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Fe-N/C-TsOH-600 as non-noble metal cathode catalyst for alkaline membrane fuel cells
Last modified: 2014-10-07
Abstract
A non-noble metal electrocatalyst (Fe-N/C-TsOH), investigated as an alternate cathode catalyst for alkaline fuel cells (AFCs), is successfully synthesized using a simple thermal method. In order to improve activity and stability, the catalysts were heat-treated at 600oC and 700oC. Both unpyrolyzed and pyrolyzed catalysts were characterized by using electrochemical measurements such as cyclic voltammetry (CV), rotating disk electrode (RDE) with Tafel theory, as well as rotating ring disk electrode (RRDE) to quantitatively obtain the oxygen reduction reaction (ORR) kinetic constants and the reaction mechanisms. The pyrolyzed catalyst showed significantly improved ORR activity as well as different ORR mechanism, indicating that heat-treatment is a necessary step for improving catalyst activity. In addition, the optimal heat-treatment temperature was found to be 600oC, and the overall ORR electron transfer numbers were found to be about 3.899, suggesting that the ORR catalyzed by Fe-N/C-TsOH-600 is a 4-electron transfer process from O2 to H2O. Furthermore, TsOH plays key role in improving the ORR activity. In order to understand the heat-treatmen effect on catalyst, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to detect surface structure changes. The results indicate that the pyrrolic-N groups are the most active sites, a finding that is supported by the correspondence between changes in pyrrolic-N content and ORR activity that occur with changing temperature. And FeS is an additional beneficial factor for the ORR in a sense.
Keywords
Non-noble metalcatalyst; Dual-dopant; Heat-treatment; Oxygen reduction reaction;Tafel
References
[1] Bashyam R, Zelenay P. Nature, 2006, 443, 63[2] Dillon R, Srinivasan S, Arico A S, Antonucci V. J. Power Sources, 2004, 127(1-2), 112[3] Qiao J L, Xu L, Ding L, Shi P H, Zhang L, Baker R, Zhang J J. Int. J. Electrochem. Sci., 2013, 8(1), 1189[4] Steele B C H, Heinzel A, Nature, 2001, 414, 345[5] Lalande G, Faubert G, Cote R, Guay D, Dodelet J P, Weng L T. J. Power Sources, 1996, 61(1-2), 227[6] Zagal J H, Griveau S, Ozoemena K I, Nyokong T, Bedioui F. J. Nanosci Nanotechno., 2009, 9(4), 2201[7] Xu Z, Li H, Cao G, Zhang Q, Li K, Zhao X. J. Mol. Catal. A: Chem., 2011, 335(1-2), 89[8] Liu H, Song C, Tang Y, Zhang J. Electrochim. Acta, 2007, 52(13), 4532[9] Bonakdarpour A, Delacote C, Yang R, Wieckowski A, Dahn J R. Electrochem. Commun., 2008, 10(4), 611[10] Garsuch A, Michaud X, Wagner G, Klepel O, Dahn J R. Electrochim. Acta, 2009, 54(4), 1350[11] Alonso-Vante N, Malakhov I V, Nikitenko S G, Savinova E R, Kochubey D I. Electrochim. Acta, 2002, 47(22-23), 3807[12] Nallathambi V, Lee J W, Kumaraguru S P, Wu G, Popov B N. J. Power Sources, 2008, 183(1), 34[13] Lee k, Zhang L, Lui H, Hui R, Shi Z, Zhang J. Electrochim. Acta, 2009, 54(20), 4704[14] Lefevre M, Proietti E, Jaouen F, Dodelet J P. Science, 2009, 324, 71[15] Fournier J, Lalande G, Cote R, Guay D, Dodelet J P. J. Electrochem. Soc., 1997, 144(1), 218[16] Lalande G, Cote R, Guay D, Dodelet J P, Weng L T, Bertand P. Electrochim. Acta, 1997, 42(9), 1379[17] Bezerra C W B, Zhang L, Lee K, Liu H, Marques A L B, Marques E P, Wang H, Zhang J. Electrochim. Acta, 2008, 53(15), 4937[18] Qiao J, Xu L, Xu P, Shi J, Wang H. Electrochim. Acta, 2013, 96: 298[19] Qiao J, Xu L, Ding L, Zhang L, Baker R, Dai X, Zhang J. Appl. Catal., B: Environmental, 2012, 125: 197[20] Wang H, Maiyalagan T, Wang X. ACS Catal., 2012, 2(5), 781[21] Liu G, Li X, Ganesan P, Popov B N. Electrochim. Acta, 2010, 55(8), 2853[22] Liu G, Li X, Ganesan P, Popov B N. Appl. Catal. B: Environ., 2009, 93(1-2), 156[23] Wu G, Chen Z, Artyushkova K, Garzon F H, Zelenay P. ECS Transactions, 2008, 16(2): 159[24] Wu G, Artyushkova K, Ferrandon M, Kropf J, Myers D, Zelenay P. ECS Transactions, 2009, 25(1): 1299[25] Bard A J, Faulkner L R. Electrochemical Methods, Fundamentals and Applications, Wiley, New York, 2000, ISBN: 978-0-471-04372-0[26] Mamuru S A, Ozoemena K I, Fukuda T, Kobayashi N, Nyokong T. Electrochimi. Acta, 2010, 55(22), 6367[27] Harrison J A, Khan Z A. J. Electroanal. Chem., 1970, 28(1), 131[28] Ni J F, Zhou H H, Chen J T, Zhang X X. Mater. Lett., 2005, 59(18), 2361[29] Hinds G. In NPL Report DEPC-MPE 019; National Physical Laboratory: Teddington, 25 Middlesex, United Kingdom, 2005: 10[30] Bezerra C W B, Zhang L, Lee K, Liu H, Zhang J, Shi Z, Marques A L B, Marques E P, Wu S, Zhang J. Electrochim. Acta, 2008, 53(26), 7703[31] Charreteur F, Ruggeri S, Jaouen F, Dodelet J P. Electrochim. Acta, 2008, 53 (23): 6881[32] Velazquez-Palenzuela A, Zhang L, Wang L, Cabot P L, Brillas E, Tsay K, Zhang J. Electrochim. Acta, 2011, 56(13), 4744[33] Li W, Haldar P. Electrochem. Solid-State Lett., 2010, 13(5), 47[34] Gojkovic S L, Gupta S, Savinell R F. J. Electroanal. Chem., 1999, 462(1), 63[35] G. Lalande, R. Cote, G. Tamizhmani, D. Guay, J.-P. Dodelet, L. Dignard-Bailey, L.-T. Weng, P. Bertrand. Electrochim. Acta, 1995, 40(16), 2635
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