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

化学催化计划支持教授卡罗琳C。Jarrold从印第安纳州大学研究电子和结构性质之间的相互作用的定义良好的集群模型用于研究催化剂载体和催化剂载体基质相互作用的固有局部现象。 一个三管齐下的方法是用来表征集群模型的新催化剂，已被确定为特别活跃的工业上重要的水煤气变换反应。(The水煤气变换反应将水和一氧化碳催化结合以产生二氢和二氧化碳。 模型集群上的阴离子光电子（PE）光谱测量提供了一个质量特定的电子分布的集群作为金属组合物和氧含量的函数。 簇结构的确定通过调和实验PE光谱与计算结果和气相反应性的研究允许簇反应性和簇分子和电子结构之间的相关性。 第一系列的研究集中在含铂的集群系统的启发，最近的文献。 还探索了具有类似（并且可能改进）属性的替代且更便宜的簇模型，并与已知的工业催化剂进行了比较。 这些研究的更广泛影响包括产生知识，可以为水煤气变换反应的改进，低成本和更节能的催化剂的设计提供信息，并评估用于研究非传统氧化态金属氧化物的新计算方法。 此外，新一代的科学家也在接受培训，以了解与工业相关的催化反应。金属氧化物经常被用作工业催化剂。 它们的组成通常是优化的，以便催化剂在较低的温度下或使用更便宜和更容易获得的材料操作。 该研究项目旨在确定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以产生二氢和二氧化碳。 实验和计算工具用于创建和研究在这个工业上重要的反应中使用的定义明确的纳米和亚纳米尺度的金属氧化物位的特性。 该项目在技术上的广泛影响包括降低该工业过程的能耗。 该项目的一个更直接和直接的成果是，利用以实际工业关切为动机的项目为中心的计算和实验平台，对青年男女进行科学方法培训。

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.