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.

在化学系化学催化研究项目的支持下，宋金教授和J.R.威斯康星大学麦迪逊分校的施密特将设计和研究新的选择性和稳定的电催化剂，以利用电力从氧气生产过氧化氢（H2 O2）。过氧化氢是一种绿色化学氧化剂，具有广泛的工业和环境应用。与目前集中的化学生产H2 O2相比，通过直接还原氧气的电化学生产H2 O2将降低成本和能耗，并能够使用可再生电力进行分布式生产。为此，最近在用于H2 O2电合成的电催化剂的开发方面取得了重大进展。然而，这些催化剂的性能及其长期稳定性仍需要改进。这个合作项目将建立在团队先前的成就，设计，研究，然后提高一系列新的金属硫属化物电催化剂。对使用新兴金属硫属化物电催化剂进行选择性氧还原的科学理解将为环境（包括水处理）和可持续发展（特别是替代化学品生产）中的无数应用提供产生H2 O2的新方法，例如，使用H2 O2作为氧化剂。在这个项目中，威斯康星大学麦迪逊分校的Jin/施密特团队将联合收割机与实验结合起来，设计和研究新兴的金属硫属化物电催化剂，以及控制其催化稳定性、活性、2 e-在酸性和中性溶液中氧电还原产生H2 O2的选择性。这种选择性2 e-氧还原反应（ORR）电催化剂可以促进分散的H2 O2的电化学生产，H2 O2是一种具有多种应用的环境友好的氧化剂。具体而言，将在实验和理论上研究新的层状金属硫族化物电催化剂，以实现对2 e-ORR的更好的选择性、活性和稳定性，特别是在中性溶液中。开发微观动力学模型的密度泛函理论计算将与多种类型的操作研究直接相关，目的是识别关键反应中间体和理解催化机制。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剂在增强电催化剂中的作用。该项目有可能促进H2 O2的高效分散电化学生产，并在环境和可持续性化学方面产生广泛的科学影响。本文中开发的机械见解和操作方法也将为使用更多样化的金属化合物解决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的法定使命，并被认为值得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来支持。