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Nanostructured Pt/MnO2 Catalysts and Their Performance for Oxygen Reduction Reaction in Air Cathode Microbial Fuel Cell

Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman


Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The asprepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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[1] B. E. Logan, Microbial fuel cells, John Wiley & Sons, 2008.
[2] B. E. Logan, B. Hamelers, R. Rozendal, U. Schröder, J. Keller, S. Freguia, P. Aelterman, W. Verstraete, K. Rabaey, “Microbial fuel cells: methodology and technology,” Environmental science & technology, vol. 40, no. 17, 2006, pp. 5181-5192.
[3] D. Pant, G. Van Bogaert, L. Diels, K. Vanbroekhoven, “A review of the substrates used in microbial fuel cells (MFCs) for sustainable energy production,” Bioresource Technology, vol. 101, no. 6, 2010, pp. 1533- 1543.
[4] S. Oh, B. E. Logan, “Hydrogen and electricity production from a food processing wastewater using fermentation and microbial fuel cell technologies,” Water Research, vol. 39, no. 19, 2005, pp. 4673-4682.
[5] M. Lu, S. Kharkwal, H. Y. Ng, S. F. Y. Li, “Carbon nanotube supported MnO2 catalysts for oxygen reduction reaction and their applications in microbial fuel cells,” Biosensors and Bioelectronics, vol. 26, no. 12, 2011, pp. 4728-4732.
[6] X. Wang, Y. Feng, N. Ren, H. Wang, H. Lee, N. Li, Q. Zhao, “Accelerated start-up of two-chambered microbial fuel cells: effect of anodic positive poised potential,” Electrochimica Acta, vol. 54, no. 3, 2009, pp. 1109-1114.
[7] Q. Wen, Y. Wu, D. Cao, L. Zhao, Q. Sun, “Electricity generation and modeling of microbial fuel cell from continuous beer brewery wastewater,” Bioresource Technology, vol. 100, no. 18, 2009, pp. 4171- 4175.
[8] T. H. Pham, K. Rabaey, P. Aelterman, P. Clauwaert, L. De Schamphelaire, N. Boon, W. Verstraete, “Microbial fuel cells in relation to conventional anaerobic digestion technology,” Engineering in Life Sciences, vol. 6, no. 3, 2006, pp. 285-292.
[9] D. Pant, A. Adholeya, “Biological approaches for treatment of distillery wastewater: A review,” Bioresource Technology, vol. 98, no. 12, 2007, pp. 2321-2334.
[10] E. Baranitharan, M. R. Khan, D. M. R. Prasad, J. B. Salihon, “Bioelectricity Generation from Palm Oil Mill Effluent in Microbial Fuel Cell Using Polacrylonitrile Carbon Felt as Electrode,” Water, Air, & Soil Pollution, vol. 224, no. 5, 2013, pp. 1-11.
[11] R. Bashyam, P. Zelenay, “A class of non-precious metal composite catalysts for fuel cells,” Nature, vol. 443, no. 7107, 2006, pp. 63-66.
[12] E. HaoYu, S. Cheng, K. Scott, B. Logan, “Microbial fuel cell performance with non-Pt cathode catalysts,” Journal of power sources, vol. 171, no. 2, 2007, pp. 275-281.
[13] K. Gong, P. Yu, L. Su, S. Xiong, L. Mao, “Polymer-assisted synthesis of manganese dioxide/carbon nanotube nanocomposite with excellent electrocatalytic activity toward reduction of oxygen,” Journal of Physical Chemistry C, vol. 111, no. 5, 2007, pp. 1882-1887.
[14] F. Cheng, Y. Su, J. Liang, Z. Tao, J. Chen, “MnO2-Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media,” Chemistry of Materials, vol. 22, no. 3, 2009, pp. 898- 905.
[15] X. Yu, J. He, D. Wang, Y. Hu, H. Tian, Z. He, “Facile controlled synthesis of Pt/MnO2 nanostructured catalysts and their catalytic performance for oxidative decomposition of formaldehyde,” Journal of Physical Chemistry C, vol. 116, no. 1, 2011, pp. 851-860.
[16] Y. Chen, C. Liu, F. Li, H.-M. Cheng, “Preparation of single-crystal α- MnO2 nanorods and nanoneedles from aqueous solution,” Journal of Alloys and Compounds, vol. 397, no. 1, 2005, pp. 282-285.
[17] C.-S. Lin, M. R. Khan, S. D. Lin, “The preparation of Pt nanoparticles by methanol and citrate,” Journal of Colloid and Interface Science, vol. 299, no. 2, 2006, pp. 678-685.
[18] J. Liqiang, S. Xiaojun, C. Weimin, X. Zili, D. Yaoguo, F. Honggang, “The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity,” Journal of Physics and Chemistry of Solids, vol. 64, no. 4, 2003, pp. 615-623.
[19] H. R. Ong, M. R. Khan, M. N. K. Chowdhury, A. Yousuf, C. K. Cheng, “Synthesis and characterization of CuO/C catalyst for the esterification of free fatty acid in rubber seed oil,” Fuel, vol. 120, no. 2014, pp. 195- 201.
[20] Z. Awaludin, M. Suzuki, J. Masud, T. Okajima, T. Ohsaka, “Enhanced electrocatalysis of oxygen reduction on Pt/TaO x/GC,” Journal of Physical Chemistry C, vol. 115, no. 51, 2011, pp. 25557-25567.
[21] D. A. Pawlak, M. Ito, M. Oku, K. Shimamura, T. Fukuda, “Interpretation of XPS O (1s) in mixed oxides proved on mixed perovskite crystals,” Journal of Physical Chemistry B, vol. 106, no. 2, 2002, pp. 504-507.
[22] C. Zhou, H. Wang, F. Peng, J. Liang, H. Yu, J. Yang, “MnO2/CNT supported Pt and PtRu nanocatalysts for direct methanol fuel cells,” Langmuir, vol. 25, no. 13, 2009, pp. 7711-7717.
[23] H. Xia, M. Lai, L. Lu, “Nanoflaky MnO2/carbon nanotube nanocomposites as anode materials for lithium-ion batteries,” Journal of Materials Chemistry, vol. 20, no. 33, 2010, pp. 6896-6902.
[24] W.-M. Chen, L. Qie, Q.-G. Shao, L.-X. Yuan, W.-X. Zhang, Y.-H. Huang, “Controllable Synthesis of Hollow Bipyramid β-MnO2 and Its High Electrochemical Performance for Lithium Storage,” ACS applied materials & interfaces, vol. 4, no. 6, 2012, pp. 3047-3053.
[25] P. Bera, K. R. Priolkar, A. Gayen, P. R. Sarode, M. S. Hegde, S. Emura, R. Kumashiro, V. Jayaram, G. N. Subbanna, “Ionic dispersion of Pt over CeO2 by the combustion method: Structural investigation by XRD, TEM, XPS, and EXAFS,” Chemistry of Materials, vol. 15, no. 10, 2003, pp. 2049-2060.
[26] R. Siburian, J. Nakamura, “Formation Process of Pt Subnano-Clusters on Graphene Nanosheets,” Journal of Physical Chemistry C, vol. 116, no. 43, 2012, pp. 22947-22953.
[27] R. V. Hull, L. Li, Y. Xing, C. C. Chusuei, “Pt nanoparticle binding on functionalized multiwalled carbon nanotubes,” Chemistry of Materials, vol. 18, no. 7, 2006, pp. 1780-1788.
[28] E. Antolini, “Formation, microstructural characteristics and stability of carbon supported platinum catalysts for low temperature fuel cells,” Journal of materials science, vol. 38, no. 14, 2003, pp. 2995-3005.