# MOF thin films and membranes

> MOF films and membranes on one page: layer-by-layer growth of SURMOFs on a self-assembled monolayer, vapour-phase conversion of ZnO into ZIF-8, the six ways to make a film (with Langmuir–Blodgett and patterning), the kinds of membrane (supported, mixed-matrix, nanosheet, hollow-fibre), seeded growth of a ZIF-8 membrane and molecular sieving of propylene from propane. Every step and number is quoted from the cited papers.

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- Open in the LabCanvas editor (LabCanvas account): https://www.labcanvas.com/editor.html?template=mof-thin-films-membranes
- Updated: 2026-10-14
- Category: MOF guides
- Method: Thin films and membranes
- Starting materials: Thiol self-assembled monolayers on gold; copper acetate and trimesic acid in ethanol; ALD ZnO and 2-methylimidazole vapour; ZIF-8 seeds on porous supports and polymer fibres
- Product: Oriented SURMOF films, ZIF-8 films and supported, mixed-matrix, nanosheet and hollow-fibre membranes
- Key result: Substrates, films, supports and pores drawn by LabCanvas from the cited papers; thicknesses, crystal counts and colours that no paper fixes are settings, and no panel is a micrograph or a permeation plot
- Figure: 1920 × 1080 px, 45 editable layers (6 generated objects with settings)

## Steps

1. **Layer by layer (SURMOF)**: A gold substrate first gets a thiol self-assembled monolayer (SAM) ending in –OH, –COOH or pyridine, then is dipped in the metal solution, rinsed, dipped in the linker solution and rinsed again; the number of cycles sets the thickness, and nothing deposits on a CH₃-terminated SAM. In the spray method the sample is sprayed in turn with ethanolic Cu acetate (1.0 mM), ethanol, ethanolic 1,3,5-benzenetricarboxylic acid (0.1 mM) and ethanol, and the cycle is repeated 40 times; the HKUST-1 SURMOFs grow with their (111) layers parallel to the surface (Ladnorg 2013). On SAM-coated quartz crystals, HKUST-1 films of well-defined thickness gave the diffusion coefficient of pyridine (Zybaylo 2010)
2. **From the vapour**: Metal-oxide films turn into MOFs in linker vapour: ALD ZnO and native CoO become ZIF-8 and ZIF-67 in 2-methylimidazole vapour, and the volume expansion fills narrow trenches (Krishtab 2019). MOF-CVD gives ZIF-8 films of uniform, controlled thickness even on high-aspect-ratio features, avoids the corrosion and contamination risks of solvents, and allows lift-off patterning (Stassen 2016)
3. **Six ways to a film**: In in-situ synthesis the substrate is dipped in a solution of both metal and linker and growth starts by nucleation on it; many such methods give polycrystalline layers of randomly oriented crystals (Ladnorg 2013). HKUST-1 seed crystals nucleated growth during a later layer-by-layer deposition and templated the final film (Brower 2017). NAFS-1, a preferentially oriented nanofilm of metalloporphyrin building units, was built at ambient temperature by combining layer-by-layer growth with the Langmuir–Blodgett method (Makiura 2010). Patterning SAMs by microcontact printing or electron-beam lithography allows highly localised deposition of SURMOF films (Zhuang 2012)
4. **Kinds of membrane**: Polycrystalline membranes perform according to their microstructure, above all their grain boundaries; one-step, in-situ counter-diffusion gave well-intergrown ZIF-8 membranes with exceptionally high propylene/propane separation (Kwon 2013). In mixed-matrix membranes a MOF filler is dispersed in a polymer (Hou 2019); copper 1,4-benzenedicarboxylate nanosheets in polymers separate CO₂ from CH₄: they cover the membrane cross-section better than isotropic crystals and close unselective paths (Rodenas 2015). 1-nm-thick MOF nanosheets built molecular-sieve membranes with H₂/CO₂ selectivities above 200 (Peng 2014). ZIF-8 grown in poly(amide-imide) hollow fibres where two solvents meet reached H₂/C₃H₈ and C₃H₆/C₃H₈ separation factors of 370 and 12 (Brown 2014)
5. **Seeded growth**: ZIF-8 membranes made by seeded growth in aqueous solution near room temperature separated ethane/propane, ethylene/propylene and ethylene/propane with factors of about 80, 10 and 167 (Pan 2011). Propylene/propane is currently separated by energy-intensive cryogenic distillation; ZIF-67 grown heteroepitaxially on ZIF-8 seed layers, then a further ZIF-8 growth, gave propylene/propane separation factors of about 200 (Kwon 2015)
6. **Sieving at the aperture**: The effective aperture of ZIF-8 for molecular sieving is 4.0–4.2 Å, larger than the 3.4 Å derived from XRD; from He (2.6 Å) to iso-C₄H₁₀ (5.0 Å) the corrected diffusivity drops by 14 orders of magnitude, and as the aperture is flexible, C₄ hydrocarbons larger than it still adsorb (Zhang 2012). Optimised ZIF-8 hollow-fibre membranes reached a C₃H₆/C₃H₈ separation factor of 180 at 1 bar and 25 °C, and 90 at 9.5 bar (Eum 2016)

## Strengths

- Patterned SAMs allow highly localised deposition of SURMOF films (Zhuang 2012)
- MOF-CVD gives films of uniform, controlled thickness even on high-aspect-ratio features (Stassen 2016)
- Nanosheet membranes reached H₂ permeances up to several thousand GPU (Peng 2014)

## Limitations

- Heterogeneous nucleation and growth of MOF crystals on porous supports is not generally favoured (Kwon 2013)
- In mixed-matrix membranes the matrix can block pores, the filler can aggregate, and the two can adhere poorly (Hou 2019)
- Many in-situ methods give polycrystalline layers of randomly oriented crystals (Ladnorg 2013)

## References

1. Ladnorg et al., “Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting”, Beilstein J. Nanotechnol. 2013. https://doi.org/10.3762/bjnano.4.71 (primary)
2. Zybaylo et al., “A novel method to measure diffusion coefficients in porous metal-organic frameworks”, Phys. Chem. Chem. Phys. 2010. https://doi.org/10.1039/b927601g (primary)
3. Krishtab et al., “Vapor-deposited zeolitic imidazolate frameworks as gap-filling ultra-low-k dielectrics”, Nat. Commun. 2019. https://doi.org/10.1038/s41467-019-11703-x (primary)
4. Stassen et al., “Chemical vapour deposition of zeolitic imidazolate framework thin films”, Nat. Mater. 2016. https://doi.org/10.1038/nmat4509 (primary)
5. Brower et al., “Tailoring the nanoscale morphology of HKUST-1 thin films via codeposition and seeded growth”, Beilstein J. Nanotechnol. 2017. https://doi.org/10.3762/bjnano.8.230 (primary)
6. Makiura et al., “Surface nano-architecture of a metal-organic framework”, Nat. Mater. 2010. https://doi.org/10.1038/nmat2769 (primary)
7. Zhuang, Friedel & Terfort, “The oriented and patterned growth of fluorescent metal-organic frameworks onto functionalized surfaces”, Beilstein J. Nanotechnol. 2012. https://doi.org/10.3762/bjnano.3.66 (primary)
8. Kwon & Jeong, “In situ synthesis of thin zeolitic-imidazolate framework ZIF-8 membranes exhibiting exceptionally high propylene/propane separation”, J. Am. Chem. Soc. 2013. https://doi.org/10.1021/ja403849c (primary)
9. Hou et al., “Metal-organic framework crystal-glass composites”, Nat. Commun. 2019. https://doi.org/10.1038/s41467-019-10470-z (primary)
10. Rodenas et al., “Metal-organic framework nanosheets in polymer composite materials for gas separation”, Nat. Mater. 2015. https://doi.org/10.1038/nmat4113 (primary)
11. Peng et al., “Metal-organic framework nanosheets as building blocks for molecular sieving membranes”, Science 2014. https://doi.org/10.1126/science.1254227 (primary)
12. Brown et al., “Interfacial microfluidic processing of metal-organic framework hollow fiber membranes”, Science 2014. https://doi.org/10.1126/science.1251181 (primary)
13. Pan & Lai, “Sharp separation of C2/C3 hydrocarbon mixtures by zeolitic imidazolate framework-8 (ZIF-8) membranes synthesized in aqueous solutions”, Chem. Commun. 2011. https://doi.org/10.1039/c1cc14051e (primary)
14. Kwon et al., “Heteroepitaxially grown zeolitic imidazolate framework membranes with unprecedented propylene/propane separation performances”, J. Am. Chem. Soc. 2015. https://doi.org/10.1021/jacs.5b06730 (primary)
15. Zhang et al., “Unexpected molecular sieving properties of zeolitic imidazolate framework-8”, J. Phys. Chem. Lett. 2012. https://doi.org/10.1021/jz300855a (primary)
16. Eum et al., “ZIF-8 membranes via interfacial microfluidic processing in polymeric hollow fibers: efficient propylene separation at elevated pressures”, ACS Appl. Mater. Interfaces 2016. https://doi.org/10.1021/acsami.6b08801 (primary)

Credit: Drawn by LabCanvas after Ladnorg et al., Beilstein J. Nanotechnol. 2013 (doi:10.3762/bjnano.4.71), Krishtab et al., Nat. Commun. 2019, Stassen et al., Nat. Mater. 2016 and Kwon & Jeong, J. Am. Chem. Soc. 2013, and the papers in the details.

## Questions

**What does the “MOF thin films and membranes” template show?** MOF films and membranes on one page: layer-by-layer growth of SURMOFs on a self-assembled monolayer, vapour-phase conversion of ZnO into ZIF-8, the six ways to make a film (with Langmuir–Blodgett and patterning), the kinds of membrane (supported, mixed-matrix, nanosheet, hollow-fibre), seeded growth of a ZIF-8 membrane and molecular sieving of propylene from propane. Every step and number is quoted from the cited papers.

**What are the steps shown in “MOF thin films and membranes”?** 1. Layer by layer (SURMOF): A gold substrate first gets a thiol self-assembled monolayer (SAM) ending in –OH, –COOH or pyridine, then is dipped in the metal solution, rinsed, dipped in the linker solution and rinsed again; the number of cycles sets the thickness, and nothing deposits on a CH₃-terminated SAM. In the spray method the sample is sprayed in turn with ethanolic Cu acetate (1.0 mM), ethanol, ethanolic 1,3,5-benzenetricarboxylic acid (0.1 mM) and ethanol, and the cycle is repeated 40 times; the HKUST-1 SURMOFs grow with their (111) layers parallel to the surface (Ladnorg 2013). On SAM-coated quartz crystals, HKUST-1 films of well-defined thickness gave the diffusion coefficient of pyridine (Zybaylo 2010). 2. From the vapour: Metal-oxide films turn into MOFs in linker vapour: ALD ZnO and native CoO become ZIF-8 and ZIF-67 in 2-methylimidazole vapour, and the volume expansion fills narrow trenches (Krishtab 2019). MOF-CVD gives ZIF-8 films of uniform, controlled thickness even on high-aspect-ratio features, avoids the corrosion and contamination risks of solvents, and allows lift-off patterning (Stassen 2016). 3. Six ways to a film: In in-situ synthesis the substrate is dipped in a solution of both metal and linker and growth starts by nucleation on it; many such methods give polycrystalline layers of randomly oriented crystals (Ladnorg 2013). HKUST-1 seed crystals nucleated growth during a later layer-by-layer deposition and templated the final film (Brower 2017). NAFS-1, a preferentially oriented nanofilm of metalloporphyrin building units, was built at ambient temperature by combining layer-by-layer growth with the Langmuir–Blodgett method (Makiura 2010). Patterning SAMs by microcontact printing or electron-beam lithography allows highly localised deposition of SURMOF films (Zhuang 2012). 4. Kinds of membrane: Polycrystalline membranes perform according to their microstructure, above all their grain boundaries; one-step, in-situ counter-diffusion gave well-intergrown ZIF-8 membranes with exceptionally high propylene/propane separation (Kwon 2013). In mixed-matrix membranes a MOF filler is dispersed in a polymer (Hou 2019); copper 1,4-benzenedicarboxylate nanosheets in polymers separate CO₂ from CH₄: they cover the membrane cross-section better than isotropic crystals and close unselective paths (Rodenas 2015). 1-nm-thick MOF nanosheets built molecular-sieve membranes with H₂/CO₂ selectivities above 200 (Peng 2014). ZIF-8 grown in poly(amide-imide) hollow fibres where two solvents meet reached H₂/C₃H₈ and C₃H₆/C₃H₈ separation factors of 370 and 12 (Brown 2014). 5. Seeded growth: ZIF-8 membranes made by seeded growth in aqueous solution near room temperature separated ethane/propane, ethylene/propylene and ethylene/propane with factors of about 80, 10 and 167 (Pan 2011). Propylene/propane is currently separated by energy-intensive cryogenic distillation; ZIF-67 grown heteroepitaxially on ZIF-8 seed layers, then a further ZIF-8 growth, gave propylene/propane separation factors of about 200 (Kwon 2015). 6. Sieving at the aperture: The effective aperture of ZIF-8 for molecular sieving is 4.0–4.2 Å, larger than the 3.4 Å derived from XRD; from He (2.6 Å) to iso-C₄H₁₀ (5.0 Å) the corrected diffusivity drops by 14 orders of magnitude, and as the aperture is flexible, C₄ hydrocarbons larger than it still adsorb (Zhang 2012). Optimised ZIF-8 hollow-fibre membranes reached a C₃H₆/C₃H₈ separation factor of 180 at 1 bar and 25 °C, and 90 at 9.5 bar (Eum 2016).

**What are the starting materials and the product?** Starting materials: Thiol self-assembled monolayers on gold; copper acetate and trimesic acid in ethanol; ALD ZnO and 2-methylimidazole vapour; ZIF-8 seeds on porous supports and polymer fibres. Product: Oriented SURMOF films, ZIF-8 films and supported, mixed-matrix, nanosheet and hollow-fibre membranes.

**Which papers is “MOF thin films and membranes” based on?** Ladnorg et al., “Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting”, Beilstein J. Nanotechnol. 2013 (doi:10.3762/bjnano.4.71); Zybaylo et al., “A novel method to measure diffusion coefficients in porous metal-organic frameworks”, Phys. Chem. Chem. Phys. 2010 (doi:10.1039/b927601g); Krishtab et al., “Vapor-deposited zeolitic imidazolate frameworks as gap-filling ultra-low-k dielectrics”, Nat. Commun. 2019 (doi:10.1038/s41467-019-11703-x); Stassen et al., “Chemical vapour deposition of zeolitic imidazolate framework thin films”, Nat. Mater. 2016 (doi:10.1038/nmat4509); Brower et al., “Tailoring the nanoscale morphology of HKUST-1 thin films via codeposition and seeded growth”, Beilstein J. Nanotechnol. 2017 (doi:10.3762/bjnano.8.230); Makiura et al., “Surface nano-architecture of a metal-organic framework”, Nat. Mater. 2010 (doi:10.1038/nmat2769); Zhuang, Friedel & Terfort, “The oriented and patterned growth of fluorescent metal-organic frameworks onto functionalized surfaces”, Beilstein J. Nanotechnol. 2012 (doi:10.3762/bjnano.3.66); Kwon & Jeong, “In situ synthesis of thin zeolitic-imidazolate framework ZIF-8 membranes exhibiting exceptionally high propylene/propane separation”, J. Am. Chem. Soc. 2013 (doi:10.1021/ja403849c); Hou et al., “Metal-organic framework crystal-glass composites”, Nat. Commun. 2019 (doi:10.1038/s41467-019-10470-z); Rodenas et al., “Metal-organic framework nanosheets in polymer composite materials for gas separation”, Nat. Mater. 2015 (doi:10.1038/nmat4113); Peng et al., “Metal-organic framework nanosheets as building blocks for molecular sieving membranes”, Science 2014 (doi:10.1126/science.1254227); Brown et al., “Interfacial microfluidic processing of metal-organic framework hollow fiber membranes”, Science 2014 (doi:10.1126/science.1251181); Pan & Lai, “Sharp separation of C2/C3 hydrocarbon mixtures by zeolitic imidazolate framework-8 (ZIF-8) membranes synthesized in aqueous solutions”, Chem. Commun. 2011 (doi:10.1039/c1cc14051e); Kwon et al., “Heteroepitaxially grown zeolitic imidazolate framework membranes with unprecedented propylene/propane separation performances”, J. Am. Chem. Soc. 2015 (doi:10.1021/jacs.5b06730); Zhang et al., “Unexpected molecular sieving properties of zeolitic imidazolate framework-8”, J. Phys. Chem. Lett. 2012 (doi:10.1021/jz300855a); Eum et al., “ZIF-8 membranes via interfacial microfluidic processing in polymeric hollow fibers: efficient propylene separation at elevated pressures”, ACS Appl. Mater. Interfaces 2016 (doi:10.1021/acsami.6b08801).

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