Modulating the Electronic States of Pt Nanoparticles on Reducible Metal-Organic Frameworks for Boosting the Oxidation of Volatile Organic Compounds.

Abstract

The adsorption and activation of pollutant molecules and oxygen play a critical role in the oxidation reaction of volatile organic compounds (VOCs). In this study, superior adsorption and activation ability was achieved by modulating the interaction between Pt nanoparticles (NPs) and UiO-66 (U6) through the spatial position effect. Pt@U6 exhibits excellent activity in toluene, acetone, propane, and aldehyde oxidation reactions. Spectroscopic studies, 16O2/18O2 kinetic isotopic experiments, and density functional theory (DFT) results jointly reveal that the encapsulated Pt NPs of Pt@U6 possess higher electron density and d-band center, which is conducive for the adsorption and dissociation of oxygen. The toluene oxidation reaction and DFT results indicate that Pt@U6 is more favorable to activate the C-H of toluene and the C═C of maleic anhydride, while Pt/U6 with lower electron density and d-band center exhibits a higher oxygen dissociation temperature and higher reactant activation energy barriers. This study provides a deep insight into the architecture-performance relation of Pt-based catalysts for the catalytic oxidation of VOCs.