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Non-Noble Metal Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells

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Advanced Electrocatalysts for Low-Temperature Fuel Cells

Abstract

Low temperature fuel cells are promising and sustainable alternative in energy generation. However, their large-scale production have been limited due at high-cost and scarce electrocatalysts based commonly in noble metals. Development of non-noble electrocatalysts has become intensive in recent years. A wide variety of materials as perovskite-type, spinel-type oxides, tungsten carbides, and heteroatom-doped carbons has been explored as alternative electrocatalysts to platinum. They have demonstrated promising electrocatalytic activity toward the oxygen reduction reaction (ORR) in alkaline electrolytes. However, these electrocatalysts are not favorable using strong acid electrolytes. Moreover, transition metal macrocycles show activity performance close to those of Pt-based electrocatalysts in acid media. In this chapter, we present the most recent developments regarding non-noble metal electrocatalyst, starting with a review of some basic electrochemistry concepts and some techniques commonly used to evaluate their performance. Then, materials used as non-noble metal electrocatalyst are presented which are divided into two groups: (1) the most promising non-noble metal electrocatalysts used in acid electrolytes and (2) in alkaline media. Finally, the conclusions and futures perspective are mentioned for these materials that should be considered as the future electrocatalysts for sustainable large-scale fuel cell commercialization.

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References

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

    Article  CAS  PubMed  Google Scholar 

  2. Zhang L, Zhang J, Wilkinson DP, Wang H (2006) Progress in preparation of non-noble electrocatalysts for PEM fuel cell reactions. J Power Sources 156:171–182

    Article  CAS  Google Scholar 

  3. Allen J, Bard LRF (2000) Electrochemical methods: fundamentals and applications, 2nd edn. Wiley, New York

    Google Scholar 

  4. Gerischer H (1997) Principles of electrochemistry. In: Gellings PJ, Bouwmeester HJM (eds) The CRC handbook of solid state electrochemistry, 1st edn. CRC Press, Boca Raton, p 656

    Google Scholar 

  5. Adzic R, Gong K (2017) Platinum-monolayer oxygen-reduction electrocatalysts: present status and future prospects. In: Mirking MV, Amemiya S (eds) Nanoelectrochemistry, 1st edn. CRC Press, Pittsburgh, pp 125–144

    Google Scholar 

  6. Soldano GJ, Schmickler W, Juarez MF, Quaino P, Santos E (2017) Electron transfer in nanoelectrochemical systems. In: Mirking MV, Amemiya S (eds) Nanoelectrochemistry, 1st edn. CRC Press, Pittsburgh, pp 3–28

    Google Scholar 

  7. Dy E, Shi Z (2014) Theoretical modeling of non-noble metal electrocatalysts for acid and alkaline PEM fuel cells. In: Chen Z, Dodelet J, Dodelet JZ (eds) Non-noble metal fuel cell catalysts. Wiley, Weinheim, pp 205–242

    Chapter  Google Scholar 

  8. Shi Z, Zhang J, Liu ZS, Wang H, Wilkinson DP (2006) Current status of ab initio quantum chemistry study for oxygen electroreduction on fuel cell catalysts. Electrochim Acta 51:1905–1916

    Article  CAS  Google Scholar 

  9. Koutecky J, Levich BG (1958) The application of the rotating disc electrode to studies of kinetic and catalytic processes. Zhurnal Fiz Khimii 32:1565–1575

    CAS  Google Scholar 

  10. Zhang HJ, Yuan X, Sun L, Zeng X, Jiang QZ, Shao Z, Ma ZF (2010) Pyrolyzed CoN4-chelate as an electrocatalyst for oxygen reduction reaction in acid media. Int J Hydrog Energy 35:2900–2903

    Article  CAS  Google Scholar 

  11. Frumkin A, Nekrasov L, Levich B, Ivanov J (1959) Die anwendung der rotierenden scheibenelektrode mit einem ringe zur untersuchung von zwischenprodukten elektrochemischer reaktionen. J Electroanal Chem 1:84–90

    Google Scholar 

  12. Song C, Zhang J (2008) Electrocatalytic oxygen reduction reaction. In: Zhang J (ed) PEM fuel cell electrocatalysts and catalyst layers: fundamentals and applications. Springer, London, pp 89–134

    Chapter  Google Scholar 

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

    Article  CAS  Google Scholar 

  14. Xia D, Liu S, Wang Z, Chen G, Zhang L, Zhang L, Hui S (Rob), Zhang J (2008) Methanol-tolerant MoN electrocatalyst synthesized through heat treatment of molybdenum tetraphenylporphyrin for four-electron oxygen reduction reaction. J Power Sources 177:296–302

    Google Scholar 

  15. Behret H, Binder H, Sandstede G, Scherer GG (1981) On the mechanism of electrocatalytic oxygen reduction at metal chelates. J Electroanal Chem Interfacial Electrochem 117:29–42

    Article  CAS  Google Scholar 

  16. Chu D, Jiang R (2002) Novel electrocatalysts for direct methanol fuel cells. Solid State Ionics 148:591–599

    Article  CAS  Google Scholar 

  17. Ding L, Xin Q, Dai X, Zhang J, Qiao J (2013) Evaluation of carbon-supported copper phthalocyanine (CuPc/C) as a cathode catalyst for fuel cells using Nafion as an electrolyte. Ionics (Kiel) 19:1415–1422

    Article  CAS  Google Scholar 

  18. Reis RM, Valim RB, Rocha RS, Lima AS, Castro PS, Bertotti M, Lanza MRV (2014) The use of copper and cobalt phthalocyanines as electrocatalysts for the oxygen reduction reaction in acid medium. Electrochim Acta 139:1–6

    Article  CAS  Google Scholar 

  19. Domínguez C, Pérez-Alonso FJ, Abdel Salam M, Gómez De La Fuente JL, Al-Thabaiti SA, Basahel SN, Peña MA, Fierro JLG, Rojas S (2014) Effect of transition metal (M: Fe, Co or Mn) for the oxygen reduction reaction with non-precious metal catalysts in acid medium. Int J Hydrog Energy 39:5309–5318

    Article  CAS  Google Scholar 

  20. Demir F, Erdoğmuş A, Koca A (2013) Oxygen reduction reaction catalyzed with titanyl phthalocyanines in nonaqueous and aqueous media. Phys Chem Chem Phys 15:15926

    Article  CAS  PubMed  Google Scholar 

  21. Beck F (1977) The redox mechanism of the chelate-catalysed oxygen cathode. J Appl Electrochem 7:239–245

    Article  CAS  Google Scholar 

  22. Zagal JH (1992) Metallophthalocyanines as catalysts in electrochemical reactions. Coord Chem Rev 119:89–136

    Article  CAS  Google Scholar 

  23. Coliman 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

    Article  Google Scholar 

  24. Li J, Wu X, Yuan R, Lin H, Yu R (1994) Cobalt phthalocyanine derivatives as neutral carriers for nitrite-sensitive poly(vinyl chloride) membrane electrodes. Analyst 119:1363

    Article  CAS  Google Scholar 

  25. Jaouen F, Marcotte S, Dodelet JP, Lindbergh G (2003) Oxygen reduction catalysts for polymer electrolyte fuel cells from the pyrolysis of iron acetate adsorbed on various carbon supports. J Phys Chem B 107:1376–1386

    Article  CAS  Google Scholar 

  26. Baranton S, Coutanceau C, Garnier E, Léger J-M (2006) How does α-FePc catalysts dispersed onto high specific surface carbon support work towards oxygen reduction reaction (orr)? J Electroanal Chem 590:100–110

    Article  CAS  Google Scholar 

  27. Faubert G, Côté R, Guay D, Dodelet JP, Dénès G, Poleunis C, Bertrand P (1998) Activation and characterization of Fe-based catalysts for the reduction of oxygen in polymer electrolyte fuel cells. Electrochim Acta 43:1969–1984

    Article  CAS  Google Scholar 

  28. Sirk AHC, Ampbell SA, Birss VI (2005) Oxygen reduction by sol derived [Co, N, C, O]-based catalysts for use in proton exchange membrane fuel cells. Electrochem Solid-State Lett 8:A104

    Article  CAS  Google Scholar 

  29. Alves MCM, Tourillon G (1996) Influence of complexation processes on the catalytic properties of some polymer-based cobalt compounds for oxygen electroreduction. J Phys Chem 100:7566–7572

    Article  CAS  Google Scholar 

  30. Liu Y, Yue X, Li K, Qiao J, Wilkinson DP, Zhang J (2016) PEM fuel cell electrocatalysts based on transition metal macrocyclic compounds. Coord Chem Rev 315:153–177

    Article  CAS  Google Scholar 

  31. Masa J, Ozoemena K, Schuhmann W, Zagal JH (2012) Oxygen reduction reaction using N4-metallomacrocyclic catalysts: fundamentals on rational catalyst design. J Porphyr Phthalocyanines 16:761–784

    Article  CAS  Google Scholar 

  32. Vante NA, Tributsch H (1986) Energy conversion catalysis using semiconducting transition metal cluster compounds. Nature 323:431–432

    Article  CAS  Google Scholar 

  33. Alonso-Vante N, Fieber-Erdmann M, Rossner H, Holub-Krappe E, Giorgetti C, Tadjeddine A, Dartyge E, Fontaine A, Frahm R (1997) The catalytic centre of transition metal chalcogenides vis-à-vis the oxygen reduction reaction: an in situ electrochemical EXAFS study. J Phys IV 7:C2-887–C2-889

    Google Scholar 

  34. Colmenares L, Jusys Z, Behm RJ (2007) Activity, selectivity, and methanol tolerance of Se-modified Ru/C cathode catalysts. J Phys Chem C 111:1273–1283

    Article  CAS  Google Scholar 

  35. Malakhov IV, Nikitenko SG, Savinova ER, Kochubey DI, Alonso-Vante N (2002) In situ EXAFS study to probe active centers of ru chalcogenide electrocatalysts during oxygen reduction reaction. J Phys Chem B 106:1670–1676

    Article  CAS  Google Scholar 

  36. Alonso-Vante N, Malakhov I, Nikitenko S, Savinova E, Kochubey D (2002) The structure analysis of the active centers of Ru-containing electrocatalysts for the oxygen reduction. An in situ EXAFS study. Electrochim Acta 47:3807–3814

    Article  CAS  Google Scholar 

  37. Alonso-Vante N, Borthen P, Fieber-Erdmann M, Strehblow H-H, Holub-Krappe E (2000) An in situ grazing incidence X-ray absorption study of ultra thin RuxSey cluster-like electrocatalyst layers. Electrochim Acta 45:4227–4236

    Article  CAS  Google Scholar 

  38. Liu G, Zhang H, Hu J (2007) Novel synthesis of a highly active carbon-supported Ru85Se15 chalcogenide catalyst for the oxygen reduction reaction. Electrochem Commun 9:2643–2648

    Article  CAS  Google Scholar 

  39. Zehl G, Schmithals G, Hoell A, Haas S, Hartnig C, Dorbandt I, Bogdanoff P, Fiechter S (2007) On the structure of carbon-supported selenium-modified ruthenium nanoparticles as electrocatalysts for oxygen reduction in fuel cells. Angew Chem Int Ed Engl 46:7311–7314

    Article  CAS  PubMed  Google Scholar 

  40. Delacôte C, Bonakdarpour A, Johnston CM, Zelenay P, Wieckowski A (2009) Aqueous-based synthesis of ruthenium–selenium catalyst for oxygen reduction reaction. Faraday Discuss 140:269–281

    Article  Google Scholar 

  41. Feng Y, Alonso-Vante N (2008) Nonprecious metal catalysts for the molecular oxygen-reduction reaction. Phys Status Solidi 245:1792–1806

    Article  CAS  Google Scholar 

  42. Alonso-Vante N (2011) 5 structure and reactivity of transition metal chalcogenides toward the molecular oxygen reduction reaction. In: Vayenas CG (ed) Interfacial phenomena in electrocatalysis. Springer, New York, pp 255–300

    Chapter  Google Scholar 

  43. Satoshi Kaneco BV, Funasaka K (2006) Photo/electrochemistry and photobiology in the environment energy and fuel. Research Signpost, Trivandrum

    Google Scholar 

  44. Feng Y, Gago A, Timperman L, Alonso-Vante N (2011) Chalcogenide metal centers for oxygen reduction reaction: activity and tolerance. Electrochim Acta 56:1009–1022

    Article  CAS  Google Scholar 

  45. Lee J-W, Popov BN (2007) Ruthenium-based electrocatalysts for oxygen reduction reaction-a review. J Solid State Electrochem 11:1355–1364

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  47. Alonso-Vante N (2003) Vielstich W, Lamm A, Gasteiger HA (eds) Handbook of fuel cells: fundamentals, technology, and applications, 2nd edn. Wiley, New York, pp 534–543

    Google Scholar 

  48. Lee K, Alonso-Vante N, Zhang J (2014) Transition metal chalcogenides for oxygen reduction electrocatalysts in PEM fuel cells. In: Non-noble metal fuel cell catalysts. Wiley, Weinheim, pp 157–182

    Chapter  Google Scholar 

  49. Susac D, Sode A, Zhu L, Wong PC, Teo M, Bizzotto D, Mitchell KAR, Parsons RR, Campbell SA (2006) A methodology for investigating new nonprecious metal catalysts for PEM fuel cells. J Phys Chem B 110:10762–10770

    Article  CAS  PubMed  Google Scholar 

  50. Feng Y, He T, Alonso-Vante N (2009) Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium. Electrochim Acta 54:5252–5256

    Article  CAS  Google Scholar 

  51. Sidik RA, Anderson AB (2006) Co9S8 as a catalyst for electroreduction of O2: quantum chemistry predictions. J Phys Chem B 110:936–941

    Article  CAS  PubMed  Google Scholar 

  52. Toth L (1971) Transition metal carbides and nitrides, 1st edn. Academic Press, New York

    Google Scholar 

  53. Oyama ST (1996) The chemistry of transition metal carbides and nitrides. Springer, Dordrecht

    Book  Google Scholar 

  54. Dong S, Chen X, Zhang X, Cui G (2013) Nanostructured transition metal nitrides for energy storage and fuel cells. Coord Chem Rev 257:1946–1956

    Article  CAS  Google Scholar 

  55. Zellner MB, Chen JG (2005) Surface science and electrochemical studies of WC and W2C PVD films as potential electrocatalysts. Catal Today 99:299–307

    Article  CAS  Google Scholar 

  56. Lee K, Ishihara A, Mitsushima S, Kamiya N, Ota K (2004) Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst. Electrochim Acta 49:3479–3485

    Article  CAS  Google Scholar 

  57. McIntyre DR, Vossen A, Wilde JR, Burstein GT (2002) Electrocatalytic properties of a nickel–tantalum–carbon alloy in an acidic electrolyte. J Power Sources 108:1–7

    Article  CAS  Google Scholar 

  58. 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 Engl 53:3749–3749

    Article  CAS  Google Scholar 

  59. 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

    Article  CAS  Google Scholar 

  60. Liang J, Zhou RF, Chen XM, Tang YH, Qiao SZ (2014) Fe-N decorated hybrids of CNTs grown on hierarchically porous carbon for high-performance oxygen reduction. Adv Mater 26:6074–6079

    Article  CAS  PubMed  Google Scholar 

  61. Zhou D, Yang L, Yu L, Kong J, Yao X, Liu W, Xu Z, Lu X (2015) Fe/N/C hollow nanospheres by Fe(III)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction. Nanoscale 7:1501–1509

    Article  CAS  PubMed  Google Scholar 

  62. Liu L, Yang X, Ma N, Liu H, Xia Y, Chen C, Yang D, Yao X (2016) Scalable and cost-effective synthesis of highly efficient Fe 2 N-based oxygen reduction catalyst derived from seaweed biomass. Small 12:1295–1301

    Article  CAS  PubMed  Google Scholar 

  63. Cao B, Neuefeind JC, Adzic RR, Khalifah PG (2015) Molybdenum nitrides as oxygen reduction reaction catalysts: structural and electrochemical studies. Inorg Chem 54:2128–2136

    Article  CAS  PubMed  Google Scholar 

  64. Sun T, Jiang Y, Wu Q, Du L, Zhang Z, Yang L, Wang X, Hu Z (2017) Is iron nitride or carbide highly active for oxygen reduction reaction in acidic medium? Cat Sci Technol 7:51–55

    Article  CAS  Google Scholar 

  65. Smith AJ, Welch AJE (1960) Some mixed metal oxides of perovskite structure. Acta Crystallogr 13:653–656

    Article  CAS  Google Scholar 

  66. Risch M (2017) Perovskite electrocatalysts for the oxygen reduction reaction in alkaline media. Catalysts 7:154

    Article  CAS  Google Scholar 

  67. Zhu Y, Zhou W, Yu J, Chen Y, Liu M, Shao Z (2016) Enhancing electrocatalytic activity of perovskite oxides by tuning cation deficiency for oxygen reduction and evolution reactions. Chem Mater 28:1691–1697

    Article  CAS  Google Scholar 

  68. Goldschmidt VM (1926) Die Gesetze der Krystallochemie. Naturwissenschaften 14:477–485

    Article  CAS  Google Scholar 

  69. Ramadass N (1978) ABO3-type oxides—their structure and properties—a bird’s eye view. Mater Sci Eng 36:231–239

    Article  CAS  Google Scholar 

  70. Sunarso J, Torriero AAJ, Zhou W, Howlett PC, Forsyth M (2012) Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium: a thin-film rotating ring-disk electrode study. J Phys Chem C 116:5827–5834

    Article  CAS  Google Scholar 

  71. Celorrio V, Dann E, Calvillo L, Morgan DJ, Hall SR, Fermin DJ (2016) Oxygen reduction at carbon-supported lanthanides: therole of the B-site. ChemElectroChem 3:283–291

    Article  CAS  Google Scholar 

  72. Suntivich J, Gasteiger HA, Yabuuchi N, Nakanishi H, Goodenough JB, Shao-Horn Y (2011) Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat Chem 3:546–550

    Article  CAS  PubMed  Google Scholar 

  73. Larsson R, Johansson LY (1990) On the catalytic properties of mixed oxides for the electrochemical reduction of oxygen. J Power Sources 32:253–260

    Article  CAS  Google Scholar 

  74. Hyodo T, Hayashi M, Miura N, Yamazoe N (1996) Catalytic activities of rare-earth manganites for cathodic reduction of oxygen in alkaline solution. J Electrochem Soc 143:L266–L267

    Article  CAS  Google Scholar 

  75. Yuan X-Z, Li X, Qu W, Ivey DG, Wang H (2011) Electrocatalytic activity of non-stoichiometric perovskites toward oxygen reduction reaction in alkaline electrolytes. ECS Trans 35:11–20

    Article  CAS  Google Scholar 

  76. Celorrio V, Calvillo L, Dann E, Granozzi G, Aguadero A, Kramer D, Russell AE, Fermín DJ (2016) Oxygen reduction reaction at LaxCa 1−xMnO3 nanostructures: interplay between A-site segregation and B-site valency. Cat Sci Technol 6:7231–7238

    Article  CAS  Google Scholar 

  77. Stoerzinger KA, Lü W, Li C, Ariando VT, Shao-Horn Y (2015) Highly active epitaxial La(1-x)SrxMnO3 surfaces for the oxygen reduction reaction: role of charge transfer. J Phys Chem Lett 6:1435–1440

    Article  CAS  PubMed  Google Scholar 

  78. Tulloch J, Donne SW (2009) Activity of perovskite La1-xSrxMnO3 catalysts towards oxygen reduction in alkaline electrolytes. J Power Sources 188:359–366

    Article  CAS  Google Scholar 

  79. Hyodo T, Hayashi M, Mitsutake S, Miura N, Yamazoe N (1997) Praseodymium-calcium manganites (Pr1-xCaxMnO3) as electrode catalyst for oxygen reduction in alkaline solution. J Appl Electrochem 27:745–746

    Article  CAS  Google Scholar 

  80. Takeda Y, Kanno R, Kondo T, Yamamoto O, Taguchi H, Shimada M, Koizumi M (1982) Properties of SrMO3-δ (M=Fe, Co) as oxygen electrodes in alkaline solution. J Appl Electrochem 12:275–280

    Article  CAS  Google Scholar 

  81. Du J, Zhang T, Cheng F, Chu W, Wu Z, Chen J (2014) Nonstoichiometric perovskite CaMnO3−δ for oxygen electrocatalysis with high activity. Inorg Chem 53:9106–9114

    Article  CAS  PubMed  Google Scholar 

  82. Poux T, Bonnefont A, Kéranguéven G, Tsirlina GA, Savinova ER (2014) Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway. ChemPhysChem 15:2108–2120

    Article  CAS  PubMed  Google Scholar 

  83. Wei C, Feng Z, Scherer GG, Barber J, Shao-Horn Y, Xu ZJ (2017) Cations in octahedral sites: a descriptor for oxygen electrocatalysis on transition-metal spinels. Adv Mater 29:1–8

    Google Scholar 

  84. Verwey EJW, Heilmann EL (1947) Physical properties and cation arrangement of oxides with spinel structures I. Cation Arrangement in Spinels. J Chem Phys 15:174–180

    Article  CAS  Google Scholar 

  85. Chakrapani K, Bendt G, Hajiyani H, Lunkenbein T, Greiner MT, Masliuk L, Salamon S, Landers J, Schlögl R, Wende H, Pentcheva R, Schulz S, Behrens M (2018) The role of composition of uniform and highly dispersed cobalt vanadium iron spinel nanocrystals for oxygen electrocatalysis. ACS Catal 8:1259–1267

    Article  CAS  Google Scholar 

  86. Zhou Y, Xi S, Wang J, Sun S, Wei C, Feng Z, Du Y, Xu ZJ (2018) Revealing the dominant chemistry for oxygen reduction reaction on small oxide nanoparticles. ACS Catal 8:673–677

    Article  CAS  Google Scholar 

  87. Zhao Q, Yan Z, Chen C, Chen J (2017) Spinels: controlled preparation, oxygen reduction/evolution reaction application, and beyond. Chem Rev 117:10121–10211

    Article  CAS  PubMed  Google Scholar 

  88. Chen D, Chen C, Baiyee ZM, Shao Z, Ciucci F (2015) Nonstoichiometric oxides as low-cost and highly-efficient oxygen reduction/evolution catalysts for low-temperature electrochemical devices. Chem Rev 115:9869–9921

    Article  CAS  PubMed  Google Scholar 

  89. Si C, Zhang Y, Zhang C, Gao H, Ma W, Lv L, Zhang Z (2017) Mesoporous nanostructured spinel-type MFe2O4 (M = Co, Mn, Ni) oxides as efficient bi-functional electrocatalysts towards oxygen reduction and oxygen evolution. Electrochim Acta 245:829–838

    Article  CAS  Google Scholar 

  90. Hong W, Li L, Xue R, Xu X, Wang H, Zhou J, Zhao H, Song Y, Liu Y, Gao J (2017) One-pot hydrothermal synthesis of Zinc ferrite/reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction. J Colloid Interface Sci 485:175–182

    Article  CAS  PubMed  Google Scholar 

  91. Zhu H, Zhang S, Huang Y-X, Wu L, Sun S (2013) Monodisperse MxFe3– xO4 (M = Fe, Cu, Co, Mn) nanoparticles and their electrocatalysis for oxygen reduction reaction. Nano Lett 13:2947–2951

    Article  CAS  PubMed  Google Scholar 

  92. Bhandary N, Ingole PP, Basu S (2018) Electrosynthesis of Mn-Fe oxide nanopetals on carbon paper as bi-functional electrocatalyst for oxygen reduction and oxygen evolution reaction. Int J Hydrog Energy 43:3165–3171

    Article  CAS  Google Scholar 

  93. 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

    Article  CAS  PubMed  Google Scholar 

  94. Liu M, Zhang R, Chen W (2014) Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications. Chem Rev 114:5117–5160

    Article  CAS  PubMed  Google Scholar 

  95. Lin Z, Waller GH, Liu Y, Liu M, Wong C (2013) 3D nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction. Nano Energy 2:241–248

    Article  CAS  Google Scholar 

  96. Wang H, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2:781–794

    Article  CAS  Google Scholar 

  97. Liang Y, Wang H, Diao P, Chang W, Hong G, Li Y, Gong M, Xie L, Zhou J, Wang J, Regier TZ, Wei F, Dai H (2012) Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes. J Am Chem Soc 134:15849–15857

    Article  CAS  PubMed  Google Scholar 

  98. Nie R, Bo X, Luhana C, Nsabimana A, Guo L (2014) Simultaneous formation of nitrogen and sulfur-doped carbon nanotubes-mesoporous carbon and its electrocatalytic activity for oxygen reduction reaction. Int J Hydrog Energy 39:12597–12603

    Article  CAS  Google Scholar 

  99. Liang J, Jiao Y, Jaroniec M, Qiao SZ (2012) Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew Chem Int Ed Engl 124:11664–11668

    Article  Google Scholar 

  100. Nasini UB, Gopal Bairi V, Kumar Ramasahayam S, Bourdo SE, Viswanathan T, Shaikh AU (2014) Oxygen reduction reaction studies of phosphorus and nitrogen co-doped mesoporous carbon synthesized via microwave technique. ChemElectroChem 1:573–579

    Article  CAS  Google Scholar 

  101. Choi CH, Chung MW, Park SH, Woo SI (2013) Additional doping of phosphorus and/or sulfur into nitrogen-doped carbon for efficient oxygen reduction reaction in acidic media. Phys Chem Chem Phys 15:1802–1805

    Article  CAS  PubMed  Google Scholar 

  102. Wang S, Zhang L, Xia Z, Roy A, Chang DW, Baek J-B, Dai L (2012) BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angew Chem Int Ed Engl 51:4209–4212

    Article  CAS  PubMed  Google Scholar 

  103. Shao Y, Zhang S, Engelhard MH, Li G, Shao G, Wang Y, Liu J, Aksay IA, Lin Y (2010) Nitrogen-doped graphene and its electrochemical applications. J Mater Chem 20:7491

    Article  CAS  Google Scholar 

  104. Geng D, Chen Y, Chen Y, Li Y, Li R, Sun X, Ye S, Knights S (2011) High oxygen-reduction activity and durability of nitrogen-doped graphene. Energy Environ Sci 4:760

    Article  CAS  Google Scholar 

  105. Carrillo-Rodríguez JC, Alonso-Lemus IL, Siller-Ceniceros AA, Martínez GE, Pizá-Ruiz P, Vargas-Gutiérrez G, Rodríguez-Varela FJ (2017) Easy synthesis of N-doped graphene by milling exfoliation with electrocatalytic activity towards the Oxygen Reduction Reaction (ORR). Int J Hydrog Energy 42:30383–30388

    Article  CAS  Google Scholar 

  106. Alonso-Lemus IL, Figueroa-Torres MZ, García-Hernández AB, Escobar-Morales B, Rodríguez-Varela FJ, Fuentes AF, Lardizabal-Gutierrez D, Quintana-Owen P (2017) Low-cost sonochemical synthesis of nitrogen-doped graphene metal-free electrocatalyst for the oxygen reduction reaction in alkaline media. Int J Hydrog Energy 42(21):30330–30338

    Article  CAS  Google Scholar 

  107. Pels JR, Kapteijn F, Moulijn JA, Zhu Q, Thomas KM (1995) Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis. Carbon 33:1641–1653

    Article  CAS  Google Scholar 

  108. Yan L, Yu J, Houston J, Flores N, Luo H (2017) Biomass derived porous nitrogen doped carbon for electrochemical devices. Green Energy Environ 2:84–99

    Article  Google Scholar 

  109. Yang S, Zhao G-L, Khosravi E (2010) First principles studies of nitrogen doped carbon nanotubes for dioxygen reduction. J Phys Chem C 114:3371–3375

    Article  CAS  Google Scholar 

  110. Reda M, Hansen HA, Vegge T (2018) DFT study of stabilization effects on N-doped graphene for ORR catalysis. Catal Today 312:118–125

    Article  CAS  Google Scholar 

  111. Zhang L, Xia Z (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C 115:11170–11176

    Article  CAS  Google Scholar 

  112. Yu H, Shang L, Bian T, Shi R, Waterhouse GIN, Zhao Y, Zhou C, Wu L-Z, Tung C-H, Zhang T (2016) Nitrogen-doped porous carbon nanosheets templated from g-C3N4 as metal-free electrocatalysts for efficient oxygen reduction reaction. Adv Mater 28:5080–5086

    Article  CAS  PubMed  Google Scholar 

  113. He C, Li Z, Cai M, Cai M, Wang J-Q, Tian Z, Zhang X, Shen PK (2013) A strategy for mass production of self-assembled nitrogen-doped graphene as catalytic materials. J Mater Chem A 1:1401–1406

    Article  CAS  Google Scholar 

  114. Luo Z, Lim S, Tian Z, Shang J, Lai L, MacDonald B, Fu C, Shen Z, Yu T, Lin J (2011) Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property. J Mater Chem 21:8038

    Article  CAS  Google Scholar 

  115. Feng L, Chen Y, Chen L (2011) Easy-to-operate and low-temperature synthesis of gram-scale nitrogen-doped graphene and its application as cathode catalyst in microbial fuel cells. ACS Nano 5:9611–9618

    Article  CAS  PubMed  Google Scholar 

  116. Deng D, Pan X, Yu L, Cui Y, Jiang Y, Qi J, Li W-X, Fu Q, Ma X, Xue Q, Sun G, Bao X (2011) Toward N-doped graphene via solvothermal synthesis. Chem Mater 23:1188–1193

    Article  CAS  Google Scholar 

  117. Tavakol H, Keshavarzipour F (2016) A sulfur doped carbon nanotube as a potential catalyst for the oxygen reduction reaction. RSC Adv 6:63084–63090

    Article  CAS  Google Scholar 

  118. Zhang L, Niu J, Li M, Xia Z (2014) Catalytic mechanisms of sulfur-doped graphene as efficient oxygen reduction reaction catalysts for fuel cells. J Phys Chem C 118:3545–3553

    Article  CAS  Google Scholar 

  119. Seredych M, László K, Bandosz TJ (2015) Sulfur-doped carbon aerogel as a metal-free oxygen reduction catalyst. ChemCatChem 7:2924–2931

    Article  CAS  Google Scholar 

  120. Wang L, Dong H, Guo Z, Zhang L, Hou T, Li Y (2016) Potential application of novel boron-doped graphene nanoribbon as oxygen reduction reaction catalyst. J Phys Chem C 120:17427–17434

    Article  CAS  Google Scholar 

  121. Su J, Cao X, Wu J, Jin C, Tian J-H, Yang R (2016) One-pot synthesis of boron-doped ordered mesoporous carbons as efficient electrocatalysts for the oxygen reduction reaction. RSC Adv 6:24728–24737

    Article  CAS  Google Scholar 

  122. Lin Y, Zhu Y, Zhang B, Kim YA, Endo M, Su DS (2015) Boron-doped onion-like carbon with enriched substitutional boron: the relationship between electronic properties and catalytic performance. J Mater Chem A 3:21805–21814

    Article  CAS  Google Scholar 

  123. Guo M, Huang J, Kong X, Peng H, Shui H, Qian F, Zhu L, Zhu W, Zhang Q (2016) Hydrothermal synthesis of porous phosphorus-doped carbon nanotubes and their use in the oxygen reduction reaction and lithium-sulfur batteries. New Carbon Mater 31:352–362

    Article  Google Scholar 

  124. Zhang X, Lu Z, Fu Z, Tang Y, Ma D, Yang Z (2015) The mechanisms of oxygen reduction reaction on phosphorus doped graphene: a first-principles study. J Power Sources 276:222–229

    Article  CAS  Google Scholar 

  125. Liu Z, Fu X, Li M, Wang F, Wang Q, Kang G, Peng F (2015) Novel silicon-doped, silicon and nitrogen-codoped carbon nanomaterials with high activity for the oxygen reduction reaction in alkaline medium. J Mater Chem A 3:3289–3293

    Article  CAS  Google Scholar 

  126. Sun X, Zhang Y, Song P, Pan J, Zhuang L, Xu W, Xing W (2013) Fluorine-doped carbon blacks: highly efficient metal-free electrocatalysts for oxygen reduction reaction. ACS Catal 3:1726–1729

    Article  CAS  Google Scholar 

  127. Yao Z, Nie H, Yang Z, Zhou X, Liu Z, Huang S (2012) Catalyst-free synthesis of iodine-doped graphenevia a facile thermal annealing process and its use for electrocatalytic oxygen reduction in an alkaline medium. Chem Commun 48:1027–1029

    Article  CAS  Google Scholar 

  128. Mena-Durán CJ, Alonso-Lemus IL, Quintana P, Barbosa R, Ordoñez LC, Escobar B (2018) Preparation of metal-free electrocatalysts from cassava residues for the oxygen reduction reaction: a sulfur functionalization approach. Int J Hydrog Energy 43:3172–3179

    Article  CAS  Google Scholar 

  129. Yang S, Mao X, Cao Z, Yin Y, Wang Z, Shi M, Dong H (2018) Onion-derived N, S self-doped carbon materials as highly efficient metal-free electrocatalysts for the oxygen reduction reaction. Appl Surf Sci 427:626–634

    Article  CAS  Google Scholar 

  130. Sun Y, Wu J, Tian J, Jin C, Yang R (2015) Sulfur-doped carbon spheres as efficient metal-free electrocatalysts for oxygen reduction reaction. Electrochim Acta 178:806–812

    Article  CAS  Google Scholar 

  131. Yang Z, Yao Z, Li G, Fang G, Nie H, Liu Z, Zhou X, Chen X, Huang S (2012) Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 6:205–211

    Article  CAS  PubMed  Google Scholar 

  132. Inamdar S, Choi H-S, Wang P, Song MY, Yu J-S (2013) Sulfur-containing carbon by flame synthesis as efficient metal-free electrocatalyst for oxygen reduction reaction. Electrochem Commun 30:9–12

    Article  CAS  Google Scholar 

  133. Sun X, Song P, Zhang Y, Liu C, Xu W, Xing W (2013) A class of high performance metal-free oxygen reduction electrocatalysts based on cheap carbon blacks. Sci Rep 3:2505

    Article  PubMed  PubMed Central  Google Scholar 

  134. Li Y, Chopra N (2015) Progress in large-scale production of graphene. Part 2: vapor methods. JOM 67:44–52

    Article  CAS  Google Scholar 

  135. Luque R (2013) Producing fuels and fine chemicals from biomass using nanomaterials, 1st edn. CRC Press, Boca Raton

    Book  Google Scholar 

  136. Antolini E (2016) Nitrogen-doped carbons by sustainable N- and C-containing natural resources as nonprecious catalysts and catalyst supports for low temperature fuel cells. Renew Sust Energ Rev 58:34–51

    Article  CAS  Google Scholar 

  137. Alonso-Lemus IL, Rodriguez-Varela FJ, Figueroa-Torres MZ, Sanchez-Castro ME, Hernandez-Ramírez A, Lardizabal-Gutierrez D, Quintana-Owen P (2016) Novel self-nitrogen-doped porous carbon from waste leather as highly active metal-free electrocatalyst for the ORR. Int J Hydrog Energy 41:23409–23416

    Article  CAS  Google Scholar 

  138. Lardizabal-Guitierrez D, González-Quijano D, Bartolo-Pérez P, Escobar-Morales B, Rodríguez-Varela FJ, Alonso-Lemus IL (2016) Communication—synthesis of self-doped metal-free electrocatalysts from waste leather with high ORR activity. J Electrochem Soc 163:H15–H17

    Article  CAS  Google Scholar 

  139. Zhang J, Wu S, Chen X, Pan M, Mu S (2014) Egg derived nitrogen-self-doped carbon/carbon nanotube hybrids as noble-metal-free catalysts for oxygen reduction. J Power Sources 271:522–529

    Article  CAS  Google Scholar 

  140. Liu F, Peng H, Qiao X, Fu Z, Huang P, Liao S (2014) High-performance doped carbon electrocatalyst derived from soybean biomass and promoted by zinc chloride. Int J Hydrog Energy 39:10128–10134

    Article  CAS  Google Scholar 

  141. Gao S, Geng K, Liu H, Wei X, Zhang M, Wang P, Wang J (2015) Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction. Energy Environ Sci 8:221–229

    Article  CAS  Google Scholar 

  142. Zhai Y, Zhu C, Wang E, Dong S (2014) Energetic carbon-based hybrids: green and facile synthesis from soy milk and extraordinary electrocatalytic activity towards ORR. Nanoscale 6:2964

    Article  CAS  PubMed  Google Scholar 

  143. Lu J, Bo X, Wang H, Guo L (2013) Nitrogen-doped ordered mesoporous carbons synthesized from honey as metal-free catalyst for oxygen reduction reaction. Electrochim Acta 108:10–16

    Article  CAS  Google Scholar 

  144. Pan F, Cao Z, Zhao Q, Liang H, Zhang J (2014) Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction. J Power Sources 272:8–15

    Article  CAS  Google Scholar 

  145. Li J, Wang S, Ren Y, Ren Z, Qiu Y, Yu J (2014) Nitrogen-doped activated carbon with micrometer-scale channels derived from luffa sponge fibers as electrocatalysts for oxygen reduction reaction with high stability in acidic media. Electrochim Acta 149:56–64

    Article  CAS  Google Scholar 

  146. Escobar B, Pérez-Salcedo KY, Alonso-Lemus IL, Pacheco D, Barbosa R (2017) N-doped porous carbon from Sargassum spp. as metal-free electrocatalysts for oxygen reduction reaction in alkaline media. Int J Hydrog Energy 42(51):30274–30283

    Article  CAS  Google Scholar 

  147. Song MY, Park HY, Yang D-S, Bhattacharjya D, Yu J-S (2014) Seaweed-derived heteroatom-doped highly porous carbon as an electrocatalyst for the oxygen reduction reaction. ChemSusChem 7:1755–1763

    Article  CAS  PubMed  Google Scholar 

  148. Chaudhari KN, Song MY, Yu JS (2014) Transforming hair into heteroatom-doped carbon with high surface area. Small 10:2625–2636

    Article  CAS  PubMed  Google Scholar 

  149. Chaudhari NK, Song MY, Yu J-S (2015) Heteroatom-doped highly porous carbon from human urine. Sci Rep 4:5221

    Article  CAS  Google Scholar 

  150. Wang R, Wang K, Wang Z, Song H, Wang H, Ji S (2015) Pig bones derived N-doped carbon with multi-level pores as electrocatalyst for oxygen reduction. J Power Sources 297:295–301

    Article  CAS  Google Scholar 

  151. Guo C-Z, Chen C-G, Luo Z-L (2014) A novel nitrogen-containing electrocatalyst for oxygen reduction reaction from blood protein pyrolysis. J Power Sources 245:841–845

    Article  CAS  Google Scholar 

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Acknowledgment

The authors would like to thank to the Mexican Council for Science and Technology (CONACyT) for financial support grant CB-2015-250632.

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Alonso-Lemus, I.L., Figueroa-Torres, M.Z. (2018). Non-Noble Metal Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells. In: Rodríguez-Varela, F., Napporn, T. (eds) Advanced Electrocatalysts for Low-Temperature Fuel Cells . Springer, Cham. https://doi.org/10.1007/978-3-319-99019-4_7

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