2D MOF with Compact Catalytic Sites for the One‐pot Synthesis of 2,5‐Dimethylfuran from Saccharides via Tandem Catalysis

• Published in: Angewandte Chemie International Edition Vol. 61; no. 34; pp. e202205453 - n/a
• Main Authors: Deng, Qiang, Hou, Xuemeng, Zhong, Yao, Zhu, Jiawei, Wang, Jun, Cai, Jianxin, Zeng, Zheling, Zou, Ji‐Jun, Deng, Shuguang, Yoskamtorn, Tatchamapan, Tsang, Shik Chi Edman
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 22-08-2022
• Edition: International ed. in English
• Subjects: 2,5-Dimethylfuran; 2D metal-organic frameworks (MOFs); 5-Hydroxymethylfurfural; Active sites; Biofuels; Carbohydrates; Cascade chemical reactions; Catalysis; Catalysts; Catalytic Domain; Cellobiose; Chemical synthesis; Composite materials; Dehydration; Diffusion rate; Fine chemicals; Furans - chemistry; Isomerization; Lewis acid; Lewis Acids; Metal-Organic Frameworks; Metals; Molecular interactions; Multifunctional Catalysis; Palladium; Polysaccharides; Saccharides; Sucrose; 2,5-Dimethylfuran; 2D metal-organic frameworks (MOFs); 5-Hydroxymethylfurfural; Multifunctional Catalysis; Saccharides
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202205453

One pot synthesis of 2,5‐dimethylfuran (2,5‐DMF) from saccharides under mild conditions is of importance for the production of biofuel and fine chemicals. However, the synthesis requires a multitude of active sites and suffers from slow kinetics due to poor diffusion in most composite catalysts. Herein, a metal‐acid functionalized 2D metal‐organic framework (MOF; Pd/NUS‐SO3H), as an ultrathin nanosheet of 3–4 nm with Lewis acid, Brønsted acid, and metal active sites, was prepared based on the diazo method for acid modification and subsequent metal loading. This new composite catalyst gives substantially higher yields of DMF than all reported catalysts for different saccharides (fructose, glucose, cellobiose, sucrose, and inulins). Characterization suggests that a cascade of reactions including polysaccharide hydrolysis, isomerization, dehydration, and hydrodeoxygenation takes place with rapid molecular interactions.
A metal‐acid functionalized 2D MOF (Pd/NUS‐SO3H), as an ultrathin nanosheet containing compact active sites (Lewis and Brønsted acid sites, and metal sites) is prepared for the first time. It can give substantial yields of 2,5‐dimethylfuran from different saccharides (fructose, glucose, cellobiose, sucrose, and inulins) in a one‐pot synthesis.