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Accelerated kinetics of alkaline hydrogen evolution/oxidation reactions on dispersed ruthenium sites through N and S dual coordination

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Abstract

Efficient, robust and cost-effective electrocatalysts that catalyze hydrogen evolution/oxidation reaction (HER/HOR) in alkaline media are highly demanded. Recently, single-atom catalysts (SACs) have emerged as new promising candidates; however, the rational design of supports and the optimization of coordination environment between supports and metal atoms are challenging. In this work, we successfully fabricate atomically dispersed ruthenium (Ru) species, which are strongly coordinated by N and S dual heteroatoms on holey graphene (RuSA/NSG), as an excellent bifunctional catalyst for HER/HOR. In alkaline media, the developed catalyst exhibits high catalytic performance with a low overpotential of 57.3 mV to drive a current density of 10 mA cm−1 for HER, and its mass activity is about 5.8 times higher than that of commercial Pt/C and Ru/C catalysts at an overpotential of 100 mV. Similarly, considerable HOR performance of RuSA/NSG is verified to be superior to Pt/C and Ru/C. Furthermore, X-ray-based spectroscopy measurements and density-functional theory calculations have confirmed that, compared with Ru-N4, the tailored Ru-N4-S2 with nearby S dopants can act as more active centers to greatly accelerate the sluggish HER/HOR kinetics in alkaline media. The present work provides a new atomic-level engineering strategy to modulate catalytic activities of SACs via the coordination design using dual heteroatoms on the carbon support.

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Acknowledgements

This work was supported by Center for Computational Science and Engineering at Southern University of Science and Technology. This work was financially supported by the National Key Research and Development Program of China (2018YFB1502503), Guangdong Provincial Key Laboratory of Energy Materials for Electric Power (2018B030322001), Shenzhen Key Laboratory Project (ZDSYS201603311013489), Shenzhen Science and Technology Projects for Sustainable Development (KCXFZ202002011010317), the Foundation Research Project of Shenzhen (JCYJ20200109141216566).

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Author notes

  1. These authors contributed equally to the work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, 150001, China

    Zhen Zhang

  2. Department of Materials Science and Engineering, Shenzhen Key Laboratory of Hydrogen Energy, Southern University of Science and Technology, Shenzhen, 518055, China

    Zhen Zhang, Liwen Ni, Zhi-Liang Zhao & Hui Li

  3. Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055, China

    Haijun Liu

  4. Research Center of Energy, Mining and Environment, National Research Council Canada, 4250 Wesbrook Mall, Vancouver, V6T1W5, Canada

    Xiao-Zi Yuan

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  1. Zhen Zhang
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  2. Liwen Ni
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  3. Haijun Liu
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  4. Zhi-Liang Zhao
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Correspondence to Hui Li.

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11426_2021_1190_MOESM1_ESM.docx

Accelerated kinetics of alkaline hydrogen evolution/oxidation reactions on dispersed ruthenium sites through N and S dual coordination

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Zhang, Z., Ni, L., Liu, H. et al. Accelerated kinetics of alkaline hydrogen evolution/oxidation reactions on dispersed ruthenium sites through N and S dual coordination. Sci. China Chem. 65, 611–618 (2022). https://doi.org/10.1007/s11426-021-1190-7

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