Solar Hydrogen Generation Using Supramolecular Photocatalysts

该奖项是根据2009年《美国复苏和再投资法案》(公法111-5)提供资金的。无机化学、生物无机化学和金属有机化学计划支持德克萨斯大学阿灵顿分校的弗雷德里克·M·麦克唐奈教授和诺玛·S·塔科尼教授的努力，研究用于太阳能制氢的超分子光催化剂(SPC)的设计、测试和详细的机理分析的综合方法。SPC是由发色团/光敏剂、桥接受体配体(用作临时电子存储中心)和析氢铂共催化剂组成的组件。详细考察了具有应用前景的光催化剂的形态、基态和激发态性质以及作用机理。机理细节解决了关于顺序与协同质子耦合电子转移(PCET)反应的几个基本科学问题。这项研究可能会使分子光催化剂的开发成为可能，这种催化剂将利用太阳能形成氢，理想情况下是从水中生成氢。参与该项目的研究生和本科生在无机络合物的合成、光化学、理论、催化以及时间和频率分辨光谱学方面接受了广泛的培训。

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). The Inorganic, Bioinorganic, and Organometallic Chemistry Program supports the efforts of Professors Frederick M. MacDonnell and Norma S. Tacconi of the University of Texas at Arlington for the investigation of an integrated approach towards the design, testing and detailed mechanistic analysis of supramolecular photocatalysts (SPCs) for solar hydrogen production. The SPCs are assemblies of chromophores/photosensitizers, bridging acceptor ligands designed to act as the site of temporary electron storage, and hydrogen-evolving platinum co-catalysts. Promising photocatalysts are examined in detail to determine the speciation, ground and excited state properties, and mechanisms of action. Mechanistic details address several fundamental scientific questions regarding sequential vs. concerted proton-coupled electron transfer (PCET) reactions. This research may enable the development of molecular photocatalysts that will use solar energy to form hydrogen, ideally from water. Graduate and undergraduate students involved in the project receive a broad training in the synthesis of inorganic complexes, photochemistry, theory, catalysis and time- and frequency-resolved spectroscopy.