Synergistic effects in Ce-V co-doped TiO2 nano-catalysts for furfural hydrogenation: A comparative study with Zr-doped Analogues

• Bimetallic Ce x V y -TiO 2 and monometallic Zr x -TiO 2 were efficient for furfural hydrogenation. • Ce 4+ /Ce 3+ redox and oxygen vacancies created active sites for H 2 dissociation and carbonyl activation. • Reaction temperature and hydrogen could act as a switch to control the product distribution. • H 2 dissociation was more facile on V 2 O 5 (310), the adsorption of dissociated hydrogen atoms and FF were more stable on Ce 2 O 3 (002). Bimetallic Ce x V y -TiO 2 and monometallic Zr x -TiO 2 catalysts were systematically evaluated for the hydrogenation of furfural (FF) to furfuryl alcohol (FA). Notably, a FF conversion of 95% with 81% yield toward FA was achieved under optimized conditions. Reaction temperature and hydrogen pressure acted as key parameters governing product distribution, enabling tunable selectivity. In particular, enhanced H 2 dissociation and activation occurred over the Ce and V oxide sites at elevated temperatures, which promoted hydrogenation while effectively suppressing the competing acetalization pathway. The performance of Ce 4 V 1 -TiO 2 is attributed to its spherical nanoparticle morphology, an optimal Brønsted-to-Lewis acid site ratio (0.06), high H 2 uptake (230.34μmol g −1 ), substantial O 2 consumption (71.24μmol g −1 ), and the presence of variable oxidation states of Ce and V that facilitate redox synergy. Density functional theory (DFT) calculations and H 2 -TPD revealed a synergistic catalytic effect between Ce and V on hydrogen adsorption and activation. Notably, V demonstrated stronger hydrogen adsorption and dissociation capacity compared to Ce. In addition, the adsorption of FF occurs more readily on the Ce 2 O 3 (002) surface, while H 2 dissociates more easily on the V 2 O 5 (310) surface. Furthermore, the adsorption of dissociated hydrogen atoms is thermically more stable on Ce 2 O 3 (002), indicating a cooperative mechanism where V sites primarily facilitated H 2 activation, and Ce sites chiefly stabilized the reaction intermediates. Overall, the Ce-V-TiO 2 catalytic system exhibits tunable reaction pathways and high catalytic activity, providing an efficient and sustainable strategy for biomass valorization toward value-added chemicals and renewable fuels in the context of green chemistry.