Highly efficient production of 2,5-dihydroxymethylfuran from biomass-derived 5-hydroxymethylfurfural over an amorphous and mesoporous zirconium phosphonate catalyst

作     者：Lei Hu Ning Li Xiaoli Dai Yuqi Guo Yetao Jiang Aiyong He Jiaxing Xu Lei Hu;Ning Li;Xiaoli Dai;Yuqi Guo;Yetao Jiang;Aiyong He;Jiaxing Xu

作者机构：Jiangsu Key Laboratory for Biomass-Based Energy and Enzyme Technology Jiangsu Collaborative Innovation Center of Regional Modern Agriculture &Environmental Protection School of Chemistry and Chemical Engineering Huaiyin Normal University 

出 版 物：《Journal of Energy Chemistry》 (能源化学（英文版）)

年 卷 期：2019年第28卷第10期

页      面：82-92页

核心收录：

学科分类：0820[工学-石油与天然气工程] 0808[工学-电气工程] 07[理学] 0817[工学-化学工程与技术] 0807[工学-动力工程及工程热物理] 0827[工学-核科学与技术] 0703[理学-化学] 0702[理学-物理学] 

基　　金：financially supported by the National Natural Science Foundation of China (21506071) the Special Foundation of Jiangsu Collaborative Innovation Center of Regional Modern Agriculture and Environmental Protection (HSXT2-316) 

主　　题：5-Hydroxymethylfurfural 2,5-Dihydroxymethylfuran 2-Butanol Zirconium phosphonate catalyst Meerwein-Ponndorf-Verley reduction 

摘      要：The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.