Generation of Single Cation Sites Supported on Oxides

氧化物负载的单阳离子位点的生成

• 批准号: 2101582
• 负责人: Matthew Conley
• 金额: $ 47.5万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-05-01 至 2024-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2101582&HistoricalAwards=false
• 关键词: Generation; Single; Cation; Sites; Supported

With the support of the Chemical Catalysis Program in the Division of Chemistry, Dr. Matthew Conley of the University of California – Riverside is studying ways to accelerate chemical reactions using designer heterogeneous catalysts. These new catalysts are engineered to provide more energy-efficient reaction conditions than traditional approaches. Professor Conley and his research team are invested in developing specialized high surface area materials that can react with metal reagents to form surface-supported metal sites with understandable structures and tunable catalytic activity. This flexible system will be employed to investigate a variety of important processes to generate commodity and specialty chemicals that are important to everyday life. Dr. Conley will be involving students from a Moreno Valley high school in this research program to help foster interest in STEM disciplines and encourage interest in STEM career paths. Single atom catalysts (SACs) provide a more atom-efficient strategy for heterogeneous catalysis than noble metal nanoparticles where only surface atoms are exposed to reagents. The generation of SACs involves the dispersion of very small quantities of noble metal atoms onto a redox active oxide support. Dr. Conley and his research team are developing a new approach to preparing single cation site catalysts (SCSs) and studying the catalytic reactivity of these new materials towards transformations that are important to both the fine and commodity chemical industries. The team will be using this synthetic technology to access high surface area oxides that support very strong silylium Lewis acids as precursors for the targeted SCSs. The silylium-coated oxides will be treated with metal-halide bonds in organometallic complexes to form single cation sites (SCSs) in well-defined coordination environments. This methodology is being used to install single transition metal cations uniformly dispersed on oxide surfaces doped with weakly coordinating anions and is complementary to known methods that generate SACs. Because this approach to generating SCSs can be paired with a variety of organometallic reagents, the Conley group is investigating a range of catalytic activity supported by these materials including olefin polymerization, hydroamination, and hydrosilylation chemistry, as well as the partial oxidation of methane. These efforts to develop SCSs for heterogeneous catalysis also will serve as a strong training environment for a diverse group of graduate, undergraduate, and high school students.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.

在化学系化学催化项目的支持下，加州大学河滨分校的 Matthew Conley 博士正在研究使用设计的多相催化剂加速化学反应的方法。这些新型催化剂经过精心设计，可提供比传统方法更节能的反应条件。康利教授和他的研究团队致力于开发专门的高表面积材料，这些材料可以与金属试剂反应，形成具有可理解结构和可调催化活性的表面支撑金属位点。这个灵活的系统将用于研究各种重要的过程，以生产对日常生活很重要的商品和特种化学品。 Conley 博士将让莫雷诺谷高中的学生参与该研究项目，以帮助培养对 STEM 学科的兴趣并鼓励对 STEM 职业道路的兴趣。与仅表面原子暴露于试剂的贵金属纳米粒子相比，单原子催化剂（SAC）为多相催化提供了更原子有效的策略。 SAC 的生成涉及将极少量的贵金属原子分散到氧化还原活性氧化物载体上。 Conley 博士和他的研究团队正在开发一种新方法来制备单阳离子位点催化剂 (SCS)，并研究这些新材料对精细化工和商品化学工业都很重要的转化的催化反应活性。该团队将利用这种合成技术来获得高表面积氧化物，这些氧化物支持非常强的硅路易斯酸作为目标 SCS 的前体。硅涂层氧化物将用有机金属配合物中的金属卤化物键进行处理，以在明确的配位环境中形成单阳离子位点（SCS）。该方法用于安装均匀分散在掺杂弱配位阴离子的氧化物表面上的单一过渡金属阳离子，并且是对生成 SAC 的已知方法的补充。由于这种生成 SCS 的方法可以与各种有机金属试剂配合使用，因此康利小组正在研究这些材料支持的一系列催化活性，包括烯烃聚合、加氢胺化和氢化硅烷化化学，以及甲烷的部分氧化。这些为多相催化开发 SCS 的努力也将为不同群体的研究生、本科生和高中生提供强大的培训环境。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值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

Formation of a Strong Heterogeneous Aluminum Lewis Acid on Silica

在二氧化硅上形成强非均相铝路易斯酸

• DOI: 10.1002/anie.202205745
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Samudrala, Kavyasripriya K.;Huynh, Winn;Dorn, Rick W.;Rossini, Aaron J.;Conley, Matthew P.
• 通讯作者: Conley, Matthew P.

Ring Contraction of a Tungstacyclopentane Supported on Silica: Direct Conversion of Ethylene to Propylene

二氧化硅负载的钨环戊烷的环收缩：乙烯直接转化为丙烯

• DOI: 10.1021/jacs.2c07934
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Rodriguez, Jessica;Boudjelel, Maxime;Mueller, Leonard J.;Schrock, Richard R.;Conley, Matthew P.
• 通讯作者: Conley, Matthew P.

The coordination chemistry of oxide and nanocarbon materials

氧化物和纳米碳材料的配位化学

• DOI: 10.1039/d2dt00459c
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Bekyarova, Elena;Conley, Matthew P.
• 通讯作者: Conley, Matthew P.