Liang Chenjia, Ren Junhao, El Hankari Samir, Huo Jia
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Provincial Hunan Key Laboratory for Graphene Materials and Devices, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan, China.
Shenzhen Research Institute of Hunan University, Shenzhen 518057, Guangdong, China.
ACS Omega. 2019 Dec 30;5(1):603-609. doi: 10.1021/acsomega.9b03192. eCollection 2020 Jan 14.
Porous coordination polymers have received intensive attention for pollution abatement, such as dye removal, because of their high porosity and specific surface areas. However, the commonly used water-stable porous coordination polymers are microporous and synthesized within organic solvents, which deters seriously their widespread application. In this report, we developed a facile strategy for the synthesis of mesoporous Zr-based coordination polymer (Zr-BDC-CP) within aqueous solutions. The morphology and structure of Zr-BDC-CP were characterized with scanning electron microscopy, powder X-ray diffraction, and Fourier transform infrared spectroscopy. Pore size distribution analysis confirms that the as-synthesized material is mesoporous, which allows the efficient adsorption of methylene blue, 2.6 times higher than that of the microporous coordination polymer, UiO-66. The decolorization ratio can reach higher than 93.5% in the range of 10 and 400 mg/L for methylene blue solutions. This Zr-based coordination polymer shows wonderful pH stability, where no significant loss of adsorption capacities was observed between pH values of 3 and 11. The simulation of adsorption isotherm indicates that the Freundlich model can fit the adsorption isotherm very well, which reflects that the surface of adsorbents is inhomogeneous. Fitting of kinetic curves shows that the dye adsorption by Zr-BDC-CP follows the pseudo-second-order model, which confirms that the rate-determining step may be a chemisorption process involving valence forces because of the defects within the frameworks of the mesoporous coordination polymer. Zr-BDC-CP also shows desirable recyclability without significant capacity loss. This work presents a facile and sustainable method for the preparation of mesoporous Zr-based coordination polymer for dye removal with excellent stability and recyclability, which could further push the porous coordination polymers for application in the areas of pollution abatement.
多孔配位聚合物因其高孔隙率和比表面积,在污染治理方面,如染料去除,受到了广泛关注。然而,常用的水稳定多孔配位聚合物是微孔的,且在有机溶剂中合成,这严重阻碍了它们的广泛应用。在本报告中,我们开发了一种简便的策略,用于在水溶液中合成介孔锆基配位聚合物(Zr-BDC-CP)。通过扫描电子显微镜、粉末X射线衍射和傅里叶变换红外光谱对Zr-BDC-CP的形貌和结构进行了表征。孔径分布分析证实,合成的材料是介孔的,这使得其对亚甲基蓝具有高效吸附能力,比微孔配位聚合物UiO-66高2.6倍。对于浓度在10至400mg/L范围内的亚甲基蓝溶液,脱色率可达到93.5%以上。这种锆基配位聚合物表现出出色的pH稳定性,在pH值为3至11之间未观察到吸附容量有显著损失。吸附等温线模拟表明,Freundlich模型能很好地拟合吸附等温线,这反映出吸附剂表面是不均匀的。动力学曲线拟合表明,Zr-BDC-CP对染料的吸附遵循准二级模型,这证实了速率决定步骤可能是一个涉及价力的化学吸附过程,这是由于介孔配位聚合物框架内的缺陷所致。Zr-BDC-CP还表现出良好的可回收性,且容量无显著损失。这项工作提出了一种简便且可持续的方法来制备用于染料去除的介孔锆基配位聚合物,该聚合物具有出色的稳定性和可回收性,这可能会进一步推动多孔配位聚合物在污染治理领域的应用。