Skip to main content
Log in

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O2-H2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. This work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Dunn, B.; Kamath, H.; Tarascon, J.-M. Electrical energy storage for the grid: A battery of choices. Science 2011, 334, 928–935.

    Article  Google Scholar 

  2. Liu, C.; Li, F.; Ma, L. P.; Cheng, H. M. Advanced materials for energy storage. Adv. Mater. 2010, 22, E28–E62.

    Article  Google Scholar 

  3. Yang, Z. G.; Zhang, J. L.; Kintner-Meyer, M. C. W.; Lu, X. C.; Choi, D.; Lemmon, J. P.; Liu, J. Electrochemical energy storage for green grid. Chem. Rev. 2011, 111, 3577–3613.

    Article  Google Scholar 

  4. Aricò, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J.-M.; van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 2005, 4, 366–377.

    Article  Google Scholar 

  5. Ng, J. W. D.; Gorlin, Y.; Hatsukade, T.; Jaramillo, T. F. A precious-metal-free regenerative fuel cell for storing renewable electricity. Adv. Energy Mater. 2013, 3, 1545–1550.

    Article  Google Scholar 

  6. Vesborg, P. C. K.; Jaramillo, T. F. Addressing the terawatt challenge: Scalability in the supply of chemical elements for renewable energy. RSC Adv. 2012, 2, 7933–7947.

    Article  Google Scholar 

  7. Wood, K. N.; O'Hayre, R.; Pylypenko, S. Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications. Energy Environ. Sci. 2014, 7, 1212–1249.

    Article  Google Scholar 

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

    Article  Google Scholar 

  9. Wang, D.-W.; Su, D. S. Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ. Sci. 2014, 7, 576–591.

    Article  Google Scholar 

  10. Zhang, J. T.; Zhao, Z. H.; Xia, Z. H.; Dai, L. M. A metalfree bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotechnol. 2015, 10, 444–452.

    Article  Google Scholar 

  11. Zhou, X. J.; Qiao, J. L.; Yang, L.; Zhang, J. J. A review of graphene-based nanostructural materials for both catalyst supports and metal-free catalysts in PEM fuel cell oxygen reduction reactions. Adv. Energy Mater. 2014, 4, 1301523.

    Article  Google Scholar 

  12. Liang, H.-W.; Zhuang, X. D.; Brüller, S.; Feng, X. L.; Müllen, K. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat. Commun. 2014, 5, 4973.

    Article  Google Scholar 

  13. Guo, B. D.; Liu, Q.; Chen, E. D.; Zhu, H. W.; Fang, L.; Gong, J. R. Controllable N-doping of graphene. Nano Lett. 2010, 10, 4975–4980.

    Article  Google Scholar 

  14. Lin, Y.-C.; Lin, C.-Y.; Chiu, P.-W. Controllable graphene N-doping with ammonia plasma. Appl. Phys. Lett. 2010, 96, 133110.

    Article  Google Scholar 

  15. Hou, Z. F.; Wang, X. L.; Ikeda, T.; Terakura, K.; Oshima, M.; Kakimoto, M.-A.; Miyata, S. Interplay between nitrogen dopants and native point defects in graphene. Phys. Rev. B 2012, 85, 165439.

    Article  Google Scholar 

  16. Guo, D. H.; Shibuya, R.; Akiba, C.; Saji, S.; Kondo, T.; Nakamura, J. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 2016, 351, 361–365.

    Article  Google Scholar 

  17. Zhao, Z. H.; Xia, Z. H. Design principles for dual-elementdoped carbon nanomaterials as efficient bifunctional catalysts for oxygen reduction and evolution reactions. ACS Catal. 2016, 6, 1553–1558.

    Article  Google Scholar 

  18. Jin, J. T.; Pan, F. P.; Jiang, L. H.; Fu, X. G.; Liang, A. M.; Wei, Z. Y.; Zhang, J. Y.; Sun, G. Q. Catalyst-free synthesis of crumpled boron and nitrogen Co-doped graphite layers with tunable bond structure for oxygen reduction reaction. ACS Nano 2014, 8, 3313–3321.

    Article  Google Scholar 

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

    Article  Google Scholar 

  20. Zhao, Y.; Nakamura, R.; Kamiya, K.; Nakanishi, S.; Hashimoto, K. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nat. Commun. 2013, 4, 2390.

    Google Scholar 

  21. Yang, H. B.; Miao, J. W.; Hung, S.-F.; Chen, J. Z.; Tao, H. B.; Wang, X. Z.; Zhang, L. P.; Chen, R.; Gao, J. J.; Chen, H. M. et al. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst. Sci. Adv. 2016, 2, e1501122.

    Article  Google Scholar 

  22. Ma, T. Y.; Ran, J. R.; Dai, S.; Jaroniec, M.; Qiao, S. Z. Phosphorus-doped graphitic carbon nitrides grown in situ on carbon-fiber paper: Flexible and reversible oxygen electrodes. Angew. Chem., Int. Ed. 2015, 54, 4646–4650.

    Article  Google Scholar 

  23. Li, R.; Wei, Z. D.; Gou, X. L. Nitrogen and phosphorus dual-doped graphene/carbon nanosheets as bifunctional electrocatalysts for oxygen reduction and evolution. ACS Catal. 2015, 5, 4133–4142.

    Article  Google Scholar 

  24. Kim, O.-H.; Cho, Y.-H.; Chung, D. Y.; Kim, M. J.; Yoo, J. M.; Park, J. E.; Choe, H.; Sung, Y.-E. Facile and gram-scale synthesis of metal-free catalysts: Toward realistic applications for fuel cells. Sci. Rep. 2015, 5, 8376.

    Article  Google Scholar 

  25. Sevilla, M.; Yu, L. H.; Fellinger, T. P.; Fuertes, A. B.; Titirici, M.-M. Polypyrrole-derived mesoporous nitrogendoped carbons with intrinsic catalytic activity in the oxygen reduction reaction. RSC Adv. 2013, 3, 9904–9910.

    Article  Google Scholar 

  26. To, J. W. F.; He, J. J.; Mei, J. G.; Haghpanah, R.; Chen, Z.; Kurosawa, T.; Chen, S. C.; Bae, W.-G.; Pan, L. J.; Tok, J. B.-H. et al. Hierarchical N-doped carbon as CO2 adsorbent with high CO2 selectivity from rationally designed polypyrrole precursor. J. Am. Chem. Soc. 2016, 138, 1001–1009.

    Article  Google Scholar 

  27. Wan, Y.; Shi, Y. F.; Zhao, D. Y. Supramolecular aggregates as templates: Ordered mesoporous polymers and carbons. Chem. Mater. 2008, 20, 932–945.

    Article  Google Scholar 

  28. Lipic, P. M.; Bates, F. S.; Hillmyer, M. A. Nanostructured thermosets from self-assembled amphiphilic block copolymer/epoxy resin mixtures. J. Am. Chem. Soc. 1998, 120, 8963–8970.

    Article  Google Scholar 

  29. Zhang, C. H.; Fu, L.; Liu, N.; Liu, M. H.; Wang, Y. Y.; Liu, Z. F. Synthesis of nitrogen-doped graphene using embedded carbon and nitrogen sources. Adv. Mater. 2011, 23, 1020–1024.

    Article  Google Scholar 

  30. Rouquerol, J.; Avnir, D.; Fairbridge, C. W.; Everett, D. H.; Haynes, J. M.; Pernicone, N.; Ramsay, J. D. F.; Sing, K. S. W.; Unger, K. K. Recommendations for the characterization of porous solids (Technical Report). Pure Appl. Chem. 1994, 66, 1739–1758.

    Article  Google Scholar 

  31. Meng, Y.; Gu, D.; Zhang, F. Q.; Shi, Y. F.; Yang, H. F.; Li, Z.; Yu, C. Z.; Tu, B.; Zhao, D. Y. Ordered mesoporous polymers and homologous carbon frameworks: Amphiphilic surfactant templating and direct transformation. Angew. Chem. 2005, 117, 7215–7221.

    Article  Google Scholar 

  32. Zhong, M. J.; Kim, E. K.; McGann, J. P.; Chun, S.-E.; Whitacre, J. F.; Jaroniec, M.; Matyjaszewski, K.; Kowalewski, T. Electrochemically active nitrogen-enriched nanocarbons with well-defined morphology synthesized by pyrolysis of self-assembled block copolymer. J. Am. Chem. Soc. 2012, 134, 14846–14857.

    Article  Google Scholar 

  33. Pels, J. R.; Kapteijn, F.; Moulijn, J. A.; Zhu, Q.; Thomas, K. M. Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis. Carbon 1995, 33, 1641–1653.

    Article  Google Scholar 

  34. Byon, H. R.; Suntivich, J.; Shao-Horn, Y. Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid. Chem. Mater. 2011, 23, 3421–3428.

    Article  Google Scholar 

  35. Zhou, X. J.; Qiao, J. L.; Yang, L.; Zhang, J. J. A review of graphene-based nanostructural materials for both catalyst supports and metal-free catalysts in PEM fuel cell oxygen reduction reactions. Adv. Energy Mater. 2014, 4, 1301523.

    Article  Google Scholar 

  36. Chung, H. T.; Won, J. H.; Zelenay, P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction. Nat. Commun. 2013, 4, 1922.

    Article  Google Scholar 

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

    Article  Google Scholar 

  38. Couturier, G.; Kirk, D. W.; Hyde, P. J.; Srinivasan, S. Electrocatalysis of the hydrogen oxidation and of the oxygen reduction reactions of Pt and some alloys in alkaline medium. Electrochim. Acta 1987, 32, 995–1005.

    Article  Google Scholar 

  39. Hsueh, K. L.; Gonzalez, E. R.; Srinivasan, S. Electrolyte effects on oxygen reduction kinetics at platinum: A rotating ring-disc electrode analysis. Electrochim. Acta 1983, 28, 691–697.

    Article  Google Scholar 

  40. Tammeveski, K.; Tenno, T.; Claret, J.; Ferrater, C. Electrochemical reduction of oxygen on thin-film Pt electrodes in 0.1 M KOH. Electrochim. Acta 1997, 42, 893–897.

    Article  Google Scholar 

  41. Kibsgaard, J.; Gorlin, Y.; Chen, Z. B.; Jaramillo, T. F. Meso-structured platinum thin films: Active and stable electrocatalysts for the oxygen reduction reaction. J. Am. Chem. Soc. 2012, 134, 7758–7765.

    Article  Google Scholar 

  42. Fuel Cell Technologies Office Multi-Year Research, Development, and Demonstration Plan. (n. d.) [Online]. http: //energy.gov/eere/fuelcells/downloads/fuel-cell-technologiesoffice-multi-year-research-development-and-22 (accessed Jan 29, 2016).

  43. Benck, J. D.; Hellstern, T. R.; Kibsgaard, J.; Chakthranont, P.; Jaramillo, T. F. Catalyzing the hydrogen evolution reaction (HER) with molybdenum sulfide nanomaterials. ACS Catal. 2014, 4, 3957–3971.

    Article  Google Scholar 

  44. Ng, J. W. D.; Hellstern, T. R.; Kibsgaard, J.; Hinckley, A. C.; Benck, J. D.; Jaramillo, T. F. Polymer electrolyte membrane electrolyzers utilizing non-precious mo-based hydrogen evolution catalysts. ChemSusChem 2015, 8, 3512–3519.

    Article  Google Scholar 

  45. Wen, Z. H.; Ci, S. Q.; Hou, Y.; Chen, J. H. Facile one-pot, one-step synthesis of a carbon nanoarchitecture for an advanced multifunctonal electrocatalyst. Angew. Chem., Int. Ed. 2014, 53, 6496–6500.

    Article  Google Scholar 

  46. Stöhr, B.; Boehm, H.; Schlögl, R. Enhancement of the catalytic activity of activated carbons in oxidation reactions by thermal treatment with ammonia or hydrogen cyanide and observation of a superoxide species as a possible intermediate. Carbon 1991, 29, 707–720.

    Article  Google Scholar 

  47. Palaniselvam, T.; Valappil, M. O.; Illathvalappil, R.; Kurungot, S. Nanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping. Energy Environ. Sci. 2014, 7, 1059–1067.

    Article  Google Scholar 

  48. Waki, K.; Wong, R. A.; Oktaviano, H. S.; Fujio, T.; Nagai, T.; Kimoto, K.; Yamada, K. Non-nitrogen doped and non-metal oxygen reduction electrocatalysts based on carbon nanotubes: Mechanism and origin of ORR activity. Energy Environ. Sci. 2014, 7, 1950–1958.

    Article  Google Scholar 

  49. Gasteiger, H. A.; Kocha, S. S.; Sompalli, B.; Wagner, F. T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B: Environ. 2005, 56, 9–35.

    Article  Google Scholar 

  50. Chen, Z. W.; Higgins, D.; Yu, A. P.; Zhang, L.; Zhang, J. J. A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ. Sci. 2011, 4, 3167–3192.

    Article  Google Scholar 

  51. Jiang, Y. F.; Yang, L. J.; Sun, T.; Zhao, J.; Lyu, Z.; Zhuo, O.; Wang, X. Z.; Wu, Q.; Ma, J.; Hu, Z. Significant contribution of intrinsic carbon defects to oxygen reduction activity. ACS Catal. 2015, 5, 6707–6712.

    Article  Google Scholar 

  52. Kim, Y.; Ihm, J.; Yoon, E.; Lee, G.-D. Dynamics and stability of divacancy defects in graphene. Phys. Rev. B 2011, 84, 075445.

    Article  Google Scholar 

  53. Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.

    Article  Google Scholar 

  54. Viswanathan, V.; Hansen, H. A.; Rossmeisl, J.; Nørskov, J. K. Universality in oxygen reduction electrocatalysis on metal surfaces. ACS Catal. 2012, 2, 1654–1660.

    Article  Google Scholar 

  55. Zhang, J. L.; Vukmirovic, M. B.; Sasaki, K.; Nilekar, A. U.; Mavrikakis, M.; Adzic, R. R. Mixed-metal Pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. J. Am. Chem. Soc. 2005, 127, 12480–12481.

    Article  Google Scholar 

  56. Strasser, P.; Koh, S.; Anniyev, T.; Greeley, J.; More, K.; Yu, C. F.; Liu, Z. C.; Kaya, S.; Nordlund, D.; Ogasawara, H. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2010, 2, 454–460.

    Article  Google Scholar 

  57. Stamenkovic, V. R.; Mun, B. S.; Mayrhofer, K. J. J.; Ross, P. N.; Markovic, N. M. Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces. J. Am. Chem. Soc. 2006, 128, 8813–8819.

    Article  Google Scholar 

  58. Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.

    Article  Google Scholar 

  59. Stephens, I. E. L.; Bondarenko, A. S.; Grønbjerg, U.; Rossmeisl, J.; Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ. Sci. 2012, 5, 6744–6762.

    Article  Google Scholar 

  60. Landon, J.; Demeter, E.; Inoglu, N.; Keturakis, C.; Wachs, I. E.; Vasic, R.; Frenkel, A. I.; Kitchin, J. R. Spectroscopic characterization of mixed Fe–Ni oxide electrocatalysts for the oxygen evolution reaction in alkaline electrolytes. ACS Catal. 2012, 2, 1793–1801.

    Article  Google Scholar 

  61. Man, I. C.; Su, H. Y.; Calle-Vallejo, F.; Hansen, H. A.; Martínez, J. I.; Inoglu, N. G.; Kitchin, J.; Jaramillo, T. F.; Nørskov, J. K.; Rossmeisl, J. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 2011, 3, 1159–1165.

    Article  Google Scholar 

  62. Liang, C. D.; Dai, S. Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction. J. Am. Chem. Soc. 2006, 128, 5316–5317.

    Article  Google Scholar 

  63. Ng, J. W. D.; Gorlin, Y.; Nordlund, D.; Jaramillo, T. F. Nanostructured manganese oxide supported onto particulate glassy carbon as an active and stable oxygen reduction catalyst in alkaline-based fuel cells. J. Electrochem. Soc. 2014, 161, D3105–D3112.

    Article  Google Scholar 

  64. Bahn, S. R.; Jacobsen, K. W. An object-oriented scripting interface to a legacy electronic structure code. Comput. Sci. Eng. 2002, 4, 56–66.

    Article  Google Scholar 

  65. Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G. L.; Cococcioni, M.; Dabo, I. et al. QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials. J. Phys.: Condens. Matter 2009, 21, 395502.

    Google Scholar 

  66. Adllan, A. A.; Dal Corso, A. Ultrasoft pseudopotentials and projector augmented-wave data sets: Application to diatomic molecules. J. Phys.: Condens. Matter 2011, 23, 425501.

    Google Scholar 

  67. Wellendorff, J.; Lundgaard, K. T.; Møgelhøj, A.; Petzold, V.; Landis, D. D.; Nørskov, J. K.; Bligaard, T.; Jacobsen, K. W. Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation. Phys. Rev. B 2012, 85, 235149.

    Article  Google Scholar 

  68. Medford, A. J.; Wellendorff, J.; Vojvodic, A.; Studt, F.; Abild-Pedersen, F.; Jacobsen, K. W.; Bligaard, T.; Nørskov, J. K. Assessing the reliability of calculated catalytic ammonia synthesis rates. Science 2014, 345, 197–200.

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0008685. We gratefully acknowledge support from the U.S. Department of Energy, Office of Sciences, Office of Basic Energy Sciences, to the SUNCAT Center for Interface Science and Catalysis. J. W. D. N. acknowledges funding from Agency of Science, Technology, and Research (A*STAR), Singapore. J. W. F. T. acknowledges support from the Croucher Foundation. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF). K. K. acknowledges support from the Future-Innovative Research Fund (No. 1.160088.01) of Ulsan National Institute of Science & Technology (UNIST).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Felix Studt, Jens K. Nørskov, Thomas F. Jaramillo or Zhenan Bao.

Additional information

These authors contributed equally to this work.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

To, J.W.F., Ng, J.W.D., Siahrostami, S. et al. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration. Nano Res. 10, 1163–1177 (2017). https://doi.org/10.1007/s12274-016-1347-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-016-1347-8

Keywords

Navigation