Homogeneous and Heterogeneous Ligand Centered Catalysts for Reversible Proton Reduction

有了这个奖项，化学部的化学催化计划资助路易斯维尔大学的克雷格格拉珀豪斯教授开发用于生产氢作为可再生燃料来源的催化剂。 寻找实用的可再生能源是我们目前面临的巨大挑战，而将太阳能转化和储存为化学能是积极追求的解决方案之一，因为植物通过光合作用实现了这一壮举。 该研究的重点是催化剂，其中金属配位可以接受或提供电子的配体;因此，配体而不是金属将直接参与与质子的化学相互作用和分子氢的产生。 这项研究为路易斯维尔大学和邻近的本科院校坎贝尔斯维尔大学的本科生和研究生创造了教育机会。 这些学生将获得合成，电化学，计算化学和催化方面的专业知识和经验。该项目还将创造与路易斯维尔大学康恩可再生能源研究中心工程师互动的机会，该中心专注于可再生能源和可持续性问题的研究，研究重点是开发以配体为中心的催化剂，用于质子可逆还原为氢气。该催化剂将被设计为促进配体为中心的机制，促进了非无辜的，氧化还原活性硫醇供体的掺入。 催化剂的功能取决于金属中心和配体之间的相互作用。 正在开发的催化剂采用强的金属-配体相互作用，有利于电子离域，从而支持催化质子还原/析氢的新的机理途径。催化剂将在溶液中制备和表征。电化学研究将探索反应机理。配体修饰加上计算研究将被用来解决电子效应的过电位和配体碱度。此外，反应中间体的分离和表征将被追求，以验证所提出的机制。 然后将成功的候选物固定在固体支持物上，用于开发可能具有更大实用性的异质衍生物。

With this award, the Chemical Catalysis Program in the Chemistry Division is funding Professor Craig Grapperhaus of the University of Louisville to develop catalysts for the production of hydrogen as a renewable fuel source. Finding practical renewable energy sources is a great challenge we currently face, and the transformation and storage of solar energy as chemical energy is one of the solutions that is actively pursued because plants have achieved this feat through photosynthesis. The research focuses on catalysts in which a metal coordinates ligands that can accept or donate electrons; consequently, the ligands rather than the metal would be directly involved in the chemical interaction with the protons and the molecular hydrogen production. This research creates educational opportunities for undergraduate and graduate students from the University of Louisville and the Campbellsville University, a neighboring undergraduate institution. These students will gain expertise and experience in synthesis, electrochemistry, computational chemistry, and catalysis. The project will also create opportunities for interactions with engineers in the Conn Center for Renewable Energy Research at the University of Louisville, which focuses on research on renewable energy and sustainability issues.The focus of the research is to develop ligand-centered catalysts for the reversible reduction of protons to hydrogen. The catalysts will be designed to promote a ligand-centered mechanism facilitated by the incorporation of non-innocent, redox-active thiolate donors. The function of the catalyst depends on the interaction between the metal center and the ligand. The catalysts under development employ strong metal-ligand interactions that favor electron delocalization, thus supporting new mechanistic pathways for catalytic proton reduction/hydrogen evolution. Catalysts will be prepared and characterized in solution. Electrochemical investigations will probe the reaction mechanism. Ligand modification coupled with computational studies will be used to address the electronic effects on overpotential and ligand basicity. Additionally, the isolation and characterization of reaction intermediates will be pursued to validate the proposed mechanism. Successful candidates will then be immobilized on a solid support for the development of heterogeneous derivatives that could have greater practical utility.