期刊
ACS APPLIED MATERIALS & INTERFACES
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.2c15524
关键词
multi-structural defects; CuCo2O4; electrocatalysis; structural defect; OER
资金
- National Natural Science Foundation of China
- Natural Science Foundation of Hunan Province, China
- Natural Science Founda-tion of Guizhou Province, China
- Research Foundation of Education Bureau of Guizhou Province, China
- [51871097]
- [2019JJ40033]
- [2022JJ40072]
- [ZK [2022] 547]
- [ZK [2022] 551]
- [[2022] 057]
By doping with vanadium and adjusting the structure, a V-doped CuCo2O4 nanoneedle with rich oxygen vacancies, partially amorphous phase, and Co2+ defects was synthesized, which exhibits enhanced oxygen evolution reaction (OER) activity due to the abundant active sites.
Rational design of multi-structural defects in the transition-metal oxides is a very alluring and challenging strategy to significantly improve its oxygen evolution reaction (OER) performance. Herein, a simple and promising element doping approach is demonstrated to fabricate a poor-crystalline V-doping CuCo2O4 (V-CuCo2O4) nanoneedle with rich oxygen vacancies (V-o), partially amorphous phase, and Co2+ defects on the carbon fiber (CF) (V-CuCo2O4/CF). The results indicate that the V doping could further weaken the crystallinity of V-CuCo2O4, providing the thoroughfares for the convenience of electrolyte penetration and the exposure of active sites. Meanwhile, [CoO6] octahedron in the V-CuCo2O4 lattice is gravely distorted due to a strong electronic interaction between the doped V and Co atoms, creating more Co2+ active species. With the merits of these multiple structural defects, V-CuCo2O4/CF exhibits rich active sites, and its intrinsically electrocatalytic activity is significantly enhanced. The optimized V-CuCo2O4/CF electrocatalyst has a significantly enhanced OER activity with a required low overpotential of similar to 204 and similar to 246 mV at a current density of 100 and 300 mA cm(-2), respectively, a small Tafel slope of 40.7 mV dec(-1), and excellent stability in an alkaline medium. Furthermore, the results from the projected partial density of states calculation not only demonstrate that the 3-fol-coordinated Co near Vo bonded with Cu and V sites (Cu-Co(surf-Vo)-V) exhibits an enhanced electronic transfer activity but also reveal that the doped V could protect the Co sites from the deactivation by intermediates overbinding on the V sites. This work provides new insights into structure engineering of spinel phase copper cobaltite, resulting in significantly boosting electrocatalytic OER activity.
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