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.

化学催化计划支持印第安纳大学 Caroline C. Jarrold 教授的努力，研究明确定义的簇模型的电子和结构特性之间的相互作用，用于研究催化剂-载体和催化剂-载体-基材相互作用的固有局部现象。 采用三管齐下的方法来表征新型催化剂的簇模型，这些催化剂已被认为对工业上重要的水煤气变换反应特别活跃。 （水煤气变换反应催化结合水和一氧化碳，产生氢气和二氧化碳。）模型团簇上的阴离子光电子 (PE) 光谱测量提供了团簇的质量特定电子分布，作为金属成分和氧含量的函数。 通过协调实验 PE 光谱与计算结果来确定簇结构，并且对簇的气相反应性研究允许簇反应性与簇分子和电子结构之间的相关性。 第一系列研究的重点是受最近文献启发的含铂簇系统。 还探索了替代且更便宜的集群模型，合理化为具有相似（并且可能改进）的属性，并与已知的工业催化剂进行比较。 这些研究的更广泛影响包括产生知识，为水煤气变换反应的改进、成本更低和更节能的催化剂的设计提供信息，以及评估用于研究非传统氧化中金属氧化物的新计算方法州。 此外，新一代科学家接受培训，了解工业相关的催化反应。金属氧化物通常用作工业催化剂。 它们的组成通常经过优化，以便催化剂在较低的温度下运行或使用更便宜和更容易获得的材料。 该研究项目旨在确定控制水煤气变换反应中使用的催化剂的基本分子尺度特征。 水煤气变换反应将水和一氧化碳结合产生氢气和二氧化碳。 实验和计算工具用于创建和研究用于这一工业重要反应的明确纳米和亚纳米级金属氧化物的特性。 该项目更广泛的技术影响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成果是，使用以实际工业问题为动机的项目为中心的计算和实验平台，对年轻男女进行科学方法方面的培训。