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钌羟基磷灰石包覆的氧化铁作为合成2,5-二呋喃甲醛的多相催化剂

Iron oxide encapsulated by ruthenium hydroxyapatite as heterogeneous catalyst for the synthesis of 2,5-diformylfuran.

作者信息

Zhang Zehui, Yuan Ziliang, Tang Dingguo, Ren Yongshen, Lv Kangle, Liu Bing

机构信息

Key Laboratory of Catalysis and Material Sciences, State Ethnic Affairs Commission & Ministry of Education, South-Central University for Nationalities, MinYuan Road 182, Wuhan (PR China), Fax: (+86) 27-67842752.

出版信息

ChemSusChem. 2014 Dec;7(12):3496-504. doi: 10.1002/cssc.201402402. Epub 2014 Aug 19.

Abstract

Magnetic γ-Fe2 O3 nanocrystallites encapsulated by hydroxyapatite (HAP), HAP@γ-Fe2 O3 , were prepared followed by cation exchange of Ca(2+) on the external HAP surface with Ru(3+) to give the γ-Fe2 O3 @HAP-Ru catalyst. The structure of the as-prepared catalyst was characterized, and its catalytic activity was studied in the aerobic oxidation of 5-hydroxymethylfurfural (HMF). γ-Fe2 O3 @HAP-Ru showed a high catalytic activity for the aerobic oxidation of HMF into 2,5-diformylfuran (DFF). A high DFF yield of 89.1 % with an HMF conversion of 100% was obtained after 4 h at 90 °C. Importantly, the synthesis of DFF from fructose was realized by two consecutive steps. The dehydration of fructose in the presence of a magnetic acid catalyst (Fe3 O4 @SiO2-SO3 H) produced HMF in a yield of 90.1%. Then the Fe3 O4 @SiO2 SO3 H catalyst was removed from the reaction solution with a permanent magnet, and HMF in the resulting solution was further oxidized to DFF with a yield of 79.1% based on fructose. The synthesis of DFF from fructose by two steps avoids the tedious separation of the intermediate HMF, which saves time and energy.

摘要

制备了羟基磷灰石(HAP)包覆的磁性γ-Fe2O3纳米微晶,即HAP@γ-Fe2O3,然后通过Ru(3+)与HAP外表面的Ca(2+)进行阳离子交换,得到γ-Fe2O3@HAP-Ru催化剂。对所制备催化剂的结构进行了表征,并研究了其在5-羟甲基糠醛(HMF)有氧氧化反应中的催化活性。γ-Fe2O3@HAP-Ru对HMF有氧氧化生成2,5-二甲基呋喃(DFF)表现出高催化活性。在90℃下反应4小时后,HMF转化率为100%,DFF产率高达89.1%。重要的是,通过连续两步实现了由果糖合成DFF。在磁性酸催化剂(Fe₃O₄@SiO₂-SO₃H)存在下,果糖脱水生成HMF的产率为90.1%。然后用永磁体从反应溶液中除去Fe₃O₄@SiO₂-SO₃H催化剂,所得溶液中的HMF进一步氧化为DFF,基于果糖的产率为79.1%。通过两步由果糖合成DFF避免了中间体HMF的繁琐分离,节省了时间和能源。

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