Synthesis of Biomass‐Based MIL‐101(Cr)@hydrochar for Efficient Conversion of Xylose to Furfural: Effects of Physicochemical Properties and Biomass Types

Developing biomass‐based solid acid catalysts and converting biomass‐derived molecules into high‐value chemicals has a dual promoting effect on the high‐value utilization of waste biomass. This study introduces a groundbreaking one‐pot hydrothermal strategy integrating biomass with MIL‐101(Cr) precursor to fabricate hierarchical carbon‐based catalysts for the highly efficient and selective dehydration of xylose to furfural, achieving 67.2%–72.0% furfural yield (a 33% enhancement over conventional biomass‐derived catalysts) under optimized conditions (180°C, 3 h) in a toluene/water biphasic system. The modified hydrochar exhibits an ultra‐high surface area of 2119.3 m 2 /g, abundant dual Lewis/Brønsted acid sites, and dispersed Cr 3+ active centers, enabled by synergistic MOF‐templated modification engineering and biomass hydrothermal carbonization. Moreover, the correlation between the physicochemical properties and catalytic performance of modified hydrochar was analyzed. Notably, biomass feedstocks with low ash content and high nitrogen content can yield modified hydrochar with more acidic active sites, which exhibits superior catalytic activity. This study provides new ideas for the high‐value utilization of waste biomass.