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Tailored Cl- Ligation on Supported Pt Catalysts for Selective Primary C-H Bond Oxidation.

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It is challenging to achieve high selectivity over Pt-metal-oxide catalysts widely used in many selective oxidation reactions because Pt is prone to over-oxidize substrates. Herein, our sound strategy for enhancing… Click to show full abstract

It is challenging to achieve high selectivity over Pt-metal-oxide catalysts widely used in many selective oxidation reactions because Pt is prone to over-oxidize substrates. Herein, our sound strategy for enhancing the selectivity is to saturate the under-coordinated single Pt atoms with Cl- ligands. In this system, the weak electronic metal-support interactions between Pt atoms and reduced TiO2 cause electron extraction from Pt to Cl- ligands, resulting in strong Pt-Cl bonds. Therefore, the two-coordinate single Pt atoms adopt a four-coordinate configuration and thus inactivated, thereby inhibiting the over-oxidation of toluene over Pt sites. The selectivity for the primary C-H bond oxidation products of toluene was increased from 50.1 to 100%. Meanwhile, the abundant active Ti3+ sites were stabilized in reduced TiO2 by Pt atoms, leading to a rising yield of the primary C-H oxidation products of 249.8 mmol gcat-1. The reported strategy holds great promise for selective oxidation with enhanced selectivity.

Keywords: tailored ligation; ligation supported; oxidation; primary bond; bond oxidation

Journal Title: Journal of the American Chemical Society
Year Published: 2023

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