Surface polymerization on metal-organic networks: boosting stability and gas separation performance

Abstract

Metal-organic networks (MONs) have gained much attention due to their high surface areas and tunable structures, which underpin their potential for gas adsorption and separation. However, the stability issue remains a significant bottleneck that severely restricts their broader practical deployment. Therefore, exploring strategies to address this issue is of great significance but full of challenges. Herein, we highlight recent advances in combining MONs with polymers through surface polymerization, an approach that effectively enhances stability without sacrificing porosity, thereby enabling operation under harsher environments. Beyond stability, polymer incorporation imparts additional functions, including improved gas separation and photo-responsiveness that are inaccessible to the individual components. Finally, we propose the promising research directions of the construction of molecular sieves or stimuli-responsive functional polymer layers that leverage the merits of surface polymerization for applying MONs.

Graphical abstract

Keywords

metal-organic networks / polymers / stability / performance enhancement / gas adsorption and separation

References

[1] Shen J X , Mao S X , Wan L , Wu W X , Jin M M , Li Y X , Liu X Q , Sun L B . Stabilizing CuI in MIL-101(Cr) by introducing long-chain alkane for adsorptive desulfurization. Separation and Purification Technology, 2022, 290: 120892

[2] Wei C , Lu M , Li J J , Diao Z J , Liu G , Liu X Q , Sun L B . A doubly interpenetrated perylene diimide-based zirconium metal-organic framework for selective oxidation of sulfides powered by blue light. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2024, 12(47): 33142–33149

[3] Uemura T , Kitagawa K , Horike S , Kawamura T , Kitagawa S , Mizuno M , Endo K . Radical polymerisation of styrene in porous coordination polymers. Chemical Communications, 2005, 48(48): 5968–5970

[4] Ren B , Li Y , Meng D , Li J , Gao S , Cao R . Encapsulating polyaniline within porous MIL-101 for high-performance corrosion protection. Journal of Colloid and Interface Science, 2020, 579: 842–852

[5] Liu G , Zhou M , Su K , Babarao R , Yuan D , Hong M . Stabilizing the extrinsic porosity in metal-organic cages-based supramolecular framework by in situ catalytic polymerization. CCS Chemistry, 2021, 3(5): 1382–1390

[6] Yang T , Li X M , Liu Y , Wei C , Gu C , Zuo M , Guo T , Liu G , Ding L , Liu X Q . et al. Improving stability, crystallinity, and photo-responsiveness of supramolecular frameworks by surface polymerization. Advanced Functional Materials, 2024, 34(39): 2404869

[7] Kalaj M , Cohen S M . Spray-coating of catalytically active MOF-polythiourea through postsynthetic polymerization. Angewandte Chemie International Edition, 2020, 59(33): 13984–13989

[8] Li J , Liu P , Chen Y , Zhou J , Li J , Yang J , Zhang D , Li J , Li L . A customized hydrophobic porous shell for MOF-5. Journal of the American Chemical Society, 2023, 145(36): 19707–19714

[9] He S , Wang H , Zhang C , Zhang S , Yu Y , Lee Y , Li T . A generalizable method for the construction of MOF@polymer functional composites through surface-initiated atom transfer radical polymerization. Chemical Science, 2019, 10(6): 1816–1822

[10] Jin M M , Li Y X , Gu C , Liu X Q , Sun L B . Tailoring microenvironment of adsorbents to achieve excellent CO₂ uptakes from wet gases. AIChE Journal, 2020, 66(11): e16645

[11] Li F , Cai X H , Qi H O , Liu J P , Wang S J , Lu M , Liu G , Sun L B . Stabilization of supramolecular frameworks by surface-confined polymerization for natural gas purification. ACS Applied Materials & Interfaces, 2025, 17(30): 43681–43689

[12] Li Y X , Ji Y N , Mao S X , Jin M M , Liu X Q , Sun L B . Construction of a superhydrophobic microenvironment via polystyrene coating: an unexpected way to stabilize CuI against oxidation. Inorganic Chemistry Frontiers, 2021, 8(24): 5169–5177

[13] Li Y X , Shen J X , Peng S S , Zhang J K , Wu J , Liu X Q , Sun L B . Enhancing oxidation resistance of Cu(I) by tailoring microenvironment in zeolites for efficient adsorptive desulfurization. Nature Communications, 2020, 11(1): 3206

[14] Liu G , Li F , Diao Z J , Li H D , Wu X , Qi H O , Ding L , Sun L B . Supramolecular framework crystallinity engineering via surface-confined polymerization for enhanced C₃H₆/C₂H₄ separation. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2025, 13(35): 29016–29026

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Higher Education Press