Understanding the sulphur-oxygen exchange process of metal sulphides prior to oxygen evolution reaction

AbstractDynamic reconstruction of metal sulphides during electrocatalytic oxygen evolution reaction (OER) has hampered the acquisition of legible evidence for comprehensively understanding the phase-transition mechanism and electrocatalytic activity origin. Herein, modelling on a series of cobalt-nickel bimetallic sulphides, we for the first time establish an explicit and comprehensive picture of their dynamic phase evaluation pathway at the pre-catalytic stage before OER process. By utilizing the in-situ electrochemical transmission electron microscopy and electron energy loss spectroscopy, the lattice sulphur atoms of (NiCo)S1.33particles are revealed to be partially substituted by oxygen from electrolyte to form a lattice oxygen-sulphur coexisting shell surface before the generation of reconstituted active species. Such S-O exchange process is benefitted from the subtle modulation of metal-sulphur coordination form caused by the specific Ni and Co occupation. This unique oxygen-substitution behaviour produces an (NiCo)OxS1.33-xsurface to reduce the energy barrier of surface reconstruction for converting sulphides into active oxy/hydroxide derivative, therefore significantly increasing the proportion of lattice oxygen-mediated mechanism compared to the pure sulphide surface. We anticipate this direct observation can provide an explicit picture of catalysts’ structural and compositional evolution during the electrocatalytic process.

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Published: Apr 07, 2023
Vol/Issue: 14(1)
License: View

Authors

Y

Yang Hu

Comprehensive Cancer Center and Departments of Internal Medicine, Pharmacology, and Medicinal Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States

Centre for Systems Biology, Samuel Lunenfeld Research Institute, Mount Sinai Hospital, 600 University Avenue, Toronto, Ontario, Canada M5G 1X5.

Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, College of Light Industry and Food, Nanjing Forestry University, Nanjing 210037, China

W

Wei Shen

1Medical Oncology, Departments of

Y

Yichao Hou

Department of Nutrition and Health, Key Laboratory of Functional Dairy China Agricultural University Beijing China

State Key Laboratory of Applied Organic Chemistry Frontiers Science Center for Rare Isotopes College of Chemistry and Chemical Engineering Lanzhou University Lanzhou 730000 P. R. China

M

Min Lu

*Department of Biochemistry, Weill Medical College of Cornell University, New York, NY 10021; and

P

Pinxian Xi

State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.

C

Chun-Hua Yan

Beijing National Laboratory for Molecular Sciences, State Key Lab of Rare Earth Materials Chemistry and Applications & PKU-HKU Joint Lab in Rare Earth Materials and Bioinorganic Chemistry, Peking University, Beijing 100871, China

Cite This Article

Yang Hu, Yao Zheng, Jing Jin, et al. (2023). Understanding the sulphur-oxygen exchange process of metal sulphides prior to oxygen evolution reaction. Nature Communications, 14(1). https://doi.org/10.1038/s41467-023-37751-y

Understanding the sulphur-oxygen exchange process of metal sulphides prior to oxygen evolution reaction

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