The disclosure relates to a method for producing a film of a 3D porous aromatic framework, or a film of a 3D covalent organic framework, in accordance with the preamble of appended claim 1.

The disclosure also relates to a film being produced by means of said method, in accordance with the preamble of appended claim 12. BACKGROUND

Inherently porous materials that are chemically and structurally robust are challenging to construct. Conventionally, dynamic chemistry is thought to be needed for the formation of uniform porous organic frameworks, but dynamic bonds can limit the stability of these materials. For this reason, all carbon linked frameworks are expected to exhibit higher stability performance than more traditional porous frameworks. However, the limited reversibility of carbon-carbon bond forming reactions has restricted the exploration of these materials. In particular, the challenges associated with producing uniform thin films of all carbon-linked frameworks has reduced the ability to study these materials in applications where well-defined films are required.

Covalent organic frameworks (COFs) were first synthesized by Yaghi and coworkers in 2005 and represent a class of porous, structurally regular materials that contain only light elements (i.e., B, C, N, H, and O). ¹ Organic framework materials have a unique suite of properties such as ultrahigh thermal stability (up to 500 °C), ^{2 3} low densities (0.13 g cm ^-3 ), ⁴ and high internal surface area (7000 m ² g ^-1 ). ⁵ This confluence of properties make this class of materials highly suitable for various applications such as chemical separations, ^{6 8} catalysis, ^{9 11} gas storage, ^{12 14} water purification, ¹⁵ drug delivery, ^{16 18} electrode materials, ^{19 20} and sensing. ²¹ Porous aromatic frameworks (PAFs) are similar to COFs that are synthesized by irreversible cross-coupling reactions. Because these materials are unable to anneal defects, due to the irreversible nature of their chemical linkages, PAFs are frequently thought to have a disordered nanoscale structure. In three-dimensional (3D) organic frameworks nonplanar building blocks are covalently cross-linked in all dimensions. ² ' ⁴ · ^{22 29} This topology leads to channels in all dimensions, with pore spaces of defined shape and size that can be chemically engineered according to a desired function. ¹¹ · ³⁰³¹ We find that 3D frameworks are underrepresented in the literature compared to two-dimensional (2D) variants. In particular, films of 3D frameworks are especially challenging to synthesize and represent a frontier in synthetic framework chemistry. This limited exploration is partially due to the higher difficulty in synthesizing homogenous films of 3D organic frameworks compared to 2D variants. ³² This difficulty is accentuated when considering the synthesis of carbon-carbon linked 3D frameworks which will be unable to anneal their defects through dynamic chemistry.

Although 3D COFs and 3D PAFs have been synthesized as microcrystalline powders, many promising applications (e.g. membranes or electronics) for these materials will require films. ³³ This understanding has inspired immense interest in synthesizing COFs and PAFs as uniform films, which can be more readily interfaced with these applications. Recently, films of 2D frameworks have been made on templated surfaces using batch solvothermal conditions. ³⁴³⁵ Other strategies for the synthesis of uniform 2D films include exfoliation and reassembly, ³⁶ interfacial crystallization of thin 2D films at liquid-liquid ³⁷ or air-liquid interfaces, ³⁸ and blade-casting of precursors. ⁶ Expanding on these batch reaction approaches, Bisbey and coworkers used a continuous flow set-up in combination with a quartz crystal microbalance to measure the deposited mass of a 2D COF on a Ti surface in real time, giving control of the film thickness. ³⁹ However, topological differences between 2D and 3D frameworks mean that methods used to construct 2D based films cannot be readily adapted for 3D framework film synthesis. Films of 3D COFs have been made using dynamic imine or boronate ester bonds. ⁴⁰ However, to date, the only example of an all carbon-linked 3D framework was described by Becker and coworkers in 2015; were they used a templated surface and batch conditions to form a 3D PAF-1 film with micron scale roughness. ⁴¹ Although this report shows that carbon-carbon bonded 3D frameworks can be obtained as films, they showed unwieldy surface roughness, powder contamination, and unpredictable thickness. However, this preliminary report led us to speculate that the synthesis of smooth 3D framework films with precise thickness based on carbon-carbon bonds is now within reach, a crucial step towards maximizing the utility of this class of promising materials.

SUMMARY

In accordance with the disclosure, there is provided an improved method with the features as defined in appended claim 1. Accordingly, there is provided a method for producing a film of a 3D porous aromatic framework with a controlled thickness. Further, accordingly, the method is also provided for producing a film of a 3D covalent organic framework with a controlled thickness.

The method comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a relatively low steady-state concentration of monomers to said pretemplated surface; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.

Here, and in accordance with different embodiments, we synthesize continuous and homogenous films of an all carbon linked 3D porous aromatic framework (PAF-1) with nanometer precision thickness. This is accomplished by kinetically promoting surface reactivity while suppressing homogenous nucleation. By connecting the PAF film to a gold substrate via a self-assembled monolayer and using flow conditions to continually introduce monomers, smooth and continuous PAF films can be grown with controlled thickness. This strategy allows traditional transition metal-mediated carbon-carbon cross coupling reactions to form porous, organic thin films. We expect that the chemical principles uncovered in this study will enable the synthesis of a variety of chemically and structurally diverse carbon-carbon linked frameworks as high-quality films, which are inaccessible by conventional methods.

The disclosure is not limited to the use of carbon in a linked 3D porous aromatic framework. As examples, nitrogen, oxygen and silicon could alternatively be used.

Further, the method, as described herein, comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a concentration of monomers to said pretemplated surface, wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.

The specific “relatively low steady-state concentration” and the specific “concentration wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction”, as described herein, are dependent on various parameters and conditions, such as, reaction parameters and conditions, e.g. temperature/s, for example, reaction temperature/s; reaction system parameters and conditions, e.g. reactor parameters and conditions, for example, continuous reactor parameters and conditions; and reaction process parameters and conditions, for example, continuous reaction parameters and conditions.

According to an embodiment, the method may comprise a step of adding said monomers in a concentration with a magnitude which is chosen so that a bulk reaction during said growth is considerably reduced in comparison with the growth of said film.

According to an embodiment the method further may comprise a step of providing said flow as a continuous flow in which said monomers and coupling reagents are mixed immediately before a reactor which is configured for growth of said surface.

According to an embodiment, the method may comprise a step of providing said pretemplated surface of a material which is adapted for connecting said porous aromatic framework to said surface.

According to an embodiment, the method may comprise a step of providing said surface in the form of gold or a similar metal. This means that other metals than gold can be used in order to provide a connection between said porous aromatic framework and said surface.

According to an embodiment, the method may comprise a step of providing said surface in the form of silicon oxide or a similar non-metal substance. This means that other non- metal substances than silicon oxide can be used in order to provide a connection between said porous aromatic framework and said surface.

According to an embodiment, the method may comprise a step of providing said monomers in the form of tetrakis(4-bromophenyl)methane (TBPM) or structurally similar molecules, i.e. having generally the same geometry.

According to an embodiment, the method may comprise a step of monitoring the growth of said film.

According to an embodiment, the method may comprise a step of monitoring the growth by means of a quartz crystal microbalance (QCM). According to an embodiment, the method may comprise a step of correlating the QCM signal by means of scanning electron microscopy (SEM) cross section imaging.

According to the disclosure, there is also provided a film as defined in appended claim 12, i.e. as produced by means of the above-mentioned method.

BRIEF DESCRIPTION OF THE FIGURES

The process and film according to the disclosure will be described in greater detail below and with reference to the figures shown in the appended drawings.

Figure 1 shows a schematic overview of a reaction leading to a film;

Figure 2 shows optical images of porous aromatic framework films;

Figure 3 shows a process of monitoring the film growth and an example of the surface morphology of said film; and

Figure 4 shows a process of confirming an elemental composition. DETAILED DESCRIPTION

Different aspects of the present disclosure will be described more fully hereinafter with reference to the enclosed drawings. The disclosure can be realized in many different forms and should not be construed as being limited to the embodiments below. According to an embodiment of the disclosure, there is provided an all carbon-linked continuous 3D porous aromatic framework film with nanometer precise controllable thickness.

Here, we show for the first time that it is possible to construct all carbon-linked 3D PAFs as smooth and continuous films with controllable thicknesses. This new synthesis method works by introducing monomers at low steady-state concentrations in flow to a pretemplated substrate. This approach favors film growth over bulk powder synthesis, which can contaminate the desired films. A quartz crystal microbalance (QCM) was used to monitor the growth of the film in real time and scanning electron microscopy (SEM) cross section imaging was used to correlate the QCM signal to film thickness, allowing for nanometer thickness control. Continuous flow conditions constantly remove in bulk formed oligomers, resulting in an improved smoothness of the obtained film by limiting the precipitation of bulk framework materials. Films were further characterized via depth dependent X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy - scanning electron microscopy (EDX-SEM), which show that the desired C- C polymerization chemistry had taken place. Furthermore, surface roughness was probed by atomic force microscopy (AFM) which demonstrated that the films were smooth, continuous, and free from powder contamination. This work provides a strategy to overcome the former restrictions of 3D film synthesis that we suspect will enable the construction of a broad range of porous materials in a useful configuration for a host of applications.

RESULTS AND DISCUSSION

To construct a film of framework material, it is crucial to spatially control polymerization. For example, frameworks synthesized by homo-coupling of a single monomer species can occur between monomers and oligomers in solution or between monomers and the film surface. C-C bonds are robust, providing rigidity and chemical stability to the obtained structure. However, C-C cross-coupling prevent dynamic rearrangement, which prevents defects from being annealed. Once the bonds are formed, they do not break and a kinetically favored rather than the thermodynamically favored product may be trapped. Therefore, that initial formation of a structurally regular material is necessary for the synthesis of a smooth, homogenous films. Additionally, if precise thicknesses, low roughness films are to be obtained, the film must be synthesized epitaxially. However, the same reaction that leads to productive surface growth may also take place in solution, resulting in larger aggregates that can contaminate the film. Stated another way, the challenge is to restrict homogenous nucleation of framework powders while promoting uniform, layer-by-layer heterogeneous growth of framework films. ⁴²⁴³

Figure 1 is a schematic overview of the reaction on the surface leading to a continuous film. A) The building block, tetrakis(4-bromophenyl)methane (TBPM). B) The self assembled monolayer (SAM) formation on the gold QCM chips. C) A continuous flow set up with three autonomous programmable syringe pumps pushing the fluids through the QCM chamber where the reaction on the surface takes place, forming the COF film.

The reaction rate between two species, whether monomers or oligomers, in solution is expected to follow second order kinetics with respect to the concentration of the monomer. In contrast, when monomer couples to the surface, the concentration of one of the reactants (the surface) is fixed and so pseudo-first order kinetics would be expected. Thus, the relevant rate equations for the monomer-monomer and the monomer-surface reactions are as follows: where ris the reaction rate and k is the relevant reduced rate constant (including the concentration of non-monomeric coupling reagents, catalysts, etc.). This difference in reaction kinetics indicates that at high concentration, monomers will predominantly react to form oligomers, which at some critical size will precipitate from solution. When reducing the concentration, the bulk reaction will be reduced in comparison to surface growth. Therefore, below a certain concentration threshold, the reaction on the surface will dominate, which we hypothesize would be ideal for the synthesis of uniform C-C linked framework films. To show that it is possible to synthesize a continues framework film, the well-known PAF system PAF-1 ⁵ · ⁴⁴ (also published as PPN-6) ⁴⁵ was chosen. In PAF-1, tetrakis(4-bromophenyl)methane (TBPM; Figure 1) is used as a building block, which forms a 3D network via Yamamoto coupling. ⁴⁶ PAF-1 has an exceptionally high surface area and excellent hydrothermal stability due to the chemical stability of the C-C bond and its powders have found use in gas storage applications. ⁵

Figure 2 shows optical images of PAF-1 films. A) Batchmode: an immersed templated gold sensor in a solution of monomers and coupling reagents, leading to a macroscopic nonuniform surface. B) Continuous flow: Mixing of monomers and coupling reagents just before the flow reactor leads to a continuous and smooth film. C) Continuous flow: Numerous cracks are evident when using a non-brominated SAM under the same reaction conditions. D) Continuous flow: Cracks and powder contamination are also present when using a ten-fold higher concentration than those used in B.

When making a film via a bottom-up approach, adhesion between the substrate and the first layer of the framework film is necessary. Because thiols are known to diffuse laterally on Au surfaces, giving the possibility for structures attached by such bonds to self- organize, we selected a thiol functionalization strategy to create a well adhered first layer of the film. To achieve this, a gold-coated QCM wafer was exposed to 4- bromothiophenole, which forms a self-assembled monolayer on the gold surface (Figure 1). ⁴¹ This molecule is bromine-functionalized at the para position, allowing for Yamamoto coupling reaction with the PAF-1 monomer (TBPM). We expect that a fully thiol functionalized SAM will react with the appropriate number of TBPMs to yield a monolayer that will serve as a template for PAF formation. Previously, researchers have used a thiol- templated surface to connect PAF-1 to a surface. ⁴¹ We have extended this strategy to yield continuous 3D PAF films by (1) limiting the steady state concentration of monomer, about 1% of the concentration previously demonstrated to synthesize PAF-1, ⁴¹ and (2) using continuous flow conditions that provide clean reagents throughout the reaction and limits powder aggregation. To accommodate these adaptations, we built a continuous flow cell set-up based on three programmable syringe pumps, a mixing unit, and a quartz crystal microbalance (QCM) flow cell (Figure 1). The monomer and coupling reagents were kept in separate syringes and mixed just before entering the QCM flow cell. Figure 2 displays microscope images of films made using bulk or flow conditions. In bulk conditions, the film is very rough (Figure 2A), which is consistent with previously reported approaches. ⁴¹ We suspect that in this case, oligomers have most first formed in solution and later bind to the surface, providing macroscopic non-uniform structures. On the other hand, flow conditions produce a film that is smooth on a macroscopic level as evident from the absence of scattering in the uniform microscope image (Figure 2B). If thiophenol instead of 4-bromothiophenol is used in the SAM layer, the ability to form covalent bonds between the SAM and the porous film is removed (Figure 2C). This results in cracks in- between relatively flat regions. The lack of connection between the surface and the framework most likely results in PAF grains first precipitating on the surface, and these grains then grow. Cracks and an uneven distribution could also be observed when using flow conditions with a 10 times higher concentration of all reagents (Figure 2D) when compared to the conditions used in Figure 2B. Furthermore, the surface roughness (as measured with AFM) increased when increasing the concentrations above a certain point (Figure S1). High concentration conditions also resulted in the formation of visible aggregates in the tubing after the mixing unit. These experiments demonstrate that surface connectivity, low concentration, and flow conditions are needed to form a uniform framework film. In the next section, we examine the build-up of the film in real time, enabling the construction of films with nanometer precision thickness.

Figure 3 shows a process of monitoring the film growth. A) Typical frequency change during the reaction. B) SEM picture with 69,000 times magnification of the film cross section, showing the existence of a smooth film. C) Plot showing a linear correlation between the frequency change and the film thickness D) AFM image of an 150 nm thick film, having a mean square roughness of 4 nm. To monitor the buildup of the framework film in real-time, a QCM was used. QCM measures the mass change as a shift of the quartz resonance frequency over time. The frequency shift correlates directly to the thickness of the film, and the slope of the frequency shift relates to the reaction rate on the film surface. Figure 3A displays the frequency shift as a function of reaction time. A nearly linear dependence between the frequency shift versus time is evident, indicating that the rate of reaction on the surface is constant when monomer concentration is held constant as indicated by equation 2. However, when reducing the flow speed under the same concentration, a lower slope in the frequency shift over time was observed (Figure S2). The boundary layer is the area of the fluid close to the solid surface (in our case the surface of the film). The velocity of the fluid in the boundary layer decreases towards zero when approaching the surface. The only possibility for building blocks to reach the surface is therefore via diffusion through this layer. The thickness of the boundary layer is flow speed dependent. When reducing the flow speed, the thickness of the boundary layer increases, which causes a reduction in the growth rate. ⁴⁷ This observation suggests that the reaction rate on the surface is limited by mass transport close to the surface, which is affected by the flow speed. Furthermore, SEM showed a completely flat film within the spatial resolution of the instrument (Figure 3B, Figures S3-S4), and AFM showed a mean roughness of less than 4 nm over an area of 4 pm ² (Figure 3D). The formed films can therefore be regarded as homogenous on the macroscopic scale and smooth on the nano scale.

In order to correlate the frequency shift to film thickness, QCM chips were broken and cross section imaging was performed via SEM (Figure 3B). Figure 3C displays a linear relation between film thickness (as measured with SEM) and frequency shift (measured with QCM), indicating that the mass density profile of the film is homogenous. This finding allowed us to calculate the frequency to thickness relationship to 0.057 nm Hz ¹ . We considered the possibility that encaged solvent molecules might influence the frequency shift and thus the measured mass. To see whether solvent contributes to the frequency shift, we compared the change in frequency shift of a film and a clean gold surface when changing the solvent from tetrahydrofuran (THF) to deuterated THF (Figure S5). We observed a difference between the two substrates, indicating that caged solvent molecules do influence the measured weight. Thus, the observed frequency shift originates not only from the film but also from caged solvent molecules. Furthermore, the constant relating frequency shift to film thickness is therefore dependent on the solvent used. Interested to evaluate the porous structure of our PAF-1 films, we evaluated the electron density with X-ray reflectivity measurements. We find that the electron density is approximately -0.6 e A ^'3 (Figure S7). While this is nearly double an idealized structure, we expect that structural defects, framework intercalation, residual solvent, and catalyst would all lead to more dense structures than that of the ideal PAF-1. Importantly, similarly dense PAF-1 materials have also been found to have exceptional surface areas. ⁴⁸ This finding is consistent with the understanding that solvent molecules are intercalated into the framework (Figure S5), giving rise to solvent dependent shifts of the observed QCM frequency. Thus, by controlling the introduction of monomers to a pretemplated surface, it is possible to create smooth, porous 3D framework films with controllable thickness.

Figure 4 shows confirming the elemental composition. A-B) Depth XPS spectrum, showing the existence of gold (B) right underneath the carbon (A) containing film. C-E) EDX-SEM measurements on the cross section of a film. The elements shown in area A (blue) match the existence of a PAF-1 based film (carbon) and the gold surface on chromium (very thin adhesive layer between silicon and gold). Area B (red) shows the existence of silicon (quartz crystal) and Cr.

To examine the chemical composition of the formed film on top of a gold substrate, we measured the XPS signal as a function of etching time. Figure 4a-4b shows the carbon and gold content of the film and substrate at varying etching times. At short distance into the film, only carbon signal was observed consistent with signal from PAF-1. In contrast, deeper in the sample the carbon signal vanished and the signal from the gold substrate concurrently appeared. This XPS analysis is consistent with our understanding of a fully carbon-hydrogen framework adhered to the gold substrate. The element composition was also explored on a film cross section (Figure 4B-C) using EDX-SEM. By targeting the film on the sensor surface (bright gray in B), the main elements found were gold, chromium, and carbon. The gold signal arises from the roughly 100-nm thick gold coating on the sensor and chromium is used as an adhesive layer between gold and the silicon crystal. The carbon signal originates from the deposited film. Measuring further away from the PAF-1 film, deeper into the sensor, only silicon and chromium gave prominent signals. The measured element composition matched the information given by the manufacturer (Biolin Scientific), further confirming the expected element composition of the PAF film (see Figures S3-4 for additional SEM images and EDX spectra).

CONCLUSION

We have successfully constructed a continuous and smooth film of a 3D porous aromatic framework (PAF-1) with nanometer precise controllable thickness. QCM was used to provide real time monitoring of the film growth and cross section SEM was used to correlate the QCM signal to film thickness. This was realized by continually introducing a sufficiently low steady-state concentration of monomers to a pretemplated surface. The approach is based on fundamental chemical principles, and we therefore believe it will enable the synthesis of a variety of 3D carbon-linked framework materials as uniform films. Furthermore, we envision that the modular flow approach described here can be used to make heterostructured framework films. We suspect that by flowing different monomers in series, diverse framework materials can be assembled sequentially within a continuous film. This approach of making 3D framework films opens up this class of material to applications where robustly adhered films of all carbon-linked porous material is required.

The method for producing a film, as described herein, as well as the embodiments, the disclosures, the aspects and the examples, also as described herein, all also apply, mutatis mutandis, to 3D covalent organic frameworks, and to films of 3D covalent organic framework produced by means of said method for producing a film, as described herein.

REFERENCES

1. Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Porous, crystalline, covalent organic frameworks. Science 2005, 310 (5751), 1166-1170.

2. El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortes, J. L; Cote, A. P.; Taylor, R. E.; O'Keeffe, M.; Yaghi, O. M., Designed synthesis of 3D covalent organic frameworks. Science 2007, 316 (5822), 268-272.

3. Evans, A. M.; Ryder, M. R.; Flanders, N. C.; Vitaku, E.; Chen, L. X.; Dichtel, W. R., Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress. Industrial & Engineering Chemistry Research 2019, 58 (23), 9883-9887.

4. Baldwin, L. A.; Crowe, J. W.; Pyles, D. A.; McGrier, P. L., Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework. J. Am. Chem. Soc. 2016, 138 (46), 15134-15137.

5. Ben, T.; Ren, H.; Ma, S. Q.; Cao, D. P.; Lan, J. H.; Jing, X. F.; Wang, W. C.; Xu,

J.; Deng, F.; Simmons, J. M.; Qiu, S. L.; Zhu, G. S., Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area. Angew. Chem. Int. Ed. 2009, 48 (50), 9457-9460.

6. Kandambeth, S.; Biswal, B. P.; Chaudhari, H. D.; Rout, K. C.; Kunjattu, H. S.;

Mitra, S.; Karak, S.; Das, A.; Mukherjee, R.; Kharul, U. K.; Banerjee, R., Selective Molecular Sieving in Self-Standing Porous Covalent-Organic-Framework Membranes. Adv. Mater. 2017, 29 (2).

7. Zhao, H.; Jin, Z.; Su, H.; Zhang, J.; Yao, X.; Zhao, H.; Zhu, G., Target synthesis of a novel porous aromatic framework and its highly selective separation of C02/CH4.

Chem. Commun. 2013, 49 (27), 2780-2782.

8. Lu, W. G.; Yuan, D. Q.; Zhao, D.; Schilling, C. I.; Plietzsch, O.; Muller, T.; Brase, S.; Guenther, J.; Blumel, J.; Krishna, R.; Li, Z.; Zhou, H. C., Porous Polymer Networks: Synthesis, Porosity, and Applications in Gas Storage/Separation. Chem. Mater. 2010, 22 (21), 5964-5972.

9. Pachfule, P.; Acharjya, A.; Roeser, J.; Langenhahn, T.; Schwarze, M.; Schomacker, R.; Thomas, A.; Schmidt, J., Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation. J. Am. Chem. Soc. 2018, 140 (4), 1423-1427.

10. Bhadra, M.; Kandambeth, S.; Sahoo, M. K.; Addicoat, M.; Balaraman, E.;

Banerjee, R., Triazine Functionalized Porous Covalent Organic Framework for Photo- organocatalytic E-Z Isomerization of Olefins. J. Am. Chem. Soc. 2019, 141 (15), 6152- 6156.

11. Ding, S.-Y.; Wang, W., Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 2013, 42 (2), 548-568.

12. Konstas, K.; Taylor, J. W.; Thornton, A. W.; Doherty, C. M.; Lim, W. X.; Bastow, T. J.; Kennedy, D. F.; Wood, C. D.; Cox, B. J.; Hill, J. M.; Hill, A. J.; Hill, M. R., Lithiated Porous Aromatic Frameworks with Exceptional Gas Storage Capacity. Angew. Chem. Int. Ed. 2012, 51 (27), 6639-6642.

13. Huang, N.; Chen, X.; Krishna, R.; Jiang, D., Two-Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel-Wall Functionalization. Angew. Chem. Int. Ed. 2015, 54 (10), 2986-2990.

14. Lee, G.-Y.; Lee, J.; Vo, H. T.; Kim, S.; Lee, H.; Park, T., Amine-Functionalized Covalent Organic Framework for Efficient S02 Capture with High Reversibility. Sci Rep. 2017, 7 (1), 557.

15. Fernandes, S. P. S.; Romero, V.; Espina, B.; Salonen, L. M., Tailoring Covalent Organic Frameworks To Capture Water Contaminants. Chem. Eur. J. 2019, 25 (26), 6461- 6473.

16. Bai, L.; Phua, S. Z. F.; Lim, W. Q.; Jana, A.; Luo, Z.; Tham, H. P.; Zhao, L.; Gao, Q.; Zhao, Y., Nanoscale covalent organic frameworks as smart carriers for drug delivery. Chem. Commun. 2016, 52 (22), 4128-4131. 17. Zhang, G.; Li, X.; Liao, Q.; Liu, Y.; Xi, K.; Huang, W.; Jia, X., Water-dispersible PEG-curcumin/amine-functionalized covalent organic framework nanocomposites as smart carriers for in vivo drug delivery. Nat. Commun. 2018, 9 (1), 2785.

18. Mitra, S.; Sasmal, H. S.; Kundu, T.; Kandambeth, S.; Illath, K.; Diaz Diaz, D.; Banerjee, R., Targeted Drug Delivery in Covalent Organic Nanosheets (CONs) via Sequential Postsynthetic Modification. J. Am. Chem. Soc. 2017, 139 (12), 4513-4520.

19. Wu, Y.; Yan, D.; Zhang, Z.; Matsushita, M. M.; Awaga, K., Electron Highways into Nanochannels of Covalent Organic Frameworks for High Electrical Conductivity and Energy Storage. Appl. Mater. Interfaces 2019, 11 (8), 7661-7665.

20. Wang, M.; Guo, H.; Xue, R.; Li, Q.; Liu, H.; Wu, N.; Yao, W.; Yang, W., Covalent Organic Frameworks: A New Class of Porous Organic Frameworks for Supercapacitor Electrodes. ChemElectroChem 2019, 0 (0).

21. Wu, X.; Han, X.; Xu, Q.; Liu, Y.; Yuan, C.; Yang, S.; Liu, Y.; Jiang, J.; Cui, Y.,

Chiral BINOL-Based Covalent Organic Frameworks for Enantioselective Sensing. J. Am. Chem. Soc. 2019, 141 (17), 7081-7089.

22. Chen, Y.; Shi, Z.-L; Wei, L; Zhou, B.; Tan, J.; Zhou, H.-L; Zhang, Y.-B., Guest- Dependent Dynamics in a 3D Covalent Organic Framework. J. Am. Chem. Soc. 2019,

141 (7), 3298-3303.

23. Yang, Y.; Goh, K.; Weerachanchai, P.; Bae, T.-H., 3D covalent organic framework for morphologically induced high-performance membranes with strong resistance toward physical aging. J. Membrane Sci. 2019, 574, 235-242.

24. Liu, Y.; Diercks, C. S.; Ma, Y.; Lyu, H.; Zhu, C.; Alshmimri, S. A.; Alshihri, S.;

Yaghi, O. M., 3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons. J.

Am. Chem. Soc. 2019, 141 (1), 677-683.

25. Han, X.; Huang, J.; Yuan, C.; Liu, Y.; Cui, Y., Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation. J. Am. Chem. Soc. 2018, 140 (3), 892-895.

26. Brucks, S. D.; Bunck, D. N.; Dichtel, W. R., Functionalization of 3D covalent organic frameworks using monofunctional boronic acids. Polymer 2014, 55 (1), 330-334.

27. Bunck, D. N.; Dichtel, W. R., Postsynthetic functionalization of 3D covalent organic frameworks. Chem. Commun. 2013, 49 (24), 2457-2459.

28. Yahiaoui, O.; Fitch, A. N.; Hoffmann, F.; Froba, M.; Thomas, A.; Roeser, J., 3D Anionic Silicate Covalent Organic Framework with srs Topology. J. Am. Chem. Soc. 2018, 140 (16), 5330-5333. 29. Fang, Q.; Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S.; Yan, Y., 3D Microporous Base- Functionalized Covalent Organic Frameworks for Size-Selective Catalysis. Angew. Chem. Int. Ed. 2014, 53 (11), 2878-2882.

30. Wang, H.; Zeng, Z.; Xu, P.; Li, L.; Zeng, G.; Xiao, R.; Tang, Z.; Huang, D.; Tang,

L.; Lai, C.; Jiang, D.; Liu, Y.; Yi, H.; Qin, L.; Ye, S.; Ren, X.; Tang, W., Recent progress in covalent organic framework thin films: fabrications, applications and perspectives. Chem. Soc. Rev. 2019, 48 (2), 488-516.

31. Lohse, M. S.; Bein, T., Covalent Organic Frameworks: Structures, Synthesis, and Applications. Adv. Fund. Mater. 2018, 28 (33), 1705553.

32. Ma, X.; Scott, T. F., Approaches and challenges in the synthesis of three- dimensional covalent-organic frameworks. Commun. Chem. 2018, 1 (1), 98.

33. Diercks, C. S.; Yaghi, O. M., The atom, the molecule, and the covalent organic framework. Sdence 2017, 355 (6328), eaal1585.

34. Fan, H.; Gu, J.; Meng, H.; Knebel, A.; Caro, J., High-Flux Membranes Based on the Covalent Organic Framework COF-LZU1 for Selective Dye Separation by Nanofiltration. Angew. Chem. Int. Ed. 2018, 57 (15), 4083-4087.

35. Fan, H.; Mundstock, A.; Feldhoff, A.; Knebel, A.; Gu, J.; Meng, H.; Caro, J., Covalent Organic Framework-Covalent Organic Framework Bilayer Membranes for Highly Selective Gas Separation. J. Am. Chem. Soc. 2018, 140 (32), 10094-10098.

36. Li, G.; Zhang, K.; Tsuru, T., Two-Dimensional Covalent Organic Framework (COF) Membranes Fabricated via the Assembly of Exfoliated COF Nanosheets. Appl. Mater. Interfaces 2017, 9 (10), 8433-8436.

37. Dey, K.; Pal, M.; Rout, K. C.; Kunjattu H, S.; Das, A.; Mukherjee, R.; Kharul, U. K.; Banerjee, R., Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films. J. Am. Chem. Soc. 2017, 139 (37), 13083-13091.

38. Kim, S.; Lim, H.; Lee, J.; Choi, H. C., Synthesis of a Scalable Two-Dimensional Covalent Organic Framework by the Photon-Assisted Imine Condensation Reaction on the Water Surface. Langmuir 2018, 34 (30), 8731-8738.

39. Bisbey, R. P.; DeBlase, C. R.; Smith, B. J.; Dichtel, W. R., Two-dimensional Covalent Organic Framework Thin Films Grown in Flow. J. Am. Chem. Soc. 2016, 138 (36), 11433-11436.

40. Rotter, J. M.; Weinberger, S.; Kampmann, J.; Sick, T.; Shalom, M.; Bein, T.; Medina, D. D., Covalent Organic Framework Films through Electrophoretic Deposition — Creating Efficient Morphologies for Catalysis. Chem. Mater. 2019. 41. Becker, D.; Heidary, N.; Horch, M.; Gernert, U.; Zebger, I.; Schmidt, J.; Fischer, A.; Thomas, A., Microporous polymer network films covalently bound to gold electrodes. Chem. Commun. 2015, 51 (20), 4283-4286.

42. Ma, T.; Kapustin, E. A.; Yin, S. X.; Liang, L; Zhou, Z.; Niu, J.; Li, L.-H.; Wang, Y.; Su, J.; Li, J.; Wang, X.; Wang, W. D.; Wang, W.; Sun, J.; Yaghi, O. M., Single-crystal x- ray diffraction structures of covalent organic frameworks. Science 2018, 361 (6397), 48- 52.

43. Evans, A. M.; Parent, L. R.; Flanders, N. C.; Bisbey, R. P.; Vitaku, E.; Kirschner,

M. S.; Schaller, R. D.; Chen, L. X.; Gianneschi, N. C.; Dichtel, W. R., Seeded growth of single-crystal two-dimensional covalent organic frameworks. Science 2018, 361 (6397), 52-57.

44. Lee, S.; Uliana, A.; Taylor, M. K.; Chakarawet, K.; Bandaru, S. R. S.; Gul, S.; Xu, J.; Ackerman, Cheri M.; Chatterjee, R.; Furukawa, H.; Reimer, J. A.; Yano, J.; Gadgil, A.; Long, G. J.; Grandjean, F.; Long, J. R.; Chang, C. J., Iron detection and remediation with a functionalized porous polymer applied to environmental water samples. Chem. Sci. 2019, 10 (27), 6651-6660.

45. Lu, W.; Yuan, D.; Sculley, J.; Zhao, D.; Krishna, R.; Zhou, H.-C., Sulfonate-Grafted Porous Polymer Networks for Preferential C02 Adsorption at Low Pressure. J. Am.

Chem. Soc. 2011, 133 (45), 18126-18129. 46. Schmidt, J.; Werner, M.; Thomas, A., Conjugated Microporous Polymer Networks via Yamamoto Polymerization. Macromolecules 2009, 42 (13), 4426-4429.

47. J. R. Welty, C. E. W., R. E. Wilson, G. Rorrer, Fundamentals of Momentum, Heat, and Mass Transfer. 4th. ed.; John Wiley & Sons, Inc.: New York / Chichester / Weinheim / Brisbane / Singapore / Toronto, 2001. 48. Thomas, J. M. H.; Trewin, A., Amorphous PAF-1: Guiding the Rational Design of Ultraporous Materials. The Journal of Physical Chemistry C 2014, 118 ( 34), 19712-19722.