Affiliation:
1. State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical Engineering Frontiers Science Centre for Rare Isotopes Lanzhou University Lanzhou 730000 China
2. School of Chemical Engineering and Advanced Materials The University of Adelaide Adelaide South Australia 5005 Australia
3. Beijing National Laboratory for Molecular Sciences State Key Laboratory of Rare Earth Materials Chemistry and Applications PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry College of Chemistry and Molecular Engineering Peking University Beijing 100871 China
Abstract
AbstractIon regulation strategy is regarded as a promising pathway for designing transition metal oxide‐based electrocatalysts for oxygen evolution reaction (OER) with improved activity and stability. Precise anion conditioning can accurately change the anionic environment so that the acid radical ions (SO42−, PO32−, SeO42−, etc.), regardless of their state (inside the catalyst, on the catalyst surface, or in the electrolyte), can optimize the electronic structure of the cationic active site and further increase the catalytic activity. Herein, we report a new approach to encapsulate S atoms at the tetrahedral sites of the NaCl‐type oxide NiO to form a tetraoxo‐tetrahedral coordination structure (S‐O4) inside the NiO (S‐NiO ‐I). Density functional theory (DFT) calculations and operando vibrational spectroscopy proves that this kind of unique structure could achieve the S‐O4 and Ni‐S stable structure in S‐NiO‐I. Combining mass spectroscopy characterization, it could be confirmed that the S‐O4 structure is the key factor for triggering the lattice oxygen exchange to participate in the OER process. This work demonstrates that the formation of tetraoxygen tetrahedral structure is a generalized key for boosting the OER performances of transition metal oxides.
Funder
National Natural Science Foundation of China
Key Technology Research and Development Program of Shandong Province