Technical Abstract: This CAREER award by the Chemical Catalysis Program of the Chemistry Division supports the work of Professor Hairong Guan of the University of Cincinnati to study the kinetic and thermodynamic driving forces that control the reactivities of metal-hydrogen and metal-heteroatom bonds of nickel and iron complexes. This mechanistic information is used to design efficient and selective catalysts for the reduction of carbon dioxide to methanol as well as various other organic transformations. The proposed research may lead to the development of homogeneous catalysis with non-precious metals and should provide significant benefits for the energy and medicinal chemistry fields.
In addition to training undergraduate and graduate students in the areas of organometallic chemistry and homogeneous catalysis, Professor Guan creates a high-achieving, learning environment for his students. His participation in the University of Cincinnati Woman in Science and Engineering Program and the American Chemical Society Project SEED Program helps in the recruitment and retention of women and other underrepresented minorities in science. The establishment of teaching and research collaborations with primarily undergraduate institutions enhances the learning experiences for students from the University of Cincinnati and collaborating colleges. The engagement of local chemical companies in education and research activities facilitates student career development and strengthens the workforce pipeline for the chemical industry.
This CAREER award by the Chemical Catalysis Program of the Chemistry Division supports the work of Professor Hairong Guan of the University of Cincinnati in the study of new environmentally-friendly and sustainable catalytic reactions. To meet the global energy and resource demand in a sustainable fashion, chemists need to develop catalytic reactions that use less energy and more renewable or readily-available materials. In the past few decades, research has focused on the use of expensive and scarce metal-based catalysts (e.g., gold, platinum, and palladium), while inexpensive metals, such as nickel and iron, received much less attention. This project examines the factors that influence the reactivity of these more abundant metals with carbon dioxide. A variety of products that are useful in energy, medicine and building materials are formed. The investigation of new ways of using of carbon dioxide may help use to reduce global warming.
In addition to training undergraduate and graduate students, Professor Guan is active in the recruitment and retention of women and other underrepresented minorities in science. He establishes collaborations with primarily undergraduate institutions that enhance the learning experiences of students from the University of Cincinnati and collaborating colleges. He also invites local chemical companies to interact with his students and this enables the students to gain industrial experience firsthand.
This project has been focused on the utilization of earth abundant metals nickel and iron for homogeneous catalysis. These metals are attractive as they are relatively inexpensive and more readily available than the precious metals widely used in catalysis today. Through a mechanism-guided approach, a number of important processes catalyzed by nickel and iron have been developed by the PI’s laboratory. Notable examples include: (1) the development of a very efficient process for the conversion of CO2, a greenhouse gas, to liquid fuels, (2) the discovery of a base-free method to add acetonitrile to a variety of aldehydes for the preparation of b-hydroxy nitriles, which are important for pharmaceutical synthesis, and (3) the identification of one of the most efficient iron catalysts for the release of hydrogen from ammonia borane, which shows high potentials as a chemical hydrogen storage material. The mechanistic details of these reactions are expected to provide important guidelines for the design of new catalysts based on first-row transition metals. These research activities have proven an effective training and outreach tool by involving 26 undergraduate students including 3 NSF-REU students and 2 visiting students from Rochester Institute of Technology, 3 ACS Project SEED students, 14 graduate students, and 4 post-graduate scholars. To further integrate research into undergraduate training, an honors inorganic laboratory course with an open-ended research project format has been established at the University of Cincinnati. The PI has also used research to establish close ties with local companies such as Shepherd Chemical Company and the Procter & Gamble Company. In addition to graduate student support, such relationships have provided the University of Cincinnati students with invaluable technical training and career guidance. Activities have included industry guest lectures to students, tours of industrial facilities, instrument sharing, undergraduate and graduate internships, and collaborative research projects.
