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分解水为可持续制氢提供了一条概念上简单且有前景的途径。该过程的核心是分子光敏剂和催化剂。虽然这种光氧化还原催化系统在合成化学的其他领域已经很成熟，但光催化水分解需要一个多电子过程，其中多个电子积累在一个分子单元中，这是一个特殊的挑战。一种有前途的分子系统新范例，可以积累多个电子电荷由一类最近开发的基于对环四烯的大环提供，其中多个电荷可以随着大环中全局芳香性的出现而稳定。帝国理工学院和拉夫堡大学正在进行的 EPSRC 项目 EP/V048686/1 正在研究它们在多电子光氧化还原催化中的应用。该项目的目的是通过详细的计算研究来支持这些努力。计算不仅可以预测氧化还原电位，还可以详细了解所涉及的电子结构，重点关注大环中全局芳香性的发生。最近开发的高效动力学方法将允许以前所未有的细节研究所需的电荷分离过程。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。交付成果-通过均相催化对光化学水分解的详细机理见解-新型催化剂的开发