Abstract: 5-Hydroxymethylfurfural (5-HMF), as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels, has been attracted extensive attention. In this research, using Pickering high internal phase emulsions (Pickering HIPEs) as template and functional metal-organic frameworks (MOFs, UiO-66-SO₃H and UiO-66-NH₂)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process, which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF. The effects of the emulsion parameters including the amount of surfactant (ranging from 0.5% to 2.0% (mass)), the internal phase volume fraction (ranging from 75% to 90%) and the acid/base Pickering particles mass ratio (ranging from 0:6 to 6:0) on the morphology and catalytic performance of solid catalyst were systematically researched. The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion, and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield. The highest 5-HMF yield, about 40.5%, can be obtained by using polymer/MOFs composite as catalyst (Poly-P12, the pore size of (53.3 ±11.3) μm, the acid density of 1.99 mmol·g^-1 and the base density of 1.13 mol·g^-1) under the optimal reaction conditions (130 ℃, 3 h). Herein, the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method, which provided a favorable experimental basis and theoretical reference for achieving efficient production of high added-value product from abundant biomass.

Key words: Catalyst, Biomass, Hydrolysis, 5-Hydroxymethylfurfural, Pickering high internal phase emulsions templated polymer, Acid-base bifunctional site

摘要： 5-Hydroxymethylfurfural (5-HMF), as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels, has been attracted extensive attention. In this research, using Pickering high internal phase emulsions (Pickering HIPEs) as template and functional metal-organic frameworks (MOFs, UiO-66-SO₃H and UiO-66-NH₂)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process, which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF. The effects of the emulsion parameters including the amount of surfactant (ranging from 0.5% to 2.0% (mass)), the internal phase volume fraction (ranging from 75% to 90%) and the acid/base Pickering particles mass ratio (ranging from 0:6 to 6:0) on the morphology and catalytic performance of solid catalyst were systematically researched. The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion, and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield. The highest 5-HMF yield, about 40.5%, can be obtained by using polymer/MOFs composite as catalyst (Poly-P12, the pore size of (53.3 ±11.3) μm, the acid density of 1.99 mmol·g^-1 and the base density of 1.13 mol·g^-1) under the optimal reaction conditions (130 ℃, 3 h). Herein, the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method, which provided a favorable experimental basis and theoretical reference for achieving efficient production of high added-value product from abundant biomass.

关键词: Catalyst, Biomass, Hydrolysis, 5-Hydroxymethylfurfural, Pickering high internal phase emulsions templated polymer, Acid-base bifunctional site