Abstract
To significantly reduce the cost of proton exchange membrane fuel cells, platinum-group metal (PGM)-free cathode catalysts are highly desirable. Current M-N-C (M: Fe, Co or Mn) catalysts are considered the most promising due to their encouraging performance. The challenge thus has been their stability under acidic conditions, which has hindered their use for any practical applications. In this review, based on the author’s research experience in the field for more than 10 years, current challenges and possible solutions to overcome these problems were discussed. The current Edisonian approach (i.e., trial and error) to developing PGM-free catalysts has been ineffective in achieving revolutionary breakthroughs. Novel synthesis techniques based on a more methodological approach will enable atomic control and allow us to achieve optimal electronic and geometric structures for active sites uniformly dispersed within the 3D architectures. Structural and chemical controlled precursors such as metal-organic frameworks are highly desirable for making catalysts with an increased density of active sites and strengthening local bonding structures among N, C and metals. Advanced electrochemical and physical characterization, such as electron microscopy and X-ray absorption spectroscopy should be combined with first principle density functional theory (DFT) calculations to fully elucidate the active site structures.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Che G, Lakshmi B B, Fisher E R, Martin C R. Carbon nanotubule membranes for electrochemical energy storage and production. Nature, 1998, 393(6683): 346–349
Yang Z, Zhang J, Kintner-Meyer M C, Lu X, Choi D, Lemmon J P, Liu J. Electrochemical energy storage for green grid. Chemical Reviews, 2011, 111(5): 3577–361
Rabis A, Rodriguez P, Schmidt T J. Electrocatalysis for polymer electrolyte fuel cells: recent achievements and future challenges. ACS Catalysis, 2012, 2(5): 864–890
Debe M K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature, 2012, 486(7401): 43–51
Shao M, Chang Q, Dodelet J P, Chenitz R. Recent advances in electrocatalysts for oxygen reduction reaction. Chemical Reviews, 2016, 116(6): 3594–3657
Jaouen F, Proietti E, Lefevre M, Chenitz R, Dodelet J P, Wu G, Chung H T, Johnston C M, Zelenay P. Recent advances in nonprecious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy & Environmental Science, 2011, 4(1): 114–130
Shao Y, Park S, Xiao J, Zhang J G, Wang Y, Liu J. Electrocatalysts for nonaqueous lithium-air batteries: status, challenges, and perspective. ACS Catalysis, 2012, 2(5): 844–857
Black R, Lee J H, Adams B, Mims C A, Nazar L F. The role of catalysts and peroxide oxidation in lithium-oxygen batteries. Angewandte Chemie International Edition, 2013, 52(1): 392–396
Wu G, More K L, Johnston C M, Zelenay P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332(6028): 443–447
Suntivich J, May K J, Gasteiger H A, Goodenough J B, Shao-Horn Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science, 2011, 334(6061): 1383–1385
Lefèvre M, Proietti E, Jaouen F, Dodelet J P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science, 2009, 324(5923): 71–74
Gong K, Du F, Xia Z, Durstock M, Dai L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009, 323(5915): 760–764
Bashyam R, Zelenay P. A class of non-precious metal composite catalysts for fuel cells. Nature, 2006, 443(7107): 63–66
Wu G, Santandreu A, Kellogg W, Gupta S, Ogoke O, Zhang H, Wang H L, Dai L. Carbon Nanocomposite catalysts for oxygen reduction and evolution reactions: from nitrogen doping to transition-metal addition. Nano Energy, 2016, 29: 83–110
Rabis A, Rodriguez P, Schmidt T J. Electrocatalysis for polymer electrolyte fuel cells: recent achievements and future challenges. ACS Catalysis, 2012, 2(5): 864–890
Osgood H, Devaguptapu S V, Xu H, Cho J P, Wu G. Transition metal (Fe, Co, Ni, and Mn) oxides for oxygen reduction and evolution bifunctional catalysts in alkaline media. Nano Today, 2016, 11(5): 601–625
Gupta S, Qiao L, Zhao S, Xu H, Lin Y, Devaguptapu S V, Wang X, Swihart M T, Wu G. Highly active and stable graphene tubes decorated with FeCoNi alloy nanoparticles via a template-free graphitization for bifunctional oxygen reduction and evolution. Advanced Energy Materials, 2016, 6(22): 1601198
Gupta S, Kellogg W, Xu H, Liu X, Cho J, Wu G. Bifunctional perovskite oxide catalysts for oxygen reduction and evolution in alkaline media. Chemistry, an Asian Journal, 2016, 11(1): 10–21
Chen C F, King G, Dickerson R M, Papin PA, Gupta S, Kellogg W R, Wu G. Oxygen-deficient BaTiO3-x perovskite as an efficient bifunctional oxygen electrocatalyst. Nano Energy, 2015, 13: 423–432
Wang X, Ke Y, Pan H, Ma K, Xiao Q, Yin D, Wu G, Swihart M T. Cu-deficient plasmonic Cu2-xS nanoplate electrocatalysts for oxygen reduction. ACS Catalysis, 2015, 5(4): 2534–2540
Jaouen F, Proietti E, Lefèvre M, Chenitz R, Dodelet J P, Wu G, Chung H T, Johnston C M, Zelenay P. Recent advances in nonprecious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy & Environmental Science, 2011, 4(1): 114–130
Wu G, Nelson M A, Mack N H, Ma S G, Sekhar P, Garzon F H, Zelenay P. Titanium dioxide-supported non-precious metal oxygen reduction electrocatalyst. Chemical Communications (Cambridge), 2010, 46(40): 7489–7491
Li Q, Xu P, Gao W, Ma S G, Zhang G Q, Cao R G, Cho J, Wang H L, Wu G. Graphene/graphene tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O2 batteries. Advanced Materials, 2014, 26(9): 1378–1386
Li Q, Cao R, Cho J, Wu G. Nanocarbon electrocatalysts for oxygen reduction in alkaline media for advanced energy conversion and storage. Advanced Energy Materials, 2014, 4(6): 1301415
Wu G, Chung H T, Nelson M, Artyushkova K, More K L, Johnston C M, Zelenay P. Graphene-enriched Co9S8-N-C non-precious metal catalyst for oxygen reduction in alkaline media. ECS Transactions, 2011, 4(1): 1709–1717
Wu G, More K L, Xu P, Wang H L, Ferrandon M, Kropf A J, Myers D J, Ma S, Johnston C M, Zelenay P. A carbon-nanotube-supported graphene-rich non-precious metal oxygen reduction catalyst with enhanced performance durability. Chemical Communications (Cambridge), 2013, 49(32): 3291–3293
Li Q, Wu G, Cullen D A, More K L, Mack N H, Chung H T, Zelenay P. Phosphate-tolerant oxygen reduction catalysts. ACS Catalysis, 2014, 4(9): 3193–3200
He Q G, Wu G, Liu K, Khene S, Li Q, Mugadza T, Deunf E, Nyokong T, Chen S W. Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media. ChemElectroChem, 2014, 1(9): 1508–1515
He Q, Li Q, Khene S, Ren X, López-Suárez F E, Lozano-Castelló D, Bueno-López A, Wu G. High-loading cobalt oxide coupled with nitrogen-doped graphene for oxygen reduction in anion-exchangemembrane alkaline fuel cells. Journal of Physical Chemistry, 2013, 117(17): 8697–8707
Wu G, Mack N H, Gao W, Ma S, Zhong R, Han J, Baldwin J K, Zelenay P. Nitrogen-doped graphene-rich catalysts derived from heteroatom polymers for oxygen reduction in nonaqueous lithium-O2 battery cathodes. ACS Nano, 2012, 6(11): 9764–9776
Li Q, Pan H, Higgins D, Cao R, Zhang G, Lv H, Wu K, Cho J, Wu G. Metal-organic framework derived bamboo-like nitrogen-doped graphene tubes as an active matrix for hybrid oxygen-reduction electrocatalysts. Small, 2015, 11(12): 1443–1452
Li Q, Wang T, Havas D, Zhang H, Xu P, Han J, Cho J, Wu G. Highperformance direct methanol fuel cells with precious-metal-free cathode. Advancement of Science, 2016, 3(11): 1600140
Wang X, Li Q, Pan H, Lin Y, Ke Y, Sheng H, Swihart M T, Wu G. Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction. Nanoscale, 2015, 7(47): 20290–20298
Parvez K, Yang S, Hernandez Y, Winter A, Turchanin A, Feng X, Müllen K. Nitrogen-doped graphene and its iron-based composite as efficient electrocatalysts for oxygen reduction reaction. ACS Nano, 2012, 6(11): 9541–9550
Qu L, Liu Y, Baek J B, Dai L. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano, 2010, 4(3): 1321–1326
Byon H R, Suntivich J, Shao-Horn Y. Graphene-based non-noblemetal catalysts for oxygen reduction reaction in acid. Chemistry of Materials, 2011, 23(15): 3421–3428
Lai L, Potts J R, Zhan D, Wang L, Poh C K, Tang C, Gong H, Shen Z, Lin J, Ruoff R S. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy & Environmental Science, 2012, 5(7): 7936–7942
Li Y, Wang J, Li X, Geng D, Banis M N, Li R, Sun X. Nitrogendoped graphene nanosheets as cathode materials with excellent electrocatalytic activity for high capacity lithium-oxygen batteries. Electrochemistry Communications, 2012, 18(0): 12–15
Li Y G, Zhou W, Wang H, Xie L, Liang Y, Wei F, Idrobo J C, Pennycook S J, Dai H. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nature Nanotechnology, 2012, 7(6): 394–400
Xiao J, Mei D, Li X, Xu W, Wang D, Graff G L, Bennett W D, Nie Z, Saraf L V, Aksay I A, Liu J, Zhang J G. Hierarchically porous graphene as a lithium–air battery electrode. Nano Letters, 2011, 11 (11): 5071–5078
Shui J L, Karan N K, Balasubramanian M, Li S Y, Liu D J. Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction. Journal of the American Chemical Society, 2012, 134(40): 16654–16661
Pylypenko S, Mukherjee S, Olson T S, Atanassov P. Non-platinum oxygen reduction electrocatalysts based on pyrolyzed transition metal macrocycles. Electrochimica Acta, 2008, 53(27): 7875–7883
Niwa H, Horiba K, Harada Y, Oshima M, Ikeda T, Terakura K, Ozaki J, Miyata S. X-ray absorption analysis of nitrogen contribution to oxygen reduction reaction in carbon alloy cathode catalysts for polymer electrolyte fuel cells. Journal of Power Sources, 2009, 187(1): 93–97
Mamtani K, Ozkan U S. Heteroatom-doped carbon nanostructures as oxygen reduction reaction catalysts in acidic media: an overview. Catalysis Letters, 2015, 145(1): 436–450
Wiggins-Camacho J D, Stevenson K J. Mechanistic discussion of the oxygen reduction reaction at nitrogen-doped carbon nanotubes. Journal of Physical Chemistry, 2011, 115(40): 20002–20010
Jaouen F, Goellner V, Lefèvre M, Herranz J, Proietti E, Dodelet J. Oxygen reduction activities compared in rotating-disk electrode and proton exchange membrane fuel cells for highly active Fe N C catalysts. Electrochimica Acta, 2013, 87: 619–628
Nallathambi V, Leonard N, Kothandaraman R, Barton S C. Nitrogen precursor effects in iron-nitrogen-carbon oxygen reduction catalysts. Electrochemical and Solid-State Letters, 2011, 14(6): B55–B58
Wu J, Yang Z, Li X, Sun Q, Jin C, Strasser P, Yang R. Phosphorusdoped porous carbons as efficient electrocatalysts for oxygen reduction. Journal of Materials Chemistry, 2013, 1(34): 9889–9896
Ramaswamy N, Tylus U, Jia Q, Mukerjee S. Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: linking surface science to coordination chemistry. Journal of the American Chemical Society, 2013, 135(41): 15443–15449
Jaouen F, Herranz J, Lefevre M, Dodelet J P, Kramm U I, Herrmann I, Bogdanoff P, Maruyama J, Nagaoka T, Garsuch A, Dahn J R, Olson T, Pylypenko S, Atanassov P, Ustinov E A. Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction. ACS Applied Materials & Interfaces, 2009, 1(8): 1623–1639
Liang J, Jiao Y, Jaroniec M, Qiao S Z. Sulfur and nitrogen dualdoped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angewandte Chemie International Edition, 2012, 51(46): 11496–11500
Jiao Y, Zheng Y, Jaroniec M, Qiao S Z. Origin of the electrocatalytic oxygen reduction activity of graphene-based catalysts: a roadmap to achieve the best performance. Journal of the American Chemical Society, 2014, 136(11): 4394–4403
Ganesan S, Leonard N, Barton S C. Impact of transition metal on nitrogen retention and activity of iron–nitrogen–carbon oxygen reduction catalysts. Physical Chemistry Chemical Physics, 2014, 16 (10): 4576–4585
Gong Y, Fei H, Zou X, Zhou W, Yang S, Ye G, Liu Z, Peng Z, Lou J, Vajtai R, Yakobson B I, Tour J M, Ajayan P M. Boron-and nitrogen-substituted graphene nanoribbons as efficient catalysts for oxygen reduction reaction. Chemistry of Materials, 2015, 27(4): 1181–1186
Strickland K, Miner E, Jia Q, Tylus U, Ramaswamy N, Liang W, Sougrati M T, Jaouen F, Mukerjee S. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination. Nature Communications, 2015, 6: 7343
Jia Q, Ramaswamy N, Hafiz H, Tylus U, Strickland K, Wu G, Barbiellini B, Bansil A, Holby E F, Zelenay P, Mukerjee S. Experimental observation of redox-induced Fe-N switching behavior as a determinant role for oxygen reduction activity. ACS Nano, 2015, 9(12): 12496–12505
Gao W, Havas D, Gupta S, Pan Q, He N, Zhang H, Wang H L, Wu G. Is reduced graphene oxide favorable for nonprecious metal oxygen-reduction catalysts? Carbon, 2016, 102: 346–356
Wu G, Johnston C M, Mack N H, Artyushkova K, Ferrandon M, Nelson M, Lezama-Pacheco J S, Conradson S D, More K L, Myers D J, Zelenay P. Synthesis-structure-performance correlation for polyaniline-Me-C non-precious metal cathode catalysts for oxygen reduction in fuel cells. Journal of Chemistry Materials, 2011, 21(30): 11392–11405
Sheng H, Wei M, D’Aloia A, Wu G. Heteroatom polymer-derived 3D high-surface-area and mesoporous graphene sheet-like carbon for supercapacitors. ACS Applied Materials & Interfaces, 2016, 8 (44): 30212–30224
Wu G, Artyushkova K, Ferrandon M, Kropf A J, Myers D, Zelenay P. Performance durability of polyaniline-derived non-precious cathode catalysts. ECS Transactions, 2009, 25(1): 1299–1311
Wu G, Zelenay P. Nanostructured non-precious metal catalysts for oxygen reduction reaction. Accounts of Chemical Research, 2013, 46(8): 1878–1889
Gupta S, Zhao S, Ogoke O, Lin Y, Xu H, Wu G. Engineering favorable morphology and structure of Fe-N-C oxygen-reduction catalysts via tuning nitrogen/carbon precursors. ChemSusChem, 2017, 10(4): 774–785
Wu G, Nelson M A, Mack N H, Ma S, Sekhar P, Garzon F H, Zelenay P. Titanium dioxide-supported non-precious metal oxygen reduction electrocatalyst. Chemical Communications, 2010, 46(40): 7489–7491
Li Q, Wu G, Cullen D A, More K L, Mack N H, Chung H, Zelenay P. Phosphate-tolerant oxygen reduction catalysts. ACS Catalysis, 2014, 4(9): 3193–3200
Wu G, More K L, Xu P, Wang H L, Ferrandon M, Kropf A J, Myers D J, Ma S, Johnston C M, Zelenay P. Carbon-nanotube-supported graphene-rich non-precious metal oxygen reduction catalyst with enhanced performance durability. Chemical Communications (Cambridge), 2013, 49(32): 3291–3293
Chung H T, Wu G, Li Q, Zelenay P. Role of two carbon phases in oxygen reduction reaction on the Co-PPy-C catalyst. International Journal of Hydrogen Energy, 2014, 39(28): 15887–15893
Ferrandon M, Kropf A J, Myers D J, Artyushkova K, Kramm U, Bogdanoff P, Wu G, Johnston C M, Zelenay P. Multitechnique characterization of a polyaniline-iron-carbon oxygen reduction catalyst. Journal of Physical Chemistry, 2012, 116(30): 16001–16013
Ferrandon M, Wang X, Kropf A J, Myers D J, Wu G, Johnston CM, Zelenay P. Stability of iron species in heat-treated polyaniline-ironcarbon polymer electrolyte fuel cell cathode catalysts. Electrochimica Acta, 2013, 110: 282–291
Weng L T, Bertrand P, Lalande G, Guay D, Dodelet J P. Surface characterization by time-of-flight SIMS of a catalyst for oxygen electroreduction: pyrolyzed cobalt phthalocyanine-on-carbon black. Applied Surface Science, 1995, 84(1): 9–21
Wu G, Nelson M, Ma S, Meng H, Cui G, Shen P K. Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction. Carbon, 2011, 49(12): 3972–3982
Lin Z, Chu H, Shen Y, Wei L, Liu H, Li Y. Rational preparation of faceted platinum nanocrystals supported on carbon nanotubes with remarkably enhanced catalytic performance. Chemical Communications, 2009, 46(46): 7167–7169
Lee S U, Belosludov R V, Mizuseki H, Kawazoe Y. Designing nanogadgetry for nanoelectronic devices with nitrogen-doped capped carbon nanotubes. Small, 2009, 5(15): 1769–1775
Matter P H, Zhang L, Ozkan U S. The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction. Journal of Catalysis, 2006, 239(1): 83–96
Zhang H, Osgood H, Xie X, Shao Y, Wu G. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks. Nano Energy, 2017, 31: 331–350
Barkholtz H M, Liu D J. Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks. Materials Horizons, 2017, 4(1): 20–37
Wang X J, Zhang H, Lin H, Gupta S, Wang C, Tao Z, Fu H, Wang T, Zheng J, Wu G, Li X. Directly converting Fe-doped metal-organic frameworks into highly active and stable Fe-N-C catalysts for oxygen reduction in acid. Nano Energy, 2016, 25: 110–119
Liu X, Park M, Kim M G, Gupta S, Wu G, Cho J. Integrating NiCo alloys with their oxides as efficient bifunctional cathode catalysts for rechargeable zinc-air batteries. Angewandte Chemie International Edition, 2015, 54(33): 9654–9658
Liu X, Liu W, Ko M, Park M, Kim M G, Oh P, Chae S, Park S, Casimir A, Wu G, Cho J. Metal (Ni, Co)-metal oxides/graphene nanocomposites as multifunctional electrocatalysts. Advanced Functional Materials, 2015, 25(36): 5799–5808
Tyminska N, Wu G, Dupuis M. Water oxidation on oxygen-deficient barium titanate: a first principles study. Journal of Physical Chemistry, 2017, 121(15): 8378–8389
Stamenkovic V, Mun B S, Mayrhofer K J, Ross P N, Markovic NM, Rossmeisl J, Greeley J, Nørskov J K. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angewandte Chemie, 2006, 118(18): 2963–2967
Stamenkovic V R, Fowler B, Mun B S, Wang G, Ross P N, Lucas C A, Markovic N M. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science, 2007, 315 (5811): 493–497
Zhang J, Sasaki K, Sutter E, Adzic R. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science, 2007, 315(5809): 220–222
Zhang L, Xia Z. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. Journal of Physical Chemistry, 2011, 115(22): 11170–11176
Yang L, Jiang S, Zhao Y, Zhu L, Chen S, Wang X, Wu Q, Ma J, Ma Y, Hu Z. Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angewandte Chemie, 2011, 123(31): 7270–7273
Holby E F, Wu G, Zelenay P, Taylor C D. Structure of Fe-Nx-C defects in oxygen reduction reaction catalysts from first principles modeling. Journal of Physical Chemistry, 2014, 118(26): 14388–14393
Hammer B, Norskov J. Why gold is the noblest of all the metals. Nature, 1995, 376(6537): 238–240
Nørskov J K, Bligaard T, Rossmeisl J, Christensen C H. Towards the computational design of solid catalysts. Nature Chemistry, 2009, 1(1): 37–46
Zhang L, Niu J, Dai L, Xia Z. Effect of microstructure of nitrogendoped graphene on oxygen reduction activity in fuel cells. Langmuir, 2012, 28(19): 7542–7550
Acknowledgements
The author acknowledges the Start-up funding from the University at Buffalo (SUNY) along with NSF (CBET-1604392) and US Department of Energy, Fuel Cell Technologies Office (FCTO) Incubator Program (DE-EE000696).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wu, G. Current challenge and perspective of PGM-free cathode catalysts for PEM fuel cells. Front. Energy 11, 286–298 (2017). https://doi.org/10.1007/s11708-017-0477-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11708-017-0477-3