Controlling Metal-Oxide Reducibility for Efficient C-H Bond Activation in Hydrocarbons

Angew Chem Int Ed Engl. 2023 Dec 4;62(49):e202310062. doi: 10.1002/anie.202310062. Epub 2023 Oct 9.

Abstract

Knowing the structure of catalytically active species/phases and providing methods for their purposeful generation are two prerequisites for the design of catalysts with desired performance. Herein, we introduce a simple method for precise preparation of supported/bulk catalysts. It utilizes the ability of metal oxides to dissolve and to simultaneously precipitate during their treatment in an aqueous ammonia solution. Applying this method for a conventional VOx -Al2 O3 catalyst, the concentration of coordinatively unsaturated Al sites was tuned simply by changing the pH value of the solution. These sites affect the strength of V-O-Al bonds of isolated VOx species and thus the reducibility of the latter. This method is also applicable for controlling the reducibility of bulk catalysts as demonstrated for a CeO2 -ZrO2 -Al2 O3 system. The application potential of the developed catalysts was confirmed in the oxidative dehydrogenation of ethylbenzene to styrene with CO2 and in the non-oxidative propane dehydrogenation to propene. Our approach is extendable to the preparation of any metal oxide catalysts dissolvable in an ammonia solution.

Keywords: C−H Activation; Dehydrogenation; Reducibility; Tailoring Catalyst Structure; Vanadium Oxide.