SusChEM: CAREER: High-Resolution X-ray Spectroscopic Studies of Base Metal Catalysis

SusChEM：职业：贱金属催化的高分辨率 X 射线光谱研究

• 批准号: 1454455
• 负责人: Kyle Lancaster
• 金额: $ 56.1万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1454455&HistoricalAwards=false
• 关键词: SusChEM; CAREER; Resolution; ray; Spectroscopic

With this CAREER award, the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division is funding Professor Kyle M. Lancaster of the Department of Chemistry and Chemical Biology at Cornell University to use cutting-edge X-ray spectroscopies to explore the reactivity of earth-abundant transition metal catalysts. The goal of this research is to determine the mechanisms by which these catalysts effect remarkable chemical transformations including the breakdown of biomass to simple sugars for biofuels and the conversion of natural gas to transportable liquid forms. Understanding the reactivity of catalysts incorporating earth-abundant metals is key to a sustainable chemical future. The proposed work incorporates elements of biochemistry, synthesis, spectroscopy, and theory, affording interdisciplinary training for undergraduate and graduate researchers. The interaction between light and matter that forms the basis of spectroscopy is the foundation for outreach efforts under this project; specifically, hands-on "lab kits" are to be developed for K-12 students to explore properties of light.Valence-to-core X-ray emission spectroscopy, high-energy-resolution fluorescence-detected X-ray absorption spectroscopy and resonant inelastic X-ray scattering are emerging, versatile methods to characterize coordination environments and ligand electronic structures. These methods are being used to probe copper catalysts, defined here as either enzymes or coordination complexes. One such catalyst to be studied is a mononuclear copper enzyme that oxidatively cleaves polysaccharides in biomass such as chitin and cellulose. Stopped-flow kinetics and rapid freeze quench methods are being used to trap reactive copper-oxygen species for X-ray spectroscopic characterization. Nature's copper catalyst for conversion of methane to methanol is a focus of this study. This catalyst is an integral membrane protein whose reactive copper-oxygen species have eluded study by conventional methods. Efforts are to be extended to an abiotic system: copper-catalyzed aerobic alcohol oxidation. This study could demonstrate that the methods to be employed do not necessarily require precise knowledge of precatalysts in order to characterize reaction constituents.

凭借这一职业奖，化学结构，动态和机制B计划的化学部门是康奈尔大学化学和化学生物学系的凯尔·M·兰卡斯特（Kyle M. 这项研究的目的是确定这些催化剂会影响显着化学转化的机制，包括生物量对生物燃料的简单糖分分解以及天然气转化为可运输的液体形式。了解掺入土壤丰富金属的催化剂的反应性是可持续化学未来的关键。拟议的工作结合了生物化学，合成，光谱和理论的要素，为本科和研究生研究人员提供了跨学科培训。光谱基础的光与物质之间的相互作用是该项目下的外展努力的基础；具体而言，要为K-12学生开发动手“实验室套件”，以探索光线X射线发射光谱，高能量分辨率 - 分辨率 - 荧光检测到的X射线吸收光谱光谱和谐振X射线内X射线散射是出现的，具有多样的均值和coorders Entrancions和Ligigant coligant Evernation和Ligand。这些方法用于探测此处定义为酶或配位络合物的铜催化剂。一种要研究的催化剂是一种单核铜酶，氧化酶在生物质（例如几丁质和纤维素）中裂解多糖。停止流动动力学和快速冷冻淬火方法用于捕获反应性铜氧物种，以进行X射线光谱特征。大自然的铜催化剂将甲烷转化为甲醇是这项研究的重点。该催化剂是一种整体膜蛋白，其反应性铜氧，通过常规方法避免了研究。努力应扩展到非生物系统：铜催化的有氧酒精氧化。这项研究可以证明，要使用的方法不一定需要精确的预催化剂知识，以表征反应成分。