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

使用均质催化剂的光化学水分分开为可持续氢生产提供了一条概念上简单而有希望的途径。这个过程的核心是分子光敏剂和催化剂。尽管这种光毒性催化系统在合成化学的其他领域已经建立了良好大环中全球芳香性的发生。在正在进行的EPSRC项目EP/V048686/1中，正在研究它们在多电体Photoredox催化中的使用。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，而且还可以详细了解涉及重点关注大环的全局芳香性的电子结构。最近开发的有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，将其特性与现有的Photoredox催化剂进行对比，并建议新的候选物。可销售的机械洞察力洞察光化学水通过均质催化新催化剂进行新催化剂分裂的洞察力