Collaborative Research: Developing an Atomistic Understanding of Electronic Metal-Support Interactions for Oxide-Supported Metal Nanoparticle Catalysis

With support from the Chemical Structure and Dynamics (CSD) and Chemical Catalysis (CAT) programs, scientists at the University of Kansas and the University of Oklahoma are investigating the mechanistic consequences of electronic metal-support interactions (EMSI) on selective ethanol dehydrogenation over oxide-supported metal nanoparticle catalysts. Due to its complexity, the molecular-level understanding of EMSI in dehydrogenation chemistries has not been fully elucidated. To develop this spatially resolved molecular understanding, the Kansas group will use a combination of scanning tunneling microscopy/spectroscopy and temperature programmed desorption to probe the structure, electronic properties, and chemical activity of model catalysts. The Oklahoma group will then use a combination of atomistic modeling, machine learning-assisted global optimizations, and kinetic modeling to provide fundamental insight into these model systems. This proposal has the potential to deliver fundamental knowledge into the origins and mechanistic consequences of EMSI, supporting the rational design of next-generation dehydrogenation catalysts. Educational and outreach efforts will train graduate and undergraduate students in state-of-the-art experimental, computational modeling, and machine learning techniques and support community engagement through hands-on science programs and educational videos, contributing to the development of a highly skilled workforce, strengthening US competitiveness in the chemical sector. This project will focus on experimental and computational studies of model oxide-supported metal nanoparticle catalysts to develop a spatially resolved understanding of the mechanistic consequences of EMSI for the selective dehydrogenation of ethanol to acetaldehyde. This will be accomplished through three interconnected aims. First, the structural and electronic properties of pristine and defected titania and zirconia supports will be understood. This will reveal how the electronic properties of a strong and weak Lewis acid vary as a function of defect density. Then, a spatially resolved understanding of the attenuation in electronic structure will be established for copper/titania and copper/zirconia systems. This will underpin the relationship between Lewis acidity and oxide identity on the degree of EMSI in oxide-supported metal nanoparticle systems. Finally, ethanol adsorption, diffusion, and reactivity will be probed on the copper/titania and copper/zirconia model catalysts, resulting in a spatially resolved understanding of the consequences of EMSI on ethanol dehydrogenation. This research is well-poised to provide fundamental insights into the origins of EMSI and the mechanistic consequences of these electronic properties for selective dehydrogenation chemistries over oxide-supported metal nanoparticle catalysts. 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. NSF Award ID: 2603169 | Program: 01002627DB NSF RESEARCH & RELATED ACTIVIT | Principal Investigator: Rachael Farber | Institution: University of Kansas Center for Research Inc, LAWRENCE, KS | Award Amount: $350,000 View on NSF Award Search: https://www.nsf.gov/awardsearch/show-award/?AWD_ID=2603169 View on Research.gov: https://www.research.gov/awardapi-service/v1/awards/2603169.html