Electrocatalytic Oxidation of Ethanol and Ethylene Glycol onto Poly (o-Anisidine)-Nickel Composite Electrode

Document Type: Research Article

Authors

1 Department of Applied Chemistry, Quchan Branch, Islamic Azad University, Quchan, I.R. IRAN

2 Department of Applied Chemistry, North Tehran Branch, Islamic Azad University, Tehran, I.R. IRAN

3 Young Researchers Club, Quchan Branch, Islamic Azad University, Quchan, I.R. IRAN

Abstract

In this work, poly (o-Anisidine) (POA) was prepared by consecutive potential cycling in an acidic monomer solution at the surface of Carbon Paste Electrode (CPE). Nickel ions were dispersed into the polymer by immersing the electrode in NiSO4 solution. The prepared Ni/POA/CPE was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, Atomic Force Microscopy (AFM) and electrochemical methods. The electrochemical oxidation of ethanol and ethylene glycol was investigated at the Ni/POA/CPE by cyclic voltammetry and chronoamperometry techniques. The results indicated that the Ni/POA/CPE in comparison with Ni/CPE exhibited excellent electrocatalytic activity towards oxidation. Then, using a chronoamperometry method, the catalytic rate constant, k, for ethanol and ethylene glycol oxidation were found to be 2.6×106 and 1.07×107 cm3/mol s, respectively. Furthermore, the effect of several parameters such as OA concentration, POA thickness, and NiSO4 concentration and accumulation times towards the ethanol oxidation as well as the long-term stability of the modified electrode has been investigated.

Keywords

Main Subjects


[1] Antolini E., Gonzalez E.R., Alkaline Direct Alcohol Fuel Cells, J. Power Sour, 195 (11): 3431-3450 (2010).

[2] Lamy C., Belgsir E.M., Léger, J.M., Electrocatalytic Oxidation of Aliphatic Alcohols: Application to the Direct Alcohol Fuel Cell (DAFC), J. Appl. Electrochem, 31 (7): 799-809 (2001).

[3] Kamarudin M.Z.F., Kamarudin S.K., Masdar M.S., Daud W.R.W., Review: Direct Ethanol Fuel Cells, International Journal of Hydrogen Energy, 38(22): 9438-9453 (2013).

[4] Liu B., Chen J.H., Zhong X.X., Cui K.Z., Zhou H.H., Kuang Y.F., Preparation and Electrocatalytic Properties of Pt–SiO2 Nanocatalysts for Ethanol Electrooxidation, J. Coll. Int. Sci., 307 (1): 139-144 (2007).

[5] Livshits V., Peled E., Progress in the Development of a High-Power, Direct Ethylene Glycol Fuel Cell (DEGFC), J. Power Sour., 161 (2): 1187-1191 (2006).

[6] Livshits V., Philosoph M., Peled E., Direct Ethylene Glycol Fuel-Cell Stack-Study of Oxidation Intermediate Products, J. Power Sour., 178 (2): 687-691 (2008).

[7] Matsuoka K., Inaba M., Iriyama Y., Abe T., Ogumi Z., Matsuoka M., Anodic Oxidation of Polyhydric Alcohols on a Pt Electrode in Alkaline Solution, Fuel. Cell., 2 (1): 35-39 (2002).

[8] Matsuoka K., Iriyama Y., Abe T., Matsuoka M., Ogumi Z., Alkaline Direct Alcohol Fuel Cells Using an Anion Exchange Membrane, J. Power Sour., 150: 27-31 (2005).

[10] An L., Zhao T.S., Xu J.B., A Bi-Functional Cathode Structure for Alkaline-Acid Direct Ethanol Fuel Cells, Inte. J. Hydrogen Energy, 36 (20): 13089-13095 (2011).

[11] Antolini E., Catalysts for Direct Ethanol Fuel Cells, J. Power Sour, 170 (1): 1-12 (2007).

[12] Christensen P.A, Hamnett A., The Oxidation of Ethylene Glycol at a Platinum Electrode in Acid and Base: An in Situ FT-IR Study, J. Electroanal. Chem. Inter. Electrochem, 260 (2): 347-359 (1989).

[13] Beden B., Kadirgan F., Kahyaoglu A., and Lamy C., Electrocatalytic Oxidation of Ethylene Glycol in Alkaline Medium on Paltinum-Gold Alloy Electrodes Modified by Under Potential Deposition of Lead Adatoms, J. Electroanal. Chem. Inter. Electrochem, 135 (2): 329-334 (1982).

[14] Habibi E., Razmi H., Kinetics of Direct Ethanol Fuel Cell Based on Pt-PoPD nano Particle Anode Catalyst, Int. J. Hydrogen Energy, 38 (13): 5442-5448 (2013).

[15] Song S., Wang Y., Shen P., Thermodynamic and Kinetic Considerations for Ethanol Electrooxidation in Direct Ethanol Fuel Cells, Chinese. J. Catal, 28(9): 752-754 (2007).

[16] Zhu M., Sun G., Li H., Cao L., Xin Q., Effect of the Sn(II)/Sn(IV) Redox Couple on the Activity of PtSn/C for Ethanol Electro-oxidation, Chinese.  J. Catal, 29 (8): 765-770 (2008).

[17] Erini N., Krause P., Gliech M., Yang R., Huang Y., Strasser P., Comparative Assessment of Synthetic Strategies Toward Active Platinum–Rhodium–tin Electrocatalysts for Eficient Ethanol Electro-Oxidation, J. Power Sour, 294: 299-304 (2015).

 [19] Xia B.Y., Wu H.B., Wang X., Lou X.W., One-Pot Synthesis of Cubic PtCu3 Nanocages with Enhanced Electrocatalytic Activity for the Methanol Oxidation Reaction, J. American Chem. Soc., 134 (34): 13934-13937 (2012).

[20] Lee E., Park I.S., Synthesis and Characterization of Pt−Sn−Pd/C Catalysts for Ethanol Electro-Oxidation Reaction, J. Phys. Chem. C, 114 (23): 10634-10640 (2010).

[22] Dutta A., Datta J., Energy Efficient Role of Ni/NiO in PdNi Nano Catalyst Used in Alkaline DEFC, J. Mat. Chem. A, 2 (9): 3237-3250 (2014).

[24] Barbosa A.F.B., Oliveira V.L., van Drunen J., Tremiliosi-Filho G., Ethanol Electro-Oxidation Reaction Using a Polycrystalline Nickel Electrode in Alkaline Media: Temperature Influence and Reaction Mechanism, J. Electroanal. Chem., 746: 31-38 (2015).

[25] Ureta-Zañartu M.S., Alarcón A., Muñoz G., Gutiérrez C., Electrooxidation of Methanol and Ethylene Glycol on Gold and on Gold Modified with an Electrodeposited polyNiTSPc Film, Electrochim. Acta., 52 (28): 7857-7864 (2007).

[26] Liu Z., Li Z., Wang F., Liu J., Ji J., Wang J., Wang W., Qin S., Zhang L., Qin L.Z., Synthesis of Multi-Walled Carbon Nanotube Supported Nickel Catalysts by Hydrazine Reduction and Their Electrocatalytic Activity on Ethanol Electro-Oxidation, Mat. Letters, 65 (23–24): 3396-3398 (2011).

[27] Rice M.E., Galus Z., Adams R.N., Graphite Paste Electrodes: Effects of Paste Composition and Surface States on Eectron-transfer Rates, J. Electroanal. Chem. Inter. Electrochem, 143 (1–2): 89-102 (1983).

[29] Raoof J.B., Ojani R., Hosseini S.R., An Electrochemical Investigation of Methanol Oxidation on Nickel Hydroxide Nanoparticles, South African J. Chem., 66: 00-00 (2013).

[31] Ghasemi S., Hosseini S.R., Asen P., Preparation of Graphene/Nickel-Iron Hexacyanoferrate Coordination Polymer Nanocomposite for Electrochemical Energy Storage, Electrochim. Acta, 160: 337-346 (2015).

[32] Bard A.J., Faulkner L.R., “Electrochemical Methods: Fundamentals and Applications”, Wiley and Sons, New York, (2001).

[33] Fleischmann M., Korinek K., Pletcher D., The Oxidation of Hydrazine at a Nickel Anode in Alkaline Solution, J. Electroanal. Chem. Inter. Electrochem, 34 (2): 499-503 (1972).

[34] Dailey D., Jungwon S., Korzeniewski C., Ethylene Glycol Electrochemical Oxidation at Platinum Probed by Ion Chromatography and Infrared Spectroscopy, Electrochimi. Acta., 44 (6–7): 1147-1152 (1998).