Role of Bismuth Promoters in Heterogeneous Pt-Bi and Pd-Bi Catalysts: Computational Insights into Main Group Promotion

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In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor J. R. Schmidt of the University of Wisconsin-Madison is examining the role of "promoter" additives in metal surface catalytic reactions. Promoters are elements or compounds that are added to catalysts to enhance the efficiency (both in terms of energy and the use of materials) of a wide variety of chemical transformations. Although such promoters are used broadly within the chemical industry, their detailed roles are often poorly understood. This project is using computer-based modeling to identify the molecular level mechanisms by which promoters influence chemical reactions, and to exploit this insight to advance the development of novel and efficient chemical transformations. Such work could lead to new and more energy efficient industrial chemical synthesis processes.Specifically, this study focuses on the role of bismuth and other p-block promoters in platinum-group metal catalyzed aerobic alcohol oxidation. Using a combination of density functional theory and kinetic modeling, several hypotheses of promotion are being critically evaluated. These results are unified to develop validated "theories" for p-block promotion in order to facilitate the discovery of novel selective oxidation reactions and to optimize existing catalytic oxidation processes. An outreach program, developed by Professor Schmidt, is exposing undergraduate students to computational chemistry methods using a web-based software package, with an emphasis on catalysis. The broader impacts of this work thus include both the potential for optimization of platinum-group metal catalysts for a wide variety of industrially-relevant chemical transformations, as well as the training of undergraduate and graduate students, both at University of Wisconsin and around the country, in modern computational methods.