Rational Design of Selective Hydrodeoxygenation Catalysts for Organic Acids

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The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor Andreas Heyden and co-PIs Professor John R. Monnier and Professor Christopher T. Williams from the University of South Carolina to investigate the underlying science that can lead to the development of highly selective, catalytic materials for upgrading of bio-oils using fast pyrolysis of lignocellulosic biomass. A combined computational and experimental research approach will (a) obtain fundamental understanding of the reaction mechanism of the heterogeneous, catalytic hydrodeoxygenation (HDO) of organic acids on Group VIII transition metal catalysts in both a gas phase and liquid phase (water and n-butanol) environment and (b) rationally design novel supported metal catalysts for the selective conversion of organic acids into alcohols and alkanes. The research approach rigorously integrates (a) state-of-the-art computational heterogeneous catalysis tools such as plane wave density functional theory (DFT), implicit continuum solvation models, d-band models, Brønsted-Evans-Polanyi (BEP) relationships, scaling relations, microkinetic modeling, Campbell's degree of rate and selectivity control, and multi-dimensional volcano curves with (b) an experimental program that combines a novel bimetallic catalyst synthesis methodology (electrode less deposition) with structural and electronic characterization techniques, in-situ vibrational spectroscopy, and kinetic evaluation using state of the art single pass flow reactors and high pressure batch reactors. The computational studies will lead to hypotheses that motivate new experiments, while experimental observations will confirm theoretical findings and inspire new computational investigations. The conversion of biomass to useful fuels and chemicals is an essential goal of sustainable chemistry. The fundamental objective of this project is to establish a scientific basis for the rational design of novel heterogeneous catalysts with superior activity and selectivity for the HDO of organic acids relevant for upgrading of bio-oils obtained from lignocellulosic biomass. The aim is to increase the understanding of HDO reaction mechanisms and reduce the time and financial resources needed for the design of new heterogeneous catalysts tailored to meet the changing needs of a world with limited resources. Finally, the PhD students involved in this project will become experts in the practice and integration of computational and experimental catalysis. Graduate students from underrepresented groups will be attracted through the ongoing Sloan Minority Graduate Fellowship and Southeast Alliance for Graduate Education and the Professoriate (SEAGEP) programs that are available within Chemical Engineering at USC. Also, the research results will be integrated into the joint graduate and undergraduate electives"Multiscale Modeling: From Electrons to Chemical Reactors" and "Catalysis" and the core chemical engineering curriculum.