Orchestrating Electron and Proton Transfer for Solar Energy Conversion

在这项由化学系化学催化计划资助的项目中，卡内基梅隆大学的斯特凡·伯恩哈德将设计、合成和研究新型的吸光金属络合物，并将其与能够从水和阳光中产生氢气的还原催化剂相结合。生物无害和廉价的第一排过渡金属离子的配位络合物将被用作催化剂和生色团。我们将探索稳定这些通常不稳定结构的强络合半笼和缠绕配体拓扑结构。先进的光谱和电化学技术将被用来了解这些配合物的结构和功能，以及它们在水分解体系中的应用，并将使用并行光反应器来研究大量的候选配合物和反应条件。通过这些光谱方法和合成方法的结合，将确定光催化体系的定量结构-活性关系。这些见解将被用于进一步提高析氢的稳健性和反应速度。然后，这些减水催化剂的溶液化学将被修饰成可扩展的光电化学系统，固定在适合于全水分解系统的透明电极上。更广泛的影响包括培训本科生和研究生，接待访问的高中教师提供暑期研究机会，教授一门关于巧克力化学的课程，以及可再生能源技术的潜在社会影响。这项工作将提供有关从水和阳光中产生氢燃料的催化剂的基础和应用知识，并可能展示如何将地球上丰富的金属用于此类技术。这项研究的结果将对能源行业以及制造需要燃料来源的商业消费品的行业，如汽车和航空航天部门，具有重要意义。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Stefan Bernhard of Carnegie Mellon University will design, synthesize and study novel light-absorbing metal complexes combined with reduction catalysts able to generate hydrogen from water and sunlight. Coordination complexes of biologically innocuous and inexpensive first-row transition metal ions will be investigated for use as catalysts and chromophores. Strongly chelating hemi-cage and wrap-around ligand topologies that stabilize these normally labile structures will be explored. Advanced spectroscopic and electrochemical techniques will be used to understand the structure and function of these complexes and their application to water-splitting systems, and parallel photoreactors will be employed to study large numbers of candidate complexes and reaction conditions. Through a combination of these spectroscopic and synthetic methods, quantitative structure-activity relationships of photocatalytic systems will be determined. These insights will be used to further improve the robustness and reaction rate of hydrogen evolution. The solution-based chemistry of these water reduction catalysts will then be modified into scalable photoelectrochemical systems immobilized on transparent electrodes suitable for use in full water-splitting systems. The broader impacts involve training undergraduate and graduate students, hosting visiting high school teachers for summer research opportunities, teaching a course on the chemistry of chocolate, and the potential societal impact of renewable energy technology. This work will provide fundamental and applied knowledge about catalysts that generate hydrogen fuel from water and sunlight, and potentially could show how earth abundant metals can be used for such technologies. Results from this research would be important to the energy industry and to industries that manufacture commercial consumer products that require fuels sources, such as the automotive and aerospace sectors.