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Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution

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Abstract

Improving the catalytic activity of non-noble metal single atom catalysts (SACs) has attracted considerable attention in materials science. Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity, it often involves in-plane modulation and requires high temperatures. Herein, we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co–S bond anchored onto graphitic carbon nitride (C3N4) at room temperature (RT). Each Co atom is bonded to four N atoms and one S atom (Co-(N, S)/C3N4). Owing to the greater electronegativity of S in the Co–S bond, the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level. Consequently, when employed for the photocatalytic hydrogen evolution reaction, the adsorption energy of intermediate hydrogen (H*) on the Co atoms is remarkably low. In the presence of the Co-(N, S)/C3N4 SACs, the hydrogen evolution rates reach up to 10 mmol/(gh), which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C3N4 and noble platinum nanoparticles (PtNPs)/C3N4 catalysts, respectively. Attributed to the tailorable axial Co-S bond in the SAC, the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions. This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (No. 22008251), Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515010318), and Shenzhen Science and Technology Program (No. JCYJ20220531095813031). The authors thank the Beijing Synchrotron Radiation Facility (beamline 1W1B) for the use of the instruments.

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Authors and Affiliations

  1. Materials Interfaces Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences (CAS), Shenzhen, 518055, China

    Ning Kang, Xue Zhang, Binlu Yu, Jiahong Wang, Xue-Feng Yu, Xin Wang & Licheng Bai

  2. Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China

    Lingwen Liao

  3. Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong, 999077, China

    Zhen He

  4. Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Kowloon, Hong Kong, 999077, China

    Zhen He

  5. Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an, 710072, China

    Yongquan Qu

  6. Department of Physics and Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong, 999077, China

    Paul K. Chu

  7. National University of Singapore (NUS) Centre for Nanofibers and Nanotechnology, Department of Mechanical Engineering, National University of Singapore, Singapore, 117542, Singapore

    Seeram Ramakrishna

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  1. Ning Kang
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  11. Xin Wang
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Correspondence to Xin Wang or Licheng Bai.

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Kang, N., Liao, L., Zhang, X. et al. Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution. Nano Res. 17, 5114–5121 (2024). https://doi.org/10.1007/s12274-024-6411-1

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