RUI: Mechanistic Investigation of Photochemical Products from Iron-Iron Hydrogenase Model Compounds; Insight into the Catalytic Generation and Activation of Molecular Hydrogen

RUI：铁-铁氢化酶模型化合物光化学产物的机理研究；

• 批准号: 1664609
• 负责人: Carmen Works
• 金额: $ 18万
• 依托单位: Sonoma State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664609&HistoricalAwards=false
• 关键词: RUI; Mechanistic; Investigation; Photochemical; Products

Professor Carmen Works is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to conduct research at Sonoma State University to elucidate the mechanism of iron-iron hydrogenase model compounds. Iron-iron hydrogenase is an organometallic enzyme that catalyzes the reversible oxidation of molecular hydrogen. The detrimental effects of fossil fuel usage on our global ecosystem as well as ever increasing energy demands have inspired much research towards the development of clean and renewable fuels. Hydrogen is seen as an ideal carbon-free energy source as its only combustion product is water. Unfortunately, the best catalysts for hydrogen generation and usage are based on the rare and very expensive platinum metal, presenting a significant economic obstacle for the large-scale production of hydrogen to meet our energy demands. However, Nature has provided efficient and robust Earth rich metal enzymes, that are able to produce hydrogen cleanly. Due to the potential importance and utility of this natural process, the present work is focused on understanding the catalytic chemistry that occurs in these enzymes in order to advance the design of new and inexpensive technological systems for hydrogen use. The approach in this project is to make small organometallic molecules that are both structural and functional models of the enzyme active site and to use spectroscopic and kinetic techniques to characterize their photochemical and thermal reactivity. The working hypothesis is that light produces the active catalysts in solution. This work is leading to a deeper understanding of the fundamental reactivity. The strategy used in this proposal is to synthesize a range of molecules that vary in both electronic and steric properties but have the general di-iron core, and to study the photochemistry under CO and H2. In addition, the thermal reactivity of the photoproducts with hydrogen as a function of solvent is being studied to understand catalysis. Experimental results are being compared with theoretical calculations. In addition, this project has a large educational impact and is providing training in the area of inorganic synthesis, spectroscopy, catalysis, photochemistry and exposed undergraduate students to theoretical chemistry. Outreach to both the scientific and local community is including undergraduate students specifically through presentations at regional and National meetings and publications.

Carmen Works教授得到化学系化学催化（CAT）项目的支持，在索诺马州立大学进行研究，以阐明铁-铁氢化酶模型化合物的机制。铁-铁氢化酶是催化分子氢可逆氧化的有机金属酶。化石燃料的使用对我们的全球生态系统的有害影响以及不断增长的能源需求激发了对清洁和可再生燃料开发的大量研究。 氢被认为是理想的无碳能源，因为它唯一的燃烧产物是水。 不幸的是，用于氢气生成和使用的最佳催化剂是基于稀有且非常昂贵的铂金属，这为大规模生产氢气以满足我们的能源需求带来了重大的经济障碍。 然而，大自然已经提供了高效和强大的富含地球的金属酶，能够清洁地产生氢气。由于这种自然过程的潜在重要性和实用性，目前的工作重点是了解这些酶中发生的催化化学，以推进新的和廉价的技术系统的设计，用于氢的使用。 在这个项目中的方法是，使小的有机金属分子的酶活性位点的结构和功能模型，并使用光谱和动力学技术来表征其光化学和热反应性。 工作假设是光在溶液中产生活性催化剂。这项工作正在导致对基本反应性的更深入理解。 在这个建议中使用的策略是合成一系列的分子，不同的电子和空间性质，但有一般的二铁核心，并研究下CO和H2的光化学。 此外，正在研究光产物与作为溶剂的氢的热反应性，以了解催化作用。 实验结果与理论计算进行了比较。此外，该项目具有很大的教育影响，并在无机合成、光谱学、催化、光化学领域提供培训，并使本科生接触理论化学。对科学界和当地社区的外联包括本科生，特别是通过在区域和国家会议和出版物上的演讲。

项目成果

Photoinduced Terminal Hydride of [FeFe]-Hydrogenase Biomimetic Complexes

[FeFe]-氢化酶仿生复合物的光诱导末端氢化物

• DOI: 10.1021/acs.inorgchem.9b01738
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Niu, Shuqiang;Nelson, Anne E.;De La Torre, Patricia;Li, Haixia;Works, Carmen F.;Hall, Michael B.
• 通讯作者: Hall, Michael B.