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.

凭借这一奖项，化学系的化学催化项目正在支持博士们。威斯康星大学麦迪逊分校的 Song Jin 和 Jordan Schmidt 将理论和实验结合起来，设计、开发和理解从分子氧生成过氧化氢 (H2O2) 的新电化学方法。过氧化氢 (H2O2) 是一种环境友好的氧化剂，具有许多工业和环境应用。它也是一种推荐的一般消毒剂，包括针对导致 COVID-19 大流行的新型冠状病毒的消毒剂。目前 H2O2 的商业化生产具有巨大的成本、能源消耗和安全问题。为了具有经济竞争力，目前的工艺在一些大型集中制造工厂中实施。相比之下，利用电力直接从氧气中小规模、分散、现场生产 H2O2 可能是一种更有效和可持续的方法。然而，H2O2 的电化学方法需要更加高效且成本更低才能可行。该项目的成功可以促进 H2O2 的高效分散生产，并对环境、可持续发展和医疗保健领域产生广泛的技术影响。该项目包括重要的教育外展部分，旨在通过包容性培训建立更加多元化的科学队伍。 Song Jin和Jordan Schmidt及其团队将理论与实验相结合，利用未开发的金属化合物电催化剂的独特属性来设计、开发和了解基于金属硫属化物的新型选择性电催化剂，用于选择性双电子氧还原反应（2e ORR）在酸性和中性溶液中。这种选择性 2e ORR 电催化剂可以促进 H2O2 的分散电化学生产，H2O2 是一种环境友好的氧化剂，在工业、环境和医疗保健环境中具有多种应用。密度泛函理论计算和动力学模型提供了对活性和选择性的详细见解，并确定了过渡金属硫属化物中有前途的候选结构，用于后续合成和性能评估。电化学和（原位）光谱研究揭示了催化剂活性、选择性和电位依赖性反应中间体，通过计算检查提供了对催化机制的机械见解以及控制催化剂选择性和稳定性的进一步设计原则。了解并合理设计用于实现各种选择性电催化反应的复杂金属化合物催化剂，可以对复杂结构基序如何影响催化剂活性和选择性产生基本且可转移的见解。该项目的成功还可以促进 H2O2 的高效分散电化学生产，因此具有广泛的科学和社会影响的潜力。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值进行评估，被认为值得支持以及更广泛的影响审查标准。

项目成果

Operando Elucidation of Electrocatalytic and Redox Mechanisms on a 2D Metal Organic Framework Catalyst for Efficient Electrosynthesis of Hydrogen Peroxide in Neutral Media

中性介质中高效电合成过氧化氢的二维金属有机骨架催化剂的电催化和氧化还原机制的操作阐明

• DOI: 10.1021/jacs.2c06810
• 发表时间: 2022-08
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Ross, R. Dominic;Sheng, Hongyuan;Ding, Yujia;Janes, Aurora N.;Feng, Dawei;Schmidt, J. R.;Segre, Carlo U.;Jin, Song
• 通讯作者: Jin, Song

Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO 3 Electrocatalyst with Enhanced Iridium Mass Activity

增强铱质量活性的 9R-BaIrO 3 电催化剂酸性析氧活性层结构的鉴定

• DOI: 10.1021/jacs.1c04087
• 发表时间: 2021-11
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Li, Na;Cai, Liang;Wang, Chao;Lin, Yue;Huang, Jinzhen;Sheng, Hongyuan;Pan, Haibin;Zhang, Wei;Ji, Qianqian;Duan, Hengli;et al
• 通讯作者: et al

Modifying redox properties and local bonding of Co3O4 by CeO2 enhances oxygen evolution catalysis in acid

CeO2 改变 Co3O4 的氧化还原性质和局部键合增强了酸中的析氧催化作用

• DOI: 10.1038/s41467-021-23390-8
• 发表时间: 2021-05-24
• 期刊: Nature Communications
• 影响因子: 16.6
• 作者: Jinzhen Huang;Hongyuan Sheng;R. Ross;Jiecai Han;Xianjie Wang;Bo Song;Song Jin
• 通讯作者: Song Jin

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

用于增强过氧化氢电合成和内置羟基自由基生成的成分调整三金属硫尖晶石催化剂

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

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

使用稳定的 NiSe2 阴极通过电芬顿过程实现甘油的线性配对电化学增值

• DOI: 10.1038/s41929-022-00826-y
• 发表时间: 2022-08-01
• 期刊: Nature Catalysis
• 影响因子: 37.8
• 作者: Hongyuan Sheng;Aurora N. Janes;R. Ross;H. Hofstetter;Kwan;J. Schmidt;S. Jin
• 通讯作者: S. Jin