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Accelerating water dissociation kinetics of Ni3N by tuning interfacial orbital coupling

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Abstract

The high unoccupied d band energy of Ni3N basically results in weak orbital coupling with water molecule, consequently leading to slow water dissociation kinetics. Herein, we demonstrate Cr doping can downshift the unoccupied d orbitals and strengthen the interfacial orbital coupling to boost the water dissociation kinetics. The prepared Cr-Ni3N/Ni displays an impressive overpotential of 37 mV at 10 mA·cmgeo−2, close to the benchmark Pt/C in 1.0 M KOH solution. Refined structural analysis reveals the Cr dopant exists as the Cr-N6 states and the average d band energy of Ni3N is also lowered. Density functional theory calculation further confirms the downshifted d band energy can strengthen the orbital coupling between the unpaired electrons in O 2p and the unoccupied state of Ni 3d, which thus facilitates the water adsorption and dissociation. The work provides a new concept to achieve on-demand functions for hydrogen evolution catalysis and beyond, by regulating the interfacial orbital coupling.

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Acknowledgements

The work was supported by the National Natural Science Foundation of China (Nos. 21771169 and 11722543), the National Key Research and Development Program of China (No. 2017YFA0206703), Anhui Provincial Natural Science Foundation (No. BJ2060190077), Collaborative Innovation Program of Hefei Science Center, CAS, and the Fundamental Research Funds for the Central Universities (Nos. WK2060190074, WK2060190081, WK2310000066, and WK2060000015). We also appreciate the Shanghai Synchrotron Radiation Facility (BL14W1, SSRF) and the Hefei National Synchrotron Radiation Laboratory (BL10B, NSRL) for the help in XAFS, UPS and XPS characterizations. The computational research in this paper has been done on the supercomputing system in the Supercomputing Center of University of Science and Technology of China.

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  1. Yishang Wu and Yufang Xie contributed equally to this work.

Authors and Affiliations

  1. Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China

    Yishang Wu, Yufang Xie, Shuwen Niu, Yipeng Zang, Jinyan Cai, Zenan Bian, Xuanwei Yin, Yanyan Fang, Da Sun, Di Niu, Zheng Lu, Amirabbas Mosallanezhad & Gongming Wang

  2. Experimental Center of Engineering and Material Science, University of Science and Technology of China, Hefei, 230026, China

    Huijuan Wang

  3. School of Materials Science and Engineering, Jiangsu University, Zhenjiang, 212013, China

    Dewei Rao

  4. Institute of Science and Technology for New Energy, Xi’an Technological University, Xi’an, 710021, China

    Hongge Pan

  5. School of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, 310027, China

    Hongge Pan

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  1. Yishang Wu
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Correspondence to Shuwen Niu, Dewei Rao or Gongming Wang.

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Wu, Y., Xie, Y., Niu, S. et al. Accelerating water dissociation kinetics of Ni3N by tuning interfacial orbital coupling. Nano Res. 14, 3458–3465 (2021). https://doi.org/10.1007/s12274-021-3562-1

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