Corresponding Author

Qing-gang HE(qghe@zju.edu.cn)


Fuel cells are highly recommended nowadays due to their intrinsic advantages such as high energy conversion efficiency, nearly no pollution, and convenient operation. With the development of anion exchange membrane, alkaline fuel cells have gone through a renaissance thanks to their superiorities such as faster reaction kinetics, wider choices for both fuels and electrocatalysts. It is essential to find an appropriate electrocatalyst for oxygen reduction reaction (ORR) to improve the performance of alkaline fuel cells. Further commercialization of the widely used Pt-based materials has suffered from disadvantages such as scarcity and high cost. As alternatives to largely investigated Pt-based materials, Fe-N-C electrocatalysts have gained increasing attention. However, Fe-N-C electrocatalysts still face problems including imperfect stability and durability, low metal loading, unclear catalytic mechanism and active sites, which has further hindered their design and synthesis. In this review, Fe-N-C electrocatalysts for alkaline fuel cells are discussed from the following three aspects, namely, the synthesis methods, the active sites and mechanisms, and their applications in recent five years. To optimize synthetic conditions, two kinds of typical synthetic methods are overviewed and some synthetic examples in the recent five years are summarized. Three active sites such as FeN4/C, Fe-N2+2/C, and Fe-N2/C, as well as those active sites concerned more widely in recent research for Fe-N-C electrocatalysts are also reviewed, which lays a good foundation for future design of Fe-N-C electrocatalysts. Furthermore, the single cell performance data are provided for the first time in order to enhance the application of the Fe-N-C electrocatalysts in alkaline fuel cells. As a whole, this review aims at providing theoretical support and guidance for future design and synthesis of commercial Fe-N-C electrocatalysts.

Graphical Abstract


fuel cells, oxygen reduction reaction, Fe-N-C, electrocatalysts

Publication Date


Online Available Date


Revised Date


Received Date



[1] Wei Z D(魏子栋). Special issue: Electrocatalyst and electrocatalysis in fuel cells preface[J]. Journal of Electrochemistry(电化学), 2016, 22(2): 99-100.
[2] He Q G, Cairns E J. Review€”Recent progress in electrocatalysts for oxygen reduction suitable for alkaline anion exchange membrane fuel cells[J]. Journal of The Electrochemical Society, 2015, 162(14): 1504-1539.
[3] Kreuer K D. Fuel cells: Selected entries from the encyclopedia of sustainability science and technology[M]. Springer Science & Business Media: 2012.
[4] Deavin O I, Murphy S, Ong A L, et al. Anion-exchange membranes for alkaline polymer electrolyte fuel cells: Comparison of pendent benzyltrimethylammonium-and benzylmethylimidazolium-head-groups[J]. Energy & Environmental Science 2012, 5(9): 8584-8597.
[5] Ramaswamy N, Mukerjee S. Influence of inner-and outer-sphere electron transfer mechanisms during electrocatalysis of oxygen reduction in alkaline media[J]. The Journal of Physical Chemistry C, 2011, 115(36): 18015-18026.
[6] Mo G, Liao S, Zhang Y, et al. Synthesis of active iron-based electrocatalyst for the oxygen reduction reaction and its unique electrochemical response in alkaline medium[J]. Electrochimica Acta 2012, (76): 430-439.
[7] Dong G, Huang M, Guan L. Iron phthalocyanine coated on single-walled carbon nanotubes composite for the oxygenreduction reaction in alkaline media[J]. Physical Chemistry Chemical Physics, 2012, 14(8): 2557-2559.
[8] Blaisdell J, Kunz A. Theoretical study of O chemisorption on NiO. Perfect surfaces and cation vacancies[J]. Physical Review B 1984, 29(2): 988-995.
[9] Vante N A, Jaegermann W, Tributsch H, et al. Electrocatalysis of oxygen reduction by chalcogenides containing mixed transition metal clusters[J]. Journal of the American Chemical Society 1987, 109(11): 3251-3257.
[10] Leslie-Pelecky D L, Zhang X, Kim S, et al. Structural properties of chemically synthesized nanostructured Ni and Ni∶Ni3C nanocomposites[J]. Chemistry of Materials, 1998, 10(1): 164-171.
[11] Ohnishi R, Katayama M, Cha D, et al. Titanium nitride nanoparticle electrocatalysts for oxygen reduction reaction in alkaline solution[J]. Journal of The Electrochemical Society 2013, 160(6): 501-506.
[12] Zeng L, Cui X, Chen L, et al. Non-noble bimetallic alloy encased in nitrogen-doped nanotubes as a highly active and durable electrocatalyst for oxygen reduction reaction[J]. Carbon, 2016, 114: 347-355.
[13] Jin X, Xie Y, Huang J. Highly effective dual transition metal macrocycle based electrocatalyst with macro-/mesoporous structures for oxygen reduction reaction[J]. Catalysts, 2017, 7(7): 201-213.
[14] Jaouen F, Proietti E, Lefèvre M, et al. Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells[J]. Energy & Environmental Science, 2010, 4(1): 114-130.
[15] Chen Z, Higgins D, Yu A, et al. A review on non-precious metal electrocatalysts for PEM fuel cells[J]. Energy & Environmental Science, 2011, 4(9): 3167-3192.
[16] Xiang Z H, Xue Y H, Cao D P, et al. Highly efficient electrocatalysts for oxygen reduction based on 2D covalent organic polymers complexed with non-precious metals[J]. Angewandte Chemie-International Edition, 2014, 53(9): 2433-2437.
[17] Jasinski R. A new fuel cell cathode catalyst[J]. Nature,1964, 201(4925): 1212-1213.
[18] Lin L, Zhu Q, Xu A W. Noble-metal-free Fe-N/C catalyst for highly efficient oxygen reduction reaction under both alkaline and acidic conditions[J]. Journal of the American Chemical Society, 2014, 136(31): 11027-11033.
[19] Li Z L, Li G L, Jiang L H, et al. Ionic liquids as precursors for efficient mesoporous iron-nitrogen-doped oxygen reduction electrocatalyst[J]. Angewandte Chemie-International Edition, 2015, 54(5): 1494-1498.
[20] Miller H A, Bellini M, Oberhauser W, et al. Heat treated carbon supported iron(ii) phthalocyanine oxygen reduction catalysts: Elucidation of the structure-activity relationship using X-ray absorption spectroscopy[J]. Physical Chemistry Chemical Physics, 2016, 18(48): 33142-33151.
[21] Chung H T, Won J H, Zelenay P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction[J]. Nature Communications, 2013, 4(5): 1922-1926.
[22] Chen C(陈驰), Zhou Z Y(周志有), Zhang X S(张新胜), et al. Synthesis of Fe,N-doped graphene/carbon black composite with high catalytic activity for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2016, 22(1): 25-31.
[23] Rauf M, Chen R, Wang Q, et al. Nitrogen-doped carbon nanotubes with encapsulated Fe nanoparticles as efficient oxygen reduction catalyst for alkaline membrane direct ethanol fuel cells[J]. Carbon, 2017, 125, 605-613.
[24] Niu W H, Li L G, Liu X J, et al. Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: An efficient electrocatalyst for oxygen reduction reaction[J]. Journal of the American Chemical Society, 2015, 137(16): 5555-5562.
[25] Meng F L, Wang Z L, Zhong H X, et al. Reactive multifunctional template-induced preparation of Fe-N-doped mesoporous carbon microspheres towards highly efficient electrocatalysts for oxygen reduction[J]. Advanced Materials, 2016, 28(36): 7948-7955.
[26] Mun Y, Min J K, Park S A, et al. Soft-template synthesis of mesoporous non-precious metal catalyst with Fe-Nx/C active sites for oxygen reduction reaction in fuel cells[J]. Applied Catalysis B-Environmental, 2017, 222: 191-199.
[27] Negro E, Videla A H A M, Baglio V, et al. Fe-N supported on graphitic carbon nano-networks grown from cobalt as oxygen reduction catalysts for low-temperature fuel cells[J]. Applied Catalysis B Environmental, 2015, 166: 75-83.
[28] Yasuda S, Furuya A, Uchibori Y, et al. Iron-nitrogen-doped vertically aligned carbon nanotube electrocatalyst for the oxygen reduction reaction[J]. Advanced Functional Materials, 2016, 26(5): 738-744.
[29] Wang Z L, Xu D, Zhong H X, et al. Gelatin-derived sustainable carbon-based functional materials for energy conversion and storage with controllability of structure and component[J]. Science Advances, 2015, 1(1): 1400035-1400035.
[30] Zhong W H, Chen J X, Zhang P X, et al. Air plasma etching towards rich active sites in Fe/N-porous carbon for oxygen reduction reaction with superior catalytic performance[J]. Journal of Materials Chemistry A, 2017, 5(32): 16605-16610.
[31] Wang X X, Wang B, Zhong J, et al. Iron polyphthalocyanine sheathed multiwalled carbon nanotubes: A high-performance electrocatalyst for oxygen reduction reaction[J]. Nano Research, 2016, 9(5): 1497-1506.
[32] Videla A H A M, Ban S, Specchia S, et al. Non-noble Fe-NX electrocatalysts supported on the reduced graphene oxide for oxygen reduction reaction[J]. Carbon, 2014, 76(18): 386-400.
[33] Sa Y J, Seo D J, Woo J, et al. A general approach to preferential formation of active Fe-N-x sites in Fe-N/C electrocatalysts for efficient oxygen reduction reaction[J]. Journal of the American Chemical Society, 2016, 138(45): 15046-15056.
[34] Cui X, Yang S, Yan X, et al. Pyridinic-nitrogen-dominated graphene aerogels with Fe-N-C coordination for highly efficient oxygen reduction reaction[J]. Advanced Functional Materials, 2016, 26(31): 5708-5717.
[35] Tang F, Lei H T, Wang S J, et al. A novel Fe-N-C catalyst for efficient oxygen reduction reaction based on polydopamine nanotubes[J]. Nanoscale, 2017, 9(44): 17364-17370.
[36] Liu J, Sun X J, Song P, et al. High-performance oxygen reduction electrocatalysts based on cheap carbon black, nitrogen, and trace iron[J]. Advanced Materials, 2013, 25(47): 6879-6883.
[37] Domínguez C, Pérez-Alonso F J, Salam M A, et al. Repercussion of the carbon matrix for the activity and stability of Fe/N/C electrocatalysts for the oxygen reduction reaction[J]. Applied Catalysis B-Environmental, 2016, 183: 185-196.
[38] Chen C, Yang X D, Zhou Z Y, et al. Aminothiazole-derived N,S,Fe-doped graphene nanosheets as high performance electrocatalysts for oxygen reduction[J]. Chemical Communications 2015, 51(96): 17092-17095.
[39] Wu G, Johnston C M, Mack N H, et al. Synthesis-structure-performance correlation for polyaniline-Me-C nonprecious metal cathode catalysts for oxygen reduction in fuel cells[J]. Journal of Materials Chemistry, 2011, 21(30): 11392-11405.
[40] Kramm U I, Wurmbach I A, Geppert I H, et al. Influence of the electron-density of FeN4-centers towards the catalytic activity of pyrolyzed FeTMPPCl-based ORR-
electrocatalysts[J]. Journal of the Electrochemical Society, 2011, 158(1): B69-B78.
[41] Kramm U I, Herranz J, Larouche N, et al. Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells[J]. Physical Chemistry Chemical Physics, 2012, 14(33): 11673-11688.
[42] Cheng N, Kemna C, Goubert-Renaudin S, et al. Reduction reaction by porphyrin-based catalysts for fuel cells[J]. Electrocatalysis 2012, 3(3/4): 238-251.
[43] Chen C(陈驰), Lai Y J(赖愉姣), Zhou Z Y(周志有), et al. Thermo-stability and active site structure of Fe/N/C electrocatalyst for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2017, 23(4): 400-408.
[44] Cai Z F(蔡镇锋), Sun B(孙兵), Jiang W J(江文杰), et al. STM investigation of oxygen reduction reactioin on solid interface in fuel cell[J]. Journal of Electrochemistry(电化学), 2016, 22(6): 561-569.
[45] Artyushkova K, Kiefer B, Halevi B, et al. Density functional theory calculations of XPS binding energy shift for nitrogen-containing graphene-like structures[J]. Chemical Communications, 2013, 49(25): 2539-2541.
[46] Serov A, Robson M H, Halevi B, et al. Highly active and durable templated non-PGM cathode catalysts derived from iron and aminoantipyrine[J]. Electrochemistry Communicationsm, 2012, 22(1): 53-56.
[47] Serov A, Artyushkova K, Atanassov P. Fe-N-C oxygen reduction fuel cell catalyst derived from carbendazim: Synthesis, structure, and reactivity[J]. Advanced Energy Materials, 2014, 4(10): 919-926.
[48] Unni S M, Devulapally S, Karjule N, et al. Graphene enriched with pyrrolic coordination of the doped nitrogen as an efficient metal-free electrocatalyst for oxygen reduction[J]. Journal of Materials Chemistry, 2012, 22(44): 23506-23513.
[49] Lai L, Potts J R, Zhan D, et al. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction[J]. Energy & Environmental Science, 2012, 5(7): 7936-7942.
[50] Herranz J, Jaouen F, Lefèvre M, et al. Unveiling N-protonation and anion-binding effects on Fe/N/C catalysts for O2 reduction in proton-exchange-membrane fuel cells[J]. Journal of Physical Chemistry C, 2011, 115(32): 16087-16097.
[51] Schulenburg H, Stankov S, Schünemann V, et al. Catalysts for the oxygen reduction from heat-treated iron(III) tetramethoxyphenylporphyrin chloride: Structure and stability of active sites[J]. The Journal of Physical Chemistry B, 2003, 107(34): 9034-9041.
[52] Bouwkamp-Wijnoltz A L, Visscher W, Veen J A R V, et al. On active-site heterogeneity in pyrolyzed carbon-supported iron porphyrin catalysts for the electrochemical reduction of oxygen: An in situ möissbauer study[J]. Journal of Physical Chemisty B, 2002, 106(50): 12993-13001.
[53] M L, Dodelet J P, Bertrand P. Molecular oxygen reduction in PEM fuel cells: Evidence for the simultaneous presence of two active sites in Fe-based catalysts[J]. Journal of Physical Chemisty B, 2002, 106(34): 8705-8713.
[54] Franke R, Ohms D, Wiesener K. Investigation of the influence of thermal treatment on the properties of carbon materials modified by N4-chelates for the reduction of oxygen in acidic media[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1989, 260(1): 63-73.
[55] Wiesener K. N4-chelates as electrocatalyst for cathodic oxygen reduction[J]. Electrochimica Acta, 1986, 31(8): 1073-1078.
[56] Wen Z H, Ci S Q, Zhang F, et al. Nitrogen-enriched core-shell structured Fe/Fe(3)C-C nanorods as advanced electrocatalysts for oxygen reduction reaction[J]. Advanced Materials, 2012, 24(11): 1399-1404.
[57] Van Veen J, Colijn H, Van Baar J. On the effect of a heat treatment on the structure of carbon-supported metalloporphyrins and phthalocyanines[J]. Electrochimica Acta, 1988, 33(6): 801-804.
[58] Van Veen J R, Van Baar J F, Kroese K J. Effect of heat treatment on the performance of carbon-supported transition-metal chelates in the electrochemical reduction of oxygen[J]. Journal of The Chemical Society-Faraday Transactions I, 1981, 77(11): 2827-2843.
[59] Scherson D, Gupta S, Fierro C, et al. Cobalt tetramethoxyphenyl porphyrin€”emission Mossbauer spectroscopy and O2 reduction electrochemical studies[J]. Electrochimica Acta, 1983, 28(9): 1205-1209.
[60] Yeager E. Electrocatalysts for O2 reduction [J]. Electrochimica Acta, 1984, 29(11): 1527-1537.
[61] Charreteur F, Jaouen F, Ruggeri S, et al. 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[J]. Electrochimica Acta, 2008, 53(6): 2925-2938.
[62] Strickland K, Miner E, Jia Q, et al. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination[J]. Nature Communications, 2015, 6: 7343-7350.
[63] Jiang W J, Gu L, Li L, et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx[J]. Journal of the American Chemical Society, 2016, 138(10): 3570-3578.
[64] Guo D, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts[J]. Science, 2016, 351(6271): 361-365.
[65] Qian W, Texter J, Yan F. Frontiers in poly(ionic liquid)s: Syntheses and applications[J]. Chemical Society Reviews, 2017, 46(4): 1124-1159.
[66] Kang H L, Cho D H, Kim Y M, et al. Highly conductive and durable poly(arylene ether sulfone) anion exchange membrane with end-group cross-linking[J]. Energy & Environmental Science, 2017, 10(1): 275-285.
[67] Pan J, Chen C, Li Y, et al. Constructing ionic highway in alkaline polymer electrolytes[J]. Energy & Environmental Science, 2013, 7(1): 354-360.
[68] Song P, Zhang Y W, Pan J, et al. Cheap carbon black-based high-performance electrocatalysts for oxygen reduction reaction[J]. Chemical Communications, 2015, 51(10): 1972-1975.
[69] Sa Y J, Park C, Jeong H Y, et al. Carbon nanotubes/heteroatom-doped carbon core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells[J]. Angewandte Chemie International Edition, 2014, 53(16): 4102-4106.
[70] Rao C V, Ishikawa Y. Activity, selectivity, and anion-exchange membrane fuel cell performance of virtually metal-free nitrogen-doped carbon nanotube electrodes for oxygen reduction reaction[J]. Journal of Physical Chemistry C, 2012, 116(6): 4340-4346.
[71] Lee S, Choun M, Ye Y, et al. Designing a highly active metal-free oxygen reduction catalyst in membrane electrode assemblies for alkaline fuel cells: Effects of pore size and doping-site position[J]. Angewandte Chemie-International Edition, 2015, 54(32): 9230-9234.
[72] Kim O H, Cho Y H, Chung D Y, et al. Facile and gramscale synthesis of metal-free catalysts: Toward realistic applications for fuel cells[J]. Scientific Reports, 2015, 5: 8376-8383.
[73] Ng J W D, Gorlin Y, Nordlund D, et al. Nanostructured manganese oxide supported onto particulate glassy carbon as an active and stable oxygen reduction catalyst in alkaline-based fuel cells[J]. Journal of The Electrochemical Society, 2014, 161(7): 3105-3112.
[74] He Q G, Li Q, Khene S, et al. High-loading cobalt oxide coupled with nitrogen-doped graphene for oxygen reduction in anion-exchange-membrane alkaline fuel cells[J]. Journal of Physical Chemistry C, 2013, 117(17): 8697-8707.
[75] Mamlouk M, Kumar S M S, Gouerec P, et al. Electrochemical and fuel cell evaluation of Co based catalyst for oxygen reduction in anion exchange polymer membrane fuel cells[J]. Journal of Power Sources, 2011, 196(18): 7594-7600



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.