Synergistic effect of silanols in mesopores leading to unexpected catalysis of dendritic mesoporous silica particles in the aqueous-phase synthesis of 5-hydroxymethylfurfural from fructose

Synthesis of 5-hydroxymethylfurfural (5-HMF) from fructose in water over acids catalysts usually produces unsatisfactorily low yield and selectivity due to inevitable side reactions, i.e., rehydration and condensation. Unprecedentedly, these complications in the aqueous phase synthesis of 5-HMF could be overcome by dendritic mesoporous silica particles (DMSNs). In the hydrothermal reactions of fructose, it was discovered that the synergy of silanols and mesopores transformed seemingly inert DMSNs into active catalysts, leading to a fructose conversion and 5-HMF yield of over 90%. The silanols on DMSNs offered weak Brønsted acid sites for catalyzing the dehydration of fructose to 5-HMF, while undesired reactions were substantially prohibited. The presence of glucose in the reaction suggests that fructose converts to 5-HMF via the acyclic route, and the competing reaction is indeed the isomerization. As revealed experimentally, mesopores full of silanols promoted the conversion of fructose to 5-HMF, but mesopores with a few silanols were relatively hydrophobic, offering a preferential partitioning of 5-HMF in mesopores of DMSNs. DFT analysis theoretically supported that in the presence of silanols, transforming fructose to 5-HMF is thermodynamically more favorable than the isomerization of fructose to glucose.