Selective production of ethanol and 1,2-propylene glycol from cellulose over multifunctional tungsten–carbon catalysts

Tungsten–carbon catalysts were designed for pathway-controlled cellulose hydrogenolysis. • Complete cellulose conversion with tunable selectivity to ethanol or diols was achieved. • WO x -derived Lewis acidity promoted selective C–C bond cleavage of glucose. • Metal–oxide interfacial sites enabled deep hydrogenolysis toward ethanol formation. • SO 3 H-modified catalysts regulated acid–metal cooperation toward C3 diol production. Cellulose, as the most abundant renewable carbon resource, offers great potential for the sustainable production of low-carbon alcohols. However, its catalytic hydrogenolysis remains challenging due to the difficulty in controlling product distribution and reaction pathways. Herein, two tungsten–carbon–based catalytic systems were rationally designed to direct cellulose hydrogenolysis toward ethanol or 1,2-propylene glycol through site-dependent catalysis. A multifunctional Mo-Pt-WO x /WC catalyst was constructed for ethanol production, while a sulfonated Mo/WC-SO 3 H catalyst was developed for selective formation of 1,2-propylene glycol. Under optimized conditions (245 ℃, 2 h, 5 MPa H 2 ), complete cellulose conversion was achieved over Mo-Pt-WO x /WC, delivering a total low-carbon alcohol yield of 68.1C% with an ethanol yield of 57.8C%. In contrast, Mo/WC-SO 3 H enabled complete cellulose conversion with a high 1,2-propylene glycol yield of 62.9C%. Experimental characterization suggests that SO 3 H-derived acidity may promote cellulose hydrolysis, while Mo-containing surface species may facilitate glucose isomerization and retro -aldol C–C bond cleavage. Density functional theory (DFT) calculations further reveal that WO x -derived acid sites favor selective C–C bond scission of glucose, whereas deep hydrogenolysis of ethylene glycol to ethanol is kinetically favored at Pt-MoO x interfacial sites. This work provides a practical strategy for steering cellulose hydrogenolysis toward different low-carbon alcohols through rational active-site design, and offers guiding principles for the rational development of multifunctional catalysts for biomass valorization. Download: Download high-res image (164KB) Download: Download full-size image