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Modelling of photochemical water splitting based on charge accumulation in macrocycles

基于大环电荷积累的光化学分解水建模

基本信息

批准号：
2889683
负责人：
金额：
--
依托单位：
Loughborough University
依托单位国家：
英国
项目类别：
Studentship
财政年份：
2023
资助国家：
英国
起止时间：
2023 至无数据
项目状态：
未结题

来源：
https://gtr.ukri.org/projects?ref=studentship-2889683
关键词：
Modelling photochemical water splitting based

项目摘要

Photochemical water splitting using homogeneous catalysts provides a conceptually simple and promising route towards sustainable hydrogen production. At the heart of this processes lies a molecular photosensitizer along with a catalyst. Whereas such photoredox catalytic systems are well-established in other areas of synthetic chemistry, it is a particular challenge that photocatalytic water splitting requires a multielectron process where several electrons are accumulated in one molecular unit.A promising new paradigm for molecular systems that can accumulate several charges is provided by a class of recently developed macrocycles based on paracyclophanetetraene, where multiple charges can be stabilized with the occurrence of global aromaticity in the macrocycle. Their use in multielectron photoredox catalysis is being investigated in the on-going EPSRC project EP/V048686/1 in collaboration betweenImperial College and Loughborough. It is the purpose of this project to support these efforts with detailed computational studies. Computations will not only predict redox potentials but will give detailed insight into the electronic structure involved focussing on the occurrence of global aromaticity in the macrocycle. Recently developed efficient dynamics methods will allow to study the required charge separation processes in unprecedented detail. The project will investigate prototype macrocyclic catalysts, contrast their properties with existing photoredox catalysts and suggest new candidates.Deliverables-Detailed mechanistic insight into photochemical water splitting via homogeneous catalysis-Development of new catalysts

使用均相催化剂的光化学水裂解提供了一种概念简单且有前途的可持续制氢途径。这个过程的核心是分子光敏剂沿着催化剂。尽管这样的光氧化还原催化体系在合成化学的其他领域中已经很好地建立，但是光催化水裂解需要多电子过程，其中在一个分子单元中积累几个电子，这是一个特别的挑战。最近开发的一类基于对环芳四烯的大环化合物为可以积累几个电荷的分子体系提供了一个有前途的新范例，其中多个电荷可以随着大环中整体芳香性的出现而稳定。它们在多电子光氧化还原催化中的应用正在帝国理工学院和拉夫堡大学合作进行的EPSRC项目EP/V048686/1中进行研究。本项目的目的是通过详细的计算研究来支持这些努力。计算将不仅预测氧化还原电位，但将详细了解所涉及的电子结构集中在大环的全局芳香性的发生。最近开发的有效的动力学方法将允许研究所需的电荷分离过程中前所未有的细节。该项目将研究原型大环催化剂，将其性能与现有的光氧化还原催化剂进行对比，并提出新的候选催化剂。