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Working-in-tandem mechanism of multi-dopants in enhancing electrocatalytic nitrogen reduction reaction performance of carbon-based materials

Abstract

Developing carbon-based electrocatalysts with excellent N2 adsorption and activation capability holds the key to achieve highly efficient nitrogen reduction reaction (NRR) for reaching its practical application. Here, we report a highly active electrocatalyst—metal-free pyrrolic-N dominated N, S co-doped carbon (pyrr-NSC) for NRR. Based on theoretical and experimental results, it is confirmed that the N and S-dopants practice a working-in-tandem mechanism on pyrr-NSC, where the N-dopants are utilized to create electropositive C sites for enhancing N2 adsorption and the S-dopants are employed to induce electron backdonation for facilitating N2 activation. The synergistic effect of the pyrrolic-N and S-dopants can also suppress the irritating hydrogen evolution reaction, further boosting the NRR performance. This work gives an indication that the combination of two different dopants on electrocatalyst can enhance NRR performance by working in the two tandem steps—the adsorption and activation of N2 molecules, providing a new strategy for NRR electrocatalyst design.

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Acknowledgements

This work was financially supported in part by the National Key R&D Program of China (No. 2017YFA0207301), the National Natural Science Foundation of China (Nos. 21725102, U1832156, 91961106, 22075267, and 21950410514), CAS Key Research Program of Frontier Sciences (No. QYZDB-SSW-SLH018), CAS Interdisciplinary Innovation Team, Science and Technological Fund of Anhui Province for Outstanding Youth (No. 2008085J05), Youth Innovation Promotion Association of CAS (No. 2019444), Chinese Academy of Sciences President’s International Fellowship Initiative (Nos. 2019PC0114 and 2020T130627), China Postdoctoral Science Foundation (No. 2019M652190), Young Elite Scientist Sponsorship Program by CAST, and DNL Cooperation Fund, CAS (No. DNL201922). DRIFTS and SVUV-PIMS measurements were performed at BL01B and BL04B in the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China. We thank the support from USTC Center for Micro- and Nanoscale Research and Fabrication.

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Correspondence to Ran Long or Yujie Xiong.

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Working-in-tandem mechanism of multi-dopants in enhancing electrocatalytic nitrogen reduction reaction performance of carbon-based materials

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Zhang, W., Mao, K., Low, J. et al. Working-in-tandem mechanism of multi-dopants in enhancing electrocatalytic nitrogen reduction reaction performance of carbon-based materials. Nano Res. 14, 3234–3239 (2021). https://doi.org/10.1007/s12274-021-3315-1

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Keywords

  • N2 reduction reaction
  • metal-free catalyst
  • heteroatoms doping
  • asymmetric charge distribution
  • electrocatalysis