CAREER: Theoretical Development of Bio-Inspired Water Splitting Photocatalysts

职业：仿生水分解光催化剂的理论发展

• 批准号: 0955515
• 负责人: Christine Aikens
• 金额: $ 59.95万
• 依托单位: Kansas State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-08-01 至 2016-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0955515&HistoricalAwards=false
• 关键词: CAREER; Theoretical; Development; Bio; Inspired

Technical Abstract: This award by the Chemical Catalysis Program of the Chemistry Division supports the efforts of Professor Christine M. Aikens of Kansas State University to analyze which aspects of the oxygen-evolving center (OEC) of photosystem II contribute to its effectiveness as a catalyst for water splitting and therefore to predict which structural and electronic aspects are required in synthetic catalysts used for oxygen evolution. Professor Aikens employs a variety of electronic structure methods in order to accomplish this aim including: density functional theory, second-order perturbation theory, and multireference methods. Combined quantum mechanical/molecular mechanical (QM/MM) methods that include electrostatic embedding are employed to examine the role of the protein or solid-state support on catalytic activity. Some of the issues that are studied include the role of the protein backbone on structure and charge distribution in the Mn4Ca core, the impact of transition state energies on predicted overpotentials, the proper theoretical methods required to accurately model the catalytic cycle, how metal oxide clusters, single crystal surfaces, and nanostructured supports change the charge distribution and efficiency of the Mn4Ca reaction center, and whether the stoichiometry of the OEC plays a role in its effectiveness as a catalyst.Molecular modeling software is incorporated into the Chemistry 1 laboratories at Kansas State University in order to help students learn how to visualize molecular geometries. An annual one-day Energy and Sustainability Workshop for middle-school students focuses on topics such as solar power, biological energy, and other technology related to renewable energy and materials. Students attend introductory seminars and engage in hands-on activities. This workshop seeks to include rural students from sparsely populated areas as a means of broadening participation in science.Non-technical Abstract:This award by the Chemical Catalysis Program of the Chemistry Division supports the efforts of Professor Christine M. Aikens of Kansas State University to study aspects of the oxygen-evolving center (OEC) of photosystem II, a complex, naturally-occurring protein which uses light to produce oxygen, electrons and hydrogen ions (protons) from water. Biological systems have evolved efficient catalysts for water splitting to form oxygen during photosynthesis, but natural systems do not normally evolve hydrogen. This theoretical and computational research analyzes aspects of the oxygen-evolving center of photosystem II that contribute to its effectiveness as a catalyst for water splitting. Similar aspects are then targeted in synthetic materials. This research aids in the development of clean and renewable sources of energy for the 21st century. Molecular modeling software is incorporated into the Chemistry 1 laboratories at Kansas State University in order to help students learn how to visualize molecular geometries. An annual one-day Energy and Sustainability Workshop for middle-school students focuses on topics such as solar power, biological energy, and other technology related to renewable energy and materials. Students attending the workshop engage in hands-on, introductory activities. This workshop seeks to include rural students from sparsely populated areas as a means of broadening participation in science.

技术摘要：该奖项由化学系化学催化项目颁发，支持堪萨斯州立大学克里斯汀·M·艾肯斯教授的努力，他分析了光系统II的放氧中心(OEC)的哪些方面有助于其作为分解水的催化剂的有效性，从而预测用于放氧的合成催化剂需要哪些结构和电子方面。为了实现这一目标，艾肯斯教授使用了多种电子结构方法，包括：密度泛函理论、二阶微扰理论和多重参考方法。采用包括静电嵌入的量子力学/分子力学(QM/MM)相结合的方法来考察蛋白质或固体载体对催化活性的影响。研究的一些问题包括蛋白质骨架对Mn4Ca核心结构和电荷分布的作用，过渡态能量对预测的超势的影响，准确模拟催化循环所需的适当理论方法，金属氧化物团簇、单晶表面和纳米结构载体如何改变Mn4Ca反应中心的电荷分布和效率，以及OEC的化学计量比是否对其作为催化剂的有效性起到作用。分子模拟软件被整合到堪萨斯州立大学的化学1实验室，以帮助学生学习如何可视化分子几何。每年为中学生举办为期一天的能源与可持续发展研讨会，重点讨论太阳能、生物能源以及其他与可再生能源和材料相关的技术。学生们参加介绍性研讨会并参与实践活动。该研讨会旨在将来自人口稀少地区的农村学生纳入其中，作为扩大科学参与度的一种手段。非技术摘要：该奖项由化学系化学催化计划颁发，支持堪萨斯州立大学的Christine M.Aikens教授研究光系统II的放氧中心(OEC)的各个方面，光系统II是一种复杂的自然存在的蛋白质，它利用光从水中产生氧、电子和氢离子(质子)。生物系统已经进化出高效的催化剂，用于在光合作用过程中分解水形成氧气，但自然系统通常不会放出氢。这项理论和计算研究分析了光系统II放氧中心的一些方面，这些方面有助于它作为分解水的催化剂的有效性。然后，类似的方面也针对合成材料。这项研究有助于开发21世纪的清洁和可再生能源。分子建模软件被整合到堪萨斯州立大学的化学1实验室，以帮助学生学习如何可视化分子几何。每年为中学生举办为期一天的能源与可持续发展研讨会，重点讨论太阳能、生物能源以及其他与可再生能源和材料相关的技术。参加工作坊的学生参与实践和介绍性活动。该讲习班旨在将来自人烟稀少地区的农村学生纳入其中，作为扩大对科学的参与的一种手段。