Abstract
AbstractSingle-atom catalysts are becoming increasingly significant to numerous energy conversion reactions. However, their rational design and construction remain quite challenging due to the poorly understood structure–function relationship. Here we demonstrate the dynamic behavior of CuN2C2 site during operando oxygen reduction reaction, revealing a substrate-strain tuned geometry distortion of active sites and its correlation with the activity. Our best CuN2C2 site, on carbon nanotube with 8 nm diameter, delivers a sixfold activity promotion relative to graphene. Density functional theory and X-ray absorption spectroscopy reveal that reasonable substrate strain allows the optimized distortion, where Cu bonds strongly with the oxygen species while maintaining intimate coordination with C/N atoms. The optimized distortion facilitates the electron transfer from Cu to the adsorbed O, greatly boosting the oxygen reduction activity. This work uncovers the structure–function relationship of single-atom catalysts in terms of carbon substrate, and provides guidance to their future design and activity promotion.
Funder
National Natural Science Foundation of China
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry
Reference56 articles.
1. Zhang, J. et al. Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions. J. Am. Chem. Soc. 141, 20118–20126 (2019).
2. Chen, Y. et al. Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell. Nat. Commun. 9, 5422 (2018).
3. Jiang, H.-L. et al. From MOFs to single Fe atoms implanted n-doped porous carbons: efficient oxygen reduction in both alkaline and acidic media. Angew. Chem. Int. Ed. 9, 819–830 (2018).
4. Hou, Y. et al. Atomically dispersed nickel–nitrogen–sulfur species anchored on porous carbon nanosheets for efficient water oxidation. Nat. Commun. 10, 1392 (2019).
5. Cao, L. et al. Dynamic oxygen adsorption on single-atomic ruthenium catalyst with high performance for acidic oxygen evolution reaction. Nat. Commun. 10, 4849 (2019).
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