Photoelectrochemically Driven Water-Oxidation Catalysis by Perylene Diimide Plus Cobalt-Oxide Based Photoanodes: Fundamental Studies En Route to Second-Generation Systems

化学学部的化学催化项目支持Richard G. Finke教授的项目。芬克教授是科罗拉多州立大学化学系的教员。他的研究重点是开发廉价、高效、富含地球元素的低成本材料，这种材料可以收集太阳能，然后利用太阳能将水氧化成氧和氢成分。氢气可以作为一种可再生能源。该项目包括使用廉价、坚固的苝二亚胺染料（例如用于红色到黑色的汽车漆）来捕获太阳能，再加上地球上丰富的钴氧化物作为水氧化催化剂。该项目是无机，有机和材料化学加上化学催化的界面，使其成为培养下一代能够进行能源相关研究的基础广泛的科学家的理想选择。涉及少数族裔服务机构的大学生，包括路易斯堡学院（一个西班牙裔服务机构）和北科罗拉多大学（一个主要的本科大学，有15%的西班牙裔和34%的第一代学生），是该项目的一个组成部分。从技术上看，作为研究的三个具体目标的一部分，解决了三个主要问题：首先，仔细选择用于进一步研究的七种苝型染料中哪一种能产生最好的光电分解电池，为什么？重要的是，膦酸盐官能团存在于苝二酰亚胺染料中，对于将有机染料膜偶联到无机氧化钴水氧化催化剂至关重要吗？其次，如果采用染料敏化的光电解析池结构，其中苝二亚胺染料单层可以吸附在基于钛、锡和钨的半导体金属氧化物的高表面积烧结纳米颗粒膜上，那么光电解析池的性能是否会大大提高？或者，另一种假设是否证明增强的空穴/电子复合在染料敏化光电解电池结构中占主导地位？如果是，为什么？第三，有机光收集器是否具有足够的抗氧化稳定性，在未来的水氧化催化和其他类似的光阳极中占据重要地位？与其他材料相比，有机染料具有显著的优势，包括低成本、合成柔韧性和易于调节的性能。这些光电池中的失活途径是什么？因此，基于这种有机光收集材料的更长的光阳极寿命的最佳策略是什么？教育拓展包括Finke教授为本科生和一年级研究生讲课，他被邀请访问多个机构，讨论“通过适当的科学方法进行批判性阅读和分析技能”的关键主题。

The Chemical Catalysis Program of the Chemistry Division supports the project by Professor Richard G. Finke. Professor Finke is a faculty member in the Department of Chemistry at Colorado State University. His research is focused on developing cheap, efficient, earth-element-abundant and hence low cost materials that can collect solar energy, and then use that energy to oxidize water into its oxygen and hydrogen components. The hydrogen then serves as a renewable energy source. The project involves the use of cheap, robust perylene diimide dyes (used, for example, in red to black car paints) to capture the solar energy, plus earth-abundant cobalt oxide as the water-oxidation catalyst. The project is at the interface of inorganic, organic, and materials chemistries plus chemical catalysis, making it ideal for training the next generation of broad-based scientists able to perform energy-related research. Outreach involving college students at the minority serving institutions of Fort Lewis College, a Hispanic Serving institution, and the University of Northern Colorado, a primarily undergraduate university with 15% Hispanic and 34% first-generation students, is an integral part of the project.Looking deeper technically, three main questions are addressed as part of the three specific aims of the research: First, which of seven perylene-type dyes, carefully selected for further investigation, yields the best photoelectrolysis cell and why? Importantly, are phosphonate functional groups present in the perylene diimide dye employed crucial for coupling the organic dye film to the inorganic cobalt oxide water-oxidation catalyst? Second, is the photoelectrolysis cell performance greatly improved if one employs a dye-sensitized photoelectrolysis cell architecture in which a perylene diimide dye monolayer can be adsorbed onto a high-surface-area sintered nanoparticle film of semiconducting metal oxides based on titanium, tin, and tungsten? Or, does the alternative hypothesis prove true that enhanced hole/electron recombination dominates in the dye-sensitized photoelectrolysis cell architecture? If so, why? Third, do organic light-harvesters possess sufficient stability against oxidation to merit an important position in future water-oxidation catalysis and other such photoanodes? Organic dyes have notable advantages over other materials including low cost, synthetic flexibility and easily tunable properties. What are the deactivation pathways active in these photocells and, thus, best strategies for longer photoanode lifetimes based on such organic light-harvesting materials? The education outreach includes lectures that Professor Finke gives to undergraduates and first-year graduate students, at multiple institutions he has been invited to visit, addressing the crucial topic of "Critical Reading and Analysis Skills via a Proper Scientific Method."