Mechanistic Insights into Pt‐Catalyzed Glycerol Oxidation: Effects of pH and Potential

Abstract This study investigates the thermodynamics of glycerol (GLY) electro‐oxidation to all possible C3 products on Pt(111) under varying pH and potential by explicitly considering coadsorbed oxide species as well as the formation of conjugate bases. Despite similar major products observed in previous experimental studies, our computational analysis of the thermodynamics reveals mechanistic differences between the Pt(111) surfaces. GLY oxidation on the bare surface favors the formation of dihydroxyacetone (DHA) over glyceraldehyde (GLD); however, DHA can isomerize to GLD via keto‐enol tautomerization. A moderately oxidized Pt(111) surface adsorbs glycerol (GLY) more strongly and favors the formation of GLD, both contributing to the increased activity previously observed under these conditions. GLY adsorbs more weakly on a more oxidized surface, and multiple routes exhibit similar energetics. Limiting potentials defined by early oxidation processes suggest kinetics inhibit the formation of later oxidation products.