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

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-WOx/WC catalyst was constructed for ethanol production, while a sulfonated Mo/WC-SO3H catalyst was developed for selective formation of 1,2-propylene glycol. Under optimized conditions (245 ℃, 2 h, 5 MPa H2), complete cellulose conversion was achieved over Mo-Pt-WOx/WC, delivering a total low-carbon alcohol yield of 68.1C% with an ethanol yield of 57.8C%. In contrast, Mo/WC-SO3H enabled complete cellulose conversion with a high 1,2-propylene glycol yield of 62.9C%. Experimental characterization suggests that SO3H-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 WOx-derived acid sites favor selective C-C bond scission of glucose, whereas deep hydrogenolysis of ethylene glycol to ethanol is kinetically favored at Pt-MoOx 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.