Engineering of Electronic States on Co<sub>3</sub>O<sub>4</sub> Ultrathin Nanosheets by Cation Substitution and Anion Vacancies for Oxygen Evolution Reaction

Authors: Qichen Wang, Xiongxiong Xue, Yongpeng Lei, Yuchao Wang, Yexin Feng, Xiang Xiong, Dingsheng Wang, Yadong Li

Published: 2020-05-11

DOI: 10.1002/smll.202001571

Source: Full article


Abstract

AbstractDue to the earth abundance and tunable electronic properties, etc., transition metal oxides (TMOs) show attractive attention in oxygen evolution reaction. O‐vacancies (Vo) play important roles in tailoring the local surface and electronic environment to lower the activation barriers. Herein, an effective strategy is shown to enhance the oxygen evolution reduction (OER) performance on Co3O4 ultrathin nanosheets via combined cation substitution and anion vacancies. The oxygen‐deficient Fe‐Co‐O nanosheets (3–4 nm thickness) display an overpotential of 260 mV@10 mA cm−2 and a Tafel slope of 53 mV dec−1, outperforming those of the benchmark RuO2 in 1.0 m KOH. Further calculations demonstrate that the combined introduction of Fe cation and Vo with appropriate location and content finely tune the intermediate absorption, consequently lowering the rate‐limiting activation energy from 0.82 to as low as 0.15 eV. The feasibility is also proved by oxygen‐deficient Ni‐Co‐O nanosheets. This work not only establishes a clear atomic‐level correlation between cation substitution, anion vacancies, and OER performance, but also provides valuable insights for the rational design of highly efficient catalysts for OER.