Introducing anion and cation vacancies into Co-based oxides is a promising strategy to promote their catalytic activity. However, the mild and effective methods for synthesizing cobalt oxide and vacancies are rarely proposed. In this work, via an innovative one-step hydrothermal process, we synthesized Co3O4-based catalyst, which was successively proven rich with oxygen vacancies (VO) and cobalt vacancies (VCo). As an electrocatalyst for benzyl alcohol (BA) oxidation, the vacancy-rich Co3O4 on nickel foam (NF) with optimized electronic structure displayed a super high conversion (> 99%) and selectivity (> 99%) for benzoic acid (BAc) with excellent recyclability, representing one of the best Co‐based catalysts. X-ray photoelectron spectroscopy (XPS) and X-ray adsorption near-edge structure (XANES) technologies coupled with density functional theory calculations (DFT) demonstrated the obvious electronic delocalization caused by vacancies not only lowered the adsorption energy of BA and improved the intrinsic activity of catalytic Co sites for faster reaction kinetics, but also narrowed the band gap for better electrical conductivity. This work opens up a new simple synthetic idea to construct the high-performance electrocatalysts by tuning electronic structure.

中文翻译：

---

一步水热法合成镍泡沫上的多空位 Co3O4 用于高效电催化苯甲醇氧化

将阴离子和阳离子空位引入 Co 基氧化物是提高其催化活性的有前途的策略。然而，很少有人提出合成氧化钴和空位的温和有效的方法。在这项工作中，我们通过创新的一步水热工艺合成了基于 Co3O4 的催化剂，该催化剂先后被证明富含氧空位 (VO) 和钴空位 (VCo)。作为苯甲醇 (BA) 氧化的电催化剂，具有优化电子结构的泡沫镍 (NF) 上的富空位 Co3O4 显示出对苯甲酸 (BAc) 的超高转化率 (> 99%) 和选择性 (> 99%)优异的可回收性，是最好的钴基催化剂之一。X射线光电子能谱（XPS）和X射线吸附近边结构（XANES）技术结合密度泛函理论计算（DFT）证明了由空位引起的明显电子离域不仅降低了BA的吸附能，而且提高了本征催化 Co 位点的活性以加快反应动力学，但也缩小了带隙以获得更好的导电性。这项工作开辟了一个新的简单合成思路，通过调整电子结构来构建高性能电催化剂。