John A. Keith, PhD

R.K. Mellon Faculty Fellow in Energy Associate Professor

804 Benedum Hall | 3700 O’Hara Street | Pittsburgh, PA 15261 P: 412-624-7016

jakeith@pitt.edu www.klic.pitt.edu

Keith Lab in Computational Catalysis

John A. Keith is the R.K. Mellon Faculty Fellow in Energy, a tenure-track assistant professor in the Chemical and Petroleum Engineering Department in the Swanson School of Engineering. His research interests are in the first-principles based computational modeling of reaction mechanisms, particular those pertaining to homogeneous and heterogeneous catalytic transformations for energy and sustainability. Dr. Keith has ~20 years of experience in computational chemistry modeling atomic scale reaction mechanisms. Current research projects include:

Carbon Neutral Chemical and Fuel

Generation: Our society heavily relies on energy dense liquid fuels, but there is a pressing need to sustainably produce carbon neutral liquid fuels (CNLFs). Several independent researchers have reported energetically efficient CO2 reduction (CO2R) into methanol, but there are many open questions about the mechanisms for these processes. Our group aims to elucidate if and how this chemistry can occur. Our central hypothesis is that that if hydrogen transfer agents can catalyze CO2R, they do so serendipitously in specific electrochemical environments that facilitate unsuspected modes of hydrogenation. Our technique is to computationally characterize (electro) chemical phase diagrams for hypothetical catalysts to identify thermodynamically accessible states at ambient conditions as well as energetically efficient reaction pathways.

Funding: ACS Petroleum Research Fund, NSF Recent publication: S. Ilic et al., “Thermodynamic Hydricities of Biomimetic Organic Hydride Donors,” J. Am. Chem. Soc. 140 (2018) 4569. Modeling Local Solvation Effects: Computationally modeling atomic scale chemical reaction mechanisms in solvents is very challenging. The reliable and robust schemes usually involve dynamics-based treatments with explicit solvation models that involve large numbers of electronic structure calculations. While such efforts can be very insightful, they can also bring very large computational costs and/or technical challenges that restrict their use in more complex systems. Our group is developing calculation schemes that can be used to better design environmentally green chelates and analyze local solvation effects in mixed composition ionic and molten solvents.

Funding: NSF, Pitt MCSI Recent publication: Y. Basdogan and J. A. Keith, “A paramedic treatment for modeling explicitly solvated chemical reaction mechanism,” Chem. Sci. 9 (2018) 5341

Accelerated Methods for High-Throughput Screening of Catalyst Sites:

Density functional theory (DFT)-based investigations of hypothetical catalysts are too computationally demanding for wide searches across materials space. We have been developing fast and accurate computational methods to accelerate characterizations of reaction energies and barrier heights across diverse materials space.

Funding: R. K. Mellon Foundation, Naval Research Lab Recent publication: K. Saravanan, J. R. Kitchin, O. A. von Lilienfeld, J. A. Keith, “Alchemical Predictions for Computational Catalysis: Potential and Limitations,” J. Phys. Chem. Lett., 2017, 8, 5002-5007.