CAS: CAREER: Light-Initiated C-H Functionalization by Metal Oxo Complexes for Sustainable Light Hydrocarbon Upgrading

CAS：事业：通过金属氧配合物进行光引发的 C-H 官能化，实现可持续轻质烃升级

• 批准号: 2238488
• 负责人: Matthew Chambers
• 金额: $ 73.71万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-05-15 至 2028-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2238488&HistoricalAwards=false
• 关键词: CAS; CAREER; Light; Initiated; Functionalization

With the funding from the Chemical Catalysis (CAT) Program of the Division of Chemistry (CHE) and the Established Program to Stimulate Competitive Research (EPSCoR) office, Matthey Chambers of the Louisiana State University (LSU) will work to develop methods to employ solar energy (light) as a renewable energy source to drive the conversion of hydrocarbons to commodity chemicals. Hydrocarbon functionalization is the cornerstone of the chemical industry and the energy economy, but methods for generating value-added commodity chemicals and fuels today typically rely on high temperatures, high pressures, and environmentally hazardous reagents. This has the consequence of dramatic energy usage, as steam reforming and related processes account for 1-10% of global energy consumption. Motivated by biological systems that efficiently use special molecular cofactors containing metal-oxygen active sites, this project will investigate the manner in which interactions with light can actuate these motifs to selectively mediate the catalytic conversion of inert hydrocarbons to products. As the director of LSU’s ChemDemo program, Dr. Chambers will actively engage communities and provides hands-on science experiences to underserved and underrepresented K-12 students throughout the region. This project has potential long term broader impacts related to sustainable catalysis of relevance to the chemical industry.Matthew Chambers and his group will investigate the factors that underpin early transition metal oxo photochemical properties (light absorption, emission energy, and lifetimes) and reactivity patterns. Photochemical characterization will be achieved via steady-state and transient luminescence spectroscopy and product distributions will be determined by NMR spectroscopy and GC-MS analysis. An emphasis will be placed on more oxophilic platforms as, upon excitation, these systems may efficiently activate C–H bonds while allowing the activated substrate to undergo a diverse array of follow-up reactivity to achieve a broad range of products. The selectivity of these transformations is related experimentally and computationally to the M–OH bond dissociation energies of the intermediates as this is thought to be the critical parameter influencing product selectivity. Also under investigation will be methodologies to achieve efficient and stable photocatalytic platforms. Kinetic studies will aim to identify the key steps during the reoxidation of the metal oxo photocatalyst while ancillary ligand field variations are directed at developing an understanding of the critical features impacting photocatalysis. Collectively, these aims are expected to lead to enhanced understanding of metal oxo photochemistry and the parameters that underpin selectivity. Understanding the factors that influence the catalytic reactivity of photoexcited metal oxos would constitute enabling technology, with potential applicability to the development of new petrochemical technologies and fuel-forming reactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

借助化学催化（CAT）化学催化计划（CHE）和启用竞争性研究的既定计划（EPSCOR）办公室的资金，路易斯安那州立大学（LSU）的Matthey Chambers（LSU）将致力于开发用于采用太阳能（Light）作为可再生能源的方法，以推动可再生能源来推动氢键化学化学化学化学化学化学物质化学物质的转化。碳氢化合物功能化是化学工业和能源经济的基石，但是当今产生增值商品化学物质和燃料的方法通常依赖于高温，高压和环境危险的试剂。由于蒸汽改革和相关过程占全球能源消耗的1-10％，因此这具有巨大的能源使用情况。该项目由有效使用含有金属氧活性位点的特殊分子辅因子的生物系统动机，该项目将调查与光可以活跃的这些基序相互作用的方式，以选择性地介导惰性碳氢化合物向产品的催化转化。作为LSU Chemdemo计划的主任，钱伯斯博士将积极参与社区，并为整个地区服务不足和代表性欠佳的K-12学生提供动手科学经验。该项目具有与化学工业相关性可持续催化有关的潜在长期长期影响。MatthewChambers和他的小组将研究基于早期过渡金属金属氧化物光化学特性（轻滥用，排放能量和生命值）和降低效率模式的因素。光化学表征将通过稳态和瞬态发光光谱实现，产品分布将通过NMR光谱和GC-MS分析确定。将重点放在更多的Oxo系统平台上，因为在激动时，这些系统可以有效激活C – H键，同时允许激活的底物经历一系列的潜水后续反应性，以实现广泛的产品。这些转换的选择性在实验和计算上与中间体的M – OH键解离能有关，因为这被认为是关键参数会影响乘积选择性。还将研究的方法是实现高效且稳定的光催化平台的方法。动力学研究将旨在确定金属氧光催化剂再次氧化过程中的关键步骤，而辅助配体场变化旨在发展对影响光催化的关键特征的理解。总体而言，这些目标有望提高对金属氧光化学和基础选择性参数的理解。了解影响光激发金属OXO的催化反应性的因素将构成促进技术，并有可能适用于开发新的石化技术和燃料形成反应。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识和更广泛的影响来通过评估来获得支持的珍贵的，这是珍贵的支持。