Collaborative Research: Regulating homogeneous and heterogeneous mechanisms in six-electron water oxidation

合作研究：调节六电子水氧化的均相和非均相机制

• 批准号: 1855657
• 负责人: Maureen Tang
• 金额: $ 25.03万
• 依托单位: Drexel University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-01-01 至 2024-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855657&HistoricalAwards=false
• 关键词: Collaborative; Research; Regulating; homogeneous; heterogeneous

Professor John A. Keith of the University of Pittsburgh and Professor Maureen H. Tang of Drexel University are supported by the Chemical Catalysis Program of the Division of Chemistry to conduct a combined experimental/theoretical study to understand the formation of ozone through the electrocatalytic oxidation of water. The largest use of ozone (O3) is in the preparation of pharmaceuticals, synthetic lubricants, and other commercially-useful organic compounds. Ozone is also used to kill bacteria in municipal drinking water. Electrochemical ozone production involves heterogeneous (on electrode surfaces) and homogeneous (in solution) chemical steps. Specifically, the study seeks to understand how and why this process occurs the way it does through the use of computational catalysis modeling in tandem with experimental measurements. Once the mechanism is established, recently developed computational high-throughput screening methods will be used to theoretically design and experimentally validate catalysts for ozone production. The project is expected to deliver fundamental knowledge on electrocatalytic reactions. Success is expected to satisfy the basic societal need for such a commodity. Students are trained in combined experimental and theoretical chemistry research tools. Middle schools in urban areas with high populations of underrepresented groups are targeted with outreach plans. Existing activities that leverage the facilities of the Office of Diversity and Drexel's Lindy Center are continued and expanded. The project addresses the production of ozone via electrocatalytic oxidation of water. Specifically, the study seeks to understand how and why electrochemical steps occur in solution phase (homogeneously) and on an electrode surface (heterogeneously). Computational catalysis modeling while accounting for local solvation environments are combined with experimental ex situ electron paramagnetic resonance studies, differential electrochemical mass spectroscopy, and photocatalysis techniques to develop a complete understanding of the electrochemical ozone production mechanism (EOP). Three basic scientific questions are addressed: 1) what is the key EOP intermediate that leads to ozone and how is it generated? 2) why do certain catalyst materials and configurations uniquely improve EOP selectivity? and 3) can improved mechanistic understanding lead to novel and improved EOP catalysts? This project is expected to lay important foundational work that is needed to understand fundamental electrocatalysis reaction mechanisms that involve homogeneous and heterogeneous steps. It is also expected to validate EOP as a means to sustainable production of ozone.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.

John A.匹兹堡大学的基思和莫琳·H. 德雷克塞尔大学的Tang教授在化学系化学催化项目的支持下进行了一项综合实验/理论研究，以了解通过水的电催化氧化形成臭氧。 臭氧（O3）的最大用途是制备药物，合成润滑剂和其他商业上有用的有机化合物。臭氧也被用来杀死城市饮用水中的细菌。 电化学臭氧生产涉及非均相（电极表面）和均相（溶液中）化学步骤。 具体来说，该研究旨在了解这个过程是如何以及为什么会发生的，它通过使用计算催化建模与实验测量相结合。 一旦建立了机制，最近开发的计算高通量筛选方法将用于理论设计和实验验证臭氧生产催化剂。 该项目预计将提供关于电催化反应的基础知识。 预计成功将满足这种商品的基本社会需求。 学生接受实验和理论化学研究工具相结合的培训。 在代表性不足群体人口较多的城市地区，中学是外联计划的目标。 利用多样性办公室和德雷克塞尔的林迪中心的设施的现有活动将继续和扩大。 该项目涉及通过水的电催化氧化产生臭氧。具体而言，该研究旨在了解电化学步骤如何以及为什么发生在溶液相（均匀）和电极表面（不均匀）。 计算催化建模，同时占当地溶剂化环境相结合的实验非原位电子顺磁共振研究，差分电化学质谱，和电化学臭氧生成机制（EOP）的发展一个完整的理解。 三个基本的科学问题得到解决：1）什么是导致臭氧的关键EOP中间体，它是如何产生的？2)为什么某些催化剂材料和结构独特地提高EOP选择性？和3）改进的机理理解能导致新的和改进的EOP催化剂吗？该项目有望为理解涉及均相和非均相步骤的基本电催化反应机理奠定重要的基础工作。 该奖项反映了NSF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。

项目成果

Gd‐Ni‐Sb‐SnO2 electrocatalysts for active and selective ozone production

Gd-Ni-Sb-SnO2 电催化剂用于主动和选择性臭氧生产

• DOI: 10.1002/aic.17486
• 发表时间: 2021
• 期刊: AIChE Journal
• 影响因子: 3.7
• 作者: Lansing, James L.;Zhao, Lingyan;Siboonruang, Tana;Attanayake, Nuwan H.;Leo, Angela B.;Fatouros, Peter;Park, So Min;Graham, Kenneth R.;Keith, John A.;Tang, Maureen
• 通讯作者: Tang, Maureen