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Atomic-level tuning of Co–N–C catalyst for high-performance electrochemical H2O2 production

Nature Materials volume 19, pages 436–442 (2020)Cite this article

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Abstract

Despite the growing demand for hydrogen peroxide it is almost exclusively manufactured by the energy-intensive anthraquinone process. Alternatively, H2O2 can be produced electrochemically via the two-electron oxygen reduction reaction, although the performance of the state-of-the-art electrocatalysts is insufficient to meet the demands for industrialization. Interestingly, guided by first-principles calculations, we found that the catalytic properties of the Co–N4 moiety can be tailored by fine-tuning its surrounding atomic configuration to resemble the structure-dependent catalytic properties of metalloenzymes. Using this principle, we designed and synthesized a single-atom electrocatalyst that comprises an optimized Co–N4 moiety incorporated in nitrogen-doped graphene for H2O2 production and exhibits a kinetic current density of 2.8 mA cm−2 (at 0.65 V versus the reversible hydrogen electrode) and a mass activity of 155 A g−1 (at 0.65 V versus the reversible hydrogen electrode) with negligible activity loss over 110 hours.

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Fig. 1: Theoretical predictions of catalyst materials.
Fig. 2: Structural characterization of GO, Co1–NG(O) and Co1–NG(R).
Fig. 3: Electrochemical ORR performance.
Fig. 4: Summary of H2O2 production activity and stability.

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Data availability

All data is available in the main text or in the Supplementary Information.

References

  1. Yang, S. et al. Toward the decentralized electrochemical production of H2O2: a focus on the catalysis. ACS Catal. 8, 4064–4081 (2018).

    Article  CAS  Google Scholar 

  2. Pulidindi, K. & Pandey, H. Hydrogen Peroxide Market Size by End-User (Paper & Pulp, Chemical, Waste Water Treatment, Mining) Report GMI851 (Global Market Insights, 2016).

  3. Riedl, H.-J. & Pfleiderer, G. Production of hydrogen peroxide. US patent 2,158,525 (1939).

  4. Campos-Martin, J. M., Blanco-Brieva, G. & Fierro, J. L. G. Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew. Chem. Int. Ed. 45, 6962–6984 (2006).

    Article  CAS  Google Scholar 

  5. Siahrostami, S. et al. Enabling direct H2O2 production through rational electrocatalyst design. Nat. Mater. 12, 1137–1143 (2013).

    Article  CAS  Google Scholar 

  6. Verdaguer-Casadevall, A. et al. Trends in the electrochemical synthesis of H2O2: enhancing activity and selectivity by electrocatalytic site engineering. Nano Lett. 14, 1603–1608 (2014).

    Article  CAS  Google Scholar 

  7. Jirkovský, J. S. et al. Single atom hot-spots at Au–Pd nanoalloys for electrocatalytic H2O2 production. J. Am. Chem. Soc. 133, 19432–19441 (2011).

    Article  CAS  Google Scholar 

  8. Sheng, Y. et al. Superoxide dismutases and superoxide reductases. Chem. Rev. 114, 3854–3918 (2014).

    Article  CAS  Google Scholar 

  9. McCord, J. M. & Fridovich, I. Superoxide dismutase. J. Biol. Chem. 244, 6049–6055 (1969).

    CAS  Google Scholar 

  10. Chen, R., Li, H., Chu, D. & Wang, G. Unraveling oxygen reduction reaction mechanisms on carbon-supported Fe-phthalocyanine and Co-phthalocyanine catalysts in alkaline solutions. J. Phys. Chem. C 113, 20689–20697 (2009).

    Article  CAS  Google Scholar 

  11. Yamanaka, I., Tazawa, S., Murayama, T., Iwasaki, T. & Takenaka, S. Catalytic synthesis of neutral hydrogen peroxide at a CoN2Cx cathode of a polymer electrolyte membrane fuel cell (PEMFC). ChemSusChem 3, 59–62 (2010).

    Article  CAS  Google Scholar 

  12. Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).

    Article  CAS  Google Scholar 

  13. Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–800 (2016).

    Article  CAS  Google Scholar 

  14. Duchesne, P. N. et al. Golden single-atomic-site platinum electrocatalysts. Nat. Mater. 17, 1033–1039 (2018).

    Article  CAS  Google Scholar 

  15. Guan, J. et al. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 1, 870–877 (2018).

    Article  CAS  Google Scholar 

  16. Lee, B.-H. et al. Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts. Nat. Mater. 18, 620–626 (2019).

    Article  CAS  Google Scholar 

  17. Chung, H. T. et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357, 479–484 (2017).

    Article  CAS  Google Scholar 

  18. Yang, H. B. et al. Atomically dispersed Ni(ı) as the active site for electrochemical CO2 reduction. Nat. Energy 3, 140–147 (2018).

    Article  CAS  Google Scholar 

  19. Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015).

    Article  CAS  Google Scholar 

  20. Fei, H. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 1, 63–72 (2018).

    Article  CAS  Google Scholar 

  21. Pan, Y. et al. A bimetallic Zn/Fe polyphthalocyanine-derived single-atom Fe–N4 catalytic site: a superior trifunctional catalyst for overall water splitting and Zn–air batteries. Angew. Chem. Int. Ed. 57, 8614–8618 (2018).

    Article  CAS  Google Scholar 

  22. Li, J. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 1, 935–945 (2018).

    Article  CAS  Google Scholar 

  23. Choi, C. H. et al. The Achilles’ heel of iron-based catalysts during oxygen reduction in an acidic medium. Energy Environ. Sci. 11, 3176–3182 (2018).

    Article  CAS  Google Scholar 

  24. He, Y. et al. Highly active atomically dispersed CoN4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy. Energy Environ. Sci. 12, 250–260 (2019).

    Article  CAS  Google Scholar 

  25. Abild-Pedersen, F. et al. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. Phys. Rev. Lett. 99, 016105 (2007).

    Article  CAS  Google Scholar 

  26. Bagri, A. et al. Structural evolution during the reduction of chemically derived graphene oxide. Nat. Chem. 2, 581–587 (2010).

    Article  CAS  Google Scholar 

  27. Li, X. et al. Simultaneous nitrogen doping and reduction of graphene oxide. J. Am. Chem. Soc. 131, 15939–15944 (2009).

    Article  CAS  Google Scholar 

  28. Chen, D., Feng, H. & Li, J. Graphene oxide: preparation, functionalization, and electrochemical applications. Chem. Rev. 112, 6027–6053 (2012).

    Article  CAS  Google Scholar 

  29. Lin, L.-C. & Grossman, J. C. Atomistic understandings of reduced graphene oxide as an ultrathin-film nanoporous membrane for separations. Nat. Commun. 6, 8335 (2015).

    Article  CAS  Google Scholar 

  30. Andreiadis, E. S. et al. Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H2 evolution under fully aqueous conditions. Nat. Chem. 5, 48–53 (2013).

    Article  CAS  Google Scholar 

  31. Ramaswamy, N. & Mukerjee, S. Influence of inner- and outer-sphere electron transfer mechanisms during electrocatalysis of oxygen reduction in alkaline media. J. Phys. Chem. C 115, 18015–18026 (2011).

    Article  CAS  Google Scholar 

  32. Lu, Z. et al. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials. Nat. Catal. 1, 156–162 (2018).

    Article  CAS  Google Scholar 

  33. Kim, H. W. et al. Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts. Nat. Catal. 1, 282–290 (2018).

    Article  Google Scholar 

  34. Zheng, Z., Ng, Y. H., Wang, D.-W. & Amal, R. Epitaxial growth of Au–Pt–Ni nanorods for direct high selectivity H2O2 production. Adv. Mater. 28, 9949–9955 (2016).

    Article  CAS  Google Scholar 

  35. Yang, S., Kim, J., Tak, Y. J., Soon, A. & Lee, H. Single-atom catalyst of platinum supported on titanium nitride for selective electrochemical reactions. Angew. Chem. Int. End. 55, 2058–2062 (2016).

    Article  CAS  Google Scholar 

  36. Verdaguer-Casadevall, A., Hernandez-Fernandez, P., Stephens, I. E. L., Chorkendorff, I. & Dahl, S. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum. J. Power Sources 220, 205–210 (2012).

    Article  CAS  Google Scholar 

  37. Jirkovský, J. S., Halasa, M. & Shiffrin, D. J. Kinetics of electrocatalytic reduction of oxygen and hydrogen peroxide on dispersed gold nanoparticles. Phys. Chem. Chem. Phys. 12, 8042–8052 (2010).

    Article  CAS  Google Scholar 

  38. Sa, Y. J., Kim, J. H. & Joo, S. H. Active edge-site-rich carbon nanocatalysts with enhanced electron transfer for efficient electrochemical hydrogen peroxide production. Angew. Chem. Int. Ed. 58, 1100–1105 (2019).

    Article  CAS  Google Scholar 

  39. Chen, S. et al. Designing boron nitride islands in carbon materials for efficient electrochemical synthesis of hydrogen peroxide. J. Am. Chem. Soc. 140, 7851–7859 (2018).

    Article  CAS  Google Scholar 

  40. Edwards, J. K. et al. Switching off hydrogen peroxide hydrogenation in the direct synthesis process. Science 323, 1037–1041 (2009).

    Article  CAS  Google Scholar 

  41. Wang, X. X., Prabhakaran, V., He, Y., Shao, Y. & Wu, G. Iron-free cathode catalysts for proton-exchange-membrane fuel cells: cobalt catalysts and the peroxide mitigation approach. Adv. Mater. 31, 1805126 (2019).

    Article  CAS  Google Scholar 

  42. Shahriary, L. & Athawale, A. A. Graphene oxide synthesized by using modified Hummers approach. Int. J. Renew. Energy Environ. Eng. 2, 58–63 (2014).

    Google Scholar 

  43. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  44. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  45. Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

    Article  Google Scholar 

  46. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Article  Google Scholar 

  47. Man, I. C. et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011).

    Article  CAS  Google Scholar 

  48. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Article  CAS  Google Scholar 

  49. Calle-Vallejo, F., Martínez, J. I. & Rossmeisl, J. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions. Phys. Chem. Chem. Phys. 13, 15639–15643 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Synthesis and physicochemical property analysis of the catalysts were supported by the Research Center Program of the IBS (IBS-R006-D1) in Korea (T.H.). Electrochemical analysis was supported by Research Center Program of the IBS (IBS-R006-A2, Y.-E.S.). X-ray absorption spectra characterization at the Pohang Accelerator Laboratory (PAL) 8C beamline was supported by a National Research Foundation of Korea (NRF) grant funded by the Korea government (no. 2018M1A2A2061998). Theoretical analysis was supported by the 2019 Research Fund of the University of Seoul (J.S.Y.).

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Author notes

  1. These authors contributed equally: Euiyeon Jung, Heejong Shin, Byoung-Hoon Lee.

Authors and Affiliations

  1. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul, Republic of Korea

    Euiyeon Jung, Heejong Shin, Byoung-Hoon Lee, Hyeon Seok Lee, Jiheon Kim, Wytse Hooch Antink, Subin Park, Yung-Eun Sung & Taeghwan Hyeon

  2. School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    Euiyeon Jung, Heejong Shin, Byoung-Hoon Lee, Hyeon Seok Lee, Jiheon Kim, Wytse Hooch Antink, Subin Park, Yung-Eun Sung & Taeghwan Hyeon

  3. Department of Chemical Engineering, University of Seoul, Seoul, Republic of Korea

    Vladimir Efremov, Suhyeong Lee & Jong Suk Yoo

  4. Pohang Accelerator Laboratory (PAL), Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea

    Kug-Seung Lee

  5. National Center for Inter-University Research Facilities, Seoul National University, Seoul, Republic of Korea

    Sung-Pyo Cho

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Contributions

E.J., H.S., B.-H.L., J.S.Y., Y.-E.S. and T.H. conceived the research. E.J., H.S. and B.-H.L. designed the experiments. E.J., B.-H.L., H.S.L., J.K. and W.H.A. performed and analysed the results. H.S. and S.P. performed electrochemical measurements. V.E., S.L. and J.S.Y. performed the computational analysis. S.-P.C. conducted the high-angle annular dark-field scanning transmission electron microscopy analysis. K.-S.L. contributed to the X-ray absorption experiments and analysis. E.J., H.S., B.-H.L., J.S.Y., Y.-E.S. and T.H. wrote the manuscript. J.S.Y., Y.-E.S. and T.H. supervised the project. All the authors commented on the manuscript.

Corresponding authors

Correspondence to Jong Suk Yoo, Yung-Eun Sung or Taeghwan Hyeon.

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Supplementary Notes, Figs. 1–41, Tables 1–4 and references 1–18.

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Jung, E., Shin, H., Lee, BH. et al. Atomic-level tuning of Co–N–C catalyst for high-performance electrochemical H2O2 production. Nat. Mater. 19, 436–442 (2020). https://doi.org/10.1038/s41563-019-0571-5

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