Acidity drives selectivity: tuning reaction pathways under hydrodeoxygenation conditions

The design and tuning of active sites (e.g., metallic, acid, and redox sites) are crucial for developing active, selective, and stable catalysts. Metal-support interactions (MSI) and the creation of interfacial sites can tailor the catalytic performance of metal/oxide catalysts for various reactions, directly impacting C-O, C-C, and C-H bond activation and H2 spillover. By modulating the acidity of the support (i.e., Brønsted-rich or Lewis-rich), we elucidate the role of acid sites over the acetone hydrodeoxygenation reaction pathways. Brønsted-rich catalysts favor the formation of selective C-O bond cleavage products, whereas Lewis-rich catalysts favor C-C coupling + C-O bond cleavage cascade products. We demonstrate that tailoring active sites from the support and constructing active metal-oxide interfacial sites can tune the catalytic performance toward targeted reaction pathways with enhanced stability. Our findings provide insights into C-O, C-C, and C-H bond activation, cleavage, and coupling that can be expanded to multiple catalytic reactions, contributing to the development of new functional materials with enhanced performance.