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Understanding Photocatalytic Overall Water Splitting of β-Ketoamine COFs through the N–C Site Synergistic Mechanism
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-12-01 , DOI: 10.1021/acsami.3c14311 Rui Zhang 1 , Zhao-Di Yang 1 , Yan Yang 1 , Feng-Ming Zhang 1 , Guiling Zhang 1
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-12-01 , DOI: 10.1021/acsami.3c14311 Rui Zhang 1 , Zhao-Di Yang 1 , Yan Yang 1 , Feng-Ming Zhang 1 , Guiling Zhang 1
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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.
中文翻译：
通过 N-C 位点协同机制了解 β-酮胺 COF 的光催化整体水分解
克服析氧反应（OER）的缓慢反应动力学是光催化剂整体水分解实际应用的决定因素。二维共价有机框架（2D-COF）因其卓越的化学可调性和高光捕获效率，为整体水分解领域的催化剂设计提供了理想的平台。在这项工作中，构建并优化了四种 β-酮胺 2D-COF，由 1,3,5-三甲酰基间苯三酚 (Tp) 基团和带有吡啶片段的不同连接体组成。通过第一性原理计算，系统地计算和研究了光催化析氢反应（HER）和OER的能带结构、自由能变化以及电荷密度分布，以讨论活性位点的可见光响应、整体水分解活性，以及电荷转移和分离的特性。来自双H 2 O闭环H键吸附模型的质子化吡啶N可以有效诱导吡啶N与其邻位C之间的N-C位点协同作用，从而最小化OER能垒并增强电荷转移和分离。AN-C位点协同机制的提出为实验结果提供了全面的解释，并为设计用于整体水分解的新型2D-COF光催化剂提供了新策略。
更新日期：2023-12-01
中文翻译：
通过 N-C 位点协同机制了解 β-酮胺 COF 的光催化整体水分解
克服析氧反应（OER）的缓慢反应动力学是光催化剂整体水分解实际应用的决定因素。二维共价有机框架（2D-COF）因其卓越的化学可调性和高光捕获效率，为整体水分解领域的催化剂设计提供了理想的平台。在这项工作中，构建并优化了四种 β-酮胺 2D-COF，由 1,3,5-三甲酰基间苯三酚 (Tp) 基团和带有吡啶片段的不同连接体组成。通过第一性原理计算，系统地计算和研究了光催化析氢反应（HER）和OER的能带结构、自由能变化以及电荷密度分布，以讨论活性位点的可见光响应、整体水分解活性，以及电荷转移和分离的特性。来自双H 2 O闭环H键吸附模型的质子化吡啶N可以有效诱导吡啶N与其邻位C之间的N-C位点协同作用，从而最小化OER能垒并增强电荷转移和分离。AN-C位点协同机制的提出为实验结果提供了全面的解释，并为设计用于整体水分解的新型2D-COF光催化剂提供了新策略。
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