Most biomass intermediates contain multiple functional groups. Therefore, achieving reduction and oxidation of only the desired functional groups is critical for efficient and selective upgrading of biomass intermediates. For reductive biomass upgrading, many intermediates containing oxygenated moieties such as carbonyl and alcohol groups must be selectively reduced to form desired fuels and chemicals. Thus, controlling the selectivity between hydrogenation and hydrogenolysis is of great importance for these transformations. (In this presentation, the term hydrogenation refers to the reaction involving the addition of H–atoms to an unsaturated C=O bond without breaking the C–O bond to form an alcohol group and the term hydrogenolysis refers to the reaction involving the addition of H–atoms to C=O or C–OH bonds that results in cleavage of the C–O bond and removal of O as H2O to form CHx.) Hydrogenolysis, which not only adds hydrogen but also eliminates oxygen, considerably increases the energy density of the starting molecule and is of great importance in any reductive organic conversion reactions. Thus, establishing a mechanistic foundation for electrochemical hydrogenolysis will be highly beneficial. Recent results from our and other research groups suggest that electrochemical aldehyde hydrogenation is not an initial step for electrochemical aldehyde hydrogenolysis. Instead, these two reactions are competing reactions. This means that they involve different mechanistic steps and/or different reaction intermediates. Currently, no atomic-level understanding is available to explain their mechanistic differences. In this presentation, we will discuss our combined experimental and computational investigations to understand the differences between electrochemical hydrogenation and hydrogenolysis and our strategies to promote electrochemical hydrogenolysis.

Understanding and promoting electrochemical hydrogenolysis

Where thousands of chemistry professionals meet to share ideas and advance scientific and technical knowledge. Spring 2023 abstracts, posters, and presentations will launch at the end of March.

ACS Spring 2023

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