Synergistic Interfacial Engineering and Orbital Hybridization in Polyoxometalates@Porous Aromatic Framework Catalyst for Efficient Ethanol Oxidative Esterification

Abstract

The efficient oxidation esterification of bioethanol in the liquid-phase remains challenging. Herein, polyoxometalates supported on a porous aromatic framework catalyst (PW11Co@iPAF-2) are synthesized for the one-pot production of ethyl acetate (EA) from ethanol, yielding 89.6% EA. The interaction between PW11Co and iPAF-2 effectively regulates the orbital electron distribution of Co 2+ , promoting the activation of ethanol by PW11Co. Furthermore, the pore structure of iPAF-2 excludes water molecules, thereby reducing the local water concentration around the PW11Co active site. This localized anhydrous microenvironment is conducive to the reversible reaction proceeding in the forward direction, leading to high selectivity for EA. This research offers a new perspective on designing more efficient esterification catalysts.