Understanding the restructuring of model metal catalysts in reactant gases

了解反应气体中模型金属催化剂的重组

• 批准号: 1800601
• 负责人: Philippe Sautet
• 金额: $ 32.02万
• 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: 2018
• 资助国家: 美国
• 起止时间: 2018-09-15 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800601&HistoricalAwards=false
• 关键词: Understanding; restructuring; model; metal; catalysts

Transition metals play key roles as catalysts in applications ranging from chemical and energy production to environmental remediation. Ample evidence indicates that catalyst structures do not remain unchanged during use. Instead, substantial and important restructuring occurs due to rearrangement of the metal atoms to make new structures. This restructuring has major consequences on catalytic properties, sometimes beneficial and sometimes not. Currently, scientists do not understand how the restructuring occurs at the atomic scale or under conditions similar to those used during catalysis. With funding from the NSF Chemical Catalysis Program, this research is providing a fundamental understanding of this chemistry under relevant gas pressures and reaction temperatures. It is being performed with a combination of cutting edge experiments by Dr. Franklin Tao from University of Kansas and computational modeling by Dr. Philippe Sautet from University of California Los Angeles. Drs. Tao and Sautet are incorporating this theoretical modeling and experimental work into the education and training of high school, undergraduate, and graduate students. Summer research internships for public high school students in their laboratories are also being provided. With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Tao of the University of Kansas and Dr. Sautet from UCLA are combining advanced in situ/operando characterization and first principle based modelling to develop a fundamental understanding of the metal catalyst restructuring process. The research compares several metals (Pt, Pd, Ni, Co, Cu) under a pressure of carbon monoxide and other reactants. The experimental methods include high pressure scanning tunneling microscopy (HP-STM) and operando Ambient Pressure X-ray Photoelectron Spectroscopy. These surface-sensitive surface techniques allow for uncovering surface chemistry and structure of metals under a pressure of gas and provide an initial global view of the mechanism and determine global kinetic rates. Theoretical modelling brings an understanding of the atomistic elementary steps and of their energies. It also provides kinetic results that are compared with experimental measurement, hence validating the approach. Since large systems are required for the calculation, energies are obtained by using an accurate high dimensional neural network potential, previously trained from a density functional theory database. The influence of restructuring on catalytic reaction is being explored with the example of the water-gas shift reaction on Pt and Cu surfaces. Drs. Tao and Sautet are developing an outreach program focused on introducing high-school students to model catalysis research and on undergraduate student training.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.

过渡金属作为催化剂在从化学和能源生产到环境修复的应用中发挥着关键作用。充足的证据表明催化剂结构在使用过程中不会保持不变。相反，由于金属原子重新排列以形成新的结构，因此发生了大量且重要的重组。这种重组对催化性能有重大影响，有时有益，有时有害。目前，科学家们还不了解重组是如何在原子尺度上或在类似于催化过程中使用的条件下发生的。在美国国家科学基金会化学催化计划的资助下，这项研究为相关气压和反应温度下的化学反应提供了基本的了解。该研究结合了堪萨斯大学 Franklin Tao 博士的前沿实验和加州大学洛杉矶分校 Philippe Sautet 博士的计算模型。博士。陶和索泰正在将这一理论建模和实验工作融入到高中、本科生和研究生的教育和培训中。还为公立高中学生在实验室提供暑期研究实习机会。在化学系化学催化项目的资助下，堪萨斯大学的Tao博士和加州大学洛杉矶分校的Sautet博士将先进的原位/操作表征和基于第一原理的建模相结合，以发展对金属催化剂重组的基本理解过程。该研究在一氧化碳和其他反应物的压力下比较了几种金属（铂、钯、镍、钴、铜）。实验方法包括高压扫描隧道显微镜（HP-STM）和操作环境压力X射线光电子能谱。这些表面敏感的表面技术可以揭示气体压力下金属的表面化学和结构，并提供该机制的初始全局视图并确定全局动力学速率。理论建模带来了对原子基本步骤及其能量的理解。它还提供了与实验测量进行比较的动力学结果，从而验证了该方法。由于计算需要大型系统，因此通过使用先前从密度泛函理论数据库训练的精确高维神经网络势来获得能量。以 Pt 和 Cu 表面的水煤气变换反应为例，探讨了重组对催化反应的影响。博士。陶和索泰正在开发一项外展计划，重点是向高中生介绍催化研究模型和本科生培训。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

项目成果

Optimal Packing of CO at a High Coverage on Pt(100) and Pt(111) Surfaces

• DOI: 10.1021/acscatal.0c01971
• 发表时间: 2020-08-21
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Sumaria, Vaidish;Nguyen, Luan;Sautet, Philippe
• 通讯作者: Sautet, Philippe

Atomic-Scale Mechanism of Platinum Catalyst Restructuring under a Pressure of Reactant Gas

反应气体压力下铂催化剂重构的原子尺度机理

• DOI: 10.1021/jacs.2c10179
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Sumaria, Vaidish;Nguyen, Luan;Tao, Franklin Feng;Sautet, Philippe
• 通讯作者: Sautet, Philippe

Reaction product-driven restructuring and assisted stabilization of a highly dispersed Rh-on-ceria catalyst

• DOI: 10.1038/s41929-022-00741-2
• 发表时间: 2022-02
• 期刊: Nature Catalysis
• 影响因子: 37.8
• 作者: Ge Yan;Yu Tang;Yuting Li;Yixiao Li;L. Nguyen;T. Sakata;K. Higashi;F. Tao;P. Sautet