Probing metal catalyst-support interactions using small cluster models: Gas-phase reactivity studies, anion photoelectron spectroscopy, and DFT calculations

使用小簇模型探测金属催化剂-载体相互作用：气相反应性研究、阴离子光电子能谱和 DFT 计算

• 批准号: 1265991
• 负责人: Caroline Jarrold
• 金额: $ 46.25万
• 依托单位: Indiana University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1265991&HistoricalAwards=false
• 关键词: Probing; metal; catalyst; support; interactions

The Chemical Catalysis Program supports the efforts of Professor Caroline C. Jarrold from Indiana University to study the interplay between electronic and structural properties of well-defined cluster models used to study the inherently local phenomenon of catalyst-support and catalyst-support-substrate interactions. A three-pronged approach is used to characterize cluster models of new catalysts that have been identified as particularly active toward the industrially-important water-gas shift reaction. (The water gas shift reaction catalytically combines water and carbon monoxide to produce dihydrogen and carbon dioxide.) Anion photoelectron (PE) spectroscopy measurements on model clusters provide a mass-specific electronic profile of the clusters as a function of both metal composition and oxygen content. Cluster structures are determined by reconciling experimental PE spectra with computational results and gas-phase reactivity studies on the clusters allow for the correlation between cluster reactivity and cluster molecular and electronic structures. The first series of studies focus on platinum-containing cluster systems inspired by recent literature. Alternative and less expensive cluster models rationalized to have similar (and possibly improved) attributes are also explored and compared to known industrial catalysts. The broader impacts of these studies include the generation of knowledge that can inform the design of improved, lower-cost and more energy-efficient catalysts for water gas shift reactions and the evaluation of new computational approaches used to study metal oxides in non-traditional oxidation states. In addition, a new generation of scientists are trained to understand industrially-relevant catalysis reactions.Metal oxides are often used as industrial catalysts. Their composition is often optimized so that the catalysts operate at lower temperatures or with cheaper and more readily available materials. This research project is designed to determine the essential molecular-scale features that govern catalysts used in the water gas shift reaction. The water gas shift reaction combines water and carbon monoxide to make dihydrogen and carbon dioxide. Experimental and computational tools are used to create and study the properties of well-defined nano- and sub-nanometer scale bits of metal oxides used in this industrially important reaction. The technical broader implications of this project include a reduced energy consumption for this industrial process. A more immediate and direct outcome of this project is the training of young women and men in the scientific method using computational and experimental platforms centered on a project that motivated by practical industrial concerns.

该化学催化计划支持印第安纳大学的Caroline C. Jarrold教授的努力，研究了用于研究固有的催化剂支持和催化剂 - 支持 - 支持 - 基形成型的固有局部现象的电子和结构性质之间的相互作用。 一种三管齐下的方法用于表征新催化剂的聚类模型，这些催化剂的簇模型被确定为对工业至关重要的水电偏移反应特别活跃。 （水气体移位反应催化结合水和一氧化碳，产生二氢和二氧化碳。）模型簇上的阴离子光电子（PE）光学谱测量值可提供集群的质量特异性电子剖面作为金属成分和氧气含量的函数。 群集结构是通过将实验性PE光谱与计算结果和气相反应性研究对簇进行调解的确定，从而使簇反应性与群集分子和电子结构之间的相关性。 第一系列研究的重点是受近期文献启发的含铂集群系统。 还探索了与已知的工业催化剂相比，替代和较便宜的聚类模型合理化为具有相似（可能有改进的）属性。 这些研究的更广泛的影响包括可以为水气转移反应的改进，低成本和更节能的催化剂设计的知识的产生，以及用于研究非传统氧化态中金属氧化物的新计算方法的评估。 此外，对新一代的科学家进行了培训，以了解与工业相关的催化反应。金属氧化物通常用作工业催化剂。 它们的组成通常被优化，以便催化剂在较低的温度或更便宜且更容易获得的材料下运行。 该研究项目旨在确定主要的分子尺度特征，该特征控制水气体转移反应中使用的催化剂。 水气体转移反应结合了水和一氧化碳，使二氢和二氧化碳。 实验和计算工具用于创建和研究该工业重要反应中使用的金属氧化物的纳米和亚纳米尺度位的特性。 该项目的技术更广泛的含义包括减少该工业过程的能源消耗。 该项目的一个更直接和直接的结果是，使用科学方法和实验平台培训年轻男性和男性，该方法以实用工业问题激励的项目为中心。