CAREER: Main-Group Element Catalysis Enabled with Outer Functional Spheres of Molecular Catalysts

职业：利用分子催化剂的外部功能球实现主族元素催化

• 批准号: 2041436
• 负责人: Jianbing Jiang
• 金额: $ 68.5万
• 依托单位: University of Cincinnati Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-04-01 至 2026-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2041436&HistoricalAwards=false
• 关键词: CAREER; Main; Group; Element; Catalysis

With funding from the Chemical Catalysis program in the Division of Chemistry, Professor Jiang of the University of Cincinnati will create metal-free catalysts for carbon dioxide reduction and organohalide dehalogenation. The development of inexpensive and robust catalysts is an important step towards efficient production of chemicals and remediation of environmental pollutants. Traditionally, expensive and rare elements are employed to prepare the catalysts for small molecule conversion due to the high reactivity of the rare elements; however, these systems suffer from toxicity, low abundance, and high cost. In this project, the catalytic activity will be enhanced through the modification of molecular environment around the catalytic active site. Professor Jiang will actively engage a diverse group of underrepresented students in science, technology, engineering and mathematics (STEM) disciplines and the general public in outreach activities focused on chemistry of sustainability. In addition, Professor Jiang's group will develop and maintain an interactive, open-source website for foot-of-the-wave analysis, a powerful technique for evaluating the performance of electrocatalysts. The construction of the website will start soon and be integrated into Professor Jiang's research website for easy access by the community. The results of the proposed research will contribute to the achievement of energy-efficient conversion of abundant small molecules such as carbon dioxide and halogenated pollutants into value-added products, which is both scientifically challenging and strategically important for our society.This project will explore under-developed main-group element catalysis and aims to provide both mechanistic insight and a rational design framework concerning the roles of structural flexibility, pKa, and the size of outer functional spheres in the catalytic activity of tailored 3-dimensional molecular architectures. The proposed study focuses on using bifunctional ligands with redox activity along with outer functional spheres to compensate for the fact that main-group elements lack outer shell d-orbitals. Specifically, Group15-based catalysts using porphyrin ligands with a diverse set of outer functional spheres will be designed, synthesized, and evaluated for carbon dioxide reduction and organohalide dehalogenation. The catalytic performance of the main-group element-based catalysts will be compared to current transition metal-based counterparts. A combination of solution- and surface-based techniques, in conjunction with density-functional theory calculations, will be used to identify reaction intermediates and help elucidate the catalytic mechanism. This research seeks to enrich the understanding of how interactions between redox-active ligands with outer functional spheres and Group 15 elements can be used as a strategy for bond activation, and how the use of a ligand with an outer functional sphere enables Group 15 element catalysis.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资助下，辛辛那提大学的蒋教授将创造用于二氧化碳还原和有机卤化物脱卤的无金属催化剂。开发廉价和耐用的催化剂是有效生产化学品和修复环境污染物的重要一步。传统上，由于稀有元素的高反应性，使用昂贵和稀有元素来制备用于小分子转化的催化剂;然而，这些系统具有毒性、低丰度和高成本。在本计画中，将借由修饰催化活性位周围的分子环境来提升催化活性。江教授将积极吸引科学，技术，工程和数学（STEM）学科中代表性不足的学生和公众参与以可持续发展化学为重点的外展活动。此外，江教授的团队将开发和维护一个用于波脚分析的互动式开源网站，这是一种评估电催化剂性能的强大技术。该网站的建设将很快开始，并将纳入江教授的研究网站，以方便社会各界访问。拟议研究的结果将有助于实现将二氧化碳和卤化污染物等丰富的小分子高效转化为增值产品，这对我们的社会既具有科学挑战性，又具有战略重要性。该项目将探索欠发达的主要-族元素催化，旨在提供关于结构柔性，pKa，以及外部功能球的尺寸在定制的三维分子结构的催化活性中的作用。所提出的研究集中于使用具有氧化还原活性的双官能配体沿着外功能球以补偿主族元素缺乏外壳d-轨道的事实。具体而言，15族为基础的催化剂，使用卟啉配体与一组不同的外部功能球将被设计，合成，并评估二氧化碳还原和有机卤化物脱卤。将主族元素基催化剂的催化性能与当前过渡金属基对应物进行比较。结合溶液和表面为基础的技术，结合密度泛函理论计算，将被用来确定反应中间体，并帮助阐明催化机制。这项研究旨在丰富对氧化还原活性配体与外部功能球和第15族元素之间的相互作用如何可用作键活化策略的理解，该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的评估来支持。影响审查标准。

项目成果

Main group elements in electrochemical hydrogen evolution and carbon dioxide reduction

电化学析氢和二氧化碳还原的主族元素

• DOI: 10.1039/d3cc03606e
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Sinha, Soumalya;Jiang, Jianbing “Jimmy”
• 通讯作者: Jiang, Jianbing “Jimmy”

Electrocatalytic Hydrogen Evolution Using A Molecular Antimony Complex under Aqueous Conditions: An Experimental and Computational Study on Main‐Group Element Catalysis

水相条件下使用分子锑配合物电催化析氢：主族元素催化的实验和计算研究

• DOI: 10.1002/chem.202201323
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Williams, Caroline K.;McCarver, Gavin A.;Chaturvedi, Ashwin;Sinha, Soumalya;Ang, Marcus;Vogiatzis, Konstantinos D.;Jiang, Jianbing “Jimmy”
• 通讯作者: Jiang, Jianbing “Jimmy”

A PEGylated Tin Porphyrin Complex for Electrocatalytic Proton Reduction: Mechanistic Insights into Main‐Group‐Element Catalysis

用于电催化质子还原的聚乙二醇化锡卟啉配合物：对主族元素催化的机理见解

• DOI: 10.1002/anie.202206325
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Chaturvedi, Ashwin;McCarver, Gavin A.;Sinha, Soumalya;Hix, Elijah G.;Vogiatzis, Konstantinos D.;Jiang, Jianbing
• 通讯作者: Jiang, Jianbing