Aldehyde Hydrogenation by Pt/TiO2 Catalyst in Aqueous Phase: Synergistic Effect of Oxygen Vacancy and Solvent Water

The aldehyde hydrogenation for stabilizing and upgrading biomass is typically performed in aqueous phase with supported metal catalysts. By combining density functional theory calculations and ab initio molecular dynamics simulations, the model reaction of formaldehyde hydrogenation with a Pt/TiO2 catalyst is investigated with explicit solvent water molecules. In aqueous phase, both the O vacancy (Ov) on support and solvent molecules could donate charges to a Pt cluster, where the Ov could dominantly reduce the Pt cluster from positive to negative. During the formaldehyde hydrogenation, the water molecules could spontaneously protonate the O in the aldehyde group by acid/base exchange, generating the OH at the metal-support interface by long-range proton transfer. By comparing the stoichiometric and reduced TiO2 support, it is found that the further hydrogenation of OH is hard on the positively charged Pt cluster over stoichiometric TiO2. However, with the presence of Ov on reduced support, the OH hydrogenation could become not only exergonic but also kinetically more facile, which prohibits the catalyst from poisoning. This mechanism suggests that both the proton transfer from solvent water molecules and the easier OH hydrogenation from Ov could synergistically promote aldehyde hydrogenation. That means, even for such simple hydrogenation in water, the catalytic mechanism could explicitly relate to all of the metal cluster, oxide support, and solvent waters. Considering the ubiquitous Ov defects in reducible oxide supports and the common aqueous environment, this synergistic effect may not be exclusive to Pt/TiO2, which can be crucial for supported metal catalysts in biomass conversion.

Automated summary

Through DFT calculations and ab initio molecular dynamics simulations, the model reaction of formaldehyde hydrogenation with a Pt/TiO2 catalyst is studied with explicit solvent water molecules. In aqueous phase, both the O vacancy on support and solvent molecules could donate charges to a Pt cluster, with O vacancy dominantly reducing the Pt cluster from positive to negative. During the formaldehyde hydrogenation, the water molecules can protonate the O in the aldehyde group, generating the OH at the metal-support interface by long-range proton transfer. The presence of O vacancy on reduced support promotes the hydrogenation of OH, making it exergonic and kinetically more facile.