PO4 3- Coordinated Robust Single-Atom Platinum Catalyst for Selective Polyol Oxidation

Angew Chem Int Ed Engl. 2022 May 16;61(21):e202116059. doi: 10.1002/anie.202116059. Epub 2022 Mar 23.

Abstract

Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single-atom Pt1 /hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1 /HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2 -C4 polyols to corresponding primary hydroxy acids. It is found that the Pt-(O-P) linkages with strong electron-withdrawing function of PO4 3- (Pt1 -OPO4 3- pair active site) not only realize the activation of the C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO4 3- -coordination effect provides electrostatic stabilization for single-atom Pt, ensuring the highly efficient catalysis of Pt1 /HAP for over 160 hours with superior leaching resistance.

Keywords: Coordination Effects; Hydroxyl Acid; Polyols; Selective Oxidation; Single-Atom Catalysts.