Carboxylic acids undergo hydro-deoxygenation at moderate to high temperatures and H<sub>2</sub> pressures over metal surfaces to yield a variety of products. These form through complex reaction networks comprised of multiple parallel and sequential C-O scission, C-C scission, hydrogenation, disproportionation, and water-gas shift reactions. The number of accessible pathways under typical reaction conditions makes it is difficult to control selectivity (particularly to partial HDO products) over monometallic catalysts, and bimetallics are used in practice. As experimental kineticists, our goal is generally to quantify the rates of all such processes such that we can begin to infer how the structure and composition of the catalyst combine with reactor operating conditions to dictate performance such that we may inform future catalyst design. This can be challenging during carboxylic acid hydrodeoxygenation due to the complexity of the network and the number of observable products that form through redundant pathways. Here, we examine the prevalence of all pathways and attempt to reconcile experimental observables with a microscopic view of carboxylic acid hydrogenation on metal surfaces. Paul’s ability to derive rational and fundamental insights from enormously complex systems has always been an inspiration for our group. Here, we try follow his approach in outlining the rules of selective hydrodeoxygenation of carboxylic acids.

Microscopic view of observable trends in reactor performance during the hydrodeoxygenation of carboxylic acids

2019 Spring National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.