Selective Conversion of Glycerol to Value‐Added C3 Products: Effect of Catalyst Surface Structure

Abstract

AbstractGlycerol, a major byproduct of biodiesel processing, could be leveraged as a platform to higher‐value products if the selectivity of its transformations could be improved. Herein, density functional theory (DFT) calculations are used to identify reactivity trends for the initial glycerol dehydrogenation steps involving C−H and O−H bond cleavage on a variety of transition metals including Ag, Au, Cu, Pd, Pt, and Rh considering both (111) and (100) surface facets. Additional activation energies calculated on Pt(111), Pt(100), Au(111), and Au(100) surfaces indicate that the most energetically favorable pathway is highly sensitive to the local surface structure and depends on the adsorption strength of reactive intermediates to the metal surface. Finally, adsorbate‐based and structure‐based energy scaling approaches for glycerol are identified, suggesting the ability to screen candidate materials using both structure‐ and composition‐based reactivity descriptors.