Qi Defeng, Xu Jie, Zhou Yitong, Zhang Hao, Shi Jianqiao, He Kun, Yuan Yifei, Luo Jun, Wang Shun, Wang Yong
Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, P. R. China.
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China.
Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202307355. doi: 10.1002/anie.202307355. Epub 2023 Aug 4.
Co-based material catalysts have shown attractive application prospects in the 2 e oxygen reduction reaction (ORR). However, for the industrial synthesis of H O , there is still lack of Co-based catalysts with high production yield rate. Here, novel cyclodextrin-supported Co(OH) cluster catalysts were prepared via a mild and facile method. The catalyst exhibited remarkable H O selectivity (94.2 % ~ 98.2 %), good stability (99 % activity retention after 35 h), and ultra-high H O production yield rate (5.58 mol g h in the H-type electrolytic cell), demonstrating its promising industrial application potential. Density functional theory (DFT) reveals that the cyclodextrin-mediated Co(OH) electronic structure optimizes the adsorption of OOH* intermediates and significantly enhances the activation energy barrier for dissociation, leading to the high reactivity and selectivity for the 2 e ORR. This work offers a valuable and practical strategy to design Co-based electrocatalysts for H O production.
钴基材料催化剂在二电子氧还原反应（ORR）中展现出了诱人的应用前景。然而，对于工业合成过氧化氢而言，仍缺乏高产率的钴基催化剂。在此，通过一种温和简便的方法制备了新型环糊精负载的氢氧化钴簇催化剂。该催化剂表现出显著的过氧化氢选择性（94.2% ~ 98.2%）、良好的稳定性（35小时后活性保留99%）以及超高的过氧化氢产率（在H型电解槽中为5.58 mol g⁻¹ h⁻¹），证明了其具有广阔的工业应用潜力。密度泛函理论（DFT）表明，环糊精介导的氢氧化钴电子结构优化了OOH*中间体的吸附，并显著提高了解离的活化能垒，从而导致对二电子ORR具有高反应活性和选择性。这项工作为设计用于生产过氧化氢的钴基电催化剂提供了一种有价值且实用的策略。
