(56a) How a Molecular View of Dynamic Events at Liquid-Solid Interfaces Enables Deliberate Modulation of Reaction Kinetics and Catalyst Stability in Liquid-Phase Process

Chemical kinetics in liquid phase catalytic processes are partially controlled by entropic effects resulting from many-body noncovalent interactions between reactant species and surrounding solvent molecules. Progress in combining detailed reaction kinetics investigations with innovative computational tools has revealed a wealth of detailed insight around the role of solvent molecules in mediating charge transfer and proton shuttling mechanisms; modulating the free energy of transition states by preferential solvation; and otherwise facilitating distinct chemistry relative to gas phase reaction sequences. These insights have enabled a number of innovative approaches to control the selectivity of liquid phase processes by deliberately modulating the composition of the solvent system; and some key examples in this context are biomass conversion studies. However, techonomic analyses have revealed managing complex solvent mixtures as a key cost driver in these otherwise promising bio-renewable chemical technologies.

Here, I will briefly review some of my own Ph.D. thesis work (at the University of Wisconsin – Madison), exploring the role of mixed solvent systems in controlling the rates and selectivities of acid-catalyzed biomass conversion processes. I will furthermore describe my industrial experience (at the ExxonMobil Research and Engineering Company) where we leveraged these fundamental insights in practice; and quantified the importance of process intensity and catalyst reliability to derisk real-world technologies. Finally, will introduce the seminal work from my research group at Syracuse University, where we are tethering polymer grafts of precisely tuned dimensions onto acid-functionalized nanoparticles to create tailored local solvation environments near the catalyst surface, eliminating the need for an expensive organic cosolvent. We are furthermore exploring the role of post-transition elements in modulating the dissolution resistance of first-row transition metal catalysts during electrochemical oxidation reactions; and developing strategies to improve the alkali metal tolerance of zeolite pyrolysis catalysts. I will describe some of our preliminary efforts toward these ends.