CAS: Design and Mechanistic Understanding of Selective Electrocatalysts Based on Earth-Abundant Metal Compounds

CAS：基于地球储量丰富的金属化合物的选择性电催化剂的设计和机理理解

• 批准号: 1955074
• 负责人: Song Jin
• 金额: $ 65万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-15 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955074&HistoricalAwards=false
• 关键词: CAS; Design; Mechanistic; Understanding; Selective

With this award,the Chemical Catalysis Program of the Division of Chemistry is supporting Drs. Song Jin and Jordan Schmidt of the University of Wisconsin-Madison to combine theory and experiment to design, develop, and understand new electrochemical methods to generated hydrogen peroxide (H2O2) from molecular oxygen. Hydrogen peroxide (H2O2) is an environmentally benign oxidant with many industrial and environmental applications. It is also a recommended disinfectant in general, including for the novel coronavirus responsible for the COVID-19 pandemic. The current commercial production of H2O2 is characterized by significant cost, energy consumption, and safety concerns. To be economically competitive the current process is practiced in a few large, centralized manufacturing plants. In comparison, small scale, decentralized, on-site production of H2O2 directly from oxygen using electricity could be a more effective and sustainable approach. However, electrochemical approaches to H2O2 need to be much more efficient and less costly to be viable. The success of this project can facilitate the efficient decentralized production of H2O2 and have broad technological impacts related to the environment, sustainability, and the healthcare fiels. This project includes a significant educational outreach component and seeks to build a more diverse scientific workforce through inclusive training.Drs. Song Jin and Jordan Schmidt and their team combine theory and experiment to exploit the unique attributes of unexplored metal compound electrocatalysts to design, develop, and understand new and selective electrocatalysts based on metal chalcogenides for the selective two-electron oxygen reduction reaction (2e ORR) in acidic and neutral solutions. Such selective 2e ORR electrocatalysts can facilitate decentralized electrochemical production of H2O2, an environmentally benign oxidant with diverse applications in industrial, environmental, and healthcare settings. Density functional theory calculations and kinetic models provide detailed insights into activity and selectivity and identify promising candidate structures among transition metal chalcogenides for subsequent synthesis and performance evaluation. Electrochemical and (in situ) spectroscopic studies reveal catalyst activity, selectivity, and potential-dependent reaction intermediates, with computational examination providing mechanistic insights into the catalytic mechanism(s) and further design principles governing catalyst selectivity and stability. Understanding and rationally designing complex metal compound catalysts for enabling various selective electrocatalytic reactions can lead to fundamental and transferrable insights into how complex structural motifs influence catalyst activity and selectivity. The success of this project can also facilitate the efficient decentralized electrochemical production of H2O2 and, as such, has the potential for broad scientific and societal impact.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.

有了这个奖项，化学系的化学催化计划正在支持DRS。威斯康星大学麦迪逊分校的Song Jin和Jordan Schmidt结合了理论和实验，以设计，开发和理解从分子氧中产生过氧化氢（H2O2）的新的电化学方法。过氧化氢（H2O2）是一种具有许多工业和环境应用的环境良性氧化剂。通常，这也是推荐的消毒剂，其中包括负责COVID-19大流行的新型冠状病毒。 H2O2的当前商业生产的特征是大量成本，能源消耗和安全问题。为了在经济上具有竞争力，目前的过程是在几个大型的集中制造厂中进行的。相比之下，直接使用电力从氧气中直接从氧气中的小规模，分散的H2O2现场生产可能是一种更有效和可持续的方法。但是，H2O2的电化学方法需要更有效，并且成本较低。该项目的成功可以促进H2O2的有效分散生产，并具有与环境，可持续性和医疗保健菲尔斯有关的广泛技术影响。该项目包括一个重要的教育外展部分，并试图通过包容性培训来建立更多样化的科学劳动力。 Song Jin和Jordan Schmidt及其团队结合了理论和实验，以利用未探索的金属化合物复合电催化剂的独特属性，以设计，开发和理解基于金属硫代基化的新的和选择性的电催化剂，以基于选择性的两种含氧氧化物的酸和中性溶液中选择性的两种电氧降低反应（2E ORR）。这种选择性2E ORR电催化剂可以促进H2O2的分散化电化学生产，这是一种环境良性氧化剂，在工业，环境和医疗保健环境中具有多种应用。密度功能理论的计算和动力学模型提供了对活动和选择性的详细见解，并确定过渡金属金属核化合物之间有希望的候选结构，以进行随后的合成和绩效评估。电化学和（原位）光谱研究揭示了催化剂活性，选择性和潜在依赖性反应中间体，计算检查提供了对催化机制的机械见解，并提供了有关催化剂选择性和稳定性的进一步设计原理。理解和合理设计用于实现各种选择性电催化反应的复杂金属复合催化剂可以导致对复杂结构基序如何影响催化剂活性和选择性的基本和可转让的见解。该项目的成功还可以促进H2O2的有效分散化的电化学生产，因此，这一奖项反映了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的审查标准来通过评估来支持的。

项目成果

Linear paired electrochemical valorization of glycerol enabled by the electro-Fenton process using a stable NiSe2 cathode

• DOI: 10.1038/s41929-022-00826-y
• 发表时间: 2022-08
• 期刊: Nature Catalysis
• 影响因子: 37.8
• 作者: Hongyuan Sheng;Aurora N. Janes;R. Ross;H. Hofstetter;Kwan-Young Lee;J. Schmidt;S. Jin

Compositionally Tuned Trimetallic Thiospinel Catalysts for Enhanced Electrosynthesis of Hydrogen Peroxide and Built-In Hydroxyl Radical Generation

• DOI: 10.1021/acscatal.1c03349
• 发表时间: 2021-09-30
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Ross, R. Dominic;Sheng, Hongyuan;Jin, Song
• 通讯作者: Jin, Song

Torsion strained iridium oxide for efficient acidic water oxidation in proton exchange membrane electrolyzers

• DOI: 10.1038/s41565-021-00986-1
• 发表时间: 2021-10-25
• 期刊: NATURE NANOTECHNOLOGY
• 影响因子: 38.3
• 作者: Hao, Shaoyun;Sheng, Hongyuan;Jin, Song
• 通讯作者: Jin, Song

Metal-Compound-Based Electrocatalysts for Hydrogen Peroxide Electrosynthesis and the Electro-Fenton Process

• DOI: 10.1021/acsenergylett.2c01945
• 发表时间: 2022-11
• 期刊: ACS Energy Letters
• 影响因子: 22
• 作者: Hongyuan Sheng;R. Ross;J. R. Schmidt;S. Jin