CAS: Voltage-Driven Molecular Catalysis

在化学系化学催化（CAT）项目的支持下，纽约城市大学皇后学院的Michael Mirkin教授和Guoxiang Hu教授将电化学技术与理论和计算方法相结合，研究电压驱动的分子催化。提高对电压驱动分子催化的理解可以促进下一代混合催化剂的发展，对能源技术和合成化学都具有重要意义。该项目还为研究生和本科生提供培训机会，他们将接受电催化、扫描探针显微镜、计算化学和纳米科学等多学科研究培训。计划向高中学生介绍一般的科学方法，特别是催化和能源科学。在这个项目中，纽约城市大学皇后学院的Michael Mirkin教授和Guoxiang Hu教授将研究界面电位下降对表面结合分子催化剂活性的重要影响。混合电压驱动的分子催化剂正在被开发用于一些重要的能源相关过程，如析氧反应（OER）和析氢反应（HER）以及H2O2和醇的氧化。不同的氧化还原介质，包括完全有机分子催化剂TEMPO[（2,2,6,6-四甲基胡椒碱-1-基）氧]，将附着在催化惰性碳表面，并研究催化剂的化学性质、溶液离子强度等因素对反应动力学的影响。扫描电化学显微镜（SECM）将用于测量催化速率常数作为应用电位的函数。电压驱动分子催化的概念也将应用于电合成。电压驱动的分子催化剂可以促进电合成反应，如果没有电场的帮助，它就没有催化能力。研究了应用电位、溶剂和其他实验因素对反应收率和选择性的影响。基于密度泛函理论（DFT）的第一性原理电子结构计算将有助于阐明电压驱动分子催化机理的细节。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 Catalysis (CAT) Program of the Chemistry Division, Professors Michael Mirkin and Guoxiang Hu of the City University of New York, Queens College are using electrochemical techniques in combination with theoretical and computational approaches to investigate voltage-driven molecular catalysis. Improved understanding of voltage-driven molecular catalysis can facilitate the development of next-generation hybrid catalysts with important implications for both energy technology and synthetic chemistry. The project is also providing training opportunities for graduate and undergraduate students, who will receive multidisciplinary research training in electrocatalysis, scanning probe microscopy, computational chemistry, and nanoscience. Outreach involving high school students is planned to introduce them to the scientific approach, in general, and to catalysis and energy science in particular.In this project, Professors Michael Mirkin and Guoxiang Hu of the City University of New York, Queens College will study the fundamentally important and incompletely understood effect of the interfacial potential drop on activity of a surface-bound molecular catalyst. Hybrid voltage-driven molecular catalysts are being developed for several fundamentally important energy-related processes, such as the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) and oxidations of H2O2 and alcohols. Different redox mediators, including a fully organic molecular catalyst, TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl], will be attached to the catalytically inert carbon surface and the effects of chemical nature of the catalyst, solution ionic strength, and other factors on reaction kinetics will be investigated. Scanning electrochemical microscopy (SECM) will be used to measure catalytic rate constants as a function of the applied potential. The concept of voltage-driven molecular catalysis is also to be applied to electrosynthesis. A voltage-driven molecular catalyst can facilitate electrosynthetic reactions, which it has no capacity to catalyze without field assistance. The effects of the applied potential, solvent, and other experimental factors on the reaction yield and selectivity will be investigated. First-principles electronic structure calculations based on density-functional theory (DFT) will be performed to help elucidate details of the mechanism of voltage-driven molecular 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.