CAS: Synthesis and Reactivity of Oxygen-atom Vacancies in Molecular Vanadium Oxide Assemblies

CAS：氧化钒分子组装体中氧原子空位的合成和反应性

• 批准号: 2154727
• 负责人: Ellen Matson
• 金额: $ 49.89万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154727&HistoricalAwards=false
• 关键词: CAS; Synthesis; Reactivity; Oxygen; atom

With the support of the Chemical Synthesis program in the Division of Chemistry, Ellen Matson of the University of Rochester will study the synthesis and reactivity of oxygen-atom vacancies at the surface of vanadium oxide clusters. In considering the global challenges society faces today, the issue of securing future energy resources is particularly conspicuous. As fossil fuels are depleted, chemists have turned their focus to investigating synthetic methods for the conversion of abundant greenhouse gases into energy-rich chemical fuels. A central challenge to developing sustainable and renewable fuel production strategies is the activation of these small molecules. Industrially, solid-state metal oxide catalysts have been shown effective for the mediation of small molecule activation reactions (e.g., the reduction of CO2 to methanol). Reactive metal ions, accessed through the loss of an oxygen atom from the surface of the material, have been proposed to participate in small molecule activation reactions. To elucidate properties of multimetallic systems that inform the surface reactivity of these materials, the Matson Laboratory will study how the elemental composition of vanadium oxide clusters translates to the propensity of oxygen-atoms to be removed from the assembly. These studies will aid in the elucidation of design criteria of superior catalysts for the production of chemical fuels. Dr. Matson will continue to provide leadership in a campus-wide effort to improve diversity, equity, and inclusion in science, technology, engineering, and mathematics (STEM) departments, and in organizing the Western New York Symposium in inorganic chemistry.This project aims to develop and study the synthesis and reactivity of oxygen-atom vacancies at the surface of vanadium oxide clusters. Oxygen-atom vacancies at the surface of heterogeneous, reducible metal oxides play a critical role in the conversion of inert, energy-poor substrates to energy-rich chemical fuels. Understanding the mechanism(s) by which these defect sites form, and the structure-function relationships that define the generation and reactivity of O-atom vacancies, will provide a template for the strategic design of materials with enhanced activity. During the funding period, Matson will study new schemes for the formation of oxygen-atom defects at the surface of polyoxovanadate-alkoxide clusters. Subsequently, Matson will investigate the role cation- and anion-dopants, as well as surface ligands, play in modulating the formation of oxygen-atom vacancies at the surface of the assembly. Characterization of all complexes will be performed via 1H NMR, infrared, and electronic absorption spectroscopy, as well as electrospray ionization mass spectrometry and single crystal X-ray diffraction. Additional kinetic analysis will provide insight into mechanisms and activation parameters associated with oxygen-atom vacancy formation at the surface of the cluster.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.

在化学合成计划的支持下，罗切斯特大学的艾伦·马特森（Ellen Matson）将研究氧化物氧化物簇表面上的氧气原子空位的合成和反应性。在考虑当今社会面临的全球挑战时，确保未来能源资源的问题特别明显。随着化石燃料的耗尽，化学家将重点转移到研究合成方法中，以将丰富的温室气体转化为富含能量的化学燃料。制定可持续和可再生燃料生产策略的核心挑战是这些小分子的激活。在工业上，固态金属氧化物催化剂已显示出有效的小分子激活反应（例如，将二氧化碳还原为甲醇）。已经提出，通过材料表面损失氧原子进入的反应性金属离子已被提议参与小分子激活反应。 为了阐明为这些材料表面反应性的多金属系统的性质，Matson实验室将研究如何从组装中去除氧化物氧化物簇的元素组成转化为要去除的氧原子的倾向。这些研究将有助于阐明上催化剂的设计标准，用于生产化学燃料。 Dr. Matson will continue to provide leadership in a campus-wide effort to improve diversity, equity, and inclusion in science, technology, engineering, and mathematics (STEM) departments, and in organizing the Western New York Symposium in inorganic chemistry.This project aims to develop and study the synthesis and reactivity of oxygen-atom vacancies at the surface of vanadium oxide clusters.异质，还原金属氧化物表面的氧气原子空位在惰性，能量贫困的底物向富含能量的化学燃料的转化中起关键作用。了解这些缺陷位点形成的机制以及定义O-ATOM空缺的产生和反应性的结构功能关系，将为具有增强活动的材料的战略设计提供模板。在资金期间，Matson将研究新方案，以形成在多氧化烷酸 - 烷氧化物簇表面的氧原子缺陷。随后，Matson将研究阳离子和阴离子的角色以及表面配体在调节组件表面的氧气 - 原子空位的形成方面发挥作用。所有复合物的表征将通过1H NMR，红外和电子吸收光谱以及电喷雾电离质谱法和单晶X射线衍射。其他动力学分析将提供有关集群表面上与氧气原子空位形成相关的机制和激活参数的洞察力。该奖项反映了NSF的法定任务，并且认为值得通过基金会的智力优点和更广泛的影响审查标准通过评估来获得支持。