Density Functional Theory-Derived Group Additivity and Linear Scaling Methods for Prediction of Oxygenate Stability on Metal Catalysts: Adsorption of Open-Ring Alcohol and Polyol Dehydrogenation Intermediates on Pt-Based Metals (

摘要

Semiempirical methods for prediction of fhermochemical properties of adsorbed oxygenates are developed. Periodic density functional theory calculations are used to study the relative stability of ethanol, ethylene glycol, isopropyl alcohol, and glycerol dehydrogenation intermediates on Pt(111). For ethylene glycol dehydrogenation intermediates, it is found that the thermodynamically favored intermediates at each level of dehydrogenation are as follows: HOCH2CHOH, HOCHCHOH, HOCHCOH, HOCCOH ≈ HOCHCO, HOCCO, OCCO. Structural and energetic patterns emerge from these C2HxO2 adsorption calculations that lead to the formation of group additive properties for fhermochemical property prediction of oxygenates on Pt(111). Finally, linear scaling relationships of atomic binding energy are used to predict the binding energy of the C2H_xO2 species on the Ni(111) surface and Ni-Pt-Pt(111) bimetallic surface. It is shown that the linear scaling relationships can accurately predict the binding energy of larger oxygenates as well as of oxygenates on bimetallic catalysts. Corrections for ring strain and weak oxygen—metal and hydrogen-bonding interactions are added to increase the accuracy of group additivity and linear scaling relationships.