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Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

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Abstract

The demand for high-performance non-precious-metal electrocatalysts to replace the noble metal-based catalysts for oxygen reduction reaction (ORR) is intensively increasing. Herein, single-atomic copper sites supported on N-doped three-dimensional hierarchically porous carbon catalyst (Cu1/NC) was prepared by coordination pyrolysis strategy. Remarkably, the Cu1/NC-900 catalyst not only exhibits excellent ORR performance with a half-wave potential of 0.894 V (vs. RHE) in alkaline media, outperforming those of commercial Pt/C (0.851 V) and Cu nanoparticles anchored on N-doped porous carbon (CuNPs/NC-900), but also demonstrates high stability and methanol tolerance. Moreover, the Cu1/NC-900 based Zn-air battery exhibits higher power density, rechargeability and cyclic stability than the one based on Pt/C. Both experimental and theoretical investigations demonstrated that the excellent performance of the as-obtained Cui/NC-900 could be attributed to the synergistic effect between copper coordinated by three N atoms active sites and the neighbouring carbon defect, resulting in elevated Cu d-band centers of Cu atoms and facilitating intermediate desorption for ORR process. This study may lead towards the development of highly efficient non-noble metal catalysts for applications in electrochemical energy conversion.

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References

  1. Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652–657.

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  3. Mao, J. J.; Yang, L. F.; Yu, P.; Wei, X. W.; Mao, L. Q. Rlectrocatalytic four-electron reduction of oxygen with copper (II)-based metal-organic frameworks. Electrochem. Commun. 2012, 19, 29–31.

    CAS  Google Scholar 

  4. Li, Y. G.; Dai, H. J. Recent advances in zinc-air batteries. Chem. Soc. Rev. 2014, 43, 5257–5275.

    CAS  Google Scholar 

  5. Shao, M. H.; Chang, Q. W.; Dodelet, J. P.; Chenitz, R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem. Rev. 2016, 116, 3594–3657.

    CAS  Google Scholar 

  6. **a, B. Y.; Yan, Y.; Li, N.; Wu, H. B.; Lou, X. W.; Wang, X. A metal-organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 2016, 1, 15006.

    CAS  Google Scholar 

  7. Yang, Z. K.; Chen, B. X.; Chen, W. X.; Qu, Y. T.; Zhou, F. Y.; Zhao, C. M.; Xu, Q.; Zhang, Q. H.; Duan, X. Z.; Wu, Y. E. Directly transforming copper(I) oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach. Nat. Commun. 2019, 70, 3734.

    Google Scholar 

  8. Han, X. P.; Ling, X. F.; Yu, D. S.; **e, D. Y.; Li, L. L.; Peng, S. J.; Zhong, C.; Zhao, N. Q.; Deng, Y. D.; Hu, W. B. Atomically dispersed binary Co-Ni sites in nitrogen-doped hollow carbon nanocubes for reversible oxygen reduction and evolution. Adv. Mater. 2019, 31, 1905622.

    CAS  Google Scholar 

  9. Zhang, N. Q.; Ye, C. L.; Yan, H.; Li, L. C.; He, H.; Wang, D. S.; Li, Y. D. Single-atom site catalysts for environmental catalysis. Nana Res. 2020, 13, 3165–3182.

    Google Scholar 

  10. Sun, T. T.; Li, Y. L.; Cui, T. T.; Xu, L. B.; Wang, Y. G.; Chen, W. X.; Zhang, P. P.; Zheng, T. Y.; Fu, X. Z.; Zhang, S. L. et al. Engineering of coordination environment and multiscale structure in single-site copper catalyst for superior electrocatalytic oxygen reduction. Nana Lett. 2020, 20, 6206–6214.

    CAS  Google Scholar 

  11. Mao, J. J.; Li, J.; Pei, J. J.; Liu, Y.; Wang, D. S.; Li, Y. D. Structure regulation of noble-metal-based nanomaterials at an atomic level. Nana Today 2019, 26, 164–175.

    CAS  Google Scholar 

  12. Li, K.; Li, X. X.; Huang, H. W.; Luo, L. H.; Li, X.; Yan, X. P.; Ma, C.; Si, R.; Yang, J. L.; Zeng, J. One-nanometer-thick PtNiRh trimetallic nanowires with enhanced oxygen reduction electrocatalysis in acid media: Integrating multiple advantages into one catalyst. J. Am. Chem. Soc. 2018, 140, 16159–16167.

    CAS  Google Scholar 

  13. Yin, P. Q.; Yao, T.; Wu, Y. E.; Zheng, L. R.; Lin, Y.; Liu, W.; Ju, H. X.; Zhu, J. F.; Hong, X.; Deng, Z. X. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem., Int. Ed. 2016, 55, 10800–10805.

    CAS  Google Scholar 

  14. Mao, J. J.; Chen, Y. J.; Pei, J. J.; Wang, D. S.; Li, Y. D. Pt-M (M = Cu, Fe, Zn, etc.) bimetallic nanomaterials with abundant surface defects and robust catalytic properties. Chem. Commun. 2016, 52, 5985–5988.

    CAS  Google Scholar 

  15. Li, F.; Han, G. F.; Noh, H. J.; Kim, S. J.; Lu, Y. L.; Jeong, H. Y.; Fu, Z. P.; Baek, J. B. Boosting oxygen reduction catalysis with abundant copper single atom active sites. Energy Environ. Sci. 2018, 11, 2263–2269.

    CAS  Google Scholar 

  16. Wang, X. X.; Cullen, D. A.; Pan, Y T.; Hwang, S.; Wang, M. Y.; Feng, Z. X.; Wang, J. Y.; Engelhard, M. H.; Zhang, H. G.; He, Y. H. et al. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Adv. Mater. 2018, 30, 1706758.

    Google Scholar 

  17. Shang, H. S.; Sun, W. M.; Sui, R.; Pei, J. J.; Zheng, L. R.; Dong, J. C.; Jiang, Z. L.; Zhou, D. N.; Zhuang, Z. B.; Chen, W. X. et al. Engineering isolated Mn-N2C2 atomic interface sites for efficient bifunctional oxygen reduction and evolution reaction. Nana Lett. 2020, 20, 5443–5450.

    CAS  Google Scholar 

  18. Wu, H. H.; Li, H. B.; Zhao, X. F.; Liu, Q. F.; Wang, J.; **ao, J. P.; **e, S. H.; Si, R.; Yang, F.; Miao, S. et al. Highly doped and exposed Cu(I)-N active sites within graphene towards efficient oxygen reduction for zinc-air batteries. Energy Environ. Sci. 2016, 9, 3736–3745.

    CAS  Google Scholar 

  19. Zhang, H. G.; Hwang, S.; Wang, M. Y.; Feng, Z. X.; Karakalos, S.; Luo, L. L.; Qiao, Z.; **e, X. H.; Wang, C. M.; Su, D. et al. Single atomic iron catalysts for oxygen reduction in acidic media: Particle size control and thermal activation. J. Am. Chem. Soc. 2017, 139, 14143–14149.

    CAS  Google Scholar 

  20. Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nana Res. 2019, 12, 2067–2080.

    CAS  Google Scholar 

  21. Mao, J. J.; Yin, J. S.; Pei, J. J.; Wang, D. S.; Li, Y. D. Single atom alloy: An emerging atomic site material for catalytic applications. Nana Today 2020, 34, 100917.

    CAS  Google Scholar 

  22. Sun, J. Q.; Lowe, S. E.; Zhang, L. J.; Wang, Y. Z.; Pang, K. L.; Wang, Y.; Zhong, Y. L.; Liu, P. R.; Zhao, K.; Tang, Z. Y. et al. Ultrathin nitrogen-doped holey carbon@graphene bifunctional electrocatalyst for oxygen reduction and evolution reactions in alkaline and acidic media. Angew. Chem., Int. Ed. 2018, 57, 16511–16515.

    CAS  Google Scholar 

  23. Shang, H. S.; Zhou, X. Y.; Dong, J. C.; Li, A.; Zhao, X.; Liu, Q. H.; Lin, Y.; Pei, J. J.; Li, Z. et al. Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity. Nat. Commun. 2020, 11, 3049.

    CAS  Google Scholar 

  24. Zhang, J.; Sun, Y. M.; Zhu, J. W.; Kou, Z. K.; Hu, P.; Liu, L.; Li, S. Z.; Mu, S. C.; Huang, Y. H. Defect and pyridinic nitrogen engineering of carbon-based metal-free nanomaterial toward oxygen reduction. Nano Energy 2018, 52, 307–314.

    CAS  Google Scholar 

  25. Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. Y.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634–641.

    CAS  Google Scholar 

  26. Zhou, M.; Jiang, Y.; Wang, G.; Wu, W. J.; Chen, W. X.; Yu, P.; Lin, Y. Q.; Mao, J. J.; Mao, L. Q. Single-atom Ni-N4 provides a robust cellular NO sensor. Nat. Commun. 2020, 11, 3188.

    CAS  Google Scholar 

  27. Tian, S. B.; Hu, M.; Xu, Q.; Gong, W. B.; Chen, W. X.; Yang, J. R.; Zhu, Y. Q.; Chen, C.; He, J.; Liu, Q. et al. Single-atom Fe with FeiN3 structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene. Sci. China Mater. 2020, 10.1007/s40843-020-1443-8.

    Google Scholar 

  28. Mao, J. J.; He, C. T.; Pei, J. J.; Liu, Y.; Li, J.; Chen, W. X.; He, D. S.; Wang, D. S.; Li, Y. D. Isolated Ni atoms dispersed on Ru nanosheets: High-performance electrocatalysts toward hydrogen oxidation reaction. Nano Lett. 2020, 20, 3442–3448.

    CAS  Google Scholar 

  29. Ma, W. J.; Mao. J. J.; Yang, X. T.; Pan, C.; Chen, W. X.; Wang, M.; Yu, P.; Mao, L. Q.; Li, Y. D. A single-atom Fe-N4 catalytic site mimicking bifunctional antioxidative enzymes for oxidative stress cytoprotection. Chem. Commun. 2019, 55, 159–162.

    CAS  Google Scholar 

  30. Zhang, J.; Zheng, C. Y.; Zhang, M. L.; Qiu, Y. J.; Xu, Q.; Cheong, W. C.; Chen, W. X.; Zheng, L. R.; Gu, L.; Hu, Z. P. et al. Controlling N-do** type in carbon to boost single-atom site Cu catalyzed transfer hydrogenation of quinoline. Nano Res. 2020, 13, 3082–3087.

    Google Scholar 

  31. Xu, Q.; Guo, C. X.; Tian, S. B.; Zhang, J.; Chen, W. X.; Cheong, W. C.; Gu, L.; Zheng, L. R.; **ao, J. P.; Liu, Q. et al. Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes. Sci. China Mater. 2020, 65, 972–981.

    Google Scholar 

  32. Mao, J. J.; He, C. T.; Pei, J. J.; Chen, W. X.; He, D. S.; He, Y. Q.; Zhuang, Z. B.; Chen, C.; Peng, Q.; Wang, D. S. et al. Accelerating water dissociation kinetics by isolating cobalt atoms into ruthenium lattice. Nat. Commun. 2018, 9, 4958.

    Google Scholar 

  33. Yang, J.; Qiu, Z. Y.; Zhao, C. M.; Wei, W. C.; Chen, W. X.; Li, Z. J.; Qu, Y. T.; Dong, J. C.; Luo, J.; Li, Z. Y. et al. In situ thermal atomization to convert supported nickel nanoparticles into surface-bound nickel single-atom catalysts. Angew. Chem., Int. Ed. 2018, 57, 14095–14100.

    CAS  Google Scholar 

  34. **ao, M. L.; Zhu, J. B.; Li, G. R.; Li, N.; Li, S.; Cano, Z. P.; Ma, L.; Cui, P. X.; Xu, P.; Jiang, G. P. et al. A single-atom iridium heterogeneous catalyst in oxygen reduction reaction. Angew. Chem., Int. Ed. 2019, 58, 9640–9645.

    CAS  Google Scholar 

  35. Zhu, C. Z.; Fu, S. F.; Shi, Q. R.; Du, D.; Lin, Y. H. Single-atom electrocatalysts. Angew. Chem., Int. Ed. 2017, 56, 13944–13960.

    CAS  Google Scholar 

  36. Li, J. Z.; Chen, M. J.; Cullen, D. A.; Hwang, S.; Wang, M. Y.; Li, B. Y.; Liu, K. X.; Karakalos, S.; Lucero, M.; Zhang, H. G. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 2018, 1, 935–945.

    CAS  Google Scholar 

  37. Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.

    CAS  Google Scholar 

  38. Qu, Y. T.; Li, Z. J; Chen, W. X.; Lin, Y.; Yuan, T. W.; Yang, Z. K.; Zhao, C. M.; Wang, J.; Zhao, C.; Wang, X. et al. Direct transformation of bulk copper into copper single sites via emitting and trap** of atoms. Nat. Catal. 2018, 1, 781–786.

    CAS  Google Scholar 

  39. Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.

    CAS  Google Scholar 

  40. Li, D. H.; Jia, Y.; Chang, G. J.; Chen, J.; Liu, H. W.; Wang, J. C.; Hu, Y. F.; **a, Y. Z.; Yang, D. J.; Yao, X. D. A defect-driven metal-free electrocatalyst for oxygen reduction in acidic electrolyte. Chem 2018, 4, 2345–2356.

    CAS  Google Scholar 

  41. Hammer, B.; Norskov, J. K. Why gold is the noblest of all the metals. Nature 1995, 376, 238–240.

    CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21804319 and 21971002), the Natural Science Foundation of Anhui province (Nos. 1908085QB45 and 2008085QB81) and the Education Department of Anhui Province Foundation (No. KJ2019A0503). We thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF) and 1W1B station for XAFS measurement in Bei**g Synchrotron Radiation Facility (BSRF). The calculations in this paper have been done on the supercomputing system of the National Supercomputing Center in Changsha.

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  1. Wenjie Wu and Yan Liu contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum, Bei**g, 102249, China

    Wenjie Wu, Zhaoyi Song, **min Wang & Chunxia Wang

  2. Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Province Key Laboratory of Optoelectric Materials Science and Technology and Anhui Laboratory of Molecule-Based Materials, Anhui Normal University, Wuhu, 241002, China

    Yan Liu, Yamin Zheng, Ning Lu & Junjie Mao

  3. State key Lab of Organic-Inorganic Composites, Bei**g University of Chemical Technology, Bei**g, 100029, China

    Dong Liu

  4. Bei**g Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Bei**g Institute of Technology, Bei**g, 100081, China

    Wenxing Chen

  5. Department of Chemistry, Tsinghua University, Bei**g, 100084, China

    Yadong Li

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  1. Wenjie Wu
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Correspondence to Chunxia Wang or Junjie Mao.

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Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

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Wu, W., Liu, Y., Liu, D. et al. Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery. Nano Res. 14, 998–1003 (2021). https://doi.org/10.1007/s12274-020-3141-x

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