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

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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.