分解水
光催化
析氧
吡啶
密度泛函理论
活动站点
材料科学
催化作用
质子化
光化学
光催化分解水
吸附
化学物理
化学
化学工程
计算化学
物理化学
有机化学
工程类
离子
电化学
电极
作者
Rui Zhang,Zhao‐Di Yang,Yan Yang,Fengming Zhang,Guiling Zhang
标识
DOI:10.1021/acsami.3c14311
摘要
Overcoming the sluggish reaction kinetics of the oxygen evolution reaction (OER) is a determining factor for the practical application of photocatalysts for overall water splitting. Two-dimensional covalent organic frameworks (2D-COFs) offer an ideal platform for catalyst design in the field of overall water splitting for their exceptional chemical tunability and high efficiency of light capture. In this work, four β-ketoamine 2D-COFs, consisting of 1,3,5-triformylphloroglucinol (Tp) groups and different linkers with pyridine segments, were constructed and optimized. By means of first-principles calculations, the band structures, free energy changes of photocatalytic hydrogen evolution reaction (HER) and OER, and charge density distributions were calculated and investigated systemically to discuss the visible-light response, overall water splitting activities on active sites, and the characteristic of charge transfer and separation. The protonated pyridine N derived from the double-H2O closed-ring H-bond adsorption model could efficiently induce N-C sites' synergistic effect between pyridine N and its ortho-position C to minimize the OER energy barrier and to enhance the charge transfer and separation. A N-C site synergistic mechanism has been proposed to provide a comprehensive explanation for the experimental results and a new strategy to design novel 2D-COF photocatalysts for overall water splitting.
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