Two‐Dimensional Interlayer Space Induced Horizontal Transformation of Metal–Organic Framework Nanosheets for Highly Permeable Nanofiltration Membranes

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2023-08, Vol.19 (33), p.e2300672-n/a
• Main Authors: Wang, Zheng, Nakagawa, Keizo, Guan, Kecheng, Song, Qiangqiang, Zhou, Siyu, Tanaka, Shunsuke, Okamoto, Yasunao, Matsuoka, Atsushi, Kamio, Eiji, Li, Guangchao, Li, Molly Meng‐Jung, Yoshioka, Tomohisa, Matsuyama, Hideto
• Format: Article
• Language: English
• Subjects: anionic dye removal; Graphene; in situ transformation; Interlayers; laminar membranes; Membranes; Metal-organic frameworks; metal–organic framework nanosheets; Nanofiltration; Nanoparticles; Nanosheets; Nanotechnology; Permeability; Porphyrins; reduced graphene oxide; Tortuosity; Transformations; Vacuum filtration; Zinc oxide
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202300672

Laminar membranes comprising graphene oxide (GO) and metal–organic framework (MOF) nanosheets benefit from the regular in‐plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two‐step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4‐carboxyphenyl)porphyrin (H2TCPP) to realize in situ transformation of ZnO into Zn‐TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn‐TCPP/rGO laminar membrane exhibits preferential orientation of Zn‐TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m−2 h−1 bar−1 and high anionic dye rejection (>99% for methyl blue). A highly permeable Zn‐TCPP/rGO composite membrane for efficient nanofiltration is fabricated by in situ transformation of well‐distributed ZnO in the rGO laminate structure. The appropriate ZnO mass loading results in the optimized orientation of Zn‐TCPP to expose the uniform in‐plane pores as selective nanochannels for dye separation.