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Research Article

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

Ning Kang1, Lingwen Liao2, Xue Zhang1, Zhen He3,4, Binlu Yu1, Jiahong Wang1, Yongquan Qu5, Paul K. Chu6, Seeram Ramakrishna7, Xue-Feng Yu1, Xin Wang1( ), Licheng Bai1( )
Materials Interfaces Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences (CAS), Shenzhen 518055, China
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
Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong 999077, China
Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Kowloon, Hong Kong 999077, China
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
Department of Physics and Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong 999077, China
National University of Singapore (NUS) Centre for Nanofibers and Nanotechnology, Department of Mechanical Engineering, National University of Singapore, Singapore 117542, Singapore
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Graphical Abstract

An axial Co–S bond was designed to tailor the charge density of active Co single atom anchored onto graphite carbon nitride (C3N4) nanosheets to generate Co-(N, S)/C3N4 photocatalyst in ambient condition for highly efficient photocatalytic H2 evolution. Owing to the delicate optimization of charge density to an intermediate level by axial Co–S bond, extremely high H2 production was obtained, which is even superior to C3N4/Pt and transition metal/C3N4 single atom photocatalysts in reported works.

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/(g·h), 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.

Keywords

transition metal single-atomlocal electronic structurephotocatalytic hydrogen evolutiongraphitic carbon nitrideaxial coordination environment

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Nano Research
Volume 17 Issue 6,
June 2024
Pages 5114-5121
DOI: 10.1007/s12274-024-6411-1
Cite this article:
Kang N, Liao L, Zhang X, et al. Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution. Nano Research, 2024, 17(6): 5114-5121. https://doi.org/10.1007/s12274-024-6411-1
Topics:
Hydrogen economy

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Received: 22 August 2023
Revised: 21 November 2023
Accepted: 12 December 2023
Published: 13 January 2024
© Tsinghua University Press 2024
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