Evangelou Dimitrios A, Pournara Anastasia D, Karagianni Vasiliki I, Dimitriou Christos, Andreou Evangelos K, Deligiannakis Yiannis, Armatas Gerasimos S, Manos Manolis J
Department of Chemistry, University of Ioannina, Ioannina GR-45110, Greece.
Department of Physics, University of Ioannina, Ioannina GR-45110, Greece.
ACS Appl Mater Interfaces. 2024 Mar 13;16(10):12672-12685. doi: 10.1021/acsami.3c19536. Epub 2024 Feb 29.
The incorporation of superhydrophobic properties into metal organic framework (MOF) materials is highly desirable to enhance their hydrolytic stability, gas capture selectivity in the presence of humidity and efficiency in oil-water separations, among others. The existing strategies for inducing superhydrophobicity into MOFs have several weaknesses, such as increased cost, utilization of toxic reagents and solvents, applicability for limited MOFs, etc. Here, we report the simplest, most eco-friendly, and cost-effective process to impart superhydrophobicity to MOFs, involving a rapid (90 min) treatment of MOF materials with solutions of sodium oleate, a main component of soap. The method can be applied to both hydrolytically stable and unstable MOFs, with the porosity of modified MOFs approaching, in most cases, that of the pristine materials. Interestingly, this approach was used to isolate superhydrophobic magnetic MOF composites, and one of these materials formed stable liquid marbles, whose motion could be easily guided using an external magnetic field. We also successfully fabricated superhydrophobic MOF-coated cotton fabric and fiber composites. These composites exhibited exceptional oil sorption properties achieving rapid removal of floating crude oil from water, as well as efficient purification of oil-in-water emulsions. They are also regenerable and reusable for multiple sorption processes. Overall, the results described here pave the way for an unprecedented expansion of the family of MOF-based superhydrophobic materials, as virtually any MOF could be converted into a superhydrophobic compound by applying the new synthetic approach.
将超疏水特性引入金属有机框架(MOF)材料中非常有助于提高其水解稳定性、在潮湿环境下的气体捕获选择性以及油水分离效率等。现有的在MOF中引入超疏水性的策略存在一些缺点,例如成本增加、使用有毒试剂和溶剂、仅适用于有限的MOF等。在此,我们报告了一种最简单、最环保且最具成本效益的方法,可使MOF具有超疏水性,该方法包括用肥皂的主要成分油酸钠溶液对MOF材料进行快速(90分钟)处理。该方法可应用于水解稳定和不稳定的MOF,在大多数情况下,改性MOF的孔隙率接近原始材料。有趣的是,这种方法被用于分离超疏水磁性MOF复合材料,其中一种材料形成了稳定的液滴,其运动可以通过外部磁场轻松引导。我们还成功制备了超疏水MOF涂层的棉织物和纤维复合材料。这些复合材料表现出优异的吸油性能,能够快速去除水中的浮油,以及高效净化水包油乳液。它们还可再生并可重复用于多个吸附过程。总体而言,本文所述结果为基于MOF的超疏水材料家族的前所未有的扩展铺平了道路,因为通过应用新的合成方法,几乎任何MOF都可以转化为超疏水化合物。