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

在化学系化学合成计划的支持下，罗切斯特大学的Ellen Matson将研究氧化钒团簇表面氧原子空位的合成和反应活性。在考虑当今社会面临的全球挑战时，确保未来能源资源的安全问题尤为突出。随着化石燃料的枯竭，化学家们将重点转向研究合成方法，将丰富的温室气体转化为能源丰富的化学燃料。制定可持续和可再生燃料生产战略的一个核心挑战是激活这些小分子。在工业上，固态金属氧化物催化剂已被证明在调解小分子活化反应(例如，将二氧化碳还原为甲醇)方面是有效的。活性金属离子通过失去材料表面的一个氧原子而被认为参与了小分子的活化反应。为了阐明影响这些材料表面反应性的多金属系统的性质，马特森实验室将研究氧化钒团簇的元素组成如何转化为氧原子从组装中移除的倾向。这些研究将有助于阐明生产化学燃料的优良催化剂的设计标准。Matson博士将继续领导整个校园的努力，以提高科学、技术、工程和数学(STEM)系的多样性、公平性和包容性，并组织纽约西部无机化学研讨会。该项目旨在开发和研究氧化钒团簇表面氧原子空位的合成和反应活性。异质、可还原金属氧化物表面的氧原子空位在惰性、能源贫乏的底物转化为能源丰富的化学燃料的过程中起着关键作用。了解这些缺陷位形成的机制(S)，以及定义O-原子空位的产生和反应的结构-功能关系，将为具有增强活性的材料的战略设计提供模板。在资助期间，Matson将研究在多氧钒酸-醇盐簇合物表面形成氧原子缺陷的新方案。随后，马特森将研究阳离子和阴离子掺杂以及表面配体在调节组装表面氧原子空位形成方面所起的作用。所有配合物的表征将通过核磁共振氢谱、红外光谱、电子吸收光谱、电喷雾电离质谱仪和单晶X射线衍射法进行。额外的动力学分析将提供与星团表面氧原子空位形成相关的机制和激活参数的洞察。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.