Catalytic Conversion of Xylo-Oligomers to Furfural in Pulping Pre-Hydrolysis Liquor Using a Hydroxyl-Functionalized Covalent Organic Framework.

With the rapid development of biorefinery technology, the efficient conversion of lignocellulose into high-value platform chemicals is of great significance for enhancing the value of renewable carbon resources. In this study, a hydroxyl-functionalized covalent organic framework (COF), TAPB-DHPA, was synthesized via an in situ method and innovatively applied to the catalytic conversion of xylo-oligosaccharides (XOS) into furfural. The results demonstrated that TAPB-DHPA possesses a large specific surface area, a well-developed porous structure, and excellent thermal stability, with abundant Brønsted acid (B acid) sites, exhibiting outstanding catalytic activity. Under optimal conditions, including a catalyst loading of 0.16 wt%, a reaction temperature of 180 °C, and a reaction time of 3 h, a furfural yield of up to 65.4% was achieved. The high selectivity was primarily attributed to the p-π conjugation effect between the benzene ring and the phenolic hydroxyl group, which enhanced the ionization ability of hydroxyl hydrogen, thereby effectively promoting the hydrolysis of XOS and subsequent dehydration. Furthermore, TAPB-DHPA exhibited excellent recyclability and stability, maintaining a furfural yield of over 59.9% after six cycles. This study provides new insights into the application of functionalized COF in biomass catalytic conversion and contributes to the green transformation of the pulp and paper industry into a biorefinery-based model.