With this award from the Chemistry Research Instrumentation and Facilities: Departmental Multi-User Instrumentation program (CRIF:MU), Robert Hamers, Clark R. Landis and Shannan S. Stahl of the University of Wisconsin Department of Chemistry will acquire equipment to study solution-phase chemical reactions and catalytic processes performed at high pressures (50-3000 psig). The equipment includes reactors which allow monitoring reaction kinetics by infrared spectroscopy and attenuated total reflectance suitable for screening of reactions at high pressure. The equipment will be used to investigate at high pressures reactions with air-sensitive reagents or under anaerobic conditions including catalytic hydroformylation, polymerization and carbonylation reactions, and the study of oxidative reactions, high temperature chemistry and nitrous oxide chemistry.
High-pressure reactions have widespread significance in the chemical and pharmaceutical industries and include some of the most important large scale chemical processes: aerobic oxidation, hydrogenation and alkene polymerization. New reactions of this type and fundamental insights into existing reactions are critical to advance the field; however, such studies are complicated by the need to use specialized equipment that ensures safety. The equipment requested in this proposal will enable the discovery and mechanistic investigation of a wide range of chemical reactions under high-pressure. Students will be trained in the proper use of this equipment in their research and in course work improving their preparation for jobs in the chemical and pharmaceutical industries
The chemistry of small molecules, ranging from simple di- and triatomics (O2, H2, CO, CO2, H2O, N2O) to small organics (CH4, ethylene, propylene), has profound implications for our global welfare. Chemical reactions of these molecules are central to worldwide energy production and environmental sustainability, and they are of critical significance to the chemical industry, from commodity chemical production to pharmaceutical synthesis. A number of research groups within the Department of Chemistry at the University of Wisconsin-Madison study catalytic reactions involving these molecules. The success of these studies hinges upon the accessibility of specialized equipment to ensure the safe handling of gas-phase reagents, often at very high pressures. This NSF grant enabled the UW-Madison Department of Chemistry to establish a High-Pressure Chemistry and Catalysis Facility equipped with state-of-the-art equipment to study solution-phase chemical reactions and catalytic processes performed at high pressures (50-3000 psig). The equipment has enabled the discovery and mechanistic investigation of a wide range of important chemical reactions, including the areas of aerobic oxidation, carbonylation, and enantioselective hydroformylation. The equipment obtained from this grant included the following: Parallel reactors suitable for "primary screening" of catalytic reactions at high pressure (HEL CAT24). These reactors will significantly improve throughput in the screening of high-pressure reactions and thereby promote the discovery of new catalytic processes and chemical reactions. A computer-interfaced parallel-pressure reactor equipped with gas-uptake kinetics capabilities for "secondary screening", optimization and mechanistic investigation of catalytic reactions (HEL ChemScan). A high-pressure-compatible ReactIR instrument to enable in-situ spectroscopic studies of catalytic and other chemical reactions. This instrument provides a powerful analytical tool for mechanistic studies of high-pressure reactions. Overall, the facility provides the department with fundamentally new capabilities to promote transformative basic science research, strengthen university-industry collaborations, and impact education and outreach activities. For example, the equipment plays an important role in several new university-industry research projects with Dow Chemical, Eli Lilly, Merck and Pfizer, which were established during the period of this grant. And, the training of students in the safe use and handling of high-pressure gases plays an important role in their professional development.
