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.

在化学部化学结构、动力学和机理-A(CSDM-A)计划和既定的刺激竞争研究计划(EPSCoR)的支持下，南达科他州大学的Pere Miró和他的研究小组正在使用先进的计算方法来理解官能化聚钒-醇盐簇合物的成核和生长，以及这些簇合物催化小分子反应的能力。开发能够加速涉及许多电子的复杂化学反应的分子催化剂仍然是一个重大挑战，因为变化往往会影响这些物种在恶劣反应条件下的耐久性和行为。因此，了解和控制这些催化化合物的性质是至关重要的，并且依赖于操纵溶液中瞬时物种的演化的能力。这里正在研究的多钒酸盐-醇盐簇合物将提供一个有用的平台，更好地了解金属氧化物催化剂的合成、反应活性和耐久性的基本方面，以及小分子的催化活化。这项工作将有助于Miró研究小组的长期目标，即使用现代计算方法来发现催化金属氧化物材料的分子模拟成核的新路线图。该项目包括一个教育推广计划，包括在邻近的部落大学举办动手研讨会，让部落本科生参与科学、技术、工程和数学(STEM)研究，以及领导为K-12学校的学生举办的国家化学周活动。Pere Miró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研究第一排功能化聚钒-醇盐簇合物的成核机制-直到六聚体物种的形成-以及更好地了解动态实验条件对团簇结构-氧化还原关系和多电子反应性的影响。具体地说，以基于区域的局部对自然轨道耦合团簇和二阶完全活性空间方法为基准的密度泛函理论计算方法被用于表征成核中间体和推导神经网络势来简化成核空间的探索。这项研究旨在丰富对控制成核和电催化性质的结构-功能关系的理解。这项工作的科学影响更广泛，包括改变有机金属化学界看待这些物种的以功能为导向的合成的方式，使用计算方法并指导新功能的发现。该项目还将为研究生和本科生提供高级培训机会，包括为物理科学中代表性不足的群体的学生提供定向培训机会。该奖项反映了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。