CAREER: Understanding Structure-Function Relationships of Polyoxovanadate-Alkoxide Clusters from a Bottom-Up Perspective

职业：从自下而上的角度理解多氧钒酸盐-醇盐簇的结构-功能关系

• 批准号: 2145657
• 负责人: Pere Miro
• 金额: $ 62.5万
• 依托单位: University of South Dakota Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-03-01 至 2027-02-28
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2145657&HistoricalAwards=false
• 关键词: CAREER; Understanding; Structure; Function; Relationships

WIth support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Pere Miró and his research group at the University of South Dakota are using advanced computational approaches to understand the nucleation and growth of functionalized polyoxovanadate-alkoxide clusters, as well as the ability of these clusters to catalyze the reactions of small molecules. The development of molecular catalysts that have the ability to accelerate complex chemical reactions involving many electrons remains a major challenge due to changes that often affect the durability and behavior of such species under harsh reaction conditions. Therefore, understanding and controlling the properties of these catalytic compounds is of fundamental importance, and relies on the ability to manipulate the evolution of transient species in solution. The polyoxovanadate-alkoxide clusters under study here will provide a useful platform better understand fundamental aspects of the synthesis, reactivity, and durability of metal oxide catalysts, in general, as well as the catalytic activation of small molecules. This work will contribute to the long-term goal of the Miró research group to use modern computational methodologies to discover new roadmaps for the nucleation of molecular mimics of catalytic metal-oxide materials. The project includes an educational outreach program involving hands-on workshops at neighboring tribal colleges, the engagement of tribal undergraduate students in science, technology, engineering, and mathematics (STEM) research, and leading National Chemistry Week activities for students at K-12 schools. Pere Miró and his research team will use high-level quantum chemical calculations and neural network algorithms to examine the nucleation mechanism of first-row functionalized polyoxovanadate-alkoxide clusters--up to the formation of hexameric species--as well as to better understand the impact of dynamic experimental conditions on the structure-redox relationships and multi-electron reactivity of the clusters. Specifically, a combination of density functional theory calculations benchmarked against domain-based local pair natural orbital coupled cluster and second-order complete active space methodologies are being used to characterize nucleation intermediates and derive neural network potentials to streamline the exploration of the nucleation space. This research seeks to enrich the understanding of structure-function relationships that control nucleation and electrocatalytic properties. The scientific broader impacts of this work include transforming the way the organometallic chemistry community views function-oriented synthesis of these species using computational methodologies and to guide the discovery of new functionalities. The project also will provide advanced training opportunities for graduate and undergraduate students, including directed training opportunities for students from groups that are underrepresented in the physical sciences.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.

WIth support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Pere Miró and his research group at the University of South Dakota are using advanced computational approaches to understand the nucleation and growth of functionalized polyoxovanadate-alkoxide clusters, as well as the ability of these clusters to catalyze the reactions of small分子。具有加速涉及许多电子的复杂化学反应能力的分子催化剂的发展仍然是一个重大挑战，这通常会影响Harmsh反应条件下此类物种的耐用性和行为。因此，理解和控制这些催化化合物的性质至关重要，并且依赖于操纵溶液中短暂物质的演变的能力。这里研究的多氧烷氧化烷氧化物簇将提供一个有用的平台，更好地理解金属氧化物催化剂的合成，反应性和耐用性的基本方面，以及小分子的催化激活。这项工作将有助于Miró研究小组的长期目标，以使用现代计算方法来发现新的路线图，以构成催化金属氧化物材料的分子模仿成核。该项目包括一项涉及邻近部落学院的动手讲习班的教育外展计划，部落本科生从事科学，技术，工程和数学研究（STEM）研究以及K-12学校学生的领先国家化学周活动。 PereMiró和他的研究团队将使用高级量子化学计算和神经网络算法来检查第一行官能化的多氧化烷氧化烷氧化物 - 氧化烷氧化物群的成核机制 - 以形成甲式化物种，以便更好地理解动态实验条件对结构性实验条件对结构 - 红分关系关系的影响。具体而言，使用基于域的局部对天然轨道耦合簇和二阶完整空间方法基准的密度功能理论计算的组合用于表征核中间体，并得出神经元网络的潜在，以简化簇的探索。空间。这项研究旨在丰富对控制成核和电催化特性的结构功能关系的理解。这项工作的科学广泛影响包括使用计算方法改变有机化学社区视图以功能为导向的合成方式，并指导发现新功能的方式。该项目还将为研究生和本科生提供先进的培训机会，包括在物理科学中为来自人数不足的学生提供的指导培训机会。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分子优点和更广泛影响标准的智力优点评估来获得的支持。