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

在化学部门化学结构、动力学和机理a （CSDM-A）项目和刺激竞争研究（EPSCoR）项目的支持下，Pere Miró和他在南达科他州大学的研究小组正在使用先进的计算方法来了解功能化聚钒氧烷酸酯簇的成核和生长，以及这些簇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，因为这些变化经常影响这些物种在恶劣反应条件下的耐久性和行为。因此，理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态物种进化的能力。本文研究的多钒酸盐-醇盐簇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分子模拟物成核的新路线图。该项目包括一项教育推广计划，包括在邻近的部落学院举办实践研讨会，让部落本科生参与科学、技术、工程和数学（STEM）研究，并为K-12学校的学生举办全国化学周活动。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检查第一排官能化多钒氧烷-醇盐簇的成核机制-直到六聚体物种的形成-以及更好地理解动态实验条件对簇的结构-氧化还原关系和多电子反应性的影响。具体来说，密度泛函理论计算与基于域的局部对自然轨道耦合簇和二阶完全活动空间方法相结合，用于表征成核中间体和推导神经网络势，以简化成核空间的探索。本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。这项工作的更广泛的科学影响包括改变有机金属化学社区使用计算方法看待这些物种的功能导向合成的方式，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，包括为来自物理科学领域代表性不足的群体的学生提供定向培训机会。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.