Optimizing d-Orbital Electronic Configuration via Metal-Metal Oxide Core-Shell Charge Donation for Boosting Reversible Oxygen Electrocatalysis

被引:44
作者
Wu, Wei [1 ]
Chen, Runzhe [1 ]
Chen, Suhao [1 ]
Wang, Zichen [1 ]
Cheng, Niancai [1 ,2 ]
机构
[1] Fuzhou Univ, Coll Mat Sci & Engn, Fuzhou 350108, Peoples R China
[2] Key Lab Fuel Cell Technol Guangdong Prov, Guangzhou 510641, Peoples R China
基金
中国国家自然科学基金;
关键词
core-shell nanoparticles; d-orbital electronic configuration; oxygen electrocatalytic reactions; oxygen vacancies; zinc-air batteries; N-DOPED CARBON; CATALYTIC-ACTIVITY; SPIN-STATE; REDUCTION; NANOPARTICLES; NANOCRYSTALS;
D O I
10.1002/smll.202300621
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Tuning the d-orbital electronic configuration of active sites to achieve well-optimized adsorption strength of oxygen-containing intermediates toward reversible oxygen electrocatalysis is desirable for efficient rechargeable Zn-Air batteries but extremely challenging. Herein, this work proposes to construct a Co@Co3O4 core-shell structure to regulate the d-orbital electronic configuration of Co3O4 for the enhanced bifunctional oxygen electrocatalysis. Theoretical calculations first evidence that electron donation from Co core to Co3O4 shell could downshift the d-band center and simultaneously weak spin state of Co3O4, result in the well-optimized adsorption strength of oxygen-containing intermediates on Co3O4, thus contributing a favor way for oxygen reduction/evolution reaction (ORR/OER) bifunctional catalysis. As a proof-of-concept, the Co@Co3O4 embedded in Co, N co-doped porous carbon derived from thickness controlled 2D metal-organic-framework is designed to realize the structure of computational prediction and further improve the performance. The optimized 15Co@Co3O4/PNC catalyst exhibits the superior bifunctional oxygen electrocatalytic activity with a small potential gap of 0.69 V and a peak power density of 158.5 mW cm(-2) in ZABs. Moreover, DFT calculations shows that the more oxygen vacancies on Co3O4 contribute too strong adsorption of oxygen intermediates which limit the bifunctional electrocatalysis, while electron donation in the core-shell structure can alleviate the negative effect and maintain superior bifunctional overpotential.
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页数:10
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