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Strategies for Enhancing the Electrocatalytic Activity of M–N/C Catalysts for the Oxygen Reduction Reaction

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The development of highly active and durable nonprecious metal catalysts that can replace expensive Pt-based catalysts for the oxygen reduction reaction (ORR) is of pivotal importance in polymer electrolyte membrane fuel cells. In this line of research, metal and nitrogen codoped carbon (M–N/C) catalysts have emerged as the most promising alternatives to Pt-based catalysts. This review provides an overview of recently developed synthetic strategies for the preparation of M–N/C catalysts to enhance the catalytic activity of the ORR. We present five major strategies, namely the use of metal–organic frameworks as hosts or precursors, the use of sacrificial templates, the addition of heteroelements, the preferential generation of active sites, and a biomimetic approach. For each strategy, the advantages capable of boosting catalytic activity in the ORR are summarized, and notable examples and their catalytic performances are presented. The ORR activities and measurement conditions of high-performing M–N/C catalysts are also tabulated. Finally, we summarize this review with some suggestions for future studies.

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Fig. 1

Reproduced with permission from [60]. Copyright (2011) Nature Publishing Group (a, b); Reproduced with permission from [64]. Copyright (2015) National Academy of Sciences (c, d)

Fig. 2

Reproduced with permission from [81]. Copyright (2011) Wiley-VCH Verlag GmbH & Co. KGaA (a, b); Reproduced with permission from [90]. Copyright (2016) Wiley-VCH Verlag GmbH & Co. KGaA (c, d)

Fig. 3

Reproduced with permission from [117]. Copyright (2013) Nature Publishing Group (a, b); Reproduced with permission from [118]. Copyright (2013) American Chemical Society (c–f)

Fig. 4

Reproduced with permission from [130]. Copyright (2017) American Chemical Society

Fig. 5

Reproduced with permission from [135]. Copyright (2017) Wiley-VCH Verlag GmbH & Co. KGaA (a, b); Reproduced with permission from [138]. Copyright (2016) The Royal Society of Chemistry (c); Reproduced with permission from [139]. Copyright (2011) American Chemical Society (d)

Fig. 6

Reproduced with permission from [111]. Copyright (2012) Elsevier (a); Reproduced with permission from [141]. Copyright (2015) The Royal Society of Chemistry (b)

Fig. 7

Reproduced with permission from [151]. Copyright (2014) American Chemical Society (a); Reproduced with permission from [152]. Copyright (2015) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (b)

Fig. 8

Reproduced with permission from [158]. Copyright (2016) American Chemical Society

Fig. 9

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Fig. 10

Reproduced with permission from [161]. Copyright (2007) American Association for the Advancement of Science

Fig. 11

Reproduced with permission from [169]. Copyright (2014) American Chemical Society (a, b); Reproduced with permission from [173]. Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA (c–e)

Fig. 12

Reproduced with permission from [176]. Copyright (2015) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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  1. 1.

    Bockris JOM (2002) The origin of ideas on a hydrogen economy and its solution to the decay of the environment. Int J Hydrog Energy 27:731–740

  2. 2.

    Chu S, Majumdar A (2012) Opportunities and challenges for a sustainable energy future. Nature 488:294–303

  3. 3.

    Turner JA (2004) Sustainable hydrogen production. Science 305:972–974

  4. 4.

    Park S, Shao Y, Liu J, Wang Y (2012) Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: status and perspective. Energy Environ Sci 5:9331–9344

  5. 5.

    Katsounaros I, Cherevko S, Zeradjanin AR, Mayrhofer KJJ (2014) Oxygen electrochemistry as a cornerstone for sustainable energy conversion. Angew Chem Int Ed 53:102–121

  6. 6.

    Chu S, Cui Y, Liu N (2017) The path towards sustainable energy. Nat Mater 16:16–22

  7. 7.

    Seh ZW, Kibsgaard J, Dickens CF, Chorkendorff I, Nørskov JK, Jaramillo TF (2017) Combining theory and experiment in electrocatalysis: insights into materials design. Science 355:eaad4998

  8. 8.

    Wang Y, Chen KS, Mishler J, Cho SC, Adroher XC (2011) A review of polymer electrolyte membrane fuel cells: technology, applications, and needs on fundamental research. Appl Energy 88:981–1007

  9. 9.

    Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486:43–51

  10. 10.

    Vielstich W, Lamm A, Gasteiger HA (2003) Handbook of fuel cells: vol 2: fundamentals, technology, applications. Wiley, New York

  11. 11.

    Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Activity benchmark and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl Catal B 56:9–35

  12. 12.

    Papageorgopoulos D (2016) U.S. DOE Hydrogen and Fuel Cells Program 2016 Annual Review Meeting. https://www.hydrogen.energy.gov/pdfs/review16/fc000_papageorgopoulos_2016_o.pdf. Accessed 11 Aug 2017

  13. 13.

    Liang Y, Li Y, Wang H, Dai H (2013) Strongly coupled inorganic/nanocarbon hybrid materials for advanced electrocatalysis. J Am Chem Soc 135:2013–2036

  14. 14.

    Wu ZS, Yang S, Sun Y, Parvez K, Feng X, Müllen K (2012) 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. J Am Chem Soc 134:9082–9085

  15. 15.

    Ling T, Yan DY, Jiao Y, Wang H, Zheng Y, Zheng X, Mao J, Du XW, Hu Z, Jaroniec M, Qiao SZ (2016) Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis. Nat Commun 7:12876

  16. 16.

    Gao MR, Jiang J, Yu SH (2012) Solution-based synthesis and design of late transition metal chalcogenide materials for oxygen reduction reaction (ORR). Small 8:13–27

  17. 17.

    Deng D, Yu L, Chen X, Wang G, Jin L, Pan X, Deng J, Sun G, Bao X (2013) Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. Angew Chem Int Ed 52:371–375

  18. 18.

    Hu Y, Jensen JO, Zhang W, Cleemann LN, Xing W, Bjerrum NJ, Li Q (2014) Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. Angew Chem Int Ed 53:3675–3679

  19. 19.

    Jaouen F, Herranz J, Lefèvre M, Dodelet JP, Kramm UI, Herrmann I, Bogdanoff P, Maruyama J, Nagaoka T, Garsuch A, Dahn JR, Olson T, Pylypenko S, Atanassov P, Ustinov EA (2009) Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction. ACS Appl Mater Interfaces 1:1623–1639

  20. 20.

    Lefèvre M, Proietti E, Jaouen F, Dodelet JP (2009) Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324:71–74

  21. 21.

    Wu G, More KL, Johnston CM, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332:443–447

  22. 22.

    Bayatsarmadi B, Zheng Y, Vasileff A, Qiao SZ (2017) Recent advances in atomic metal doping of carbon-based nanomaterials for energy conversion. Small 13:1700191

  23. 23.

    Zhu YP, Guo C, Zheng Y, Qiao SZ (2017) Surface and interface engineering of noble-metal-free electrocatalysts for efficient energy conversion processes. Acc Chem Res 50:915–923

  24. 24.

    Gong K, Du F, Xia Z, Durstock M, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764

  25. 25.

    Zheng Y, Jiao Y, Jaroniec M, Jin Y, Qiao SZ (2012) Nanostructured metal-free electrochemical catalysts for highly efficient oxygen reduction. Small 8:3550–3566

  26. 26.

    Jasinski R (1964) A new fuel cell cathode catalyst. Nature 201:1212–1213

  27. 27.

    Alt H, Binder H, Sandstede G (1973) Mechanism of the electrocatalytic reduction of oxygen on metal chelates. J Catal 28:8–19

  28. 28.

    Randin JP (1974) Interpretation of the relative electrochemical activity of various metal phthalocyanines for the oxygen reduction reaction. Electrochim Acta 19:83–85

  29. 29.

    Jahnke H, Schönborn M, Zimmermann G (1976) Organic dyestuffs as catalysts for fuel cells. Top Curr Chem 61:133–181

  30. 30.

    Gupta S, Tryk D, Bae I, Aldred W, Yeager E (1989) Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction. J Appl Electrochem 19:19–27

  31. 31.

    Schulenburg H, Stankov S, Schünemann V, Radnik J, Dorbandt I, Fiechter S, Bogdanoff P, Tributsch H (2003) Catalysts for the oxygen reduction from heat-treated iron(III) tetramethoxyphenylporphyrin chloride: structure and stability of active sites. J Phys Chem B 107:9034–9041

  32. 32.

    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–N4 centers. J Phys Chem C 112:15356–15366

  33. 33.

    Kramm UI, Herranz J, Larouche N, Arruda TM, Lefèvre 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 14:11673–11688

  34. 34.

    Li Y, Zhou W, Wang H, Xie L, Liang Y, Wei F, Idrobo JC, Pennycook SJ, Dai H (2012) An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes. Nat Nanotechnol 7:394–400

  35. 35.

    Oberst JL, Thorum MS, Gewirth AA (2012) Effect of pH and azide on the oxygen reduction reaction with a pyrolyzed Fe phthalocyanine catalyst. J Phys Chem C 116:25257–25261

  36. 36.

    Tylus U, Jia Q, Strickland K, Ramaswamy N, Serov A, Atanassov P, Mukerjee S (2014) Elucidating oxygen reduction active sites in pyrolyzed metal–nitrogen coordinated non-precious-metal electrocatalyst systems. J Phys Chem C 118:8999–9008

  37. 37.

    Kramm UI, Lefèvre M, Larouche N, Schmeisser D, Dodelet JP (2014) Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques. J Am Chem Soc 136:978–985

  38. 38.

    Zitolo A, Goellner V, Armel V, Sougrati MT, Mineva T, Stievano L, Fonda E, Jaouen F (2015) Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat Mater 14:937–942

  39. 39.

    Strickland K, Miner E, Jia Q, Tylus U, Ramaswamy N, Liang W, Sougrati MT, Jaouen F, Mukerjee S (2015) Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination. Nat Commun 6:7343

  40. 40.

    Malko D, Kucernak A, Lopes T (2016) In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts. Nat Commun 7:13285

  41. 41.

    Kim JH, Sa YJ, Jeong HY, Joo SH (2017) Roles of Fe–N x and Fe–Fe3C@C species in Fe–N/C electrocatalysts for oxygen reduction reaction. ACS Appl Mater Interfaces 9:9567–9575

  42. 42.

    Zheng Y, Jiao Y, Zhu Y, Cai Q, Vasileff A, Li LH, Han Y, Chen Y, Qiao SZ (2017) Molecular-level g-C3N4 coordinated transition metals as a new class of electrocatalysts for oxygen electrode reactions. J Am Chem Soc 139:3336–3339

  43. 43.

    Yang XD, Zheng Y, Yang J, Shi W, Zhong JH, Zhang C, Zhang X, Hong YH, Peng XX, Zhou ZY, Sun SG (2017) Modeling Fe/N/C catalysts in monolayer graphene. ACS Catal 7:139–145

  44. 44.

    Wu KH, Shi W, Wang D, Xu J, Ding Y, Lin Y, Qi W, Zhang B, Su D (2017) In situ electrostatic modulation of path selectivity for the oxygen reduction reaction on Fe–N doped carbon catalyst. Chem Mater 29:4649–4653

  45. 45.

    Chung HT, Cullen DA, Higgins D, Sneed BT, Holby EF, More KL, Zelenay P (2017) Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357:479–484

  46. 46.

    Bezerra CWB, Zhang L, Lee K, Liu H, Marques ALB, Marques EP, Wang H, Zhang J (2008) A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction. Electrochim Acta 53:4937–4951

  47. 47.

    Jaouen F, Proietti E, Lefèvre M, Chenitz R, Dodelet JP, Wu G, Chung HT, Johnston CM, Zelenay P (2011) Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy Enrivon Sci 4:114–130

  48. 48.

    Morozan A, Jousselme B, Palacin S (2011) Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes. Energy Enrivon Sci 4:1238–1254

  49. 49.

    Chen Z, Higgins D, Yu A, Zhang L, Zhang J (2011) A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Enrivon Sci 4:3167–3192

  50. 50.

    Zagal JH, Koper MTM (2016) Reactivity descriptors for the activity of molecular MN4 catalysts for the oxygen reduction reaction. Angew Chem Int Ed 55:14510–14521

  51. 51.

    Jia Q, Ramaswamy N, Tylus U, Strickland K, Li J, Serov A, Artyushkova K, Atanassov P, Anibal J, Gumeci C, Barton SC, Sougrati MT, Jaouen F, Halevi B, Mukerjee S (2016) Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid. Nano Energy 29:65–82

  52. 52.

    Sa YJ, Kim JH, Joo SH (2017) Recent progress in the identification of active sites in pyrolyzed Fe–N/C catalysts and insights into their role in oxygen reduction reaction. J Electrochem Sci Technol 8(3):169–182

  53. 53.

    Masa J, Xia W, Muhler M, Schuhmann W (2015) On the role of metals in nitrogen-doped carbon electrocatalysts for oxygen reduction. Angew Chem Int Ed 54:10102–10120

  54. 54.

    Shen M, Wei C, Ai K, Lu L (2017) Transition metal–nitrogen–carbon nanostructured catalysts for the oxygen reduction reaction: from mechanistic insights to structural optimization. Nano Res 10:1449–1470

  55. 55.

    Dombrovskis JK, Palmqvist AEC (2016) Recent progress in synthesis, characterization and evaluation of non-precious metal catalysts for the oxygen reduction reaction. Fuel Cells 16:4–22

  56. 56.

    Shao M, Chang Q, Dodelet JP, Chenitz R (2016) Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev 116:3594–3657

  57. 57.

    Yaghi OM, O’Keeffe M, Ockwig NW, Chae HK, Eddaoudi M, Kim J (2003) Reticular synthesis and the design of new materials. Nature 423:705–714

  58. 58.

    Cordova KE, O’Keeffe M, Yaghi OM (2013) The chemistry and applications of metal-organic frameworks. Science 341:1230444

  59. 59.

    Liu J, Zhu D, Guo C, Vasileff A, Qiao SZ (2017) Design strategies toward advanced MOF-derived electrocatalysts for energy-conversion reactions. Adv Energy Mater 7:1700518

  60. 60.

    Proietti E, Jaouen F, Lefèvre M, Larouche N, Tian J, Herranz J, Dodelet JP (2011) Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. Nat Commun 2:416

  61. 61.

    Palaniselvam T, Biswal BP, Banerjee R, Kurungot S (2013) Zeolitic imidazolate framework (ZIF)-derived, hollow-core, nitrogen-doped carbon nanostructures for oxygen-reduction reactions in PEFCs. Chem Eur J 19:9335–9342

  62. 62.

    Zhao D, Shui JL, Grabstanowicz LR, Chen C, Commet SM, Xu T, Lu J, Liu DJ (2014) Highly efficient non-precious metal electrocatalysts prepared from one-pot synthesized zeolitic imidazolate frameworks. Adv Mater 26:1093–1097

  63. 63.

    Armel V, Hindocha S, Salles F, Bennett S, Jones D, Jaouen F (2017) Structural descriptors of zeolitic–imidazolate frameworks are keys to the activity of Fe–N–C catalysts. J Am Chem Soc 139:453–464

  64. 64.

    Shui J, Chen C, Grabstanowicz L, Zhao D, Liu DJ (2015) Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network. Proc Natl Acad Sci 112:10629–10634

  65. 65.

    Sun H, Su H, Ma X, Zhang P, Zhang X, Dai X, Gao J, Chen C, Sun SG (2016) Fe/IRMOF-3 derived porous carbons as non-precious metal electrocatalysts with high activity and stability towards oxygen reduction reaction. Electrochim Acta 205:53–61

  66. 66.

    Bhattacharyya S, Konkena B, Jayaramulu K, Schuhmann W, Maji TK (2017) Synthesis of nano-porous carbon and nitrogen doped carbon dots from an anionic MOF: a trace cobalt metal residue in carbon dots promotes electrocatalytic ORR activity. J Mater Chem A 5:13573–13580

  67. 67.

    Huang X, Yang Z, Dong B, Wang Y, Tang T, Hou Y (2017) In situ Fe2N@N-doped porous carbon hybrids as superior catalysts for oxygen reduction reaction. Nanoscale 9:8102–8106

  68. 68.

    Zhao S, Yin H, Du L, He L, Zhao K, Chang L, Yin G, Zhao H, Liu S, Tang Z (2014) Carbonized nanoscale metal–organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano 8:12660–12668

  69. 69.

    Li JS, Li SL, Tang YJ, Han M, Dai ZH, Bao JC, Lan YQ (2015) Nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrids derived from MOFs: efficient bifunctional electrocatalysts for ORR and OER. Chem Commun 51:2710–2713

  70. 70.

    Zhu QL, Xia W, Akita T, Zou R, Xu Q (2016) Metal-organic framework-derived honeycomb-like open porous nanostructures as precious-metal-free catalysts for highly efficient oxygen electroreduction. Adv Mater 28:6391–6398

  71. 71.

    Zhao D, Shui JL, Chen C, Chen X, Reprogle BM, Wang D, Liu DJ (2012) Iron imidazolate framework as precursor for electrocatalysts in polymer electrolyte membrane fuel cells. Chem Sci 3:3200–3205

  72. 72.

    Su P, Xiao H, Zhao J, Yao Y, Shao Z, Li C, Yang Q (2013) Nitrogen-doped carbon nanotubes derived from Zn–Fe-ZIF nanospheres and their application as efficient oxygen reduction electrocatalysts with in situ generated iron species. Chem Sci 4:2941–2946

  73. 73.

    Liu T, Zhao P, Hua X, Luo W, Chen S, Cheng G (2016) An Fe–N–C hybrid electrocatalyst derived from a bimetal–organic framework for efficient oxygen reduction. J Mater Chem A 4:11357–11364

  74. 74.

    Li Z, Sun H, Wei L, Jiang WJ, Wu M, Hu JS (2017) Lamellar metal organic framework-derived Fe–N–C non-noble electrocatalysts with bimodal porosity for efficient oxygen reduction. ACS Appl Mater Interfaces 9:5272–5278

  75. 75.

    Deng Y, Dong Y, Wang G, Sun K, Shi X, Zheng L, Li X, Liao S (2017) Well-defined ZIF-derived Fe–N codoped nanoframes as efficient oxygen reduction catalysts. ACS Appl Mater Interfaces 9:9699–9709

  76. 76.

    Zhang C, Wang YC, An B, Huang R, Wang C, Zhou Z, Lin W (2017) Networking pyrolyzed zeolitic imidazolate frameworks by carbon nanotubes improves conductivity and enhances oxygen-reduction performance in polymer-electrolyte-membrane fuel cells. Adv Mater 29:1604556

  77. 77.

    Pei Y, Qi Z, Li X, Maligal-Ganesh RV, Goh TW, Xiao C, Wang T, Huang W (2017) Morphology inherence from hollow MOFs to hollow carbon polyhedrons in preparing carbon-based electrocatalysts. J Mater Chem A 5:6186–6192

  78. 78.

    Lai Q, Zheng L, Liang Y, He J, Zhao J, Chen J (2017) Metal–organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal 7:1655–1663

  79. 79.

    Chen Y, Ji S, Wang Y, Dong J, Chen W, Li Z, Shen R, Zheng L, Zhuang Z, Wang D, Li Y (2017) Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew Chem Int Ed 56:6937–6941

  80. 80.

    Goenaga G, Ma S, Yuan S, Liu DJ (2010) New approaches to non-PGM electrocatalysts using porous framework materials. ECS Trans 33:579–586

  81. 81.

    Ma S, Goenaga GA, Call AV, Liu DJ (2011) Cobalt imidazolate framework as precursor for oxygen reduction reaction electrocatalysts. Chem Eur J 17:2063–2067

  82. 82.

    You B, Jiang N, Sheng M, Drisdell WS, Yano J, Sun Y (2015) Bimetal–organic framework self-adjusted synthesis of support-free nonprecious electrocatalysts for efficient oxygen reduction. ACS Catal 5:7068–7076

  83. 83.

    Hou Y, Wen Z, Cui S, Ci S, Mao S, Chen J (2015) An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv Funct Mater 25:872–882

  84. 84.

    Chen YZ, Wang C, Wu ZY, Xiong Y, Wu Q, Yu SH, Jiang HL (2015) From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater 27:5010–5016

  85. 85.

    Zhang C, An B, Yang L, Wu B, Shi W, Wang YC, Long LS, Wang C, Lin W (2016) Sulfur-doping achieves efficient oxygen reduction in pyrolyzed zeolitic imidazolate frameworks. J Mater Chem A 4:4457–4463

  86. 86.

    Li X, Jiang Q, Dou S, Deng L, Huo J, Wang S (2016) ZIF-67-derived Co-NC@CoP-NC nanopolyhedra as an efficient bifunctional oxygen electrocatalyst. J Mater Chem A 4:15836–15840

  87. 87.

    You S, Gong X, Wang W, Qi D, Wang X, Chen X, Ren N (2016) Enhanced cathodic oxygen reduction and power production of microbial fuel cell based on noble-metal-free electrocatalyst derived from metal-organic frameworks. Adv Energy Mater 6:1501497

  88. 88.

    Li Z, Shao M, Zhou L, Zhang R, Zhang C, Wei M, Evans DG, Duan X (2016) Directed growth of metal-organic frameworks and their derived carbon-based network for efficient electrocatalytic oxygen reduction. Adv Mater 28:2337–2344

  89. 89.

    Meng F, Zhong H, Bao D, Yan J, Zhang X (2016) In situ coupling of strung Co4N and intertwined N–C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn–air batteries. J Am Chem Soc 138:10226–10231

  90. 90.

    Yin P, Yao T, Wu Y, Zheng L, Lin Y, Liu W, Ju H, Zhu J, Hong X, Deng Z, Zhou G, Wei S, Li Y (2016) Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew Chem Int Ed 55:10800–10805

  91. 91.

    Aijaz A, Masa J, Rösler C, Xia W, Weide P, Botz AJR, Fischer RA, Schuhmann W, Muhler M (2016) Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angew Chem Int Ed 55:4087–4091

  92. 92.

    Ni B, Ouyang C, Xu X, Zhuang J, Wang X (2017) Modifying commercial carbon with trace amounts of ZIF to prepare derivatives with superior ORR activities. Adv Mater 29:1701354

  93. 93.

    Hou YN, Zhao Z, Yu Z, Tang Y, Wang X, Qiu J (2017) Two-dimensional graphene-like N, Co-codoped carbon nanosheets derived from ZIF-67 polyhedrons for efficient oxygen reduction reactions. Chem Commun 53:7840–7843

  94. 94.

    Wei J, Hu Y, Liang Y, Kong B, Zheng Z, Zhang J, Jiang SP, Zhao Y, Wang H (2017) Graphene oxide/core–shell structured metal–organic framework nano-sandwiches and their derived cobalt/N-doped carbon nanosheets for oxygen reduction reactions. J Mater Chem A 5:10182–10189

  95. 95.

    Yang W, Liu X, Chen L, Liang L, Jia J (2017) A metal–organic framework devised Co–N doped carbon microsphere/nanofiber hybrid as a free-standing 3D oxygen catalyst. Chem Commun 53:4034–4037

  96. 96.

    Meng J, Niu C, Xu L, Li J, Liu X, Wang X, Wu Y, Xu X, Chen W, Li Q, Zhu Z, Zhao D, Mai L (2017) General oriented formation of carbon nanotubes from metal–organic frameworks. J Am Chem Soc 139:8212–8221

  97. 97.

    Hou Y, Huang T, Wen Z, Mao S, Cui S, Chen J (2014) Metal–organic framework-derived nitrogen-doped core-shell-structured porous Fe/Fe3C@C nanoboxes supported on graphene sheets for efficient oxygen reduction reactions. Adv Energy Mater 4:1400337

  98. 98.

    Sanetuntikul J, Shanmugam S (2014) Prussian blue-carbon hybrid as a non-precious electrocatalyst for the oxygen reduction reaction in alkaline medium. Electrochim Acta 119:92–98

  99. 99.

    Zhou R, Qiao SZ (2015) An Fe/N co-doped graphitic carbon bulb for high-performance oxygen reduction reaction. Chem Commun 51:7516–7519

  100. 100.

    Wang X, Zou L, Fu H, Xiong Y, Tao Z, Zheng J, Li X (2016) Noble metal-free oxygen reduction reaction catalysts derived from Prussian blue nanocrystals dispersed in polyaniline. ACS Appl Mater Interfaces 8:8436–8444

  101. 101.

    Yang J, Hu J, Weng M, Tan R, Tian L, Yang J, Amine J, Zheng J, Chen H, Pan F (2017) Fe-cluster pushing electrons to N-doped graphitic layers with Fe3C(Fe) hybrid nanostructure to enhance O2 reduction catalysis Zn-air batteries. ACS Appl Mater Interfaces 9:4587–4596

  102. 102.

    Kong A, Lin Q, Mao C, Bu X, Feng P (2014) Efficient oxygen reduction by nanocomposites of heterometallic carbide and nitrogen-enriched carbon derived from the cobalt-encapsulated indium–MOF. Chem Commun 50:15619–15622

  103. 103.

    Lin Q, Bu X, Kong A, Mao C, Zhao X, Bu F, Feng P (2015) New heterometallic zirconium metalloporphyrin frameworks and their heteroatom-activated high-surface-area carbon derivatives. J Am Chem Soc 137:2235–2238

  104. 104.

    Afsahi F, Kaliaguine S (2014) Non-precious electrocatalysts synthesized from metal–organic frameworks. J Mater Chem A 2:12270–12279

  105. 105.

    Volosskiy B, Fei H, Zhao Z, Lee S, Li M, Lin Z, Papandrea B, Wang C, Huang Y, Duan X (2016) Tuning the catalytic activity of a metal–organic framework derived copper and nitrogen co-doped carbon composite for oxygen reduction reaction. ACS Appl Mater Interfaces 8:26769–26774

  106. 106.

    Yuan S, Shui JL, Grabstanowicz L, Chen C, Commet S, Reprogle B, Xu T, Yu L, Liu DJ (2013) A highly active and support-free oxygen reduction catalyst prepared from ultrahigh-surface-area porous polyporphyrin. Angew Chem Int Ed 52:8349–8353

  107. 107.

    Xiang Z, Xue Y, Cao D, Huang L, Chen JF, Dai L (2014) Highly efficient electrocatalysts for oxygen reduction based on 2D covalent organic polymers complexed with non-precious metals. Angew Chem Int Ed 53:2433–2437

  108. 108.

    Wu ZS, Chen L, Liu J, Parvez K, Liang H, Shu J, Sachdev H, Graf R, Feng X, Müllen K (2014) High-performance electrocatalysts for oxygen reduction derived from cobalt porphyrin-based conjugated mesoporous polymers. Adv Mater 26:1450–1455

  109. 109.

    Lin Q, Bu X, Kong A, Mao C, Bu F, Feng P (2015) Heterometal-embedded organic conjugate frameworks from alternating monomeric iron and cobalt metalloporphyrins and their application in design of porous carbon catalysts. Adv Mater 27:3431–3436

  110. 110.

    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

  111. 111.

    Serov A, Robson MH, Smolnik M, Atanassov P (2012) Templated bi-metallic non-PGM catalysts for oxygen reduction. Electrochim Acta 80:213–218

  112. 112.

    Serov A, Artyushkova K, Atanassov P (2014) Fe-N-C oxygen reduction fuel cell catalyst derived from carbendazim: synthesis, structure, and reactivity. Adv Energy Mater 4:1301735

  113. 113.

    Santoro C, Serov A, Stariha L, Kodali M, Gordon J, Babanova S, Bretschger O, Artyushkova K, Atanassov P (2016) Iron based catalysts from novel low-cost organic precursors for enhanced oxygen reduction reaction in neutral media microbial fuel cells. Energy Environ Sci 9:2346–2353

  114. 114.

    Zhou M, Yang C, Chan KY (2014) Structuring porous iron-nitrogen-doped carbon in a core/shell geometry for the oxygen reduction reaction. Adv Energy Mater 4:1400840

  115. 115.

    Yu Q, Xu J, Wan C, Wu C, Guan L (2015) Porous cobalt–nitrogen-doped hollow graphene spheres as a superior electrocatalyst for enhanced oxygen reduction in both alkaline and acidic solutions. J Mater Chem A 3:16419–16423

  116. 116.

    Silva R, Voiry D, Chhowalla M, Asefa T (2013) Efficient metal-free electrocatalysts for oxygen reduction reaction: polyaniline-derived N- and O-doped mesoporous carbons. J Am Chem Soc 135:7823–7826

  117. 117.

    Cheon JY, Kim T, Choi YM, Jeong HY, Kim MG, Sa YJ, Kim J, Lee Z, Yang TH, Kwon K, Teraski O, Park GG, Adzic RR, Joo SH (2013) Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction. Sci Rep 3:2715

  118. 118.

    Liang HW, Wei W, Wu ZS, Feng X, Müllen K (2013) Mesoporous metal–nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. J Am Chem Soc 135:16002–16005

  119. 119.

    Dombrovkis JK, Jeong HY, Fossum K, Terasaki O, Palmqvist AEC (2013) Transition metal ion-chelating ordered mesoporous carbons as noble metal-free fuel cell catalysts. Chem Mater 25:856–861

  120. 120.

    Kong A, Dong B, Zhu X, Kong Y, Zhang J, Shan Y (2013) Ordered mesoporous Fe-porphyrin-like architectures as excellent cathode materials for the oxygen reduction reaction in both alkaline and acidic media. Chem Eur J 19:16170–16175

  121. 121.

    Kong A, Zhu X, Han Z, Yu Y, Zhang Y, Dong B, Shan Y (2014) Ordered hierarchically micro- and mesoporous Fe–Nx-embedded graphitic architectures as efficient electrocatalysts for oxygen reduction reaction. ACS Catal 4:1793–1800

  122. 122.

    Yan XH, Xu BQ (2014) Mesoporous carbon material co-doped with nitrogen and iron (Fe–N–C): high-performance cathode catalyst for oxygen reduction reaction in alkaline electrolyte. J Mater Chem A 2:8617–8622

  123. 123.

    Yang DS, Bhattacharjya D, Song MY, Razmjooei F, Ko J, Yang QH, Yu JS (2015) Nitrogen-doped ordered mesoporous carbon with different morphologies for the oxygen reduction reaction: effect of iron species and synergy of textural properties. ChemCatChem 7:2882–2890

  124. 124.

    Cheon JY, Kim K, Sa YJ, Sahgong SH, Hong Y, Woo J, Yim SD, Jeong HY, Kim Y, Joo SH (2016) Graphitic nanoshell/mesoporous carbon nanohybrids as highly efficient and stable bifunctional oxygen electrocatalysts for rechargeable aqueous Na–air batteries. Adv Energy Mater 6:1501794

  125. 125.

    Woo J, Sa YJ, Kim JH, Lee HW, Pak C, Joo SH (2018) Impact of textural properties of mesoporous porphyrinic carbon electrocatalysts on oxygen reduction reaction activity. ChemElectroChem. https://doi.org/10.1002/celc.201800183

  126. 126.

    Niu W, Li L, Liu X, Wang N, Liu J, Zhou W, Tang Z, Chen S (2015) Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction. J Am Chem Soc 137:5555–5562

  127. 127.

    Meng FL, Wang ZL, Zhong HX, Wang J, Yan JM, Zhang XB (2016) Reactive multifunctional template-induced preparation of Fe-N-doped mesoporous carbon microspheres towards highly efficient electrocatalysts for oxygen reduction. Adv Mater 28:7948–7955

  128. 128.

    Li JC, Hou PX, Shi C, Zhao SY, Tang DM, Cheng M, Liu C, Cheng HM (2016) Hierarchically porous Fe-N-doped carbon nanotubes as efficient electrocatalyst for oxygen reduction. Carbon 109:632–639

  129. 129.

    Sun T, Wu Q, Zhuo O, Jiang Y, Bu Y, Yang L, Wang X, Hu Z (2016) Manganese oxide-induced strategy to high-performance iron/nitrogen/carbon electrocatalysts with highly exposed active sites. Nanoscale 8:8480–8485

  130. 130.

    Wang B, Wang X, Zou J, Yan Y, Xie S, Hu G, Li Y, Dong A (2017) Simple-cubic carbon frameworks with atomically dispersed iron dopants toward high-efficiency oxygen reduction. Nano Lett 17:2003–2009

  131. 131.

    Song LT, Wu ZY, Zhou F, Liang HW, Yu ZY, Yu SH (2016) Sustainable hydrothermal carbonization synthesis of iron/nitrogen-doped carbon nanofiber aerogels as electrocatalysts for oxygen reduction. Small 12:6398–6406

  132. 132.

    Zhu C, Fu S, Song J, Shi Q, Su D, Engelhard MH, Li X, Xiao D, Li D, Estevez L, Du D, Lin Y (2017) Self-assembled Fe–N-doped carbon nanotube aerogels with single-atom catalyst feature as high-efficiency oxygen reduction electrocatalysts. Small 13:1603407

  133. 133.

    Lu B, Smart TJ, Qin D, Lu JE, Wang N, Chen L, Peng Y, Ping Y, Chen S (2017) Nitrogen and iron-codoped carbon hollow nanotubules as high-performance catalysts toward oxygen reduction reaction: a combined experimental and theoretical study. Chem Mater 29:5617–5628

  134. 134.

    Ahn SH, Klein MJ, Manthiram A (2017) 1D Co- and N-doped hierarchically porous carbon nanotubes derived from bimetallic metal organic framework for efficient oxygen and tri-iodide reduction reactions. Adv Energy Mater 7:1601979

  135. 135.

    Ahn SH, Yu X, Manthiram A (2017) “Wiring” Fe-N x -embedded porous carbon framework onto 1D nanotubes for efficient oxygen reduction reaction in alkaline and acidic media. Adv Mater 29:1606534

  136. 136.

    Ding W, Li L, Xiong K, Wang Y, Li W, Nie Y, Chen S, Qi X, Wei Z (2015) Shape fixing via salt recrystallization: a morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction. J Am Chem Soc 137:5414–5420

  137. 137.

    Niu W, Li L, Wang N, Zeng S, Liu J, Zhao D, Chen S (2016) Volatilizable template-assisted scalable preparation of honeycomb-like porous carbons for efficient oxygen electroreduction. J Mater Chem A 4:10820–10827

  138. 138.

    Zhang Y, Huang LB, Jiang WJ, Zhang X, Chen YY, Wei Z, Wan LJ, Hu JS (2016) Sodium chloride-assisted green synthesis of a 3D Fe–N–C hybrid as highly active electrocatalyst for the oxygen reduction reaction. J Mater Chem A 4:7781–7787

  139. 139.

    Chung DY, Kim MJ, Kang N, Yoo JM, Shin H, Kim OH, Sung YE (2017) Low-temperature and gram-scale synthesis of two-dimensional Fe–N–C carbon sheets for robust electrochemical oxygen reduction reaction. Chem Mater 29:2890–2898

  140. 140.

    Xu J, Xin S, Liu JW, Wang JL, Lei Y, Yu SH (2016) Elastic carbon nanotube aerogel meets tellurium nanowires: a binder- and collector-free electrode for Li-Te batteries. Adv Funct Mater 26:3580–3588

  141. 141.

    Brüller S, Liang HW, Kramm UI, Krumpfer JW, Feng X, Müllen K (2015) Bimetallic porous porphyrin polymer-derived non-precious metal electrocatalysts for oxygen reduction reactions. J Mater Chem A 3:23799–23808

  142. 142.

    Zhang R, He S, Lu Y, Chen W (2015) Fe, Co, N-functionalized carbon nanotubes in situ grown on 3D porous N-doped carbon foams as a noble metal-free catalyst for oxygen reduction. J Mater Chem A 3:3559–3567

  143. 143.

    Sahraie NR, Kramm UI, Steinberg J, Zhang Y, Thomas A, Reier T, Paraknowitsch JP, Strasser P (2015) Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts. Nat Commun 6:8618

  144. 144.

    Lin L, Yang ZK, Jiang YF, Xu AW (2016) Nonprecious bimetallic (Fe, Mo)–N/C catalyst for efficient oxygen reduction reaction. ACS Catal 6:4449–4454

  145. 145.

    Su CY, Cheng H, Li W, Liu ZQ, Li N, Hou Z, Bai FQ, Zhang HX, Ma TY (2017) Atomic modulation of FeCo–nitrogen–carbon bifunctional oxygen electrodes for rechargeable and flexible all-solid-state zinc–air battery. Adv Energy Mater 7:1602420

  146. 146.

    Herrmann I, Kramm UI, Radnik J, Fiechter S, Bogdanoff P (2009) Influence of sulfur on the pyrolysis of CoTMPP as electrocatalyst for the oxygen reduction reaction. J Electrochem Soc 156:B1283–B1292

  147. 147.

    Kramm UI, Herrmann I, Fiechter S, Zehl G, Zizak I, Abs-Wurmbach I, Radnik J, Dorbandt I, Bogdanoff P (2009) On the influence of sulphur on the pyrolysis process of FeTMPP-Cl-based electro-catalysts with respect to oxygen reduction reaction (ORR) in acidic media. ECS Trans 25:659–670

  148. 148.

    Kramm UI, Herrmann-Geppert I, Fiechter S, Zehl G, Zizak I, Dorbandt I, Schmeißer D, Bogdanoff P (2014) Effect of iron-carbide formation on the number of active sites in Fe–N–C catalysts for the oxygen reduction reaction in acidic media. J Mater Chem A 2:2663–2670

  149. 149.

    Ferrandon M, Kropf AJ, Myers DJ, Artyushkova K, Kramm U, Bogdanoff P, Wu G, Johnston CM, Zelenay P (2012) Multitechnique characterization of a polyaniline–iron–carbon oxygen reduction catalyst. J Phys Chem C 116:16001–16013

  150. 150.

    Chang Y, Hong F, He C, Zhang Q, Liu J (2013) Nitrogen and sulfur dual-doped non-noble catalyst using fluidic acrylonitrile telomer as precursor for efficient oxygen reduction. Adv Mater 25:4794–4799

  151. 151.

    Sahraie NR, Paraknowitsch JP, Göbel C, Thomas A, Strasser P (2014) Noble-metal-free electrocatalysts with enhanced ORR performance by task-specific functionalization of carbon using ionic liquid precursor systems. J Am Chem Soc 136:14486–14497

  152. 152.

    Wang YC, Lai YJ, Song L, Zhou ZY, Liu JG, Wang Q, Yang XD, Chen C, Shi W, Zheng YP, Rauf M, Sun SG (2015) S-doping of an Fe/N/C ORR catalyst for polymer electrolyte membrane fuel cells with high power density. Angew Chem Int Ed 54:9907–9910

  153. 153.

    Chen C, Yang XD, Zhou ZY, Lai YJ, Rauf M, Wang Y, Pan J, Zhuang L, Wang Q, Wang YC, Tian N, Zhang XS, Sun SG (2015) Aminothiazole-derived N,S,Fe-doped graphene nanosheets as high performance electrocatalysts for oxygen reduction. Chem Commun 51:17092–17095

  154. 154.

    Hu K, Tao L, Liu D, Huo J, Wang S (2016) Sulfur-doped Fe/N/C nanosheets as highly efficient electrocatalysts for oxygen reduction reaction. ACS Appl Mater Interfaces 8:19379–19385

  155. 155.

    Oh S, Kim JH, Kim MJ, Nam DH, Park JY, Cho EA, Kwon HS (2016) Synergetic effects of edge formation and sulfur doping on the catalytic activity of a graphene-based catalyst for the oxygen reduction reaction. J Mater Chem A 4:14400–14407

  156. 156.

    Elumeeva K, Ren J, Antonietti M, Fellinger TP (2015) High surface iron/cobalt-containing nitrogen-doped carbon aerogels as non-precious advanced electrocatalysts for oxygen reduction. ChemElectroChem 2:584–591

  157. 157.

    Cheon JY, Kim JH, Kim JH, Goddeti KC, Park JY, Joo SH (2014) Intrinsic relationship between enhanced oxygen reduction reaction activity and nanoscale work function of doped carbons. J Am Chem Soc 136:8875–8878

  158. 158.

    Kramm UI, Herrmann-Geppert I, Behrends J, Lips K, Fiechter S, Bogdanoff P (2016) On an easy way to prepare metal–nitrogen doped carbon with exclusive presence of MeN4-type sites active for the ORR. J Am Chem Soc 138:635–640

  159. 159.

    Sa YJ, Seo DJ, Woo J, Lim JT, Cheon JY, Yang SY, Lee JM, Kang D, Shin TJ, Shin HS, Jeong HY, Kim CS, Kim MG, Kim TY, Joo SH (2016) A general approach to preferential formation of active Fe–N x sites in Fe–N/C electrocatalysts for efficient oxygen reduction reaction. J Am Chem Soc 138:15046–15056

  160. 160.

    Shang L, Yu H, Huang X, Bian T, Shi R, Zhao Y, Waterhouse GIN, Wu LZ, Tung CH, Zhang T (2016) Well-dispersed ZIF-derived Co,N-co-doped carbon nanoframes through mesoporous-silica-protected calcination as efficient oxygen reduction electrocatalysts. Adv Mater 28:1668–1674

  161. 161.

    Collman JP, Devaraj NK, Decréau RA, Yang Y, Yan YL, Ebina W, Eberspacher TA, Chidsey CED (2007) A cytochrome c oxidase model catalyzes oxygen to water reduction under rate-limiting electron flux. Science 315:1565–1568

  162. 162.

    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 Mössbauer study. J Phys Chem B 106:12993–13001

  163. 163.

    Kramm UI, Abs-Wurmbach I, Herrmann-Geppert I, Radnik J, Fiechter S, Bogdanoff P (2011) Influence of the electron density of FeN4-centers towards the catalytic activity of pyrolyzed FeTMPPCl-based ORR-electrocatalysts. J Electrochem Soc 158:B69–B78

  164. 164.

    Jia Q, Ramaswamy N, Hafiz H, Tylus U, Strickland K, Wu G, Barbiellini B, Bansil A, Holby EF, Zelenay P, Mukerjee S (2015) Experimental observation of redox-induced Fe–N switching behavior as a determinant role for oxygen reduction activity. ACS Nano 9:12496–12505

  165. 165.

    Jiang Y, Lu Y, Lv X, Han D, Zhang Q, Niu L, Chen W (2013) Enhanced catalytic performance of Pt-free iron phthalocyanine by graphene support for efficient oxygen reduction reaction. ACS Catal 3:1263–1271

  166. 166.

    Lv G, Cui L, Wu Y, Liu Y, Pu T, He X (2013) A novel cobalt tetranitrophthalocyanine/graphene composite assembled by an in situ solvothermal synthesis method as a highly efficient electrocatalyst for the oxygen reduction reaction in alkaline medium. Phys Chem Chem Phys 15:13093–13100

  167. 167.

    Levy N, Mahammed A, Kosa M, Major DT, Gross Z, Elbaz L (2015) Metallocorroles as nonprecious-metal catalysts for oxygen reduction. Angew Chem Int Ed 54:14080–14084

  168. 168.

    Tang H, Yin H, Wang J, Yang N, Wang D, Tang Z (2013) Molecular architecture of cobalt porphyrin multilayers on reduced graphene oxide sheets for high-performance oxygen reduction reaction. Angew Chem Int Ed 52:5585–5589

  169. 169.

    Hijazi I, Bourgeteau T, Cornut R, Morozan A, Filoramo A, Leroy J, Derycke V, Jousselme B, Campidelli S (2014) Carbon nanotube-templated synthesis of covalent porphyrin network for oxygen reduction reaction. J Am Chem Soc 136:6348–6354

  170. 170.

    Xi Y, Wei PJ, Wang RC, Liu JG (2015) Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction. Chem Commun 51:7455–7458

  171. 171.

    Collman JP, Denisevich P, Konai Y, Marrocco M, Koval C, Anson FC (1980) Electrode catalysis of the four-electron reduction of oxygen to water by dicobalt face-to-face porphyrins. J Am Chem Soc 102:6027–6036

  172. 172.

    Cao R, Thapa R, Kim H, Xu X, Kim MG, Li Q, Park N, Liu M, Cho J (2013) Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst. Nat Commun 4:2076

  173. 173.

    Wei PJ, Yu GQ, Naruta Y, Liu JG (2014) Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions. Angew Chem Int Ed 53:6659–6663

  174. 174.

    Liu JG, Shimizu Y, Ohta T, Naruta Y (2010) Formation of an end-on ferric peroxo intermediate upon one-electron reduction of a ferric superoxo heme. J Am Chem Soc 132:3672–3673

  175. 175.

    Chlistunoff J, Sansiñena JM (2014) Effects of axial coordination of the metal center on the activity of iron tetraphenylporphyrin as a nonprecious catalyst for oxygen reduction. J Phys Chem C 118:19139–19149

  176. 176.

    Han J, Sa YJ, Shim Y, Choi M, Park N, Joo SH, Park S (2015) Coordination chemistry of [Co(acac)2] with N-doped graphene: implications for oxygen reduction reaction reactivity of organometallic Co-O4-N species. Angew Chem Int Ed 54:12622–12626

  177. 177.

    Chung HT, Won JH, Zelenay P (2013) Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction. Nat Commun 4:1922

  178. 178.

    Zhong X, Liu L, Wang X, Yu H, Zhuang G, Mei D, Li X, Wang J (2014) A radar-like iron based nanohybrid as an efficient and stable electrocatalyst for oxygen reduction. J Mater Chem A 2:6703–6707

  179. 179.

    Lin L, Zhu Q, Xu AW (2014) Noble-metal-free Fe–N/C catalyst for highly efficient oxygen reduction reaction under both alkaline and acidic conditions. J Am Chem Soc 136:11027–11033

  180. 180.

    Zhu Y, Zhang B, Liu X, Wang DW, Su DS (2014) Unraveling the structure of electrocatalytically active Fe–N complexes in carbon for the oxygen reduction reaction. Angew Chem Int Ed 53:10673–10677

  181. 181.

    Xiao M, Zhu J, Feng L, Liu C, Xing W (2015) Meso/microporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers as an efficient and robust catalyst for the oxygen reduction reaction in both acidic and alkaline solutions. Adv Mater 27:2521–2527

  182. 182.

    Wu H, Li H, Zhao X, Liu Q, Wang J, Xiao J, Xie S, Si R, Yang F, Miao S, Guo X, Wang G, Bao X (2016) Highly doped and exposed Cu(I)–N active sites within graphene towards efficient oxygen reduction for zinc–air batteries. Energy Enrivon Sci 9:3736–3745

  183. 183.

    Jiang WJ, Gu L, Li L, Zhang Y, Zhang X, Zhang LJ, Wang JQ, Hu JS, Wei Z, Wan LJ (2016) Understanding the high activity of Fe–N–C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe–N x . J Am Chem Soc 138:3570–3578

  184. 184.

    Guan BY, Yu L, Lou XW (2016) A dual-metal–organic-framework derived electrocatalyst for oxygen reduction. Energy Environ Sci 9:3092–3096

  185. 185.

    Gupta S, Zhao S, Ogoke O, Lin Y, Xu H, Wu G (2017) Engineering favorable morphology and structure of Fe-N-C oxygen-reduction catalysts through tuning of nitrogen/carbon precursors. ChemSusChem 10:774–785

  186. 186.

    Fu X, Zamani P, Choi JY, Hassan FM, Jiang G, Higgins DC, Zhang Y, Hoque MA, Chen Z (2017) In situ polymer graphenization ingrained with nanoporosity in a nitrogenous electrocatalyst boosting the performance of polymer-electrolyte-membrane fuel cells. Adv Mater 29:1604456

  187. 187.

    Rauf M, Zhao YD, Wang YC, Zheng YP, Chen C, Yang XD, Zhou ZY, Sun SG (2016) Insight into the different ORR catalytic activity of Fe/N/C between acidic and alkaline media: protonation of pyridinic nitrogen. Electrochem Commun 73:71–74

  188. 188.

    Dong G, Fang M, Wang H, Yip S, Cheung HY, Wang F, Wong CY, Chu ST, Ho JC (2015) Insight into the electrochemical activation of carbon-based cathodes for hydrogen evolution reaction. J Mater Chem A 3:13080–13086

  189. 189.

    Chen R, Yang C, Cai W, Wang HY, Miao J, Zhang L, Chen S, Liu B (2017) Use of platinum as the counter electrode to study the activity of nonprecious metal catalysts for the hydrogen evolution reaction. ACS Energy Lett 2:1070–1075

  190. 190.

    Zhou R, Zheng Y, Jaroniec M, Qiao SZ (2016) Determination of the electron transfer number for the oxygen reduction reaction: from theory to experiment. ACS Catal 6:4720–4728

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This research was supported by the National Research Foundation (NRF) of Korea Grant funded by the Ministry of Science and ICT (NRF-2015M1A2A2056560, NRF-2017R1A2B2008464, and NRF-2017R1A4A1015564), the Korea Institute for Advancement of Technology (KIAT) funded by the Ministry of Trade, Industry and Energy (MOTIE) (KIAT_N0001754) and the Korea Evaluation Institute of Industrial Technology (KEIT) funded by the MOTIE (10050509) and the Ministry of Trade, Industry and Energy (KIAT_N0001754).

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Correspondence to Sang Hoon Joo.

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Sa, Y.J., Woo, J. & Joo, S.H. Strategies for Enhancing the Electrocatalytic Activity of M–N/C Catalysts for the Oxygen Reduction Reaction. Top Catal 61, 1077–1100 (2018). https://doi.org/10.1007/s11244-018-0935-0

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  • M‒N/C
  • Electrocatalyst
  • Oxygen reduction reaction
  • Synthetic strategy