(127e) First Principles Studies of Biomass-Related Chemistry At Metal and Metal/Oxide Interfaces

The catalytic production of chemicals from biomass is a field of growing importance in the quest to identify renewable sources of fuels and fine chemicals.  Within this broad class of catalytic processes, a particular reaction of interest in our program is the reforming of biomass intermediates to produce hydrogen.  Although a variety of experimental studies of this and related reactions have been carried out over the past ten years, relatively little fundamental mechanistic information about these processes exists.   First principles calculations have, recently, begun to shed light on some of the mechanistic details of these processes, but the complexity and computational cost of treating biomolecules larger than ethanol has slowed progress in this area. 

In this talk, we describe a strategy that combines DFT calculations and a novel bond order conservation-based scheme to estimate both the activity and selectivity of Pt(111) surfaces for hydrogen production from glycerol.  We further develop a series of scaling relationships to extend these Pt values to other transition metal surfaces, and we generate comprehensive free energy diagrams of glycerol decomposition to permit the comparison of trends in the selectivity and activity on these surfaces, together with the surfaces of simple bifunctional alloys. 

If time permits, we will extend our discussion of bifunctional catalysts to water-gas shift chemistry at gold nanowire/oxide support interfaces.