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: 1856460
• 负责人: John Keith
• 金额: $ 22.28万
• 依托单位: University of Pittsburgh
• 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 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856460&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.

匹兹堡大学的约翰·基思（John A. Keith）教授和德雷克塞尔大学（Drexel University）的莫琳·H·唐（Maureen H. 臭氧（O3）的最大用途是制备药物，合成润滑剂和其他商业使用的有机化合物。臭氧还用于杀死市政饮用水中的细菌。 电化学臭氧的产生涉及异质（在电极表面）和均质（在溶液中）化学步骤。 具体而言，该研究试图了解该过程是如何以及为什么通过使用计算催化建模与实验测量相结合的方式进行的。 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上设计，并实验验证催化剂以生产臭氧。 预计该项目将提供有关电催化反应的基本知识。 预计成功将满足这种商品的基本社会需求。 学生接受了合并的实验和理论化学研究工具的培训。 人群中代表性不足的群体人口众多的中学均采用外展计划。 利用多元化办公室和德雷克塞尔林迪中心设施的现有活动继续进行并扩大。 该项目通过水的电催化氧化来解决臭氧的生产。具体而言，该研究试图了解电化学步骤在溶液阶段（同质）和电极表面（异质性）的原因以及为什么发生。 计算催化模型在考虑局部溶剂化环境的同时，将实验性的电磁磁共振共鸣研究，差异电化学质谱和光催化技术结合在一起，以完全了解电化学臭氧生产机制（EOP）。 解决了三个基本的科学问题：1）导致臭氧的关键EOP中间体是什么？如何产生？ 2）为什么某些催化剂材料和配置独特地提高了EOP选择性？ 3）可以提高机械理解会导致新颖和改善的EOP催化剂吗？预计该项目将奠定重要的基础工作，以了解涉及均匀和异质步骤的基本电催化反应机制。 预计它将验证EOP作为可持续生产臭氧的一种手段。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛影响的审查标准来评估值得支持的。

项目成果

Deeper learning in electrocatalysis: realizing opportunities and addressing challenges

• DOI: 10.1016/j.coche.2022.100824
• 发表时间: 2022-06
• 期刊: Current Opinion in Chemical Engineering
• 影响因子: 6.6
• 作者: J. Keith;James R. McKone;J. Snyder;Maureen H. Tang

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

Machine learning corrected alchemical perturbation density functional theory for catalysis applications

• DOI: 10.1002/aic.17041
• 发表时间: 2020-10
• 期刊: Aiche Journal
• 影响因子: 3.7
• 作者: Charles D Griego;Lingyan Zhao;K. Saravanan;J. Keith

Computationally Guided Searches for Efficient Catalysts through Chemical/Materials Space: Progress and Outlook

通过化学/材料空间计算引导寻找高效催化剂：进展与展望

• DOI: 10.1021/acs.jpcc.0c11345
• 发表时间: 2021
• 期刊: The Journal of Physical Chemistry C
• 作者: Griego, Charles D.;Maldonado, Alex M.;Zhao, Lingyan;Zulueta, Barbaro;Gentry, Brian M.;Lipsman, Eli;Choi, Tae Hoon;Keith, John A.
• 通讯作者: Keith, John A.