Establishing the Role of Metal, Interface, and Vacancy Sites in Pt/TiO₂-Catalyzed Acetic Acid Hydrodeoxygenation

Catalytic hydrodeoxygenation (HDO) following catalytic fast pyrolysis (CFP) offers an approach to convert the vapor-phase product of biomass pyrolysis to a stable bio-oil product by reducing the oxygen content. Fundamental insights into the HDO of carboxylic acids, which are a corrosive and acidic CFP product, on promising catalyst materials, such as Pt/TiO₂, are needed to inform the design of multifunctional HDO catalysts with improved carbon efficiency. In this contribution, density functional theory (DFT) calculations were used to assess the role of Pt-metal and Pt-TiO₂-interface sites on acetic acid HDO (AA-HDO), and to determine the effect of interfacial oxygen vacancies at the Pt-TiO₂ interface, by calculating the reaction energetics for key AA-HDO surface intermediates and elementary steps on each site type. Pt-metal sites, modeled via Pt(111), preferred to form undesired decarboxylation products (CH₄ and CO₂), whereas Pt-TiO₂-interface sites, modeled via an anatase-supported Pt nanowire, favored the formation of desired deoxygenation products (acetaldehyde and ethane). Interfacial-vacancy sites lowered the activation energy barrier for the first C-O bond-scission step in AA-HDO, predicted to be the rate-limiting step for AA-HDO at the Pt-TiO₂ interface in the absence of a vacancy. These atomistic insights reveal the importance of metal-metal oxide interface sites in AA-HDO selectivity and can be used to inform the rational design of improved HDO catalysts.