Selective adsorption and hydrogenolysis of C-OH bond in biomass derived furanic compounds over Ni-TT-Nb₂O₅

The selective hydrogenolysis of C-OH in renewable furanic compounds to corresponding high-value products has been attractive yet challenging, and the mechanism remains vague. Herein, a non-noble catalyst (Ni-TT-Nb₂O₅) was prepared to address this challenge. Batch and continuous reaction results show that Ni-TT-Nb₂O₅ can selectively hydrodeoxygenate 5-hdyroxymethylfurfural to 5-methylfurfural with a very high selectivity of 99%. Moreover, Ni-TT-Nb₂O₅ can also selectively hydrodeoxygenate various furanic, benzenoid and aliphatic alcohols, achieving up to > 95% selectivity. In-situ FTIR and DFT calculations showed that compared with other Ni-supported (supports = Al₂O₃, CeO₂, SiO₂, ZrO₂) catalysts, HMF was adsorbed on Ni-TT-Nb₂O₅ surface via parallel mode exclusively, and the C-OH bond was easier to be activated. This work therefore explained the mechanism of selective hydrogenolysis of C-OH in HMF over Ni-TT-Nb₂O₅, and offered an advanced approach for the upgrading of C-OH-containing furanic compounds as well as benzenoid and aliphatic alcohols. © 2024 Elsevier Inc.