Abstract
The development of high-performance non-precious metal catalysts (NPMC) for use at the cathode of polymer electrolyte membrane fuel cells will provide immense economic advantages over the current platinum-based catalyst technologies, perpetuating the sustainable widespread commercialization of these devices. It is imperative to develop NPMC that can effectively combine excellent oxygen reduction activities, high catalyst utilization, and long-term operational durability. This chapter focuses on recent advances made in the past 3–4 years and research trends in this field, with a particular focus on pyrolyzed carbon-supported nitrogen-coordinated transition metal (Fe and/or Co) complexes which have high potential of replacing conventional platinum-based catalysts.
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References
James D, Kalinoski J (2010) Mass production cost estimation for direct H2 PEM fuel cell systems for automotive applications: 2010 update. http://www1.eere.energy.gov/hydrogenand fuelcells/pdfs/dti_80kwW_fc_system_cost_analysis_report_2010.pdf
Qu L, Liu Y, Baek J-B, Dai L (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3):1321–1326
Higgins D, Chen Z, Chen Z (2011) Nitrogen doped carbon nanotubes synthesized from aliphatic diamines for oxygen reduction reaction. Electrochim Acta 56:1570–1575
Gong K, Du F, Xia Z, Durstock M, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323(5915):760–764
Chen Z, Higgins D, Tao H, Hsu R, Chen Z (2009) Highly active nitrogen-doped carbon nanotubes for oxygen reduction reaction in fuel cell applications. J Phys Chem C 113(49):21008–21013
Bashyam R, Zelenay P (2006) A class of non-precious metal composite catalysts for fuel cells. Nature 443(7107):63–66
Sulub R, Martinez-Millan W, Smit MA (2009) Study of the catalytic activity for oxygen reduction of polythiophene modified with cobalt or nickel. Int J Electrochem Sci 4(7):1015–1027
Feng YJ, He T, Alonso-Vante N (2009) Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium. Electrochim Acta 54(22):5252–5256
Feng YJ, He T, Alonso-Vante N (2010) Carbon-supported CoSe2 nanoparticles for oxygen reduction reaction in acid medium. Fuel Cells 10(1):77–83
Lee K, Zhang L, Zhang JJ (2007) Ternary non-noble metal chalcogenide (W-Co-Se) as electrocatalyst for oxygen reduction reaction. Electrochem Commun 9(7):1704–1708
Ishihara A, Ohgi Y, Matsuzawa K, Mitsushima S, Ota K (2010) Progress in non-precious metal oxide-based cathode for polymer electrolyte fuel cells. Electrochim Acta 55(27):8005–8012
DOE (2011) Technical plan – fuel cells. http://www1.eere.energy.gov/hydrogenandfuelcells/mypp/pdfs/fuel_cells.pdf
Othman R, Dicks AL, Zhu Z (2012) Non precious metal catalysts for the PEM fuel cell cathode. Int J Hydrogen Energy 37(1):357–372
Jaouen F, Proietti E, Lefèvre M, Chenitz R, Dodelet JP, Wu G, Chung HT, Johnston CM, Zelenay P (2010) Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy Environ Sci 4:114–130
Chen Z, Higgins D, Yu A, Zhang L, Zhang J (2011) A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ Sci 4(9):3167–3192
Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl Catal B Environ 56(1–2):9–35
Gasteiger HA, Markovic NM (2009) Just a dream – or future reality? Science 324(5923):48–49
Jasinski R (1964) New fuel cell cathode catalyst. Nature 201(492):1212–1213
Alt H, Binder H, Sandsted G (1973) Mechanism of electrocatalytic reduction of oxygen on metal-chelates. J Catal 28(1):8–19
Gruenig G, Wiesener K, Gamburzev S, Iliev I, Kaisheva A (1983) Investigations of catalysts from the pyrolyzates of cobalt-containing and metal-free dibenzotetraazaannulenes on active-carbon for oxygen electrodes in an acid-medium. J Electroanal Chem 159(1):155–162
Franke R, Ohms D, Wiesener K (1989) Investigation of the influence of thermal-treatment on the properties of carbon materials modified by N-4-chelates for the reduction of oxygen in acidic media. J Electroanal Chem 260(1):63–73
van der Putten A, Elzing A, Visscher W, Barendrecht E (1986) Oxygen reduction on pyrolyzed carbon-supported transition-metal chelates. J Electroanal Chem 205(1–2):233–244
Gupta S, Tryk D, Bae I, Aldred W, Yeager E (1989) Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction. J Appl Electrochem 19(1):19–27
Jaouen F, Dodelet JP (2007) Non-noble electrocatalysts for O2 reduction: how does heat treatment affect their activity and structure? Part I. Model for carbon black gasification by NH3: parametric calibration and electrochemical validation. J Phys Chem C 111(16):5963–5970
Jaouen F, Lefevre M, Dodelet JP, Cai M (2006) Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores? J Phys Chem B 110(11):5553–5558
Jaouen F, Serventi AM, Lefevre M, Dodelet JP, Bertrand P (2007) Non-noble electrocatalysts for O2 reduction: how does heat treatment affect their activity and structure? Part II. Structural changes observed by electron microscopy, Raman, and mass spectroscopy. J Phys Chem C 111(16):5971–5976
Charreteur F, Jaouen F, Ruggeri S, Dodelet JP (2008) Fe/N/C non-precious catalysts for PEM fuel cells: influence of the structural parameters of pristine commercial carbon blacks on their activity for oxygen reduction. Electrochim Acta 53(6):2925–2938
Lefevre M, Proietti E, Jaouen F, Dodelet JP (2009) Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324(5923):71–74
Wu G, More KL, Johnston CM, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332(6028):443
Wu L, Nabae Y, Moriya S, Matsubayashi K, Islam NM, Kuroki S, Kakimoto M, Ozaki J, Miyata S (2010) Pt-free cathode catalysts prepared via multi-step pyrolysis of Fe phthalocyanine and phenolic resin for fuel cells. Chem Commun (Camb) 46(34):6377–6379
Liu G, Li XG, Ganesan P, Popov BN (2009) Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon. Appl Catal B Environ 93(1–2):156–165
Li Y, Zhou W, Wang H, Xie L, Liang Y, Wei F, Idrobo J-C, Pennycook SJ, Dai H (2012) An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat Nanotechnol 7(6):394–400
Matter PH, Zhang L, Ozkan US (2006) The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction. J Catal 239(1):83–96
Ikeda T, Boero M, Huang S-F, Terakura K, Oshima M, Ozaki J-i (2008) Carbon alloy catalysts: active sites for oxygen reduction reaction. J Phys Chem C 112(38):14706–14709
Choi CH, Park SH, Woo SI (2012) Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. ACS Nano. doi:10.1021/nn3021234
Nabae Y, Moriya S, Matsubayashi K, Lyth SM, Malon M, Wu LB, Islam NM, Koshigoe Y, Kuroki S, Kakimoto MA, Miyata S, Ozaki J (2010) The role of Fe species in the pyrolysis of Fe phthalocyanine and phenolic resin for preparation of carbon-based cathode catalysts. Carbon 48(9):2613–2624
Ozaki J, Tanifuji S, Furuichi A, Yabutsuka K (2010) Enhancement of oxygen reduction activity of nanoshell carbons by introducing nitrogen atoms from metal phthalocyanines. Electrochim Acta 55(6):1864–1871
Matter PH, Wang E, Millet JMM, Ozkan US (2007) Characterization of the iron phase in CNx-based oxygen reduction reaction catalysts. J Phys Chem C 111(3):1444–1450
Li XG, Liu G, Popov BN (2010) Activity and stability of non-precious metal catalysts for oxygen reduction in acid and alkaline electrolytes. J Power Sources 195(19):6373–6378
Bouwkamp-Wijnoltz AL, Visscher W, van Veen JAR, Boellaard E, van der Kraan AM, Tang SC (2002) On active-site heterogeneity in pyrolyzed carbon-supported iron porphyrin catalysts for the electrochemical reduction of oxygen: an in situ Mossbauer study. J Phys Chem B 106(50):12993–13001
Tributsch H, Koslowski UI, Dorbandt I (2008) Experimental and theoretical modeling of Fe-, Co-, Cu-, Mn-based electrocatalysts for oxygen reduction. Electrochim Acta 53(5):2198–2209
Kramm U, Abs-Wurmbach I, Herrmann-Geppert I, Radnik J, Fiechter S, Bogdanoff P (2011) Influence of the electron-density of FeN-centers towards the catalytic activity of pyrolyzed FeTMPPCl-based ORR-electrocatalysts. J Electrochem Soc 158:B69–B78
Olson TS, Pylypenko S, Fulghum JE, Atanassov P (2010) Bifunctional oxygen reduction reaction mechanism on non-platinum catalysts derived from pyrolyzed porphyrins. J Electrochem Soc 157:B54–B63
Proietti E, Jaouen F, Lefèvre M, Larouche N, Tian J, Herranz J, Dodelet J-P (2011) Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. Nat Commun 2:416–425
Zagal JH (1992) Metallophthalocyanines as catalysts in electrochemical reactions. Coord Chem Rev 119:89–136
Baker R, Wilkinson DP, Zhang JJ (2008) Electrocatalytic activity and stability of substituted iron phthalocyanines towards oxygen reduction evaluated at different temperatures. Electrochim Acta 53(23):6906–6919
Zagal JH, Ponce I, Baez D, Venegas R, Pavez J, Paez M, Gulppi M (2012) A possible interpretation for the high catalytic activity of heat-treated non-precious metal Nx/C catalysts for O2 reduction in terms of their formal potentials. Electrochem Solid State Lett 15(6):B90–B92
Kramm U, Herranz J, Larouche N, Arruda T, Lefevre M, Jaouen F, Bogdanoff P, Fiechter S, Abs-Wurmbach I, Mukerjee S, Dodelet JP (2012) Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells. Phys Chem Chem Phys. doi:10.1039/c1030xx00000x
Soboleva T, Zhao X, Malek K, Xie Z, Navessin T, Holdcroft S (2010) On the micro-, meso-, and macroporous structures of polymer electrolyte membrane fuel cell catalyst layers. ACS Appl Mater Interfaces 2(2):375–384
Ignaszak A, Ye S, Gyenge E (2008) A study of the catalytic interface for O2 electroreduction on Pt: the interaction between carbon support meso/microstructure and ionomer (Nafion) distribution. J Phys Chem C 113(1):298–307
Choi J, Hsu R, Chen Z (2010) Highly active porous carbon-supported nonprecious metal-N electrocatalyst for oxygen reduction reaction in PEM fuel cells. J Phys Chem C 114(17):8048–8053
Huang H-C, Shown I, Chang S-T, Hsu H-C, Du H-Y, Kuo M-C, Wong K-T, Wang S-F, Wang C-H, Chen L-C, Chen K-H (2012) Pyrolyzed cobalt corrole as a potential non-precious catalyst for fuel cells. Adv Funct Mater. doi:10.1002/adfm.201200264
Liu G, Li XG, Ganesan P, Popov BN (2010) Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells. Electrochim Acta 55(8):2853–2858
Garsuch A, Dahn T, Klepel O, Garsuch RR, Dahn JR (2008) Oxygen reduction behavior of highly porous non-noble metal catalysts prepared by a template-assisted synthesis route. J Electrochem Soc 155:B236–B243
Garsuch A, MacIntyre K, Michaud X, Stevens DA, Dahn JR (2008) Fuel cell studies on a non-noble metal catalyst prepared by a template-assisted synthesis route. J Electrochem Soc 155(9):B953–B957
Liu HS, Shi Z, Zhang JL, Zhang L, Zhang JJ (2009) Ultrasonic spray pyrolyzed iron-polypyrrole mesoporous spheres for fuel cell oxygen reduction electrocatalysts. J Mater Chem 19(4):468–470
Serov A, Robson MH, Smolnik M, Atanassov P (2012) Templated bi-metallic non-PGM catalysts for oxygen reduction. Electrochim Acta. doi:10.1016/j.electacta.2012.1007.1008
Wang XQ, Lee JS, Zhu Q, Liu J, Wang Y, Dai S (2010) Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction. Chem Mater 22(7):2178–2180
Herrmann I, Kramm U, Fiechter S, Bogdanoff P (2009) Oxalate supported pyrolysis of CoTMPP as electrocatalysts for the oxygen reduction reaction. Electrochim Acta 54(18):4275–4287
Xie J, Xu F, Wood Iii DL, More KL, Zawodzinski TA, Smith WH (2010) Influence of ionomer content on the structure and performance of PEFC membrane electrode assemblies. Electrochim Acta 55(24):7404–7412
Liu Y, Ji C, Gu W, Baker DR, Jorne J, Gasteiger HA (2010) Proton conduction in PEM fuel cell cathodes: effects of electrode thickness and ionomer equivalent weight. J Electrochem Soc 157(8):B1154–B1162
Li W, Yu A, Higgins DC, Llanos BG, Chen Z (2010) Biologically inspired highly durable iron phthalocyanine catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells. J Am Chem Soc 132:17056–17058
Borup R, Meyers J, Pivovar B, Kim YS, Mukundan R, Garland N, Myers D, Wilson M, Garzon F, Wood D, Zelenay P, More K, Stroh K, Zawodzinski T, Boncella J, McGrath JE, Inaba M, Miyatake K, Hori M, Ota K, Ogumi Z, Miyata S, Nishikata A, Siroma Z, Uchimoto Y, Yasuda K, Kimijima KI, Iwashita N (2007) Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev 107(10):3904–3951
Li S, Zhang L, Kim J, Pan M, Shi Z, Zhang J (2010) Synthesis of carbon-supported binary FeCo-N non-noble metal electrocatalysts for the oxygen reduction reaction. Electrochim Acta 55(24):7346–7353
Wu G, Artyushkova K, Ferrandon M, Kropf AJ, Myers D, Zelenay P (2009) Performance durability of polyaniline-derived non-precious cathode catalysts. ECS Trans 25(1):1299–1311
Lefevre M, Dodelet JP (2003) Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts. Electrochim Acta 48(19):2749–2760
Koslowski UI, Abs-Wurmbach I, Fiechter S, Bogdanoff P (2008) Nature of the catalytic centers of porphyrin-based electrocatalysts for the ORR: a correlation of kinetic current density with the site density of Fe-N-4 Centers. J Phys Chem C 112(39):15356–15366
Charreteur F, Jaouen F, Dodelet JP (2009) Iron porphyrin-based cathode catalysts for PEM fuel cells: influence of pyrolysis gas on activity and stability. Electrochim Acta 54(26):6622–6630
Schilling T, Bron M (2008) Oxygen reduction at Fe–N-modified multi-walled carbon nanotubes in acidic electrolyte. Electrochim Acta 53(16):5379–5385
Byon HR, Suntivich J, Crumlin EJ, Shao-Horn Y (2011) Fe-N-modified multi-walled carbon nanotubes for oxygen reduction reaction in acid. Phys Chem Chem Phys 13(48):21437–21445
Choi JY, Higgins D, Chen Z (2012) Highly durable graphene nanosheet supported iron catalyst for oxygen reduction reaction in PEM fuel cells. J Electrochem Soc 159:B87–B90
Byon HR, Suntivich J, Shao-Horn Y (2011) Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid. Chem Mater 23(15):3421–3428
Meng H, Larouche N, Lefèvre M, Jaouen F, Stansfield B, Dodelet J (2010) Iron porphyrin-based cathode catalysts for polymer electrolyte membrane fuel cells: effect of NH3 and Ar mixtures as pyrolysis gases on catalytic activity and stability. Electrochim Acta 55(22):6450–6461
Herranz J, Jaouen F, Lefèvre M, Kramm UI, Proietti E, Dodelet J-P, Bogdanoff P, Fiechter S, Abs-Wurmbach I, Bertrand P, Arruda TM, Mukerjee S (2011) Unveiling N-protonation and anion-binding effects on Fe/N/C catalysts for O2 reduction in proton-exchange-membrane fuel cells. J Phys Chem C 115(32):16087–16097
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Higgins, D., Chen, Z. (2013). Recent Development of Non-precious Metal Catalysts. In: Shao, M. (eds) Electrocatalysis in Fuel Cells. Lecture Notes in Energy, vol 9. Springer, London. https://doi.org/10.1007/978-1-4471-4911-8_9
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