Supporting Information

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1 Supporting Information Confined Synthesis of Two-Dimensional Covalent Organic Frameworks Thin Films within Superspreading Water Layer Qing Hao,, Chuangqi Zhao, Bing Sun, Cheng Lu,, Jian Liu,, MingJie Liu,* Li-Jun Wan, Dong Wang*, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences and Beijing National Laboratory for Molecular Sciences, Beijing , P.R. China Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, International Research Institute for Multidisciplinary Science, Beihang University, Beijing , P.R. China University of the Chinese Academy of Sciences, Beijing , P.R. China School of Science, China University of Geosciences (Beijing), Beijing , P.R. China S1

2 Supporting Figures Figure S1. Images of the superspreading processes of a water droplet (5 µl) achieves on PAAm hydrogel surfaces in a tridecane phase. Figure S2. Schematic of transfering thin COF films from hydrogel surfaces. S2

3 Figure S3. Pictures of hydrogel, TTA swollen hydrogel, and hydrogel with COF films. Figure S4. TGA curves of COF films (red) and powders (black) under N 2 atmosphere. Figure S5. N1s and C1s XPS spectra of COF TTA-DHTA film. S3

4 Figure S6. GIWAXS data showing the projection of COF TTA-DHTA (001) peak. Figure S7. (A) The relationship between film thickness and the volume of superspreading water at 5 µm TTA swollen hydrogel. (B) The relationship between film thickness and the concentration of TTA with 10 µl superspreading water. S4

5 Figure S8. The in situ UV absorption at 340 nm as a function of time shows the TTA released to the water environment from the hydrogels. Figure S9. AFM images of films obtained from hydrogel surface at reaction time of 1 h (A), 3 h (B) and 6h (C). S5

6 Figure S10. (A) Illustration of preparation of films by superspreading water on hydrogel, superspreading TTA solution on hydrogel and tridecane/water interface reaction respectively, in which the concentration of DHTA in tridecane is 40 µm and TTA solution is 40 µm. (B) AFM images of the films obtained from corresponding method and the thickness and roughness of these films. Table S1. Thickness, crystallinity data and orientation data of different method for preparation of COF films. Method Lowest thickness Crystallinity data Orientation data Ref. liquid/liquid sub-100 nm PXRD 1 colloid method >10 µm GIWAXS GIWAXS (no) 2 air/liquid 2 nm GIXS* GIXS (yes) 3 liquid/liquid 2.5 nm GIWAXS GIWAXS (no) 4 This work 2 nm GIWAXS GIWAXS (yes) *Grazing Incidence X-Ray Scattering *Note. Several works 5 using Langmuir-Blodgett method could grow covalent organic monolayer on air/water interface, and show excellent experimental results especially in term of ultrathin film preparation. However, limited by the characterization methods, no diffraction data were provided in those works. S6

7 Figure S11. UV-visible spectra of COF TTA-DHTA film on ITO electrode. Figure S12. Linear calibration curves of 50 nm (A) and 15 nm (B) COF TTA-DHTA films. Error bars indicate the standard deviation of three repeated measurements. Figure S13. (A) COF TpPA on filter membrane. UV vis spectra of aqueous solutions of (B) Au nanoparticles solution before and after filtration. The inset are photographs of aqueous solutions of Au nanoparticles before and after filtration. (C) RhB solution before and after filtration. S7

8 Figure S14. (A) Optical microscopy image of the COFTpPA film; dark blue areas show the SiO2/Si wafer, and the light blue areas show the film. (B) SEM images of COFTpPA film on TEM grids. (C) SEM images of COFTpPA film on Si wafer. (D) Peakforce tapping AFM height image of COFTpPA film on SiO2/Si wafer and corresponding line profiles. Figure S15. (A) Raman spectra of COFTpPA film and powders with the corresponding monomers (TFP and PA) (B) N1s XPS spectrum of COFTpPA films. (C) PXRD of COFTpPA powders. (D) HRTEM images of COFTpPA film on TEM grids. S8

9 Figure S16. Optical microscope images (A) and AFM images (B) of COFTpBD films. Optical microscope images (A) and AFM images (B) of COFTAPP-DHTA films. Optical microscope images (A) and AFM images (B) of COFTTA-PDA films. Figure S17. (A) SEM images of ZIF-8 film on Si wafer. (B) TEM image of ZIF-8 film, Inset: SAED pattern of the film. S9

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