RUI: Reductive Activation of Carbon Dioxide by Binuclear Copper Complexes with a Copper-Copper Unit

RUI：具有铜-铜单元的双核铜配合物对二氧化碳的还原活化

• 批准号: 1856438
• 负责人: Lei Yang
• 金额: $ 13.98万
• 依托单位: University of Central Arkansas
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-06-15 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856438&HistoricalAwards=false
• 关键词: RUI; Reductive; Activation; Carbon; Dioxide

Dr. Lei Yang at the University of Central Arkansas is leading a program aimed at converting carbon dioxide into useful chemicals. This theme is attractive because carbon dioxide is abundant. To accelerate the reactions of carbon dioxide, metal-based catalysts are often used. The way by which these catalysts operate is still not well understood, which slows commercial applications. To address this gap, detailed studies are required for known catalysts to understand how they operation. This will help in the design of new catalysts. Dr. Yang's project emphasizes both directions - building understanding and new design. In this project, Dr. Yang's group is making special ligands that hold pairs of copper atoms together. Preliminary tests show that these di-copper catalysts are promising for conversions of carbon dioxide. These activities are well suited for training students. Under the guidance of Dr. Yang, undergraduate students gain hands-on experience in both organic and inorganic chemistry. Additionally, students receive training with state-of-the-art instrumentation. This training is designed to spark their interest in technology careers. This project is jointly funded by CHE and the Established Program to Stimulate Competitive Research (EPSCoR).To convert carbon dioxide (CO2) to value-added chemicals for industry, Dr. Lei Yang's group at the University of Central Arkansas is focusing on the development of new binuclear copper catalysts featuring pairs of CuI centers. The metals are held in close proximity by special binucleating ligands that enforce close Cu-Cu interaction. The functions of the Cu-Cu unit are to reduce CO2 in a cooperative fashion through one electron transfer process and to stabilize the reduction intermediates and products. The distinctive ligand design promises high catalytic efficiency and product selectivity. The structures of the catalysts are characterized by X-ray crystallography. Additional spectroscopic characterization is provided by ultraviolet-visible (UV-vis), Fourier-transform infrared (FT-IR), electron paramagnetic resonance (EPR), and X-ray photoelectron (XPS) spectroscopies. The goal is to obtain fundamental insights into the mechanisms of CO2 reduction. Density functional theory (DFT) computational studies are conducted to predict intermediate structures and interpret spectroscopic data. Dr. Yang supervises undergraduate students in this research program to enhance their understanding of chemical sciences and improve their experimental and teamwork skills. This project serves as a way to inspire and prepare students for successful careers in STEM fields.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.

中阿肯色大学的杨雷博士正在领导一项旨在将二氧化碳转化为有用化学物质的项目。 这个主题很有吸引力，因为二氧化碳储量丰富。为了加速二氧化碳的反应，通常使用金属基催化剂。这些催化剂的运作方式仍不清楚，这阻碍了商业应用。为了解决这一差距，需要对已知催化剂进行详细研究，以了解它们的工作原理。 这将有助于设计新的催化剂。杨博士的项目强调两个方向——建立理解和新设计。在这个项目中，杨博士的团队正在制造特殊的配体，将成对的铜原子固定在一起。初步测试表明这些双铜催化剂有望用于二氧化碳的转化。 这些活动非常适合培训学生。 在杨博士的指导下，本科生获得了有机和无机化学的实践经验。 此外，学生还接受使用最先进仪器的培训。 该培训旨在激发他们对技术职业的兴趣。该项目由 CHE 和刺激竞争性研究既定计划 (EPSCoR) 联合资助。为了将二氧化碳 (CO2) 转化为工业用增值化学品，中阿肯色大学雷扬博士的团队致力于开发具有成对 CuI 中心的新型双核铜催化剂。这些金属通过特殊的双核配体紧密结合在一起，从而增强了铜-铜之间的紧密相互作用。 Cu-Cu单元的功能是通过一个电子转移过程以协同方式还原CO2并稳定还原中间体和产物。独特的配体设计保证了高催化效率和产物选择性。催化剂的结构通过X射线晶体学表征。 紫外-可见 (UV-vis)、傅里叶变换红外 (FT-IR)、电子顺磁共振 (EPR) 和 X 射线光电子 (XPS) 光谱可提供其他光谱表征。目标是获得对二氧化碳减排机制的基本见解。进行密度泛函理论 (DFT) 计算研究来预测中间结构并解释光谱数据。杨博士指导该研究项目的本科生，以增强他们对化学科学的理解并提高他们的实验和团队合作技能。该项目旨在激励学生并为其在 STEM 领域的成功职业做好准备。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

Synthesis and Characterization of Cu(II) and Mixed-Valence Cu(I)Cu(II) Clusters Supported by Pyridylamide Ligands

吡啶酰胺配体支持的 Cu(II) 和混合价 Cu(I)Cu(II) 簇的合成与表征

• DOI: 10.1021/acs.inorgchem.0c00008
• 发表时间: 2020-04
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Schneider, Joseph D.;Smith, Brett A.;Williams, Grant A.;Powell, Douglas R.;Perez, Felio;Rowe, Gerard T.;Yang, Lei
• 通讯作者: Yang, Lei