CAS: Collaborative Research: Separating Electronic and Geometric Effects in Compound Catalysts: Examining Unique Selectivities for Hydrogenolysis on Transition Metal Phosphides

The conversion of biomass, shale, and petroleum feedstocks into value-added fuels and chemicals requires costly and rare metal catalysts to speed up the chemical reactions. This design of less expensive and more earth abundant catalysts is a major challenge to materials chemists and engineers. Combining inexpensive elements with rare metals can reduce costs while maintaining or improving catalyst performance. Previously, this strategy has been limited because the dependence of the performance and stability on the structure and composition of these catalysts was not understood. In this project, Dr. Hibbitts (University of Florida), Dr. Flaherty (University of Illinois – Urbana-Champaign), and Dr. Plaisance (Louisiana State University) are collaborating to understand the fundamental behavior of metal catalysts with an initial focus on metal phosphide materials. This understanding will guide the design of future catalysts that provide targeted improvements in reaction rates and selectivities of interest to the chemical industry. Drs. Hibbitts, Flaherty, and Plaisance participate in outreach activities that excite and motivate students into studying topics within STEM. Summer internships, mentor-mentee formations, and interactive workshops are just some of the activities these faculty use at their respective institutions to increase the size and diversity of the future chemistry workforce. Funding from the Chemical Catalysis Program of the Division of Chemistry is enabling a multi-investigator collaboration among Dr. Hibbitts (University of Florida), Dr. Flaherty (University of Illinois – Urbana-Champaign), and Dr. Plaisance (Louisiana State University). These researchers will develop a fundamental understanding of how the electronic and geometric effects of P-atoms in transition metal phosphides lead to regioselective rupture of C–O bonds in biomass-derived oxygenates. Transition metal phosphides are stable, inexpensive, and productive catalysts for hydrodeoxygenation because they selectively cleave sterically-hindered C–O bonds that are difficult to activate with other metal catalysts. These C–O rupture pathways produce value-added chemicals from biomass molecules. A broad understanding of this class of materials and guiding structure-function relationships do not currently exist but will be addressed in this project. Where possible, synthesis and characterization of these materials will validate density functional theory (DFT) predictions and models. 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.