CAS: Design and Mechanistic Understanding of Emerging Metal Chalcogenide Electrocatalysts for Selective Two-Electron Oxygen Reduction

CAS：用于选择性双电子氧还原的新兴金属硫属化物电催化剂的设计和机理理解

• 批准号: 2247519
• 负责人: Song Jin
• 金额: $ 69万
• 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: 2023
• 资助国家: 美国
• 起止时间: 2023-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247519&HistoricalAwards=false
• 关键词: CAS; Design; Mechanistic; Understanding; Emerging

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professors Song Jin and J. R. Schmidt of the University of Wisconsin-Madison will design and study new selective and stable electrocatalysts to produce hydrogen peroxide (H2O2) from oxygen using electricity. Hydrogen peroxide is a green chemical oxidant with many industrial and environmental applications. In contrast to current centralized chemical production of H2O2, electrochemical production of H2O2 by direct reduction of oxygen would reduce cost and energy consumption, and enable distributed production using renewable electricity. To this end, there have been significant recent advances in the development of electrocatalysts for H2O2 electrosynthesis. Nonetheless, the performance of these catalysts and their long-term stability still need improvement. This collaborative project will build on the team’s prior accomplishments to design, investigate and then enhance a series of new metal chalcogenide electrocatalysts. The scientific understanding of selective oxygen reduction using emerging metal chalcogenide electrocatalysts will enable new approaches for the generation of H2O2 for myriad applications in environment, including water treatment, and in sustainability, particularly for alternative chemical production, for example, with H2O2 as oxidant. Concerted efforts on educational outreach to K-12 students and fostering a more diverse scientific community will also be undertaken.In this project, the collaborative Jin/Schmidt team at the University of Wisconsin-Madison will combine theory and experiment to design and investigate emerging metal chalcogenide electrocatalysts and the factors that govern their catalytic stability, activity, selectivity for 2e- electroreduction of oxygen to produce H2O2 in acidic and neutral solutions. Such selective 2e- oxygen reduction reaction (ORR) electrocatalysts can facilitate decentralized electrochemical production of H2O2, an environmentally benign oxidant with diverse applications. Specifically, new layered metal chalcogenide electrocatalysts will be investigated experimentally and theoretically to achieve better selectivity, activity and stability for 2e– ORR, especially in neutral solutions. Density functional theory calculations to develop microkinetic models will be directly connected with multiple types of operando studies with the aim of identifying key reaction intermediates and understanding catalytic mechanism. Systematic electrochemical studies and molecular dynamics simulations followed by in situ measurements will be undertaken to help elucidate the role of cations and solvents in enhancing the electrocatalysts. This project has the potential to facilitate the efficient decentralized electrochemical production of H2O2 and in so doing have broad scientific impact in environmental and sustainability chemistry. The mechanistic insights and operando approaches developed herein will also lay the groundwork for addressing increasingly complex challenges in selective electrocatalysis using more diverse metal compounds.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.

在化学催化计划的支持下，威斯康星大学麦迪逊分校的宋金和J. R. Schmidt教授将设计和研究新的选择性和稳定的电催化剂，以使用电气从氧气中产生过氧化氢（H2O2）。过氧化氢是一种具有许多工业和环境应用的绿色化学氧化物。与当前H2O2的集中化学生产相反，直接减少氧气通过直接降低氧的电化学生产将降低成本和能源消耗，并使用可再生电力实现分布式生产。为此，H2O2电合成的电催化剂的发展最近取得了重大进展。但是，这些催化剂的性能及其长期稳定性仍然需要改进。这个协作项目将基于团队的先前成就，以设计，调查然后增强一系列新的金属果仁型电催化剂。使用新兴的金属硫化剂电催化剂对选择性氧的科学理解将使您能够在包括水处理，尤其是用于替代化学生产的环境中的众多环境中生成H2O2的新方法，例如，H2O2 AS氧化剂。 Concerted efforts on educational outreach to K-12 students and fostering a more divers scientific community will also be undertaken.In this project, the collaborative Jin/Schmidt team at the University of Wisconsin-Madison will combine theory and experiment to design and investigate emerging metal chalcogenide electrocatalysts and the factors that govern their catalytic stability, activity, selectivity for 2e-electroreduction of oxygen to produce H2O2 in酸性和中性溶液。这种选择性的2E氧还原反应（ORR）电催化剂可以促进H2O2的分散化电化学生产，这是一种具有潜水员应用的环境良性氧化物。具体而言，将在实验和理论上对新的分层金属葡萄干化的电催化剂进行研究，以实现2E – ORR的更好选择性，活性和稳定性，尤其是在中性溶液中。开发微动力学模型的密度功能理论计算将直接与多种类型的Operado研究联系起来，以识别关键反应中间体并了解催化机制。将进行系统的电化学研究和分子动力学模拟，然后进行原位测量，以帮助阐明阳离子和溶液在增强电催化剂方面的作用。该项目有可能促进H2O2的有效分散化电化学生产，因此，对环境和可持续性化学产生了广泛的科学影响。本文开发的机制洞察力和操作方法还将为选择性电催化中日益复杂的挑战奠定基础。该奖项反映了NSF的法定任务，并被认为是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的珍贵支持。