Acetic acid ketonization on tetragonal zirconia: Role of surface reduction
2016
Tosoni, Sergio | Pacchioni, Gianfranco
The ketonization reaction of acetic acid on the (101) surface of tetragonal zirconia, a process relevant in the catalytic upgrade of cellulosic biomass has been studied by means of DFT+U calculations. The aim was to better understand the role of catalyst pre-reduction. Acetic acid adsorbs strongly on the zirconia surface, and deprotonation to acetate takes place easily. Then, a proton transfer from the methyl group of the acetate ion, CH3COO⁻, to the surface occurs to form an eno-species, CH2COO²⁻ (intermediate 1). In a parallel step, acetate ions convert into acyl fragments, CH3CO, by oxygen extraction (intermediate 2). Once formed, the acyl intermediate 2 is able to attack the eno-species intermediate 1, to form a β-keto-acid. On stoichiometric zirconia, the formation of the intermediate 1, CH2COO²⁻, is unfavorable; oxygen vacancies on the reduced surface stabilize the reaction product and strongly reduce the activation energy. Reduced Zr³⁺ centers are essential to stabilize the acyl intermediate 2. The present work shows at an atomistic level the beneficial role of O vacancies and reduced Zr³⁺ centers for the ketonization process.
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