalysts for the electroreduction of oxygen in acidic media. The electrocatalytic activity of platinum catalyst is dependent on many factors [2,3]. Among them, the good properties of the catalyst supports, such as high surface area and good electronic property, are essential for Pt catalyst to produce high catalytic activity [4]. Carbon nanotubes (CNTs), as a new form of carbon, have received numerous theoretical and experimental studies [5]. Due to their nanometer size and interesting properties, CNTs are also of great interest for many applications, for example, batteries [6], at panel displays [7], chemical sensor [8], etc. Further-

Corresponding author. Tel./fax: +86-731-882-1818. E-mail address: chenjinhua@hnu.cn (J.H. Chen).

more, high accessible surface area, low resistance and high stability [9] suggest that CNTs are suitable materials for electrodes and catalyst supports in PEMFC. The metallic particles with electrocatalytic activity may decorate the external walls or be encapsulated in the interior of the nanotubes [10]. Several papers have focused on this area using tangled and substrate-free carbon nanotubes [1116]. Pt has been deposited on activated single or multi-wall carbon nanotubes by chemical reduction method and the resultant electrodes show good electrocatalytic properties for hydrogenation [11] and oxygen reduction [12,13]. For the applications in electrode and catalyst support, two kinds of CNT electrodes have been developed: binder-free [17] and binder-enriched [18]. In the binder-free electrode, carbon nanotubes are mechanically and electrically loose. When a binder is used, it brings impurities into the electrode and degrades the electrochemical performance. Furthermore, both methods result in a high contact resistance between the active material (CNT) and current collectors (graphitic or metallic substrate). In this paper, the well-aligned carbon nanotubes are grown directly on the titanium

0008-6223/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2003.10.023

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(Ti) substrate and used for the rst time as catalyst support for fuel cell. This not only simplies the preparation of CNT electrodes but also can greatly reduce the contact resistance of CNTs and Ti substrate. Additionally, compared with the tangled CNTs or at electrode (such as graphite disk and carbon cloth), the well-aligned CNT arrays with a space between each of CNTs will be helpful to disperse Pt catalyst on each of CNTs. On the other hand, for preparation of the platinum catalysts, chemical reduction method is commonly used [1114]. However, the impurities are easily involved from the bath solutions, which may deteriorate the catalytic activity of platinum catalysts. At the same time, the electrodeposition of platinum particles has received more and more attention due to its advantages, such as high purity of deposits and simple procedure for deposition. Furthermore, electrodeposition method can control easily the loading mass of the metallic catalyst [19]. This paper reports the uniform deposition of platinum catalysts on each of wellaligned carbon nanotube arrays by potential-step electrodeposition method and their electrochemical characterizations. The main concern in this paper is to investigate the eect of the CNT electrode with threedimensional structure on the dispersion and electrocatalytic properties of Pt catalyst. For comparison, a at electrode, graphite disk, is also investigated in this paper.The morphology of the platinum catalysts is characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrocatalytic properties of Pt/CNT electrode for ORR are investigated by cyclic voltammetry (CV) and linear sweep voltammetry.

Fig. 1. The SEM image of carbon nanotube arrays on Ti substrate.

SEM (JSM 5600 LV, operating at 20 kV), TEM (HITACHI H800, operating at 200 kV) and energy dispersive X-ray spectroscopy (EDS) (Vantage 4105, NORAN), respectively.

2.2. Platinum deposition and electrochemical studies Using a standard three-electrode cell, platinum catalysts were electrodeposited on the CNT arrays by potential-step deposition method from N2 saturated 7.7 mM H2 PtCl6 + 0.5 M HCl aqueous solution. The potential jumped from 0.65 V (the open-circuit potential of the CNT/Ti electrode in N2 saturated H2 PtCl6 aqueous solution) to )0.15 V (SCE) with a pulse width 0.001 s and carried out successively until a predetermined Pt deposition charge (Qdep ) had reached. The high opencircuit potential of CNT/Ti electrode (+0.65 V) may result from the TiOx passivation lms formed on Ti substrate during the following pretreatment process. Before platinum deposition, the CNT electrode was pretreated in 30 wt.% HNO3 aqueous solutions for 40 min to remove the metallic nickel particles that served as catalyst for the growth of CNTs. To further increase the electrochemical activity of CNTs in water solution [21], the CNT electrode was then cycled in N2 saturated 0.1 M H2 SO4 for 10 cycles under the potential range of )0.15 to 1.3 V at a sweep rate of 50 mV s1 . After platinum deposition, the samples were cleaned by double-distilled water. The electrochemical properties of the Pt/CNT electrode for oxygen reduction were then investigated by linear sweep voltammetry in 0.1 M H2 SO4 aqueous solution. An air ow of 50 cm3 min1 was introduced into the cell throughout the experiment to supply oxygen (O2 ). For comparison, platinum particles were also electrodeposited on the graphite disk electrode (geometry area 1.71 cm2 ). All experiments were carried out at ambient temperature. All the potentials were referred to SCE.

2. Experimental 2.1. Chemicals and instruments The well-aligned CNT arrays (geometry area 1 cm2 ) were used as working electrode. The detailed description of the synthesis of well-aligned carbon nanotubes has been reported in a previous paper [20]. The SEM image of the well-aligned carbon nanotubes used in this paper is shown in Fig. 1. The diameter of each nanotube is 50 70 nm with a length of 34 lm. A platinum foil served as the counter electrode and a saturated calomel electrode (SCE) was used as the reference electrode. CHI660A electrochemical workstation (CH Instruments, Inc.) was employed for the synthesis and electrochemical studies of platinum catalysts. All chemicals are of analytical grade. Freshly double-distilled water was used throughout. The morphology and elemental composition of Pt/ CNT and Pt/graphite electrodes were investigated by

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3. Results and discussion 3.1. The morphology and elemental composition of Pt/ CNT electrode Platinum was electrodeposited on the surface of wellaligned carbon nanotubes by potential-step deposition method. The morphology of the Pt/CNT electrode with dierent Pt Qdep has been shown in Fig. 2. For comparison, the SEM images of the surface and the crosssection of the Pt/graphite electrode are shown in Fig. 3. From Fig. 2(A), it is shown when Qdep is 9.744 lC cm2 , a great deal of platinum nanoparticles with size of 3070 nm (Fig. 2(B)) were uniformly deposited on the surface of CNT arrays. However, the diameter of the platinum particles on graphite electrode is about 100150 nm (Fig. 3(A)) at Qdep 11:69 lC cm2 . It is probably due to the nanoscale eect of the carbon nanotubes on the platinum deposition. It is also worth noting that the higher dispersion and real surface area of platinum nanoparticles were obtained at CNT electrode. The interesting three-dimensional structure of Pt/CNT, high dispersion and small Pt nanoparticles may result in good electrocatalytic activity. The signicant dierence is obvious between Fig. 2(A) and (C). When the Qdep of platinum is small, the

platinum nanoparticles disperse individually and the nanotubes form bundles due to the surface tension (Fig. 2(A)). With the increase of Qdep , the surface of the bundles of carbon nanotubes are coated uniformly by a thin platinum lm (Fig. 2(C)) and the thickness of the platinum lm is about 65 nm at Qdep 572:5 lC cm2 (Fig. 2(D)). From Fig. 2(C) and (D), no obvious platinum particles can be observed. However, for graphite electrode, when Qdep increases, the platinum particles will accumulate and form large particles. At Qdep 537:7 lC cm2 , as shown in Fig. 3(B), the Pt particle size is about 400 nm. From the corresponding SEM cross-section image (Fig. 3(C)), the thickness of the platinum lm is about 1000 nm. Furthermore, some cracks can be observed in Fig. 3(B). This means that the adhesion of platinum catalysts on graphite electrode is weak and may be easily peeled o from the substrate. However, the good adhesion between CNT and the thin uniform platinum lm prevents peeling o of Pt from CNTs even when Qdep is 572.5 lC cm2 . This may imply that Pt/CNT electrodes possess longterm stability. Fig. 4 is the energy dispersive X-ray spectroscopy (EDS) of Pt/CNT electrode. It indicates that Pt and Ti are the major elements plus C. The EDS results conrm that the nanoparticles on the CNTs are platinum.

Fig. 2. SEM (A, C) and TEM (B, D) images of platinum catalysts on well-aligned carbon nanotube arrays. (A), (B): Qdep 9:744 lC cm2 ; (C), (D): Qdep 572:5 lC cm2 .

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Fig. 4. The EDS spectra of Pt/CNT electrode (Qdep 9:744 lC cm2 ).

.750 Current Density (mA/cm )

2

.500 .250 0.000 II -.250 B 0.000 I

-.150 Specific Current (mA/C)

II

-.300 I C 0.000 -.045

-.450

II

Fig. 3. SEM images of platinum nanoparticles on graphite electrode with dierent loading mass (Qdep ). (A) 11.69 lC cm2 , (B) 573.7 lC cm2 and (C) cross-section SEM image of B.

-.090 -.135

I 0.00 .25 .50 .75 1.00 1.25

3.2. Electrocatalytic properties of Pt/CNT electrode The electrochemical and electrocatalytic properties of CNT, graphite, Pt/CNT and Pt/graphite electrodes have been investigated in 0.1 M H2 SO4 aqueous solution. The corresponding results are presented in Fig. 5. Typical cyclic voltammogram of CNT electrode is observed in Fig. 5(A) (line I). A similar result has also been obtained for single wall carbon nanotubes [22]. The background current, which is the nature of capacitive current, is larger than that of graphite electrode (Fig. 5(A), line II).

Potential (V vs SCE)
Fig. 5. The cyclic voltammograms of CNT and graphite electrodes in N2 saturated 0.1 M H2 SO4 aqueous solution (A), linear sweep voltammograms (B and C) of Pt/CNT and Pt/graphite electrodes in 50 cm3 min1 air ow bubbled H2 SO4 aqueous solution. (A) Line I, CNT electrode; line II, graphite electrode (CV sweep rate 50 mV s1 ). (B) Line I, Pt/CNT electrode (Qdep 9:744 lC cm2 ); line II, Pt/graphite electrode (Qdep 11:69 lC cm2 ). Linear sweep rate 200 mV s1 . (C) Line I, Pt/CNT electrode (Qdep 572:5 lC cm2 ); line II, Pt/graphite electrode (Qdep 573:7 lC cm2 ). Linear sweep rate 200 mV s1 .

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195
150 120 I 90 II 60 30 0 0 5 10 15 20 25 R=0.9955

This is attributed to the high specic surface area of the CNTs. On the other hand, it is shown that no O2 reduction current is observed at CNT and graphite electrodes over the study potential range (Fig. 5(A)). This means that the carbon nanotubes and graphite substrate have no obvious electrocatalytic activity for ORR. Fig. 5(B) and (C) are the linear sweep voltammograms of Pt/CNT and Pt/graphite electrodes at different Pt Qdep . For Pt/CNT electrode, a large oxygen reduction current can be observed at 0.36 V (SCE), which is the typical potential for oxygen electroreduction on platinum catalysts in H2 SO4 solution [23]. Specic current [24], dened by peak current density (mA cm2 ) per unit of Qdep (lC cm2 ), is used to evaluate the electrocatalytic activity of Pt catalysts for ORR. When the Pt loading mass is low (Qdep 9:744 lC cm2 ), the specic current of Pt/CNT electrode (Fig. 5(B), line I) is 0.41 mA lC1 , which is 1.4 times as large as that of Pt/ graphite electrode (Fig. 5(B), line II). At high Qdep (572.5 lC cm2 ), the specic current of Pt/CNT electrode (Fig. 5(C), line I) is almost twice as large as that of Pt/graphite electrode (Fig. 5(C), line II). These results imply that the Pt/CNT electrode possess high electrocatalytic activity for ORR. For Pt/CNT electrode, the increase in O2 reduction activity may be attributed to the following factors: (i) High dispersion of Pt on the three-dimensional structure of CNT electrode can provide high acceptable surface area of Pt for oxygen reduction. (ii) The particular structure and electrical properties of CNTs may be benecial to the electrocatalytical reduction of oxygen. Britto et al. [25] studied the dissociation of adsorptive oxygen on the surface of CNTs as well as the charge transfer process and suggested that CNTs have the ability to promote electron-transfer reactions. Additionally, the activity of the catalyst, which could be involved in the interaction between metallic catalyst and catalyst support, can be strongly aected by properties of the support materials [24]. These results may imply that well-aligned carbon nanotube arrays may be good candidate for the cathodic catalyst supports in PEMFC. 3.3. The kinetics of oxygen reduction reaction at Pt/CNT electrode In order to investigate the kinetics of oxygen reduction reaction at Pt/CNT electrode, the relationship of peak current density (Ip ) and peak potential (Ep ) for ORR with linear sweep rate (t) have been studied. The results are shown in Figs. 6 and 7. Fig. 6 shows a linear relationship between peak current density and t1=2 for Pt/CNT and Pt/graphite electrodes. This may imply that the ORR is controlled by diusion process of oxygen [26]. These results are thought to be due to the relatively low concentration of dissolved oxygen and consequent limitation of mass transport. However, the slope of line I (Fig. 6, Pt/CNT electrode) is 6.7296, which is twice as

Peak Current Density (mA/cm2)

R=0.9937

1/2

(mV/s)1/2

Fig. 6. Dependence of the peak current density (Ip ) of oxygen reduction upon the t1=2 in 0.1 M H2 SO4 aqueous solutions with air ow rate 50 cm3 min1 . Line I, Pt/CNT electrode (Qdep 572:5 lC cm2 ); line II, Pt/graphite electrode, (Qdep 573:7 lC cm2 ).

.56 Peak Potential (V vs SCE) .42 .28 .14 0.00 -.14 0.00 .75 log () 1.50 2.25 3.0 II I

(mV/s)

Fig. 7. The relationship between peak potential (Ep ) of oxygen reduction and log (t) in 0.1 M H2 SO4 aqueous solutions with air ow rate 50 cm3 min1 . Line I, Pt/CNT electrode (Qdep 572:5 lC cm2 ); line II, Pt/graphite electrode (Qdep 573:7 lC cm2 ).

large as that of line II (Fig. 6, Pt/graphite electrode, the slope 3.3886). This result can also be observed for other carbon materials with high surface area [27] and is related to Ai (the active surface area of Pt catalysts per unit geometric area of electrode) of Pt/CNT and Pt/ graphite electrodes. According to the Nicholsons results [28], the peak current density of ORR is proportional with Ai (i.e.: Ip / Ai ) when other parameters are identical. From the slopes of the lines I and II, it may be deduced that the Ai of Pt/CNTs is almost one fold larger than that of Pt/graphite electrode. Fig. 7 is the dependence of peak potential for ORR upon the logt at Pt/CNT and Pt/graphite electrodes. In Fig. 7, Ep at both Pt/CNT and Pt/graphite electrodes are shifted negatively when t increases. For these two kinds of electrodes, no obvious dierence can be observed until t is larger than 25 mV s1 . When t is larger than 25 mV s1 , the linear relationship between peak potential and logt can be observed obviously (Fig. 7, lines I, II) and the linear slope for Pt/CNT electrode is

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smaller than that for Pt/graphite electrode. The Ep of the Pt/graphite electrode is lower than that of Pt/CNT electrode at the same t. At t 200 mV s1 , Ep shifts negatively by 170 and 236 mV (relative to Ep at t 1 mV s1 ) for Pt/CNT and Pt/graphite electrodes, respectively. This may imply that larger cathodic polarization occurs and the electrocatalytic properties of the electrode are deteriorated for Pt/graphite electrode. On the other hand, for an electrochemical reduction reaction at high t, the linear relationship between Ep and logt can be represented by the following equation [29,30]: Ep A 2:3RT log t anF 1

nese Scholars, State Education Ministry under the grant 2001-498. The work performed at Boston College is partly supported by the US Department of Energy under a grant DE-FG02-00ER45805. References
[1] McNicol BD, Rand DAJ, Williams KR. Direct methanolair fuel cell for road transportation. J Power Sources 1999;83(12):1531. [2] Kabbabi A, Gloaguen F, Andolfatto F, Durand R. Particle size eect for oxygen reduction and methanol oxidation on Pt/C inside a proton exchange membrane. J Electroanal Chem 1994;373(1 2):2514. [3] Gamez A, Richard D, Gallezot P, Gloaguen F, Faure R, Durand R. Oxygen reduction on well-dened platinum nanoparticles inside recast ionomer. Electrochim Acta 1996;41(2):30714. [4] Yu JS, Kang S, Yoon SB, Chai G. Fabrication of ordered uniform porous carbon networks and their application to a catalyst supporter. J Am Chem Soc 2002;124:93823. [5] Baughman RH, Zakhidov AA, Heer WA. Carbon nanotubes the route toward applications. Science 2002;297:78792. [6] Che G, Lakshmi BB, Martin CR, Fisher ER. Metal-nanoclusterlled carbon nanotubes: catalytic properties and possible applications in electrochemical energy storage and production. Langmuir 1999;15(3):7508. [7] Wilder JWG, Venema LC, Rinzler AG, Smalley RE, Dekker C. Electronic structure of atomically resolved carbon nanotubes. Nature 1998;391:5962. [8] Kong J, Franklin NR, Zhou C, Chapline MG, Peng S, Cho K, Dai H. Nanotube molecular wires as chemical sensors. Science 2000;287:6225. [9] Dai H, Wong EW, Lieber CM. Probing electrical transport in nanomaterials: conductivity of individual carbon nanotubes. Science 1996;272:5236. [10] Ebbesen TW, Ajayan PM. Large-scale synthesis of carbon nanotubes. Nature 1992;358:2202. [11] Lordi V, Yao N, Wei J. Method for supporting platinum on single-walled carbon nanotubes for a selective hydrogenation catalyst. Chem Mater 2001;13:7337. [12] Li WZ, Liang CH, Qiu JS, Zhou WJ, Han HM, Wei ZB, et al. Carbon nanotubes as support for cathode catalyst of a direct methanol fuel cell. Carbon 2002;40(5):7914. [13] Liu ZL, Lin XH, Lee JY, Zhang WD, Han M, Gan LM. Preparation and characterization of platinum-based electrocatalysts on multiwalled carbon nanotubes for proton exchange membrane fuel cell. Langmuir 2002;18:405460. [14] Yu RQ, Chen LW, Liu QP, Lin JY, Tan KL, Ng SC, et al. Platinum deposition on carbon nanotubes via chemical modication. Chem Mater 1998;10:71822. [15] Planeix JM, Coustel N, Coq B, Brotons V, Kumbhar PS, Dutartre R, et al. Application of carbon nanotubes as supports in heterogeneous catalysis. J Am Chem Soc 1994;116(17):79356. [16] Luo JZ, Gao LZ, Leong YL, Au CT. The decomposition of NO on CNTs and 1 wt% Rh/CNTs. Catal Lett 2000;66(12):917. [17] Niu C, Sichel EK, Hoch R, Moy D, Tennent H. High power electrochemical capacitors based on carbon nanotube electrodes. Appl Phys Lett 1997;70(11):14802. [18] Ma R, Liang J, Wei B, Zhang B, Xu C, Wu D. Processing and performance of electric double-layer capacitors with block-type carbon nanotube electrodes. Bull Chem Soc Jpn 1999;72:2563 6. [19] Goodenough JB, Hamnett A, Kennedy BJ, Manoharan R, Weeks SA. Porous carbon anodes for the direct methanol fuel cellI. The role of the reduction method for carbon supported platinum electrodes. Electrochim Acta 1990;35:199207.

where A is a constant, which is related with the formal electrode potential (E0 ) and standard rate constant at E0 . The transfer coecient (a), which characterizes the eect of electrochemical potential on energy of activation of an electrochemical reaction [31], can be calculated according to the slope of Ep $ logt in linear range. From Fig. 7, the a values are calculated and equal to 0.124 and 0.097 (giving n 2) for Pt/CNT and Pt/ graphite electrodes, respectively. These indicated that ORR at both Pt/CNT and Pt/graphite electrodes was irreversible and the energy of activation for Pt/CNT electrode was smaller than that for Pt/graphite electrode at the same cathodic over-potential [31]. The smaller energy of activation for Pt/CNT electrode suggests that CNTs have a benecial eect on the kinetics of oxygen reduction.

4. Conclusion Highly dispersed platinum catalysts are electrodeposited by potential-step method on well-aligned carbon nanotube arrays. The electrocatalytic properties of Pt/ CNT electrode for ORR have been investigated and high electrocatalytic activity is observed. This may be attributed to the high dispersion of nanoscale platinum catalysts and the particular properties of carbon nanotubes (such as unique electrical property, three dimensional structure and nanometer size, etc.). It also implies that well-aligned carbon nanotube arrays have good potential application in proton exchange membrane fuel cell. Additionally, the kinetics of ORR at Pt/ CNT electrode has also been investigated. The ORR may be controlled by the diusion process of oxygen.

Acknowledgements This work is supported by the Natural Science Foundation of China under a grant 50172014 and 20275009 and the Project Sponsored by the Scientic Research Foundation for the Returned Overseas Chi-

H. Tang et al. / Carbon 42 (2004) 191197 [20] Ren ZF, Huang ZP, Xu JW, Wang JH, Bush P, Siegal MP, Provencio PN. Synthesis of large arrays of well-aligned carbon nanotubes on glass. Science 1998;282:11057. [21] Raymundo-Pi~ ero E, Cazorla-Amors D, Linares-Solano A, n o Delpeux S, Frackowiak E, Szostak K, et al. High surface area carbon nanotubes prepared by chemical activation. Carbon 2002;40:16147. [22] Liu C, Bard AJ, Wudl F, Weitz I, Heath JR. Electrochemical characterization of lms of single-walled carbon nanotubes and their possible application in supercapacitors. Electrochem SolidState Lett 1999;2:5778. [23] Perez J, Gonzalez ER, Ticianelli EA. Impedance studies of the oxygen reduction on thin porous coating rotating platinum electrodes. J Electrochem Soc 1998;145:230714. [24] Kinoshita K. Particle size eects for oxygen reduction on highly dispersed platinum in acid electrolytes. J Electrochem Soc 1990;137(3):8458. [25] Britto PJ, Santhanam KSV, Rubio A, Alonso JA, Ajayan PM. Improved charge transfer at carbon nanotube electrodes. Adv Mater 1999;11:1547.

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[26] Dong SJ, Qiu QS. Electrodeposition of platinum particles on glassy carbon modied with cobalt porphyrin and Naon lm and their electro catalytic reduction of dioxygen. J Electroanal Chem 1991;314:22339. [27] Ticianelli EA, Derouin CR, Srinivasan S. Localization of platinum in low catalyst electrode to attain high power densities in SPE fuel cells. J Electroanal Chem 1988;251:27595. [28] Nicholson RS, Shain I. Theory of stationary electrode polarography. Anal Chem 1964;36(4):70623. [29] Laviron E. General expression of the linear potential sweep voltammogram in the case of diusionless electrochemical systems. J Electroanal Chem 1979;101(1):1928. [30] Laviron E, Roullier L. General expression of the linear potential sweep voltammogram for a surface redox reaction with interactions between the adsorbed molecules. Application to modied electrode. J Electroanal Chem 1980;115(1):65 74. [31] Conway BE. Theory and principles of electrode processes. In: Crawford Jr B, editor. Modern Concepts in Chemistry. New York: The Ronald Press Company; 1965. p. 92101.