Adsorption characteristics of reduced Mo and Ni–Mo catalysts in the hydrodeoxygenation of benzofuran

The promotional effect of Ni on the hydrodeoxygenation (HDO) of benzofuran (BF) over reduced Ni–Mo/γ-Al2O3 catalysts was studied. The adsorption characteristics of Al2O3 support, mono-metallic Mo, and bi-metallic Ni–Mo catalysts that were pre-reduced were investigated using the feed molecule (BF) and a probe molecule (NO) as adsorbates. NO was used to probe the coordinatively unsaturated sites (CUS). Three adsorption modes for benzofuran over reduced Al2O3 support, Mo, and Ni–Mo catalysts were proposed that involved OH groups, Brønsted acid sites, and CUS, respectively. Benzofuran molecule adsorbed more strongly on B acid sites and CUS than on OH groups and was activated with weakening of the C–O bond. With increasing catalytic hydrogenation activity (increasing CUS) and/or decreasing hydrogenolysis activity (decreasing acidity), the reaction pathway for benzofuran HDO changes from a hydrogenolysis route to a route that involves saturation of the benzene ring before any heteroatom removal takes place.

Graphical abstractThree adsorption modes for benzofuran over reduced Al2O3 support, Mo, and Ni–Mo catalysts were proposed that involved OH groups, Brønsted acid sites, and CUS, respectively. With increasing catalytic hydrogenation activity (increasing CUS) and/or decreasing hydrogenolysis activity (decreasing acidity), the reaction pathway for benzofuran HDO changes from a hydrogenolysis route to a route that involves saturation of the benzene ring before any heteroatom removal takes place. Figure optionsDownload full-size imageDownload as PowerPoint slide