The Strong-Metal Support Interaction: Insights from Molecular Theories and Experiments

强金属支持相互作用：分子理论和实验的见解

• 批准号: 1804712
• 负责人: Jeffrey Greeley
• 金额: $ 45万
• 依托单位: Purdue University
• 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: 2018-09-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1804712&HistoricalAwards=false
• 关键词: Strong; Metal; Support; Interaction; Insights

Catalysts play an essential 'behind-the-scenes' role in many aspects of modern society. For example, catalysts lower the energy loss of producing high performance gasoline from crude oil. In the production of plastics, catalysts selectively lead chemical reactions down a certain pathway to produce desired products. The number of potential pathways in catalytic reactions is large, and the catalyst structure itself may change significantly during the reactions. Due to this complexity, molecular-level aspects of many phenomena in catalysis have not been fully elucidated. Despite being discovered nearly thirty years ago, the strong metal-support interaction (SMSI) is one such phenomenon that remains poorly understood at a molecular level. SMSI refers to the strong interaction between a catalytic metal nanoparticle and an oxide support, to which the metal is anchored. Under reaction conditions that are relatively common, a portion of the oxide support may actually form a film that partially covers the catalytic nanoparticle. This film can either promote or inhibit catalytic processes, depending upon the particular catalytic materials involved, and a general strategy to understand and control its properties does not exist. The central goal of this project is, therefore, to unravel the molecular science of how the different components of these catalyst systems work together to enhance catalyst performance. To use SMSI to promote catalysis by leveraging molecular-level insights, this project will combine periodic Density Functional Theory calculations with surface science experiments and measurements on model nanoparticles to study trends in the structure, energetics, and electronic properties of ultrathin (hydroxy)oxide films on transition metal substrates. Rigorous models of the films' structures as a function of ambient pressures and temperatures will be developed. The predictions will be performed on single crystal substrate models, and will be refined against a series of ultrahigh vacuum surface science experiments. The trends that emerge from these combined theoretical and experimental studies will then be validated on nanoparticle models. It is anticipated the project will provide a wealth of information about ultrathin (hydroxy)oxide/metal interfaces and will suggest new strategies for controlling and exploiting the SMSI. This fundamental knowledge may, in turn, lead to the development of robust catalysts for energy and health applications. The work will be carried out by two graduate students who will be trained in state-of-the-art techniques in theoretical and experimental catalysis. The students will be assisted by high school interns from economically disadvantaged backgrounds who will also be exposed to these forefront scientific methods.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.

催化剂在现代社会的许多方面发挥着重要的“幕后”作用。例如，催化剂降低了从原油生产高性能汽油的能量损失。 在塑料生产中，催化剂选择性地引导化学反应沿着特定途径产生所需的产品。 催化反应中潜在的路径数量很大，并且催化剂结构本身在反应过程中可能发生显着变化。 由于这种复杂性，催化中许多现象的分子水平尚未完全阐明。尽管近三十年前就发现了强金属-载体相互作用（SMSI），但这种现象在分子水平上仍然知之甚少。 SMSI 是指催化金属纳米颗粒和金属固定在其上的氧化物载体之间的强相互作用。 在相对常见的反应条件下，一部分氧化物载体实际上可以形成部分覆盖催化纳米颗粒的膜。 该薄膜可以促进或抑制催化过程，具体取决于所涉及的特定催化材料，并且不存在理解和控制其性质的通用策略。 因此，该项目的中心目标是揭示这些催化剂系统的不同成分如何协同工作以提高催化剂性能的分子科学。 为了利用 SMSI 通过分子水平的见解来促进催化作用，该项目将定期密度泛函理论计算与表面科学实验和模型纳米颗粒测量相结合，以研究过渡金属基底上超薄（羟基）氧化物薄膜的结构、能量学和电子特性的趋势。 将开发薄膜结构随环境压力和温度变化的严格模型。这些预测将在单晶衬底模型上进行，并将根据一系列超高真空表面科学实验进行完善。 这些理论和实验相结合的研究得出的趋势将在纳米颗粒模型上得到验证。 预计该项目将提供有关超薄（羟基）氧化物/金属界面的大量信息，并将提出控制和利用 SMSI 的新策略。 这些基础知识反过来可能会导致能源和健康应用的强大催化剂的开发。 这项工作将由两名研究生完成，他们将接受最先进的理论和实验催化技术培训。 这些学生将得到来自经济困难背景的高中实习生的帮助，他们也将接触到这些最前沿的科学方法。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

Structural and Chemical Transformations of Zinc Oxide Ultrathin Films on Pd(111) Surfaces

• DOI: 10.1021/acsami.1c07510
• 发表时间: 2021-07-18
• 期刊: ACS APPLIED MATERIALS & INTERFACES
• 影响因子: 9.5
• 作者: Gao, Junxian;Sawant, Kaustubh J.;Greeley, Jeffrey P.
• 通讯作者: Greeley, Jeffrey P.

Molybdenum Oxide, Oxycarbide, and Carbide: Controlling the Dynamic Composition, Size, and Catalytic Activity of Zeolite-Supported Nanostructures

• DOI: 10.1021/acs.jpcc.9b05449
• 发表时间: 2019-08
• 期刊: The Journal of Physical Chemistry C
• 作者: Yiteng Zheng;Yadan Tang;James R. Gallagher;Jie Gao;Jeffrey T. Miller;I. Wachs;S. Podkolzin

Origin of Stability and Activity Enhancements in Pt‐based Oxygen Reduction Reaction Catalysts via Defect‐Mediated Dopant Adsorption

通过缺陷介导的掺杂剂吸附提高 Pt 基氧还原反应催化剂的稳定性和活性的起源

• DOI: 10.1002/ange.202312747
• 发表时间: 2023
• 期刊: Angewandte Chemie
• 作者: Sawant, Kaustubh J.;Zeng, Zhenhua;Greeley, Jeffrey P.
• 通讯作者: Greeley, Jeffrey P.