Low-Coordinate 3d Metal Complexes as Alternatives to Platinum Group Metals for Hydrogen Evolution Reaction

低配位 3d 金属配合物作为析氢反应铂族金属的替代品

• 批准号: 2889261
• 金额: --
• 依托单位: University of Nottingham
• 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-2889261
• 关键词: Low; Coordinate; 3d; Metal; Complexes

The production of hydrogen through the reduction of water via the Hydrogen Evolution Reaction (HER) is promising sustainable alternative to the use of hydrocarbon feedstocks. The current state of the art uses platinum as it operates at low overpotential with high turnover frequencies. However, the low abundance of platinum (37 ppb in the Earth's crust) leads to high economic and environmental cost, and its high toxicity leads to the production significant waste streams. The use of alternative catalysts featuring earth abundant metals that exhibit low cost, high natural abundance, uniform global distribution and low toxicity is essential to improving the sustainability of this reaction, and therefore as a source of hydrogen. Catalysts featuring cobalt are excellent candidates for this reaction, where mechanistic studies of the HER evolution reaction have identified key processes such as the protonation of CoI to CoIII-H species as key intermediates in the formation of H-H bonds.This project will develop a range of cobalt(I) organometallic complexes as single metal HER catalysts, where the metal centre is stabilised using highly sterically encumbering ligands. These unique complexes have never been investigated for HER chemistry, despite their favourable redox chemistry and substrate binding environment. The cobalt(I) compounds will be investigated for their redox chemistry and sensitivity to acid, along with their electrochemical response in the HER conditions. Information gained from this investigation will allow us to develop the ligand design in order to improve the reaction. The student will benefit from training in synthetic chemical techniques (e.g. organometallic chemistry, spectroscopy, crystallography and kinetic investigations) and electrochemistry. Determination of reaction mechanisms through spectroscopic, structural and kinetic investigations allows the optimisation of the reactions. We anticipate that such investigations will also allow improvements in the reaction conditions and catalyst loadings required for hydrogen release.Deliverables-New earth abundant catalysts for HER-Mechanistic understanding for these reactions, and information to inform catalyst/ligand design in HER-Optimisation of HER reactions

通过析氢反应（HER）还原水来生产氢气是使用烃原料的有前景的可持续替代方案。现有技术使用铂，因为其在低过电位下以高转换频率操作。然而，铂的低丰度（地壳中为37 ppb）导致高经济和环境成本，其高毒性导致产生大量废物流。使用以地球上丰富的金属为特征的替代催化剂，其表现出低成本、高天然丰度、均匀的全球分布和低毒性，对于改善该反应的可持续性是必不可少的，因此作为氢的来源。以钴为特征的催化剂是该反应的理想候选者，HER演化反应的机理研究已经确定了关键过程，例如CoI质子化为CoIII-H物种作为形成H-H键的关键中间体。本项目将开发一系列钴（I）有机金属配合物作为单金属HER催化剂，其中金属中心使用高度空间位阻配体稳定。这些独特的复合物从未被研究过HER化学，尽管它们具有有利的氧化还原化学和底物结合环境。钴（I）化合物将被研究它们的氧化还原化学和对酸的敏感性，沿着它们在HER条件下的电化学响应。从这次调查中获得的信息将使我们能够开发的配体设计，以改善反应。学生将受益于合成化学技术（例如有机金属化学，光谱学，晶体学和动力学研究）和电化学的培训。通过光谱、结构和动力学研究确定反应机理可以优化反应。我们预计，这样的调查也将允许在反应条件和催化剂的负载所需的氢气释放的改进。可再生能源-新地球丰富的催化剂HER-这些反应的机理的理解，并提供信息，以通知催化剂/配体设计HER-优化HER反应