CAREER: Elucidating and Harnessing Metal-Support Interactions using Designer Nanoclusters as Functional Models

职业：使用设计纳米团簇作为功能模型来阐明和利用金属支持相互作用

• 批准号: 1944843
• 负责人: Alexandra Velian
• 金额: $ 67.5万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-02-01 至 2025-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1944843&HistoricalAwards=false
• 关键词: CAREER; Elucidating; Harnessing; Metal; Support

Many industrial processes involve chemical reactions that take place on the surface of metallic solids. While solid materials are very effective in converting one chemical to another, they do not dissolve in liquids that commonly are necessary for many reactions and that can slow the reaction speeds. The synthesis of small molecules that mimic the behavior of solid surfaces in speeding up reactions while dissolving in solution could improve chemical manufacturing. In this project Professor Alexandra Velian, Chemistry Department, University of Washington, is supported by the Chemical Synthesis Program of the Chemistry Division to prepare small molecule species that address this challenge. Her synthetic targets are small clusters of atoms that contain an exposed metal site where chemical reactivity can occur. These materials can be dissolved in solution and thus, they may improve the selectivity, stability, and tunability of the reactions they promote. The research gives a fundamental understanding of how reactions at a single metal atom occur. This knowledge then may be used to determine the basic steps in important industrial-scale chemical conversions. The research is integrated with a broad-based outreach effort to engage, enable and retain first-generation, underrepresented or low-income students in the STEM pipeline, and empower them to attain their professional potential. To achieve these goals, Professor Velian provides one-on-one mentorship to students, enables hands on research via “Chemistry Frontiers” - a new course to inform and engage students in contemporary research early in their undergraduate careers, and connects faculty with research active students. The surface functionalization of Co6Se8 clusters is used to synthesize nanoclusters with surface-embedded, tunable single atom active sites. These systems serve as functional models for metal–support constructs. The parameters that govern how metal–support interaction and vicinal active site activity alter the reactivity profile of key intermediates in typical reaction cycles are evaluated. This leads to a synthetic paradigm to design and prepare modular single atom materials from surface-functionalized Co6Se8-based nanoclusters. Concurrent with these research efforts Dr. Velian and her team actively work to promote diversity, inclusion and equity in science through an initiative that integrates mentorship, engagement in research, and immersion into the research community, with a focus on disenfranchised students at the University of Washington and in the greater Seattle area. The team also engages and educates the broader scientific and non-scientific community about the significance of heterogeneous catalysis on industrial processes.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.

许多工业过程涉及在金属固体表面发生的化学反应。虽然固体材料在将一种化学物质转化为另一种化学物质方面非常有效，但它们不溶于液体，而液体通常是许多反应所必需的，会减缓反应速度。小分子的合成可以模拟固体表面在溶解时加速反应的行为，这可能会改善化学制造。在这个项目中，华盛顿大学化学系的Alexandra Velian教授得到了化学系化学合成计划的支持，以准备应对这一挑战的小分子物种。她的合成目标是微小的原子簇，其中包含一个暴露的金属位置，在那里可以发生化学反应。这些物质可以溶解在溶液中，因此它们可以提高它们促进的反应的选择性、稳定性和可调性。这项研究对单个金属原子的反应是如何发生的有了基本的了解。这些知识可以用来确定重要的工业规模的化学转化的基本步骤。这项研究与基础广泛的外联工作相结合，以吸引、帮助和留住STEM渠道中的第一代、代表性不足或低收入学生，并增强他们实现职业潜力的能力。为了实现这些目标，韦利安教授为学生提供一对一的指导，通过“化学前沿”-一门新课程，让学生在本科生涯早期就了解并参与当代研究，并将教师与活跃于研究的学生联系起来。Co6Se8团簇的表面功能化被用来合成具有表面嵌入的、可调谐的单原子活性中心的纳米团簇。这些系统充当金属支撑结构的功能模型。对控制金属-载体相互作用和邻近活性中心活性如何改变典型反应周期中关键中间体的反应性分布的参数进行了评估。这导致了一种从表面功能化的Co6Se8纳米团簇设计和制备模块化单原子材料的合成范式。在这些研究工作的同时，Velian博士和她的团队积极致力于促进科学的多样性、包容性和公平性，通过一项将导师指导、参与研究和沉浸于研究社区的倡议，重点关注华盛顿大学和大西雅图地区被剥夺公民权的学生。该团队还参与并教育了更广泛的科学和非科学社区，使他们了解多相催化对工业过程的重要性。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。

项目成果

Probing Edge/Support Electronic Cooperativity in Single Edge Fe/Co 6 Se 8 Clusters

探测单边缘 Fe/Co 6 Se 8 团簇中的边缘/支持电子协同性

• DOI: 10.1021/acs.inorgchem.3c01661
• 发表时间: 2023
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Mitchell, Benjamin S.;Chirila, Andrei;Anderton, Kevin J.;Kaminsky, Werner;Velian, Alexandra
• 通讯作者: Velian, Alexandra

Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst

Cr/Co/Se 分子簇催化剂上的多活性位点动力学

• DOI: 10.1021/jacs.2c00234
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Kephart, Jonathan A.;Mitchell, Benjamin S.;Kaminsky, Werner;Velian, Alexandra
• 通讯作者: Velian, Alexandra

Tuning the Electronic Structure of Atomically Precise Sn/Co/Se Nanoclusters via Redox Matching of Tin(IV) Surface Sites

• DOI: 10.1021/acs.inorgchem.1c00313
• 发表时间: 2021-04-11
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Mitchell, Benjamin S.;Kaminsky, Werner;Velian, Alexandra
• 通讯作者: Velian, Alexandra

Metal/Support Interactions Regulate Substrate Binding in Fe/Co/Se Cluster Catalysts

金属/载体相互作用调节 Fe/Co/Se 簇催化剂中的底物结合

• DOI: 10.1021/acs.inorgchem.3c01601
• 发表时间: 2023
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Mitchell, Benjamin S.;Chirila, Andrei;Zhou, Daniel Y.;Kephart, Jonathan A.;Velian, Alexandra
• 通讯作者: Velian, Alexandra

Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters

• DOI: 10.1039/d0dt02416c
• 发表时间: 2020-12-07
• 期刊: DALTON TRANSACTIONS
• 影响因子: 4
• 作者: Kephart, Jonathan A.;Boggiano, Andrew C.;Velian, Alexandra
• 通讯作者: Velian, Alexandra