Efficient Conversion of Cellulose to 5‐Hydroxymethylfurfural in NaHSO 4 /ZrO 2 /H 2 O‐THF Biphasic System

Abstract 5‐hydroxymethylfurfural (HMF) is an important bio‐based platform chemical for liquid fuel production. Herein, efficient conversion of cellulose to HMF in NaHSO 4 /ZrO 2 /H 2 O‐THF biphasic system was investigated with a high HMF yield up to 86.5%. In the co‐catalytic system, H + ions given from NaHSO 4 was promotive to all steps of the cellulose‐to‐HMF conversion; abundant alkaline sites of ZrO 2 was particularly favorable to the glucose‐to‐fructose isomerization. The accelerated conversion of glucose as well as the fast extraction of HMF from aqueous phase to tetrahydrofuran (THF) phase, favored the inhibition of humins which was generated from condensation between glucose and HMF. Only a trace amount of humins over ZrO 2 was detected after reaction, which guaranteed the reusability of ZrO 2 in six running experiments without any post‐treatment. The good reusability of ZrO 2 , the low ‐cost of NaHSO 4 , and the biomass‐derived THF were advantageous for potential industrial application.