Calorimetric Benchmark Energies of Adsorbed Intermediates, Solvent Effects and Solvent / Catalyst Bonding

更好的催化剂和电催化剂对于能源效率和环境友好的燃料和化学品制造以及减少碳排放和减轻环境污染物的先进工艺至关重要。 然而，为特定应用优化催化剂需要详细了解反应步骤和催化剂加速这些步骤的机制。 该项目将生成关于小分子与催化金属表面的结合强度的数据，包括有溶剂和没有溶剂的情况。 结合强度可用于改进催化剂性能的理论模型，加速改进催化剂和催化工艺的发现和设计。具体而言，该项目将采用研究人员实验室开发的最先进的量热方法来测量小分子在单晶表面上的吸附能力，并估计与多相催化和电催化中的各种应用相关的溶剂效应。该项目涉及三个主要的能量测量目标：1）小分子物质在铜（Cu）单晶表面上的吸附，作为对早期过渡金属表面上所做的大量工作的补充; 2）凝聚溶剂在单晶表面上的粘附;以及3）在共吸附溶剂存在下小分子物质的吸附。这项工作扩展了研究人员以前对铂（Pt）和镍（Ni）单晶的气体吸附研究，同时进一步研究了Cu的研究，包括液相电催化反应中重要的溶剂效应。 该研究将推进实验吸附能数据库，可用于校准从头算模型及其基组，从而加强实验和理论催化之间的联系。 该项目的结构是这样的，研究人员将提供深入的培训，研究生和本科生就他独特的量热仪器和分析工具。 他还将与一位年轻的副教授合作，作为继任计划的一部分，以确保对他实验室已经建立的吸附生物学关键数据库的长期贡献。该奖项由化学，生物工程，环境，该奖项反映了NSF的法定使命，并被认为是值得的。通过使用基金会的知识价值和更广泛的影响审查标准进行评估来提供支持。

Better catalysts and electrocatalysts are essential for energy-efficient and environmentally benign manufacturing of fuels and chemicals, and for advanced processes to reduce carbon emissions and mitigate environmental pollutants. Optimizing catalysts for specific applications, however, requires detailed knowledge of reaction steps and the mechanisms by which the catalyst accelerates those steps. The project will generate data on the bonding strength of small molecules to catalytic metal surfaces, both in the presence and absence of solvents. The bonding strength can then be used to refine theoretical models of catalyst performance and accelerate the discovery and design of improved catalysts and catalytic processes.Specifically, the project will employ state-of-the-art calorimetric methods developed in the investigator’s laboratory to measure adsorption enthalpies of small molecules on single crystal surfaces, and estimate solvent effects that are relevant to various applications in heterogeneous catalysis and electrocatalysis. The project involves three main energy-measurement objectives: 1) adsorption of small molecular species on copper (Cu) single crystal surfaces, as a complement to the extensive work that has been done on earlier transition metal surfaces; 2) adhesion of condensed solvents on single crystal surfaces; and 3) adsorption of small molecular species in the presence of a co-adsorbed solvent. This work extends the investigator’s previous gas adsorption studies on platinum (Pt) and nickel (Ni) single-crystals to Cu single crystals, while furthering the Cu study to include solvent effects important in liquid-phase electrocatalytic reactions. The study will advance a database of experimental adsorption energies that can be used to calibrate ab initio models and their basis sets, thereby strengthening links between experimental and theoretical catalysis. The project is structured such that the investigator will provide in-depth training to both graduate and undergraduate students with respect to his unique calorimetric instrumentation and analysis tools. He will also collaborate with a young associate professor as part of a succession plan to ensure long-term contributions to the critical database of adsorption enthalpies already established in his laboratory.This award is co-funded by the Catalysis Program in the Division of Chemical, Bioengineering, Environmental, and Transport Systems and the Chemical Catalysis Program in the Division of Chemistry.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.