Mechanistic Regulation by Oxygen Vacancies in Structural Evolution Promoting Electrocatalytic Water Oxidation

Zhou, Dinghua1; Li, Fusheng1; Zhao, Yilong1; Wang, Linqin2; Zou, Haiyuan3,4; Shan, Yu1; Fu, Junwei5; Ding, Yunxuan2; Duan, Lele3,4; Liu, Min5; Sun, Licheng1,2; Fan, Ke1

2023-03-01

10.1021/acscatal.2c06339

ACS CATALYSIS   Impact Factor & Quartile

2155-5435

Introduction of oxygen vacancies (Vo) has been considered an effective strategy for promoting the oxygen evolution reaction (OER) performance of electrocatalysts. However, the role of Vo in improving OER activity is unclear. Herein, a Vo-rich spinel Co3O4 was used as a model catalyst to explore the mechanism of Vo in structural evolution during OER. The results suggest that the Vo-rich environment facilitates the reconstruction of Co3O4 to the Co(OH)2 intermediate with proton vacancies (Co(II)Ox(OH)y), which is favorable for the formation of the active species of CoOOH. Correlative operando characterizations and electrokinetic analyses indicate that a moderate Vo density can switch the O-O bond formation pathway, from a water nucleophilic attack to an intramolecular nucleophilic attack pathway, which is more kinetically favorable for water oxidation. However, a high Vo density quenches the formation of highly valent active intermediates. This study provides significant insights into the crucial role of vacancy defects during OER.

oxygen vacancy Co3O4 operando O-O bond formation reconstruction

SCI

English

Others

National Key R&D Program of China["2022YFA0911900","2022YFA0911904"] ; National Natural Science Foundation of China["22088102","22172011","21872174","22002189","U1932148"] ; Fundamental Research Funds for the Central Universities["DUT22LK01","DUT22QN213"] ; Natural Science Foundation of Liaoning Province[2021-MS-126] ; International Science and Technology Cooperation Program["2017YFE0127800","2018YFE0203402"] ; Hunan Provincial Key Research and Development Program[2020WK2002] ; Hunan Provincial Natural Science Foundation of China["2020JJ2041","2020JJ5691"] ; Shenzhen Science and Technology Innovation Project[JCYJ20180307151313532] ; Zhejiang Province Selected Funding for Postdoctoral Research Projects[ZJ2021001]

Chemistry

Chemistry, Physical

WOS:000954979600001

AMER CHEMICAL SOC

Web of Science

1.Dalian Univ Technol, Inst Artificial Photosynth, Inst Energy Sci & Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China
2.Westlake Univ, Ctr Artificial Photosynth Solar Fuels, Sch Sci, Hangzhou 310024, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Energy Mat Elect Power, Shenzhen 518055, Peoples R China
5.Cent South Univ, Hunan Joint Int Res Ctr Carbon Dioxide Resource Ut, Sch Phys & Elect, State Key Lab Powder Met, Changsha 410083, Hunan, Peoples R China

Zhou, Dinghua,Li, Fusheng,Zhao, Yilong,et al. Mechanistic Regulation by Oxygen Vacancies in Structural Evolution Promoting Electrocatalytic Water Oxidation[J]. ACS CATALYSIS,2023.

Zhou, Dinghua.,Li, Fusheng.,Zhao, Yilong.,Wang, Linqin.,Zou, Haiyuan.,...&Fan, Ke.(2023).Mechanistic Regulation by Oxygen Vacancies in Structural Evolution Promoting Electrocatalytic Water Oxidation.ACS CATALYSIS.

Zhou, Dinghua,et al."Mechanistic Regulation by Oxygen Vacancies in Structural Evolution Promoting Electrocatalytic Water Oxidation".ACS CATALYSIS (2023).