An alternative reaction pathway triggered by oxygen vacancies for boosting selective hydrodeoxygenation reactions

Selective hydrodeoxygenation transformations constitute the most pivotal industrial processes in chemistry and catalysis. Herein, we have rationally designed a heterogeneous Co/CoOx catalytic system with metallic Co and oxygen vacancies in CoOx for selective hydrodeoxygenation of structurally diverse ketones and nitro compounds under mild conditions (80–100 °C and 10 bar H2), which shows a superior performance compared to state-of-the-art noble-metal catalysts. Experimental results and DFT calculation revealed that oxygen vacancies not only promote the adsorption and activation of substrates and the intermediates via electronic interactions, but also enable the hydrodeoxygenation reactions in a low-energy pathway via the direct hydrogenolysis process, instead of the dehydration–hydrogenation process. Given its generality and efficiency, it is believed that this method can serve as a practical, economically viable approach for selective hydrodeoxygenation reactions, which should impact both the chemical industry and scientific research.