Isolated Hf‐Isomorphously Substituted Zeolites for One‐Pot HMF Synthesis from Glucose

Abstract The direct conversion of glucose to 5‐hydroxymethylfurfural (HMF) is a crucial process in biorefinery. However, it still suffers from the rational design of highly efficient catalysts for one‐pot HMF production. Herein, the pioneering design of bifunctional hafnium (Hf)‐incorporated zeolites with fine‐tuned Brønsted/Lewis acidity and hierarchical features has been illustrated via one‐pot hydrothermally prepared protocols. Most importantly, the rationally designed catalyst presents the highly dispersed isolated Hf species located at the zeolite framework, which is close to the Brønsted acid site. The designed catalysts eventually reveal superb catalytic performances in glucose conversion (95.4 ± 1.1%) and HMF yield (63.2 ± 2.0%), as well as excellent catalytic stability, which are significantly improved compared to the well‐known tin‐beta zeolite. In addition, the catalytic activity and mechanistic studies of the Hf‐beta zeolite are confirmed by the density functional theory calculations.