Electrocatalytic Reduction of Oxygen at Perovskite (BSCF)-MWCNT Composite Electrodes


A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.

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Yusoff, F. , Mohamed, N. , Aziz, A. and Ghani, S. (2014) Electrocatalytic Reduction of Oxygen at Perovskite (BSCF)-MWCNT Composite Electrodes. Materials Sciences and Applications, 5, 199-211. doi: 10.4236/msa.2014.54025.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Babcock, G.T. and Wikström, M. (1992) Oxygen Activation and the Conservation of Energy in Cell Respiration. Nature, 356, 301-309. http://dx.doi.org/10.1038/356301a0
[2] Kendig, M. and Jeanjaquet, S. (2002) Cr (VI) and Ce (III) Inhibition of Oxygen Reduction on Copper. Journal of the Electrochemical Society, 149, B47-B51. http://dx.doi.org/10.1149/1.1430717
[3] Nørskov, J.K., Rossmeisl, J., Logadottir, A., et al. (2004) Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. The Journal of Physical Chemistry B, 108, 17886-17892. http://dx.doi.org/10.1021/jp047349j
[4] Schmidt, T., Paulus, U., Gasteiger, H., et al. (2001) The Oxygen Reduction Reaction on a Pt/Carbon Fuel Cell Catalyst in the Presence of Chloride Anions. Journal of Electroanalytical Chemistry, 508, 41-47.
[5] Srivastava, R., Mani, P., Hahn, N., et al. (2007) Efficient Oxygen Reduction Fuel Cell Electrocatalysis on Voltammetrically Dealloyed Pt-Cu-Co Nanoparticles. Angewandte Chemie International Edition, 46, 8988-8991.
[6] Qu, L., Liu, Y., Baek, J.-B., et al. (2010) Nitrogen-Doped Graphene as Efficient Metal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells. ACS Nano, 4, 1321-1326. http://dx.doi.org/10.1021/nn901850u
[7] Fernández, J.L., Raghuveer, V., Manthiram, A., et al. (2005) Pd-Ti and Pd-Co-Au Electrocatalysts as a Replacement for Platinum for Oxygen Reduction in Proton Exchange Membrane Fuel Cells. Journal of the American Chemical Society, 127, 13100-13101. http://dx.doi.org/10.1021/ja0534710
[8] Mukerjee, S. and Srinivasan, S. (1993) Enhanced Electrocatalysis of Oxygen Reduction on Platinum Alloys in Proton Exchange Membrane Fuel Cells. Journal of Electroanalytical Chemistry, 357, 201-224.
[9] Zhang, J., Sasaki, K., Sutter, E., et al. (2007) Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters. Science, 315, 220-222. http://dx.doi.org/10.1126/science.1134569
[10] Zhao, F., Harnisch, F., Schröder, U., et al. (2005) Application of Pyrolysed Iron (II) Phthalocyanine and CoTMPP Based Oxygen Reduction Catalysts as Cathode Materials in Microbial Fuel Cells. Electrochemistry Communications, 7, 1405-1410. http://dx.doi.org/10.1016/j.elecom.2005.09.032
[11] Yeager, E. (1984) Electrocatalysts for O2 Reduction. Electrochimica Acta, 29, 1527-1537.
[12] Collman, J.P., Denisevich, P., Konai, Y., et al. (1980) Electrode Catalysis of the Four-Electron Reduction of Oxygen to Water by Dicobalt Face-to-Face Porphyrins. Journal of the American Chemical Society, 102, 6027-6036.
[13] Maricle, D. and Hodgson, W. (1965) Reducion of Oxygen to Superoxide Anion in Aprotic Solvents. Analytical Chemistry, 37, 1562-1565. http://dx.doi.org/10.1021/ac60231a027
[14] Damjanovic, A. and Brusic, V. (1967) Electrode Kinetics of Oxygen Reduction on Oxide-Free Platinum Electrodes. Electrochimica Acta, 12, 615-628. http://dx.doi.org/10.1016/0013-4686(67)85030-8
[15] Ishihara, T., Kudo, T., Matsuda H., et al. (1995) Doped PrMnO3 Perovskite Oxide as a New Cathode of Solid Oxide Fuel Cells for Low Temperature Operation. Journal of the Electrochemical Society, 142, 1519-1524.
[16] Xie, Z., Zhao, H., Du, Z., et al. (2012) Effects of Co Doping on the Electrochemical Performance of Double Perovskite Oxide Sr2MgMoO6-δ as an Anode Material for Solid Oxide Fuel Cells. The Journal of Physical Chemistry C, 116, 9734-9743. http://dx.doi.org/10.1021/jp212505c
[17] Lukaszewicz, J.P., Miura, N. and Yamazoe, N. (1990) A LaF3-Based Oxygen Sensor with Perovskite-Type Oxide Electrode Operative at Room Temperature. Sensors and Actuators B: Chemical, 1, 195-198.
[18] Lukaszewicz, J.P., Miura, N. and Yamazoe, N. (1989) Application of Perovskite-Type Oxides to the Sensing Electrode of a LaF3-Based Oxygen Sensor Workable at Room Temperature. Japanese Journal of Applied Physics, 28, L711-L713. http://dx.doi.org/10.1143/JJAP.28.L711
[19] Esaka, T., Morimoto, H. and Iwahara, H. (1992) Nonstoichiometry in Perovskite-Type Oxide Ca1-x Cex MnO3-δ and Its Properties in Alkaline Solution. Journal of Applied Electrochemistry, 22, 821-824.
[20] Suntivich, J., Gasteiger, H.A., Yabuuchi, N., et al. (2011) Design Principles for Oxygen-Reduction Activity on Perovskite Oxide Catalysts for Fuel Cells and Metal-Air Batteries. Nature Chemistry, 3, 546-550.
[21] Suntivich, J., May, K.J., Gasteiger, H.A., et al. (2011) A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles. Science, 334, 1383-1385. http://dx.doi.org/10.1126/science.1212858
[22] Balasubramanian, K. and Burghard, M. (2006) Biosensors Based on Carbon Nanotubes. Analytical and Bioanalytical Chemistry, 385, 452-468. http://dx.doi.org/10.1007/s00216-006-0314-8
[23] Wang, J. and Musameh, M. (2003) Carbon Nanotube/Teflon Composite Electrochemical Sensors and Biosensors. Analytical Chemistry, 75, 2075-2079. http://dx.doi.org/10.1021/ac030007+
[24] Jiang, L., Wang, R., Li, X., et al. (2005) Electrochemical Oxidation Behavior of Nitrite on a Chitosan-Carboxylated Multiwall Carbon Nanotube Modified Electrode. Electrochemistry Communications, 7, 597-601.
[25] Wang, J., Kawde, A.-N. and Musameh, M. (2003) Carbon-Nanotube-Modified Glassy Carbon Electrodes for Amplified Label-Free Electrochemical Detection of DNA Hybridization. Analyst, 128, 912-916.
[26] Fei, S., Chen, J., Yao, S., et al. (2005) Electrochemical Behavior of L-Cysteine and Its Detection at Carbon Nanotube Electrode Modified with Platinum. Analytical Biochemistry, 339, 29-35. http://dx.doi.org/10.1016/j.ab.2005.01.002
[27] Wang, J., Deo, R.P. and Musameh, M. (2003) Stable and Sensitive Electrochemical Detection of Phenolic Compounds at Carbon Nanotube Modified Glassy Carbon Electrodes. Electroanalysis, 15, 1830-1834.
[28] Peigney, A., Laurent, C., Flahaut, E., et al. (2001) Specific Surface Area of Carbon Nanotubes and Bundles of Carbon Nanotubes. Carbon, 39, 507-514. http://dx.doi.org/10.1016/S0008-6223(00)00155-X
[29] Ma, P.C., Tang, B.Z. and Kim, J.-K. (2008) Effect of CNT Decoration with Silver Nanoparticles on Electrical Conductivity of CNT-Polymer Composites. Carbon, 46, 1497-1505. http://dx.doi.org/10.1016/j.carbon.2008.06.048
[30] Shao, Z., Yang, W., Cong, Y., et al. (2001) Investigation of the Permeation Behavior and Stability of a Ba0.5Sr0.5Co0.8Fe0.23-δ Oxygen Membrane. Journal of Membrane Science, 172, 177-188.
[31] Yang, Z., Harvey, A.S., Infortuna, A., et al. (2009) Phase Relations in the Ba-Sr-Co-Fe-O System at 1273 K in Air. Journal of Applied Crystallography, 42, 153-160. http://dx.doi.org/10.1107/S0021889809002040
[32] Mueller, D.N., De Souza, R.A., Weirich, T.E., et al. (2010) A Kinetic Study of the Decomposition of the Cubic Perovskite-Type Oxide BaxSr1-xCo0.8Fe0.2O3-δ (BSCF)(x= 0.1 and 0.5). Physical Chemistry Chemical Physics, 12, 10320-10328. http://dx.doi.org/10.1039/c0cp00004c
[33] Saini, P., Choudhary, V., Singh, B., et al. (2009) Polyaniline-MWCNT Nanocomposites for Microwave Absorption and EMI Shielding. Materials Chemistry and Physics, 113, 919-926.
[34] Li, J. and Zhitomirsky, I. (2009) Electrophoretic Deposition of Manganese Dioxide-Carbon Nanotube Composites. Journal of Materials Processing Technology, 209, 3452-3459. http://dx.doi.org/10.1016/j.jmatprotec.2008.08.001
[35] Neimark, A.V. and Ravikovitch, P.I. (2001) Capillary Condensation in MMS and Pore Structure Characterization. Microporous and Mesoporous Materials, 44, 697-707. http://dx.doi.org/10.1016/S1387-1811(01)00251-7
[36] Charinpanitkul, T., Soottitantawat, A., Tonanon, N., et al. (2009) Single-Step Synthesis of Nanocomposite of Copper and Carbon Nanoparticles Using Arc Discharge in Liquid Nitrogen. Materials Chemistry and Physics, 116, 125-128.
[37] Geng, H.-Z., Kim, T.H., Lim, S.C., et al. (2010) Hydrogen Storage in Microwave-Treated Multi-Walled Carbon Nanotubes. International Journal of Hydrogen Energy, 35, 2073-2082.
[38] López, T., Bata-García, J.L., Esquivel, D., et al. (2011) Treatment of Parkinson’s Disease: Nanostructured Sol-Gel Silica-Dopamine Reservoirs for Controlled Drug Release in the Central Nervous System. International Journal of Nanomedicine, 6, 19.
[39] Naseer, A. and Khan, A.Y. (2009) A Study of Growth and Breakdown of Passive Film on Copper Surface by Electrochemical Impedance Spectroscopy. Turkish Journal of Chemistry, 33, 739-750.
[40] Omanovic, S. and Roscoe, S.G. (2000) Interfacial Behavior of β-Lactoglobulin at a Stainless Steel Surface: An Electrochemical Impedance Spectroscopy Study. Journal of Colloid and Interface Science, 227, 452-460.
[41] Bard, A.J. and Faulkner, L.R. (1980) Electrochemical Methods: Fundamentals and Applications. Wiley, New York.
[42] Sun, W., Yang, M. and Jiao, K. (2007) Electrocatalytic Oxidation of Dopamine at an Ionic Liquid Modified Carbon Paste Electrode and Its Analytical Application. Analytical and Bioanalytical Chemistry, 389, 1283-1291.

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