Hafnium-anchored dendritic mesoporous silicananospheres with customizable acidity and particle size serves as an effective and stable catalyst for 5-hydroxymethylfurfural formation from carbohydrates

5-hydroxymethylfurfural (HMF) is a platform compound with great potential, and solid acid-catalyzed lignocellulosic carbohydrate components into HMF is a viable biomass valorization strategy. Herein, hafnium-anchored dendritic mesoporous silica nanospheres (Hf-DMSNs) with three-dimensional center-radial structures were synthesized via an in-situ co-assembly method. Characterization revealed that the acid properties and particle size of Hf-DMSNs could be regularly customized and that they acted as bifunctional catalysts capable of driving glucose (190 °C, 3 h) and cellulose (210 °C, 4 h) to achieve the desired HMF yields of 71 % and 50 %, respectively. Owing to the appropriate acidity, high accessibility, and anchored active site, the recycling of Hf-DMSNs catalyst lasted for more than twenty times with slight activity loss, which is eye-catching. Meanwhile, the intermediates detected during the conversion process confirmed that the HMF formation from cellulose components under the Hf-DMSNs catalysis was a cascade reaction consisting of three basic steps: hydrolysis, isomerization, and dehydration. The findings in this study provide a reference for the utilization of biomass-derived carbohydrates into HMF via heterogeneous catalysis.