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

Zheng Wang; Keizo Nakagawa; Kecheng Guan; Qiangqiang Song; Siyu Zhou; Shunsuke Tanaka; Yasunao Okamoto; Atsushi Matsuoka; Eiji Kamio; Guangchao Li; Molly Meng-Jung Li; Tomohisa Yoshioka; Hideto Matsuyama

doi:10.1002/smll.202300672

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

Small. 2023 Aug;19(33):e2300672. doi: 10.1002/smll.202300672. Epub 2023 Apr 18.

Authors

Zheng Wang¹, Keizo Nakagawa^{2

3}, Kecheng Guan³, Qiangqiang Song¹, Siyu Zhou¹, Shunsuke Tanaka⁴, Yasunao Okamoto³, Atsushi Matsuoka^{1

3}, Eiji Kamio^{1

3

5}, Guangchao Li⁶, Molly Meng-Jung Li⁶, Tomohisa Yoshioka^{2

3}, Hideto Matsuyama^{1

3}

Affiliations

¹ Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
² Graduate School of Science, Technology and Innovation, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
³ Research Center for Membrane and Film Technology, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
⁴ Department of Chemical, Energy and Environmental Engineering, Faculty of Environmental and Urban Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka, 564-8680, Japan.
⁵ Center for Environmental Management, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
⁶ Department of Applied Physics, The Hong Kong Polytechnic University, Kowloon, Hong Kong, 999077, P. R. China.

PMID: 37072832
DOI: 10.1002/smll.202300672

Abstract

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 (H₂ TCPP) 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).

Keywords: anionic dye removal; in situ transformation; laminar membranes; metal-organic framework nanosheets; reduced graphene oxide.

Abstract

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