Accurate stacking engineering of MOF nanosheets as membranes for precise H2 sieving

Wufeng Wu; Xitai Cai; Xianfeng Yang; Yanying Wei; Li Ding; Libo Li; Haihui Wang

doi:10.1038/s41467-024-54663-7

Accurate stacking engineering of MOF nanosheets as membranes for precise H₂ sieving

Nat Commun. 2024 Dec 30;15(1):10730. doi: 10.1038/s41467-024-54663-7.

Authors

Wufeng Wu^#¹, Xitai Cai^#¹, Xianfeng Yang², Yanying Wei³, Li Ding⁴, Libo Li⁵, Haihui Wang⁶

Affiliations

¹ State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou, 510640, China.
² Analytical and Testing Centre, South China University of Technology, Guangzhou, 510640, China.
³ State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou, 510640, China. ceyywei@scut.edu.cn.
⁴ Beijing Key Laboratory for Membrane Materials and Engineering, Department of Chemical Engineering, Tsinghua University, Beijing, 100084, China.
⁵ State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou, 510640, China. celbli@scut.edu.cn.
⁶ Beijing Key Laboratory for Membrane Materials and Engineering, Department of Chemical Engineering, Tsinghua University, Beijing, 100084, China. cehhwang@tsinghua.edu.cn.

^# Contributed equally.

Abstract

Two-dimensional (2D) metal-organic framework (MOF) nanosheet membranes hold promise for exact molecular transfer due to their structural diversity and well-defined in-plane nanochannels. However, achieving precise regulation of stacking modes between neighboring nanosheets in membrane applications and understanding its influence on separation performance remains unrevealed and challenging. Here, we propose a strategy for accurately controlling the stacking modes of MOF nanosheets via linker polarity regulation. Both theoretical calculations and experimental results demonstrate that a high linker polarity promotes neighboring nanosheets to a maximum AB stacking due to steric hindrance effects, leading to a controlled effective pore size of the membrane and consequently to improved molecular sieving. Among series of CuBDC-based 2D MOFs with different linkers, the CuBDC-NO₂ nanosheet membranes exhibit a reduced effective stacking aperture of 0.372 nm, yielding H₂ permeance of 4.44 × 10^-7 mol m^-2 s^-1 Pa^-1 with a high H₂/CO₂ and H₂/CH₄ selectivity of 266 and 536, respectively. This work represents the in-depth investigation of the accurate tuning of MOF nanosheet stacking in the field of 2D materials, offering more perspectives for broader applications with universality for various 2D materials.

Abstract

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