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A Numerical Prediction of 4th-Order Kinetics for Photocatalytic Oxygen Evolution Reactions

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Abstract

Multiple-step mechanisms have been extensively proposed in many electrocatalytic and/or photocatalytic oxygen evolution reactions. But the surface charge reaction is less studied quantitatively. More difficultly, the verification methods for new multiple-step photocatalytic reactions are rarely found, which could be one of the main reasons for the insufficient reaction mechanism study. In this work, we aim to elucidate the rate-law relationship of the multiple-charge reactions, which is derived based on the microkinetics calculation on the photophysical redox reactions using pre-equilibrium approximation and steady-state approximation. The numerical analysis demonstrates that an nth-order feature could be observed when the nth-step is a rate-determined step in a multiple-step reaction. Likely, the 4th-order charge transfer could be possibly found for oxygen evolution reaction, suggesting the analytical methods and results could further boost the fundamental studies in photocatalysts and multiple-step reactions.

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Data Availability

The datasets generated during and/or analysed during the current study are not publicly available due financial support, but are available from the corresponding author on reasonable request.

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Acknowledgements

This work is supported financially by the National Natural Science Foundation of China (Project. No. 22008163 and U1604121), the projects (20KJB150042 and 21KJB150038) from Natural Science Research Project of Higher Education Institutions in Jiangsu Province and the projects from Natural Science Foundation of Jiangsu Province (BK20210867 and BK20180103). We thank Mr. Xinwei Wang for checking the equations.

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Authors and Affiliations

  1. Institute of Materials Science and Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, 1 Kerui Road, Suzhou, 215011, China

    Guangming Cao, Jundie Hu, Jiafu Qu & Xiaogang Yang

  2. School of Physical Science and Technology, Suzhou University of Science and Technology, 1 Kerui Road, Suzhou, 215011, China

    Guangming Cao

  3. Institute of Advanced Cross-Field Science, College of Life Science, Qingdao University, Qingdao, 266071, China

    Jiaqi Jin

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Cao, G., Hu, J., Qu, J. et al. A Numerical Prediction of 4th-Order Kinetics for Photocatalytic Oxygen Evolution Reactions. Catal Lett 153, 138–149 (2023). https://doi.org/10.1007/s10562-022-03959-8

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  • DOI: https://doi.org/10.1007/s10562-022-03959-8

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