Modeling electrocatalysts in operating conditions: Surface restructuring and catalytic activity

模拟运行条件下的电催化剂：表面重组和催化活性

• 批准号: 2103116
• 负责人: Philippe Sautet
• 金额: $ 50.21万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2103116&HistoricalAwards=false
• 关键词: Modeling; electrocatalysts; operating; conditions; Surface

Electrochemistry is slated to play a large role in clean energy, chemical manufacturing, and environmental processes in coming years, as renewable electricity becomes increasingly available from sources such as wind and solar energy. The project focuses on two electrochemical reactions, the hydrogen evolution reaction (HER) to produce hydrogen from water, and the carbon dioxide reduction reaction (CO2RR) to convert CO2 to higher-value products. Both reactions are facilitated by catalysts. Copper-based catalysts are amongst the most active identified to date, but as with many electrocatalysts, their chemical structure changes under reaction conditions. The project focuses on understanding the reconstruction process with the goal of designing more active, selective, and stable catalysts. Specifically, the project develops and employs computational techniques to predict structural changes in response to key electrochemical process variables. Beyond the technical aspects, the project incorporates a training program for high-school teachers that brings the topics of sustainability and energy to their classrooms, while introducing students to the rapidly emerging area of molecular modeling. The project will determine, by unique first-principles, multi-scale stochastic theoretical simulations, how the surface of copper-based electrocatalysts used for the hydrogen evolution and CO2 electroreduction reactions restructures in realistic conditions of potential, solvent, and electrolyte. The influence of the potential-induced reconstruction on the electrocatalytic mechanism, activity, and selectivity of these reactions will be studied, in link with experiments. There is evidence from in-situ characterization that the surface structure of electrocatalysts is strongly modified in operational conditions. However, it is not yet possible to determine the atomic structure of the active surface, and thus, the implications of these reconstructions on the mechanisms are unknown. The proposed multiscale first-principle simulations appear to be the most adequate approach to elucidate the interface structure. Principally, new reaction mechanisms may emerge. The selectivity of CO2 electroreduction versus hydrogen evolution (the latter being a major hurdle in applications) will be studied. Several theoretical methods unique to the laboratories of the PIs, including the incorporation of electrochemical potential, solvent effects, global optimization algorithms, and STM image simulations, will be advanced, adapted, and merged to make this research possible. Close connection to the experiment is proposed, both for structural aspects, with operando scanning tunneling microscopy (STM), and to validate the predicted kinetics and selectivity. This project will educate young researchers in techniques of modern surface chemistry and catalysis, including realistic modeling, method development, quantum mechanics, and statistical mechanics. In addition, students will learn how to connect modeling efforts to experimental data and capabilities. The training will promote a highly-skilled workforce to address global challenges in the manufacture of sustainable fuels and chemicals.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.

未来几年，电化学将在清洁能源，化学制造和环境过程中发挥重要作用，因为可再生电力越来越多地来自风能和太阳能等能源。 该项目重点关注两个电化学反应，即从水中产生氢气的析氢反应（HER）和将二氧化碳转化为更高价值产品的二氧化碳还原反应（CO2RR）。 这两种反应都是由催化剂促进的。 铜基催化剂是迄今为止发现的最活跃的催化剂之一，但与许多电催化剂一样，它们的化学结构在反应条件下会发生变化。 该项目的重点是了解重建过程，目的是设计更活跃，选择性和稳定的催化剂。具体而言，该项目开发并采用计算技术来预测响应关键电化学过程变量的结构变化。 除了技术方面，该项目还为高中教师提供了一个培训计划，将可持续性和能源的主题带到他们的课堂上，同时向学生介绍迅速兴起的分子建模领域。该项目将通过独特的第一性原理，多尺度随机理论模拟，确定用于析氢和CO2电还原反应的铜基电催化剂的表面如何在电位，溶剂和电解质的现实条件下重构。将结合实验研究电位诱导重构对这些反应的电催化机理、活性和选择性的影响。有证据表明，从原位表征的表面结构的电催化剂是强烈修改的操作条件。 然而，目前还不可能确定活性表面的原子结构，因此，这些重建对机制的影响是未知的。建议的多尺度第一性原理模拟似乎是最适当的方法来阐明的接口结构。 原则上，可能会出现新的反应机制。将研究CO2电还原相对于析氢的选择性（后者是应用中的主要障碍）。PI实验室特有的几种理论方法，包括电化学电势，溶剂效应，全局优化算法和STM图像模拟的结合，将被改进，调整和合并，使这项研究成为可能。密切联系的实验提出，无论是结构方面，与操作扫描隧道显微镜（STM），并验证预测的动力学和选择性。该项目将教育年轻的研究人员现代表面化学和催化技术，包括现实建模，方法开发，量子力学和统计力学。此外，学生将学习如何将建模工作与实验数据和功能联系起来。该培训将促进高技能的劳动力，以应对可持续燃料和化学品生产的全球挑战。该奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

项目成果

Hydrogen-Induced Restructuring of a Cu(100) Electrode in Electroreduction Conditions

电还原条件下 Cu(100) 电极的氢致重构

• DOI: 10.1021/jacs.2c06188
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zhang, Zisheng;Wei, Ziyang;Sautet, Philippe;Alexandrova, Anastassia N.
• 通讯作者: Alexandrova, Anastassia N.

Restructuring and Activation of Cu(111) under Electrocatalytic Reduction Conditions

• DOI: 10.1002/anie.202218575
• 发表时间: 2023-04-05
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Cheng, Dongfang;Wei, Ziyang;Sautet, Philippe
• 通讯作者: Sautet, Philippe