Department of Chemical and Biomolecular Engineering , National University of Singapore , Singapore 117585 , Singapore.
Department of Chemical Engineering , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States.
ACS Appl Mater Interfaces. 2019 Dec 4;11(48):45290-45300. doi: 10.1021/acsami.9b16332. Epub 2019 Nov 21.
For the first time, continuous polycrystalline UiO-66-NH thin film supported by a cross-linked Matrimid substrate was successfully fabricated via in situ solvothermal synthesis at room temperature for organic solvent nanofiltration. The integrated structure of the formed UiO-66-NH selective layer was inferred by various characterizations including X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. We have demonstrated that pretreatment of the substrate by an organic ligand, the number of solvothermal synthesis cycles, and the reaction time play important roles in MOF film formation. The newly developed UiO-66-NH membrane possesses high surface hydrophobicity and mean pore size of 0.89 nm in diameter. It shows an exceptional rejection of 96.33% to Rose Bengal with moderate ethanol permeance of 0.88 L m h bar. Benefiting from the extraordinary chemical stability of Zr-MOF crystals, the UiO-66-NH membrane shows excellent stability in different solvents, implying their great potential for real applications. This work provides useful insights into the fabrication of continuous UiO-66-type MOF membranes on polymeric substrates, which are very promising in practical separations involving organic solvents.
首次通过室温下的原位溶剂热合成，在交联 Matrimid 基底上成功制备了连续的 UiO-66-NH 多晶薄膜，用于有机溶剂纳滤。通过 X 射线衍射、场发射扫描电子显微镜、能谱、傅里叶变换红外光谱和 X 射线光电子能谱等多种表征手段推断出形成的 UiO-66-NH 选择性层的整体结构。我们已经证明，基底的预处理、溶剂热合成循环次数和反应时间对 MOF 薄膜的形成起着重要作用。新开发的 UiO-66-NH 膜具有高表面疏水性和 0.89nm 的平均孔径。它对 Rose Bengal 的截留率达到了 96.33%，而乙醇的渗透通量为 0.88L m h bar。得益于 Zr-MOF 晶体的非凡化学稳定性，UiO-66-NH 膜在不同溶剂中表现出优异的稳定性，这意味着它们在实际应用中具有巨大的潜力。这项工作为在聚合物基底上制备连续型 UiO-66 型 MOF 膜提供了有用的见解，这在涉及有机溶剂的实际分离中非常有前景。
