Study of Hydrogen Evolution by a Series of Metal-Mabiq complexes

该项目的重点是一个家庭的大环金属配合物，以及它们作为催化剂的能力，用于制氢。氢气是一种很有前途的燃料替代品。然而，实现氢作为替代燃料需要开发用于其生产的高效、经济的催化剂。已经取得了显着的进展，朝着发展的后第一行过渡金属电催化剂，用于该反应。然而，反应机理的各个方面仍然没有得到解决，催化剂的特性仍然需要优化，这需要进一步的研究和新的催化剂平台。我们在此描述的研究，详细检查，电催化析氢由一系列的金属化合物协调的一个独特的氧化还原活性的大环配体，Mabiq。该项目包括深入的机制和结构功能研究，主要目标如下：1。考察钴-Mabiq配合物的催化性能;2.鉴定Co-Mabiq络合物和相关反应中间体的氢析出的可用途径;3.研究结构对催化剂反应性的贡献，通过另外检查含有Fe和Ni的络合物以及改性配体;4.探索配体第二金属结合位点的配位化学，包括初步研究其对催化作用的影响。该项目将采用合成、电化学和光谱方法以及反应性研究相结合的方法，旨在解决析氢反应机理中尚未解决的问题，并为增强型催化剂的设计做出贡献。

The project focuses on a family of macrocyclic metal complexes, and their ability to act as catalysts for hydrogen production. Hydrogen is a promising fuel alternative. However, the realization of hydrogen as an alternate fuel demands the development of efficient, economical catalysts for its production. Significant advances have been made toward the development of late first-row transition metal electrocatalysts for this reaction. Yet aspects of the reaction mechanism remain unresolved, and catalyst features still need to be optimized, warranting further research and new catalyst platforms. We herein describe studies to examine, in detail, electrocatalytic hydrogen evolution by a series of metal compounds coordinated by a unique redox-active macrocyclic ligand, Mabiq. The project consists of in-depth mechanistic and structure-function studies, with the following key objectives:1. to examine the catalytic performance of cobalt-Mabiq complexes;2. to identify the available pathway(s) for hydrogen evolution by the Co-Mabiq complexes, and associated reaction intermediates;3. to investigate structural contributions to catalyst reactivity, by additionally examining complexes containing Fe and Ni, and modified ligands;4. to explore the coordination chemistry of an available second metal binding site of our ligand, including an initial examination of its influence on catalysis.The project will employ a combination of synthetic, electrochemical and spectroscopic methods, and reactivity studies.The research aims to address unsettled aspects of the hydrogen evolution reaction mechanism, and to contribute to the design of enhanced catalysts.