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UIO-66由于具备多种优异性能而成为广受关注的一种有机金属框架材料(MOF),在许多领域展现了丰富的应用潜能。小批量规模化制备是当前阻碍MOF类材料大规模工业化应用的一个主要瓶颈。UIO-66类MOF多晶粉末材料一般采用经典的溶剂热法制备,需要在高温高压下静置孵化数十小时,耗时长、能耗高、安全性能差、产率低,因此不适用于大批量工业级别的生产,极大限制了这类材料的实际应用。在本工作中,我们深入研究了一种在常压开放体系中合成纳米尺度的UIO-66颗粒的方法。通过将锆源和有机配体溶于加有调节剂的N,N-二甲基甲酰胺溶液中,在配备有回流和磁力搅拌的常规玻璃反应容器中一步法合成了UIO-66。所制备的UIO-66具有大小均一和形貌为规整八面体的的特点。采用扫描电子显微镜(SEM)、傅里叶红外光谱(FT-IR)、多晶粉末X射线衍射(XRD)和N2物理吸脱附等表征手段对不同孵化时间获得的产物进行了表征分析,证明了这类材料与采用传统的高温高压溶剂热法合成的UIO-66在化学和晶型结构方面完全一致。UIO-66纳米粒子的生成过程的跟踪实验发现其生长具备Ostwald熟化的特点,而且只需3～6h即可获得化学和晶型结构确定的产物。本工作报道的这一合成方法提高了反应物的利用率,缩短了反应时间,同时具有操作简单、条件温和、对反应设备要求低等特点,有望用于UIO-66系列MOF的大批量制备。
Abstract：Among various kinds of MOF materials, UIO-66 has attracted broad interest and promised many potential applications in diverse fields, due to many unique material properties. Synthesis of MOFs on the industry scale has become the bottleneck in the field of MOF materials. UIO-66 is often synthesized via the solvothermal method that involves long-term static incubation in a sealed autoclave and at very high temperature(>120℃). Such method has the disadvantages of time and energy consuming, safety concerns as well as low yields. In the current work, we systematically investigated a method to synthesize UIO-66 under normal atmosphere and with the reaction occurring in the ordinary glass apparatus equipped with refluxing and magnetic stirring components. Scanning electron microscopy(SEM), powder X-ray diffraction(PXRD), FT-IR and N2 adsorption/desorption were deployed to follow the synthesis procedure. The resulted UIO-66 nanoparticles have well-defined shapes and sizes. Furthermore, the UIO-66 nanoparticles has the same chemical structure and crystallinity as the one obtained via the classic solvothermal synthesis. There exists an Ostwald ripening stage during the growth of the UIO-66 crystals. In addition, the timescale of synthesis was shorten to 3～6 h, which can dramatically decrease the energy consuming as needed in the solvothermal method. The current method also has the potential of scaling up.
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基本信息:
DOI：10.16026/j.cnki.iea.2020060530
中图分类号:O641.4;TB383.1
引用信息:
[1]李建垚,张珍坤,郑春熊,等.常压开放体系下UIO-66纳米粒子有机金属框架材料的合成方法[J].离子交换与吸附,2020,36(06):530-540.DOI:10.16026/j.cnki.iea.2020060530.
基金信息:
天津市自然科学基金(基金号:17JCYBJC16900)