Eco-Friendly Synthesis of SO3H-Containing Solid Acid via Mechanochemistry for the Conversion of Carbohydrates to 5-Hydroxymethylfurfural
Eco-Friendly Synthesis of SO3H-Containing Solid Acid via Mechanochemistry for the Conversion of Carbohydrates to 5-Hydroxymethylfurfural
复制标题
通过机械化学环保合成含 SO3H 的固体酸，将碳水化合物转化为 5-羟甲基糠醛
DOI：
10.1021/acssuschemeng.0c00784
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发表时间：
2020-05-11
影响因子：
8.4
通讯作者：
Shen, Feng
中科院分区：
文献类型：
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作者：
Sun, Shuang;Zhao, Lijie;Shen, Feng
提出了一种绿色、高效、便捷的球磨辅助策略，设计了一种含so3h的固体酸，用于生物质活化，其中-SH基团通过3-巯基丙基三甲氧基硅烷（MTPS）湿球磨接枝到天然粘土棒土上，然后在室温下用H2O2将-SH氧化成-SO3H。研究了球磨过程中-SO3H功能化的机理，结果表明，在球磨机械力的诱导下，MTPS通过水解和缩聚的方式接枝到凹凸棒石上。通过SEM， EDX（能量色散x射线光谱），NH3-TPD， TGA, FT-IR，元素分析和XPS等表征，证实了-SO3H改性凹凸棒土的成功，总酸度为1.81 mmol/g。该方法避免了传统方法中涉及腐蚀性磺化剂、有机溶剂或高温的恶劣条件。由于催化剂上MgO和-SO3H位点的协同作用，所制备的催化剂在将生物质来源的碳水化合物（葡萄糖、果糖、纤维素二糖、蔗糖、淀粉和纤维素）转化为更有价值的化学物质s-羟甲基糠醛方面表现出较高的活性。此外，该催化剂表现出优异的稳定性和可回收性，可重复使用5次而不损失活性。本研究为制备含so3h的多相催化剂提供了一种新的绿色方法，在其他生物质增值过程中具有很大的应用潜力。
A green, efficient, and facile ball-milling-assisted strategy was proposed to design an SO3H-containing solid acid for biomass valorization, where -SH groups were grafted on a natural clay attapulgite by wet ball milling with 3-mercaptopropyltrimethoxysilane (MTPS), followed by the oxidation of -SH to -SO3H with H2O2 at room temperature. The mechanism of the -SO3H functionalization by the ball-milling process was investigated, and the investigation indicated that the MTPS was grafted on the attapulgite through hydrolysis and condensation, which was induced by the mechanical forces of ball milling. Characterization, including SEM, EDX (energy-dispersive X-ray spectrometry), NH3-TPD, TGA, FT-IR, elemental analysis, and XPS, confirmed the success of -SO3H modification on attapulgite with a total acidity of 1.81 mmol/g. Harsh conditions involving a corrosive sulfonating agent, organic solvent, or high temperature in traditional methods are avoided in the developed approach. The prepared catalyst displayed a high activity toward the transformation of biomass-derived carbohydrates (glucose, fructose, cellobiose, sucrose, starch, and cellulose) into the more valuable chemical S-hydroxymethylfurfural due to the synergy effect of MgO and -SO3H sites on the catalyst. Moreover, the catalyst showed excellent stability and recyclability for five recycles without loss of activity. This study provides a novel green method for the preparation of an SO3H-containing heterogeneous catalyst, which should have great application potential in other processes of biomass valorization.