Commonly bound organic structures

Abstract

The chemically and thermally stable covalent organic framework (COF) materials of the present disclosure are configured and function as solid adsorbents for gas and water recovery.

Description

[Technical Field]

[0001] Introduction Covalent organic frameworks (COFs) are a group of crystalline, porous organic solid materials composed of organic structural units covalently linked in two or three dimensions. COFs can be used as gas and water adsorbents. We disclose chemically and thermally stable COF materials that can be configured and function as solid adsorbents for gas and water recovery. Summary of the Invention [Means for solving the problem]

[0002] The present invention provides a chemically and thermally stable covalent organic framework (COF) material configured and functioning as a solid adsorbent for gas and water recovery.

[0003] Aspect 1: Porous Covalent Organic Frameworks for Atmospheric Moisture Harvesting We disclose a diverse group of porous covalent organic frameworks designed and suitable for atmospheric moisture capture. One example is COF-432, a covalent organic framework with excellent moisture adsorption properties due to its unique structure. COF-432 is a porous, crystalline, two-dimensional imine-bonded COF with a square lattice topology. This high crystallinity is reflected in the absence or minimal hysteresis behavior during water adsorption. Unlike other COFs reported to date, COF-432 exhibits an S-shaped moisture adsorption isotherm with a steep pore-filling slope at low relative humidity and no hysteresis behavior, essential characteristics for energy-efficient moisture capture and desorption, fulfilling the requirements for moisture capture from air. Furthermore, COF-432 can be regenerated at ultralow temperatures and has excellent hydrolytic stability, as demonstrated by its ability to maintain its working capacity after 300 moisture adsorption / desorption cycles. The moisture adsorption capacity of COF-432 at 20-40% RH is 0.23gCOF -1 Furthermore, this structure exhibits excellent hydrolysis resistance (at least 20 days in water at room temperature) and no degradation of workability even after at least 300 consecutive water adsorption cycles. COF-432 also has a low heat of isosteric adsorption (approximately 48 kJ mol -1 ), enabling low-temperature, energy-efficient regeneration. Therefore, COF-432 is considered to be one of the best materials for water adsorption applications to provide drinking water for people and irrigate crops. Furthermore, this COF can also be used in heat pumps, dehumidifiers, adsorption refrigerators, and solar cooling systems.

[0004] In one aspect, the present invention provides a composition for capturing atmospheric moisture, comprising a porous covalent organic framework (COF), the COF having a two-dimensional or three-dimensional (2D or 3D) topology (2D topology of hcb, sql, kgm, fxt, kgd, or bex, or 3D topology of dia, ctn, bor, pts, lon, srs, ffc, or rra), and the crystalline structure of the COF contains bonds selected from imine bonds, amide bonds, imide bonds, hydrazone bonds, azine bonds, imidazole bonds, benzoxazole bonds, β-ketoenamine bonds, and olefin bonds, the bonds being formed by a combination of at least two different linkers selected from ditopic linkers, tritopic linkers, tetratopic linkers, hexatopic linkers, and octatopic linkers. See, for example, Figures 5 and 6. The above topologies (three-letter symbols) are clearly defined in reticular chemistry. 24 .

[0005] In some embodiments, the combination is a combination of a tetratopic linker and a tritopic linker; the bond is an imine (—CH═N—) bond; and / or the composition comprises a tetratopic linker, 1,1,2,2-tetrakis(4-aminophenyl)ethene [ETTA, C 26 H 16COF-432, which is composed of [(ETTA)(TFB)] and a tritopic linker, 1,3,5-triformylbenzene [TFB, C6H3(CHO)3], exhibits the mtf topology. イミン}.

[0006] In one aspect, the invention provides a device, such as an atmospheric moisture collector, a heat pump, a dehumidifier, an adsorption refrigerator, or a solar cooling system, comprising the disclosed moisture adsorbent composition.

[0007] In one aspect, the invention provides the disclosed compositions, characterized in that they comprise a step of condensing different linkers to form a crystalline structure.

[0008] In one aspect, the present invention provides the disclosed composition, characterized by comprising contacting the disclosed composition with air under conditions in which the composition adsorbs moisture from the air, preferably under conditions in which the relative humidity in the air is 20 to 40%.

[0009] Aspect 2: CO from air and exhaust gas 2 and H 2 Robust Covalent Organic Frameworks for O Harvesting The present invention provides compositions comprising one or more chemically and thermally stable covalent organic framework (COF) materials, which are configured and functional as solid adsorbents for capturing carbon dioxide and, optionally, moisture from gases, such as air or post-combustion exhaust gas mixtures. In all variations, the composition of the framework structural units, non-framework functional groups, bonding, and topology are provided independent of synthetic processes. In many variations, the COF materials are provided as being suitable for post-combustion capture (PCC) or direct air capture (DAC) processes, or both, but are not limited to these two specific processes. Criteria (e.g., "robustness" under different usage conditions) and characterization methods are provided as part of this disclosure. In some variations, the COF materials have a high affinity for HO, such that when the gas mixture contains HO (e.g., ambient air), the COF material's CO2 capture capacity increases, remains unchanged, or slightly decreases. In such variations, the COF materials are suitable for CO2 capture and moisture capture simultaneously. This approach enables the development of COF materials that represent an energy-efficient and cost-effective solution for CO2 capture from air and post-combustion exhaust gas mixtures, and also provides a solution for the simultaneous, integrated capture of CO2 and H2O in conditions where water is extremely scarce.

[0010] In one aspect, the present invention provides a composition comprising a chemically and thermally stable covalent organic framework (COF) material, the COF material configured and functioning as a solid adsorbent for capturing carbon dioxide from air or post-combustion exhaust gas mixtures, the COF material comprising a structure in which organic structural units as defined in FIG. 1, having substituents as defined in FIG. 2 and side chains as defined in FIGS. 1 and 2, are connected by bonds as defined in FIG. 4, and the COF material can have any topology as shown in FIG. 5 (e.g., layered topologies of sql, hcb, hxl, kgm, bex, kgd, tth, and mtf, and 3D topologies of dia, lon, pcu, srs, pto, pts, tbo, bor, cnt, and dia-w).

[0011] However, COFs or bonds that are not chemically or thermally stable under the conditions for capturing CO2 from air or post-combustion exhaust gas mixtures are excluded. Accordingly, the present invention is limited to a specific range of COFs, as defined in the claims, that (1) have been characterized to be chemically and thermally stable, and (2) are configured and capable of capturing CO2 from air and post-combustion exhaust gas mixtures.

[0012] In some embodiments, the composition is contained in a matrix configured as an adsorbent bed, fluidized bed, adsorbent-coated heat exchanger, or membrane, optionally positioned over, around, and / or through a flow path configured for air or a post-combustion exhaust gas mixture to pass therethrough; the composition comprises a moisture-containing air or a post-combustion exhaust gas mixture, and the COF material is configured and capable of capturing moisture from the air or the mixture, providing a secondary beneficial function of facilitating moisture capture as a potential by-product of moisture presence in the gas mixture, the COF having a structure as disclosed herein; and / or the COF is selected from COF-366-F-Co, COF-316, COF-316-CONH2, COF-316-C(NOH)NH2, and COF-701.

[0013] In one aspect, the present invention provides a system for carbon dioxide capture from air or post-combustion exhaust gas mixtures, the system comprising a matrix, such as an adsorbent bed, comprising the subject composition configured as a solid adsorbent material for the recovery of carbon dioxide, and optionally water, from air or post-combustion exhaust gas mixtures.

[0014] In one aspect, the present invention provides a method comprising the use of the subject composition as a solid adsorbent material for the recovery of carbon dioxide, and optionally water, from air or post-combustion exhaust gas mixtures.

[0015] Aspect 3: Improving moisture collection function using charged covalent organic frameworks The present invention provides methods, compositions, and systems for increasing the water adsorption capacity and rate of COFs at low to mid-range relative humidities. Unlike conventional COFs with a neutral backbone, the disclosed COFs contain a cationic or anionic backbone and counterions located within the pores of the COF. The counterions may be organic or metal ions.

[0016] The subject COF materials can be used to capture moisture from the air. The captured water can be used for drinking water or irrigation. Furthermore, such COF materials can be deployed in other applications that utilize their moisture adsorption properties, such as heat pumps, dehumidifiers, adsorption refrigerators, solar cooling systems, dryers, organic light-emitting devices, and secondary battery devices.

[0017] In one aspect, the present invention provides a composition comprising a water-stable, charged covalent organic framework (COF) material configured and capable of adsorbing or capturing moisture from a gas, such as air or exhaust, the COF material comprising a cationic or anionic framework that forms pores and organic or metallic counterions located within the pores.

[0018] In some embodiments, the composition comprises a charged functional group (see herein, e.g., Table 1), a counterion (see herein, e.g., Table 2), an organic bond (see herein, e.g., Table 3), and an organic linker (see herein, e.g., Table 4); the composition is contained in a matrix configured as an adsorbent bed, a fluidized bed, an adsorbent-coated heat exchanger, or a membrane; the composition is contained in a matrix configured as an adsorbent bed, a fluidized bed, an adsorbent-coated heat exchanger, or a membrane, the matrix being disposed in a flow path configured to pass air or exhaust air over, around, and / or through the matrix; the composition comprises air or exhaust air containing moisture; and / or the COF comprises a structure specifically disclosed herein.

[0019] In one aspect, the invention provides a system for improved moisture collection or recovery of moisture from a gas, such as air or exhaust gas, the system comprising a subject composition configured as a solid adsorbent for recovering moisture from the gas, the composition having properties of high moisture adsorption capacity and fast moisture adsorption rate at low to mid-range relative humidities.

[0020] In one aspect, the present invention provides the subject compositions as solid adsorbents for recovering moisture from gases such as air and exhaust gases, characterized by high moisture adsorption capacity and rapid moisture adsorption rate at low to mid-range relative humidities.

[0021] The present invention includes all combinations of the individual aspects and embodiments described herein, all of which are intended to be described herein. [Brief explanation of the drawings]

[0022] [Figure 1a-1b] A 4-c unimodal (single node) SQL network (a) and a (3,4,4)-c trinodal (three types of nodes) MTF network (b) are shown side-by-side. The MTF network is conceptually a SQL network with 1 / 8 of the nodes (orange) removed, and can be recognized as a gapped SQL network. Nodes in both networks are depicted as squares. Blue squares represent 4-c nodes, and yellow squares represent 3-c nodes. [Figures 2a-2c]The reaction of 1,1,2,2-tetrakis(4-aminophenyl)ethene (ETTA), representing the 4-c node, with 1,3,5-triformylbenzene (TFB), representing the 3-c node (a), yields COF-432 (c). This structure exhibits the (3,4,4)-c mtf topology, as shown in the expanded form (b). Atom colors: C, gray; N, blue; O, red. Hydrogen atoms have been omitted for clarity. The second layer of the staggered structure of COF-432 is depicted in light orange. [Figure 3] Wide-angle X-ray scattering (WAXS) pattern and Le Bail analysis of COF-432, showing the observed pattern (black), the refined Le Bail fit (red), the difference plot (green), the background (blue), and the Bragg position (pink). [Figure 4a-4b] (a) Water sorption analysis of COF-432 measured at different temperatures (10°C, 25°C, and 40°C). P: water vapor pressure. Psat: saturated water vapor pressure at a given temperature. (b) Water cycle stability test in which COF-432 was subjected to 300 adsorption-desorption cycles under constant water vapor pressure (1.7 kPa). Adsorption was performed at 30°C (40% relative humidity (RH)), and desorption was performed at 35°C (30% relative humidity (RH)). [Figure 5] Synthetic strategies and chemical structures of various linked COFs, including imine, amide, imide, hydrazone, azine, imidazole, benzoxazole, β-ketoenamine, and olefinic bonds. [Figure 6] Two-dimensional topological structure of COF. [Figure 7] Three-dimensional topological structure of COF. [Figure 8] FT-IR spectra of COF-432, TFB, and ETTA, displayed in red, blue, and black, respectively. [Figure 9] 13C CP-MAS solid-state NMR spectrum of COF-432. 13C chemical shift (ppm) assignments are shown next to the atoms in the chemical structure. [Figures 10a-10b]SEM image showing the phase purity and uniform morphology of COF-432 (a). The crystal size of COF-432 is approximately 300 nm (b). [Figure 11] Electron density map of COF-432, showing the high electron density region assigned to the ETTA fragment. [Figure 12] Le Bail refinement of the observed WAXS pattern of COF-432. The observed pattern (black) and refined fit (red) are shown. The background (blue), difference plot (green), and Bragg position (pink) are also shown. [Figure 13] Comparison of the simulated WAXS pattern (orange) and the observed WAXS pattern (black) of COF-432, with the Bragg position (pink) also shown. [Figure 14] Comparison of WASX patterns of an activated COF-432 sample, a COF-432 sample with methanol in the pores, and a COF-432 sample with water in the pores. [Figure 15] COF-432 extended mtf type network. [Figure 16] N2 adsorption isotherm for activated COF-432 at 77 K. The filled and open circles represent the adsorption and desorption curves, respectively. The line connecting the points on the N2 isotherm is included as a guide. [Figure 17] N2 adsorption isotherm for activated COF-432 at 77 K. The filled and open circles represent the adsorption and desorption curves, respectively. The line connecting the points on the N2 isotherm is included as a guide. [Figure 18] The pore size measurement of COF-432 by N2-DFT fitting showed that the pore width was 8.0 Å. [Figure 19] Thermogravimetric analysis of COF-432 under nitrogen flow. [Figure 20] Powder X-ray diffraction (PXRD) analysis of COF-432 after immersion in water for different times (3 days, 6 days, 10 days, and 20 days). [Figure 21]N2 adsorption analysis at 77 K using activated COF-432 before and after 90 hours of water immersion. The filled and open circles represent the adsorption and desorption curves, respectively. The lines connecting the points in the figure are for reference only. [Figure 22] Four consecutive measurements of water adsorption on COF-432 at 298 K. P: Water vapor partial pressure. Psat: Saturated water vapor pressure at 298 K. [Figure 23] Water adsorption analysis of COF-432 measured at different temperatures (10℃, 25℃, and 40℃). P: Water vapor partial pressure. Psat: Saturated water vapor pressure at each temperature. [Figure 24] The isosteric heat of adsorption of COF-432 was calculated by applying the Clausius-Clapeyron equation to the water adsorption isotherm of COF-432 measured at different temperatures (10°C, 25°C, and 40°C). [Figure 25] N2 adsorption analysis at 77 K using activated COF-432 before and after seven consecutive moisture adsorption measurements. The filled and hollow circles represent the adsorption and desorption curves, respectively. The lines connecting the points in the figure are for reference only. [Figure 26] A water cycle stability test was conducted on COF-432, in which 300 adsorption-desorption cycles were performed under conditions of constant water vapor pressure (1.7 kPa). Adsorption was performed at 30°C (relative humidity (RH) 40%), and desorption was performed at 35°C (relative humidity (RH) 30%). P: water vapor pressure. Psat: saturated water vapor pressure at a given temperature. [Figure 27] Schematic diagram of organic structural units. [Figure 28a-28b] 1 is a schematic representation of an organic fragment containing an organic structural unit within the scope defined in this disclosure. [Figure 29] Examples of organic structural units. [Figure 30] FIG. 1 is a schematic diagram showing bonds in the range of COFs defined in this disclosure. [Figure 31] Schematic diagram of an example COF topology. [Figure 32] FIG. 1 is a diagram illustrating an example of a breakthrough system required in an embodiment of the present disclosure. [Figure 33] Schematic diagram of COF-366-Co-F. [Figure 34] PXRD measurement results of a powder sample of COF-366-F-Co fitted by the Pawley method and grazing incidence wide-angle X-ray scattering (GIWAXS) measurement results of a COF-366-F-Co thin film on a highly oriented pyrolytic graphite (HOPG) substrate. [Figure 35] CO2 adsorption isotherms of COF-366-F-Co at 273 K (circles), 283 K (triangles), and 298 K (squares). [Figures 36a-36e] (a) Post-synthetic modification of COF-316. (b, d) PXRD patterns of COF-316-CONH2 and COF-316-C(NOH)NH2. Crystallinity is maintained, suggesting long-term stability in base. (c, e) 13C CP-MAS solid-state NMR spectra of COF-316-CONH2 and COF-316-C(NOH)NH2. Asterisks indicate spinning sidebands. [Figure 37] Comparison of PXRD patterns, FT-IR spectra, and N2 isotherms at 77 K for untreated COF-316, COF-316 treated with 6 M HCl, and COF-316 treated with 6 M NaOH. [Figure 38] Comparison of the CO2 isotherm of COF-316 (JUC-505) with the CH4 isotherm and N2 isotherm at 273K. [Figure 39] Schematic diagram of COF-701. [Fig. 40a-40f] Chemical stability testing of COF-701 using Brønsted acids (a), Brønsted bases (b), organolithium reagents (c, d), and Lewis acids (e, f). WAXS patterns (a, c, e) (including enlarged insets) and FT-IR spectra (b, d, 1900-1200 cm-1; f, 1900-900 cm-1) of the treated materials demonstrate that the crystallinity and chemical composition of COF-701 are preserved. [Figure 41] H2O isotherm of COF-701 measured at 298K. DETAILED DESCRIPTION OF THE INVENTION

[0023] Below and throughout this specification, unless otherwise understood or specified, the terms "a" and "an" mean one or more, and the term "or" means "and / or." The examples and embodiments described herein are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made based on these examples and embodiments, and such modifications and variations are intended to be within the spirit and scope of this application and the appended claims. All publications, patents, and patent applications cited herein, and the references cited therein, are hereby incorporated by reference in their entirety for all purposes.

[0024] Aspect 1: Porous Covalent Organic Frameworks for Atmospheric Moisture Harvesting Developing new materials to capture moisture from the air is one of the key efforts to address the global water crisis. 1 Ideally, such a material should have the following characteristics: (i) high hydrolytic stability and retained adsorption capacity during long-term moisture absorption / desorption cycles; (ii) exhibit an "S"-shaped moisture sorption isotherm (IUPAC Type IV or V) with a steep pore-filling process in the low relative humidity range (relative humidity (RH) less than 40%), with minimal or no hysteresis; and (iii) a low regeneration temperature, allowing water molecules to be easily released from the material by low-temperature heating. 2 .

[0025] Network-based structures such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are ideally suited to address the water scarcity crisis due to their excellent porosity, diversity of chemical compositions, and variety of available topologies. Furthermore, the water adsorption properties of these structures can be tuned in various ways. 2,3 In fact, MOFs have been identified, studied, and put to practical use as materials for capturing moisture from the air. 2,4-9However, COF has hardly been explored for this purpose. 10 This is due to the relatively low crystallinity of COFs, especially those formed with hydrolytically strong bonds. 11 This is likely due to the low crystallinity, which prevents the formation of a well-ordered molecular water network within the porous structure, which is a key prerequisite for obtaining an S-shaped moisture isotherm profile.

[0026] Therefore, in this study, we attempted to examine COFs as a material for moisture collection. Specifically, we investigated the use of a tetratopic linker, 1,1,2,2-tetrakis(4-aminophenyl)ethene [ETTA, C 26 H 16 We report a novel, highly crystalline structure composed of COF-432 {[(ETTA)(TFB)} and a tritopic linker, 1,3,5-triformylbenzene [TFB, C6H3(CHO)3]. イミン This COF, termed}, exhibits the mtf topology, a network not previously reported in COF chemistry (Figure 1). 11-13 This COF exhibits a moisture sorption isotherm with a steep pore-filling process without hysteresis in the low relative humidity range (<40% RH), and exhibits extremely high moisture sorption cycling stability and a low heat of adsorption. These findings indicate that COF-432 is a hydrolytically stable, long-term moisture capture material that requires little energy for regeneration and has a relatively high working capacity within a low partial pressure range, i.e., it can efficiently perform moisture sorption / desorption cycling using a small temperature gradient.

[0027] COF-432 was obtained by the solvothermal condensation of ETTA and TFB in a mixture of chloroform, methanol, and aqueous acetic acid (Figure 2, Supporting Information (SI), Section S2). The structure of COF-432 was determined by powder X-ray diffraction (PXRD) and analyzed by elemental analysis (EA), Fourier transform infrared absorption (FT-IR) spectroscopy, and 13This was confirmed by C cross-polarized magic-angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, thermogravimetric analysis (TGA), and N2 adsorption analysis. FT-IR analysis of COF-432 revealed that the aldehydes (ν ) present in the starting materials ETTA and TFB were soluble in water. C=O = 1692cm -1 ) stretching vibration and amine (ν N-H = 3352cm -1 ) stretching vibration was confirmed to be absent. C=N = 1628cm -1 The appearance of the stretching vibrations indicated the formation of an extended imine bond network (SI, Section S3). The formation of imine bonds is 13 This was also confirmed by C CP-MAS NMR spectroscopy, which showed a characteristic 13 C imine resonance was observed ( SI , section S4).

[0028] COF-432 has a small crystal size (approximately 100 × 100 × 300 nm 3 , SI, Section S5), and the structure was determined by PXRD pattern analysis (SI, Section S6). TOPAS 4.2 software 14 The PXRD pattern was indexed using the method, and the space group I41 / a (No. 88) was identified. 15 The electron density map (EDM) of COF-432 was calculated using the method described above, and valid results were obtained in the corresponding space group. The structure of COF-432 was then determined by identifying the position of the ETTA fragment observed in the EDM (SI, Section S6) and connecting it to an extended network. In this structure, the structural units ETTA and TFB (Fig. 2a) are connected by imine bonds to form an extended 2D framework of the mtf topology with three types of vertices and two types of edges (Fig. 1, Fig. 2b, SI, Section S7). Interestingly, this 2D network topology is similar to the predicted 3D network. 12 and the recently reported 2D BEX topology, which combines a triangular linker and a square-shaped tetratopic linker. 16This is distinct from the previous study, broadening the range of topologies observed in COF chemistry. The unit cell parameters of COF-432 were refined by the Le Bail method using wide-angle X-ray scattering (WAXS) data (I41 / a; a = 30.65 Å, c = 12.85 Å). The residual factor is R p = 2.88% and R wp = 3.96% (Figure 3; SI, section 6).

[0029] A monolayer of COF-432 (Figure 2c) contains two types of rectangular pores with diameters (based on van der Waals radii) of approximately 10.0 Å and 21.0 Å. The twisted arrangement of adjacent two-dimensional layers forms a one-dimensional cylindrical pore structure with a diameter of approximately 7.5 Å (Figure 2c). COF-432 possesses persistent porosity and a BET specific surface area of ​​895 m. 2 g -1 This value is a theoretical value (900 m) calculated from a structural model that uses N2 as a probe adsorbent and approximates the area accessible to molecules. 2 g -1 ) (radius = 3.6Å) 17 The pore volume (0.43 cm) of COF-432 determined from the N2 adsorption isotherm 3 g -1 ) is the pore volume (0.45 cm ) predicted from the structural model using the porosity calculation function of PLATON. 3 g -1 ) showed good agreement with the proposed crystal structure. Furthermore, the pore size distribution calculated from the N2 adsorption isotherm of COF-432 was a single pore with a diameter of 8.0 Å, which was in good agreement with the proposed crystal structure (SI, Section S8). To further verify this structural model, elemental analysis of COF-432 was performed, and the results showed good agreement with the predicted element ratios of this structure obtained by calculation (SI, Section S2).

[0030] To investigate the hydrolytic stability of COF-432, we first immersed activated COF-432 in water. The PXRD patterns of COF-432 before and after immersion confirmed that the crystallinity of COF-432 was maintained for at least 20 days. Furthermore, even after prolonged immersion in water (90 hours under stirring; SI, Section S10), the surface area of ​​COF-432 did not decrease. Given the excellent hydrolytic stability of this imine-based COF, we next investigated its water adsorption.

[0031] COF-432 exhibits an S-shaped moisture sorption isotherm with a steep pore-filling process at 34% RH (25 °C; Figure 4a). The maximum moisture adsorption is P / P sat = 0.95 at 30 wt% (0.3 g COF -1 ) and the working capacity at 20-40% relative humidity is 0.23g COF -1 Although MOFs with higher water adsorption capacities than COF-432 have been reported, 2 We strongly believe that expanding the range of materials suitable for atmospheric moisture capture would be extremely beneficial for this technology. Unlike other COFs, COF-432 does not exhibit hysteretic moisture adsorption behavior. This is an attractive property because it reduces the energy required for COF-432 regeneration. To further investigate the interaction of water molecules with this COF, we used moisture adsorption isotherms at different temperatures (10 °C, 25 °C, and 40 °C; Figure 4a) to measure the isosteric heat of adsorption (Q) of moisture on COF-432. st The isosteric heat of adsorption was calculated to be approximately 48 kJ mol -1 (SI, Section S11), which is the enthalpy of vaporization of water (44 kJ mol at 25 °C). -1 ), which suggests that water-water interactions are dominant in the pore-filling process. 2 In fact, the pore surface of COF-432 is mostly nonpolar, and the pore filling process at low relative humidity (<40% RH) is thought to be due to the strong confinement effect of this small structure.

[0032] Importantly, COF-432 maintained its crystallinity, BET specific surface area, and water vapor capacity after seven consecutive water sorption measurements (SI, Section S12). This is an impressive feature, as other COFs reported in the literature as promising water adsorbents exhibit a decrease in surface area after contact with and / or adsorption of water. 20-23 Based on these results, we next decided to conduct a long-term moisture adsorption / desorption cycle test on COF-432. In a thermogravimetric analyzer, COF-432 was brought into contact with water vapor under constant pressure (1.7 kPa) and the moisture was adsorbed and desorbed by varying the temperature in the range of 30 to 35°C (corresponding to 40 to 30% RH, respectively). Due to the steep pore filling process, a 0.23g COF -1 A total of 300 moisture absorption and desorption cycles were performed, but the work capacity remained unchanged during these cycles (Figure 4b), suggesting that the porous structure was maintained and that the water cycle stability was excellent.

[0033] We have synthesized novel COFs, such as COF-432, that exhibit attractive moisture adsorption properties, including: (i) excellent long-term stability in moisture adsorption / desorption cycling; (ii) a hysteresis-free moisture adsorption isotherm with a steep adsorption slope in the low relative humidity range; and (iii) a low heat of adsorption that allows regeneration with a low-temperature energy source. Such COFs are suitable materials for moisture capture from air and for use in heat pump systems and desiccant-based dehumidifiers.

[0034] References 1. Wahlgren, RV Atmospheric water vapor processor designs for potable water production: A review. Water Res. 2001, 35, 1-22. 2. Kalmutzki, M. J.; Diercks, C. S.; Yaghi, O. M. Metal-organic frameworks for water harvesting from air. Adv. Mater. 2018, 30, 1704304. 3. Yaghi, O. M.; Kalmutzki, M. J.; Diercks, C. S. Introduction to Reticular Chemistry: Metal-organic frameworks and covalent organicframeworks, Wiley-VCH, Weinheim, 2019, 509. 4. Burtch, N. C.; Jasuja, H.; Walton, K. S. Water stability and adsorption in metal-organic frameworks. Chem. Rev. 2014, 114, 10575-10612. 5. Rieth, A. J.; Yang, S.; Wang, E. N.; Dinca, M. Record atmospheric fresh water capture and heat transfer with a material operating at the water uptake reversibility limit. ACS Cent. Sci. 2017, 3, 668-672. 6. Kim, H.; Yang, S.; Rao, S. R.; Narayanan, S.; Kapustin, E. A.; Furukawa, H.; Umans, A. S.; Yaghi, O. M.; Wang, E. N. Water harvesting from air with metal-organic frameworks powered by natural sunlight. Science, 2017, 356, 430-434. 7. Kim, H.; Rao, S. R.; Kapustin, E. A.; Zhao, L.; Yang, S.; Yaghi, O. M.; Wang, E. N. Adsorption-based atmospheric water harvesting device for arid climates. Nat. Commun. 2018, 9, 1191. 8. Fathieh, F.; Kalmutzki, M. J.; Kapustin, E. A.; Waller, P. J.; Yang, J.; Yaghi, O. M. Practical water production from desert Air. Sci. Adv., 2018, 4, eaat3198. 9. Hanikel, N.; Prevot, M. S.; Fathieh, F.; Kapustin, E. A.; Lyu, H.; Wang, H.; Diercks, N. J.; Glover, T. G.; Yaghi, O. M. Rapid cycling and exceptional yield in a metal-organic frame-work water harvester. ACS Cent. Sci. 2019, 5, 1699-1706. 10. Byun, Y.; Je, S. H.; Talapaneni, S. N.; Coskun, A. Advances in porous organic polymers for efficient water capture. Chem. Eur. J. 2019, 25, 10262-10283. 11. Lohse, M. S.; Bein, T. Covalent organic frameworks: Structures, synthesis, and applications. Adv. Funct. Mater. 2018, 28, 1705553. 12. Lan, Y.; Han, X.; Tong, M.; Huang, H.; Yang, Q.; Liu, D.; Zhao, X.; Zhong, C. Materials genomics methods for high-throughput construction of COFs and targeted synthesis. Nat. Commun. 2018, 9, 5274. 13. Lyle, S. J.; Waller, P. J.; Yaghi, O. M. Covalent organic frameworks: Organic chemistry extended into two and three dimensions. Trends Chem. 2019, 1, 172-184. 14. Bruker AXS GmbH, TOPAS Manual: DOC-M88-EXX065 V4.2 - 01.2009. 15. Palatinus, L.; Chapuis, G. SUPERFLIP-A Computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Crystallogr. 2007, 40, 786-790. 16. Banerjee, T.; Haase, F.; Trenker, S.; Biswal, B. P.; Savasci, G.; Duppel, V.; Moudrakovski, I.; Ochsenfeld, C.; Lotsch, B. V. Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers. Nat. Commun. 2019, 10, 2689. 17. Duren, T.; et al. Calculating geometric surface areas as a characterization tool for metal-organic frameworks. J. Phys. Chem. C 2007, 111, 15350-15356. 18. Furukawa, H.; Gandara, F.; Zhang, Y. B.; Jiang, J.; Queen, W. L.; Hudson, M. R.; Yaghi, O. M. Water adsorption in porous metal-organic frameworks and related materials. J. Am. Chem. Soc. 2014, 136, 4369-4381. 19. Canivet, J.; et al. Structure-property relationships of water adsorption in metal-organic frameworks. New J. Chem. 2014, 38, 3102-3111. 20. Biswal, B. P.; et al. Pore surface engineering in porous, chemically stable covalent organic frameworks for water adsorption. J. Mater. Chem. A 2015, 3, 23664-23669. 21. Stegbauer, L.; Hahn, M. W.; Jentys, A.; Savasci, G.; Ochsenfeld, C.; Lercher, J. A.; Lotsch, B. V.; Tunable water and CO2absorption properties in isostructural azine-based covalent organic frameworks through polarity engineering. Chem. Mater. 2015, 27, 7874-7881. 22. Karak, S.; et al. Constructing ultraporous covalent organic frameworks in seconds via an organic terracotta process. J. Am. Chem. Soc. 2017, 139, 1856-1862. 23. Perez-carvajal, J.; et al. The imine-based COF TpPa-1 as an efficient cooling adsorbent that can be regenerated by heat or light. Adv. Energy Mater. 2019, 1901535. 24. O'Keeffe, M.; Peskov, MA; Ramsden, SJ; Yaghi, OM The reticular chemistry structure resource (RCSR) database of, and symbols for, crystal nets. Acc. Chem. Res. 2008, 41, 1782-1789.

[0035] Analysis method Elemental microanalysis (EA) was performed using a LECO CHNS-932 CHNS elemental analyzer (Section S2). Fourier transform infrared (FT-IR) spectra were collected using a Bruker ALPHA Platinum ATR-FT-IR spectrometer equipped with a single-reflection diamond ATR module (Section S3). Solid-state nuclear magnetic resonance (NMR) spectra were collected using a Tecmag Discovery spectrometer with a 7.05 T magnet. 1 H is 300.13MHz, 13C was collected at 75.48 MHz (Section S4). Scanning electron microscope (SEM) images were recorded using an FEI Quanta 3D FEG scanning electron microscope at an accelerating voltage of 10 kV and a working distance of 10.0 mm (Section S5). Powder X-ray diffraction (PXRD) data were collected using a Bruker D8 Advance Bragg-Brentano diffractometer with Ni-filtered CuKα radiation (λ = 1.54059 Å) (Section S6). Wide-angle X-ray scattering (WAXS) patterns were acquired using beamline 7.3.3 at the Advanced Light Source (ALS) with a Pilatus 2M detector (Section S6). N adsorption measurements were performed using a Micromeritics 3Flex surface characterization system (Section S8) and an ASAP 2420 system (Section 10). A liquid nitrogen bath was used for measurements at 77 K. Thermogravimetric analysis (TGA) curves were recorded under a stream of dry nitrogen using a TA Q500 thermal analysis system (Section S9).

[0036] Moisture sorption isotherms were measured using a BEL Japan BELSORP-aqua3 (Section 11). Before the adsorption experiment, water (the analyte) was degassed by five freeze / pump / thaw cycles. The measurement temperature was controlled using a water circulator. Moisture sorption / desorption cycle stability (Section 12) was investigated using a TA Instruments SDT Q600 series thermogravimetric analyzer (TGA). The first gas inlet was connected to a dry nitrogen tank. The second gas inlet was used to supply humidified nitrogen. Humidified nitrogen was generated by passing dry nitrogen gas through a 2 L gas washing bottle filled with water. Temperature and relative humidity (RH) were monitored using a high-precision thermocouple and humidity sensor downstream of the TGA chamber. The target RH was determined by adjusting the combined flow rate of the dry and humidified nitrogen gases to 250 mL min−1. -1 This was achieved by adjusting the ratio between the two while maintaining

[0037] Synthesis of 1,1,2,2-tetrakis(4-aminophenyl)ethene (ETTA) 1,1,2,2-Tetrakis(4-aminophenyl)ethene (ETTA) was synthesized according to a previously reported method. 1 .

[0038] Synthesis and activation of COF-432 A 10 × 8 mm (od × id) Pyrex tube was charged with ETTA (12 mg, 0.031 mmol), trimethylbenzene (TFB) (7.3 mg, 0.046 mmol), and a chloroform / methanol mixture (0.6 mL:0.4 mL). After sonication for 5 minutes, aqueous acetic acid (0.2 mL, 6 M) was added. The tube was flash-frozen at 77 K under liquid nitrogen, evacuated to 100 mTorr, and then flame-sealed to a length of approximately 15 cm. The reaction mixture was heated at 120 °C for 3 days to yield COF-432 as a yellow solid. The solid was isolated by filtration, washed five times with methanol, and solvent-exchanged into chloroform using a Soxhlet extractor over 24 hours. The resulting COF-432 was activated under dynamic vacuum at room temperature for 3 hours, followed by 12 hours at 85 °C. Elemental analysis of COF-432: C 114 H 72 N 12 Calculated for 6H2O: C 79.70%; H 4.93%; N 9.78%. Analytical: C 78.35%; H 4.94%; N 10.01%.

[0039] Powder X-ray diffraction (PXRD) data collection PXRD measurements were performed using a Bruker D8 Advance diffractometer equipped with a LynxEye detector in the Bragg-Brentano symmetric reflection mode using a Ni-filtered CuKα focused source (1.54059 Å, 1.54439 Å) at 1600 W (40 kV, 40 mA). The best counting statistics were obtained by sampling over the diffraction angle (2θ) range of 3–50° with a step width of 0.02° and an exposure time of 10 seconds per step. Measurements were performed at room temperature and atmospheric pressure.

[0040] Structural analysis of COF-432 Determination of unit cell The unit cell parameters are calculated using TOPAS 4.2. 2 The PXRD pattern was determined by indexing using the . COF-432 was found to have a body-centered tetragonal lattice in the space group I41 / a (No. 88). Using data from 2θ = 5 to 50°, profile fitting of the entire pattern and extraction of integrated intensities were performed. Background correction was performed using a 20-variable Chebyshev polynomial function.

[0041] Electron density calculation Superflip 3 The electron density map of COF-432 was calculated using the charge-flipping method. First, the PXRD pattern was indexed. As a result, a tetragonal lattice was identified, and then refined by fitting using the Pawley method. The parameters were input into Superflip, and the electron density map in the P1 space group was calculated. The results were converged with a success rate of 70%, suggesting the I41 / a space group.

[0042] Structural Model The structural model of COF-432 was created using the Materials Visualizer module included in Materials Studio (Materials Studio ver. 7.0, Accelrys Software Inc.) as follows: First, the ETTA linker was placed at the position indicated in the electron density map. Next, the ETTA linker was connected to the TFB structural unit. Due to the symmetry of I41 / a, one of the ETTAs was arranged irregularly. After completing the structural model, energy minimization calculations were performed using the universal force field built into the Forcite module of Materials Studio. During this process, the unit cell parameters were also optimized until they converged appropriately (the energy convergence criterion was 10 -4 kcal mol -1 was set to ).

[0043] Refinement of structural models The observed WAXS patterns were profile-fitted by the Le Bail method over the entire pattern at 2θ = 2–45°. The calculated PXRD patterns showed low residual values ​​(R wp = 3.96%, R p = 2.88%), which showed good agreement with the observed PXRD pattern, and the final unit cell parameters (a = 30.65 Å, c = 12.85 Å) were obtained.

[0044] The partial atomic coordinates and refined unit cell parameters of COF-432 are listed in Table S1, and the crystallographic information is listed in Table S2.

[0045] TIFF0007823890000001.tif224154TIFF0007823890000002.tif115155

[0046] TIFF0007823890000003.tif107146

[0047] Examination of the influence of guest molecules on PXRD patterns COF-432 was immersed in methanol and water for 2 days, respectively, and WAXS patterns were collected using the wet samples.

[0048] Topological Analysis The topology of COF-432 was determined by ToposPro software. 4 TFB is interpreted as a 3-c node, and ETTA as a 4-c node, and these are connected to form a two-dimensional (2D) mtf-type network. This network has three types of vertices and two types of edges, and the vertices are connected to form four-membered and eight-membered rings.

[0049] N 2 Adsorption analysis N2 adsorption analysis at 77 K showed that the activated COF-432 possessed persistent porosity.

[0050] Thermogravimetric analysis (TGA) The thermal stability of COF-432 was investigated by thermogravimetric analysis. COF-432 (4 mg) was dissolved in water under a nitrogen stream (60 mL min -1 ) from 30℃ to 800℃ in 5℃ min -1 The mixture was heated with a temperature gradient of 0.05.

[0051] Hydrolytic stability test Activated COF-432 was immersed in water at room temperature. PXRD analysis was performed after various time intervals (3, 6, 10, and 20 days). Comparison of the PXRD patterns revealed that COF-432 maintained its crystallinity in water for at least 20 days.

[0052] References (1) Lu, J.; Zhang, J. Facile synthesis of azo-linked porous organic frameworks via reductive homocoupling for selective CO2capture. J. Mater. Chem. A, 2014, 2, 13831-13834 (2) Bruker AXS GmbH, TOPAS Manual: DOC-M88-EXX065 V4.2 - 01.2009. (3) Palatinus, L.; Chapuis, G. SUPERFLIP-A Computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Crystallogr. 2007, 40, 786-790. (4) Blatov, VA; Shevchenko, AP; Proserpio, DM Applied topological analysis of crystal structures with the program package ToposPro. Cryst. Growth Des. 2014, 14, 3576-3586.

[0053] Aspect 2: CO from air and exhaust gas 2 and H 2 Robust Covalent Organic Frameworks for O Harvesting The anthropogenic emission of huge amounts of carbon dioxide (CO2) is a contributing factor to the global climate crisis. Because key industrial activities, such as energy generation, production, and transportation, are expected to continue to rely on fossil fuels for the foreseeable future, there is an urgent need to mitigate the problem through human efforts to capture emitted CO2 (commonly referred to as carbon capture). Depending on the source of the CO2 mixture, carbon capture processes can be broadly divided into two categories: (a) post-combustion capture (PCC) from fossil fuel combustion point sources, and (b) direct air capture (DAC) from the atmosphere.

[0054] In both cases, the key challenges are (a) selective capture of CO2 from gas mixtures, (b) efficient capture by maximizing adsorption capacity and minimizing energy loss, and (c) long-term stability of the capture material. COFs with the following composition and structure are expected to be among the most promising candidates for solving these challenges as solid adsorbents: (a) high affinity and selectivity for CO2 through chemisorption and physisorption achieved through organic functionalization; (b) very large specific surface area and generally low density, resulting in high adsorption weight; (c) low heat capacity, resulting in low energy consumption, and an interconnected pore structure, resulting in easy mass transfer; and (d) stability against water and impurities due to strong and inert covalent bonds in the material's framework. The simultaneous realization of these properties is nearly impossible with other types of materials.

[0055] Description of Specific Embodiments of Aspect 2 The present invention provides a generalized and viable method for achieving and tailoring CO2 capture performance using chemically and thermally stable covalent organic framework (COF) materials as solid adsorbents for capturing carbon dioxide from air and post-combustion exhaust gas mixtures. The physical and chemical properties of these adsorbents enable high capacity, low energy loss, and long-term cyclability, regardless of the presence or absence of water vapor or gaseous impurities. In embodiments where moisture is present in the input gas mixture, the adsorbent can capture moisture from the gas mixture in parallel with the CO2 capture process, providing a second beneficial function: facile moisture capture.

[0056] Robust covalent organic frameworks are useful as effective and efficient solid adsorbents in carbon capture processes such as direct air capture and post-combustion capture, as well as in other applications such as CO2 separation from natural gas. Prototype covalent organic frameworks are described in the following publications: (1) Zhang, B.; Wei, M.; Mao, H.; Pei, (2) Lyu, H.; Diercks, CS; Zhu, C.; Yaghi, OM Porous Crystalline Olefin-Linked Covalent Organic Frameworks. J. Am. Chem. Soc. 2019, 141, 6848-6852

[0057] Certain covalent organic structures Covalent organic frameworks are two-dimensional or three-dimensional structures that are extended by connecting organic structural units through bonds. The infinitely extended structures, which are a combination of variable structural units and bonds, are mathematically defined by their topology.

[0058] The organic structural units are defined by classification according to the number of extension points in Figure 1, but are not limited thereto. Within the defined range, each classified organic structural unit is connected to an organic fragment R m and m expansion points L m or L b It is composed of: R m The superscript m in the fragment R m has m extension points.

[0059] An extension point is defined as a covalent bond between two atoms adjacent to the extension point. In many variations, there is one such atom in the organic structural unit and one at the bond. In some other variations, the fragment (R 2 ) does not contain any atoms, and both atoms are atoms originating from the bond. In some other variations, the bond does not contain any atoms, and both atoms are atoms originating from the organic structural unit. The extension points are monodentate (one extension point is connected to one bond via one covalent bond), L m (shown as L) or bidentate (two extension points paired and connected to one bond via two covalent bonds, respectively) b (displayed as)

[0060] The present invention is based on the R m Also included are all possible fragments defined as repeated substitutions of the group.

[0061] In each example, fragment R m Any R present in the formula n is replaced by one of the fragments of Rn defined above. This process is called adding R mIn some variations, an empty R is present in the case of a closed ring, an empty R is present in the case of a direct bond, and 2 In some variations, the counter ion is omitted for clarity of notation, but is considered part of the covalent organic framework material. In some variations, a metal compound is present in the fragment, and metal ions, metal complexes (in which some ligands are coordinated only to the metal), and metal clusters are collectively designated M.

[0062] Some examples of suitable organic structural units are shown in FIG.

[0063] The coupling portion may be defined, for example, but not limited to, as defined in FIG.

[0064] A topology is a mathematical description of a structure that extends infinitely in one, two, or three dimensions as an open framework formed by covalent bonds and connections between organic building blocks. A complete list of definitions and descriptions of structural topologies is provided in the RCSR (Reticular Chemistry Structure Resource) database, where topologies are represented by network symbols. Figure 5 shows schematic representations of common COF topologies: sql, hcb, hxl, kgm, kgd, bex, tth, mtf, srs, dia, lon, bor, ctn, pts, tbo, pto, pcu, and dia-w. The COF topologies defined here are not limited to the scope shown in Figure 5.

[0065] In some variations, the COF has an interpenetrating structure in which multiple frameworks with the same connectivity are chained or intertwined. In some variations, the COF has a structure in which multiple frameworks are interpenetrating, but not all of the frameworks have the same connectivity.

[0066] In some variations, the COFs form crystals with topologies derived from simple networks, such as binary (or trinary) structures, where equivalent nodes of the topology are alternating with two (or more) linkers of the same connectivity. In some variations, the nodes of the topology are replaced by intertwined thread-like structures, where the structural units form closed ring structures (interlocking structures) or infinite thread-like structures (weaving structures).

[0067] In some variations, the COF contains only one type of structural unit or bond at equivalent nodes or edges of the topology. In other variations, the COF contains multiple types of structural units or bonds at equivalent nodes or edges of the topology of the same bulk material, but without any clear periodicity. Such COFs, although described as having the same topology, are referred to as multi-component COFs.

[0068] That is, a COF, as used herein, is a porous crystalline material composed within the above structural units, linked via the above covalent bonds, and extended with the above topological connectivity. Further criteria are described in the following sections, which define the scope of the COF claims used in this disclosure.

[0069] Characterization of COFs for carbon capture defined in this disclosure In all variations, to confirm the crystallinity of the defined compositions, i.e., to confirm the periodic structure, one or a combination of two or more techniques such as powder X-ray diffraction (PXRD), single crystal X-ray diffraction (SXRD), wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), neutron scattering, electron diffraction (ED), high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), high-resolution scanning electron microscopy (HRSEM), and variations thereof, such as grazing incidence wide-angle X-ray scattering (GIWAXS), are used. In all variations, Bragg diffraction and long-term imaging of the repeating units should be performed to confirm that they are consistent with the proposed structural model of the COF.

[0070] In all variations, one or a combination of two or more of the following techniques are used to confirm the chemical composition of the COF: Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, UV / Vis spectroscopy, photoluminescence spectroscopy, circular dichroism (CD), and solid-state nuclear magnetic resonance (NMR). Such spectroscopic signals are indicative of the presence of chemical elements, atoms, groups, or structural features. In some variations, when an isotopically enriched sample of the COF is used for the above characterization, the COF sample exhibits a corresponding isotope effect.

[0071] In all variations, one or a combination of two or more techniques, such as gas (N, O, Ar, CO, HO, and other solvent vapors) adsorption experiments and liquid-phase guest adsorption experiments, are used to confirm the persistent porosity and accessibility of the COF material. st ) is obtained by mathematically fitting the results of isothermal adsorption measurements of the gas of interest carried out at different temperatures.

[0072] In certain embodiments of CO2 capture COFs, the CO2 adsorption capacity at the temperature and CO2 partial pressure of use must be sufficient to achieve the desired capture capacity, and in variations with parallel moisture capture, the HO adsorption capacity at the temperature and humidity of use must be sufficient to achieve the desired capacity.

[0073] In certain embodiments of COFs for CO2 capture, thermal and chemical stability is required for long-term use as solid adsorbents, with or without moisture capture.

[0074] In all of these variations, one or a combination of two or more of the following techniques are used to examine the behavior of the COF over the temperature range of the conditions of use: thermogravimetric analysis (TGA), TGA-GC, TGA-RGA, and TGA-MS, as well as other in-situ measurements. To confirm the absence of chemical decomposition, compound release (e.g., guest release from pores), or loss of crystallinity or porosity before and after the process, one or a combination of two or more of the following techniques are used: NMR, FT-IR, GC, GC-MS, XRD, and adsorption experiments.

[0075] In all of these variations, the COFs are exposed to chemicals (e.g., CO2, O2, HO, SO2, SO3, NO, NO2, bases, acids, oxidizing agents, reducing agents) in gas, liquid, solution, or solid form under preparation, storage, transportation, and operating conditions for short and long periods to determine their chemical stability under a range of preparation and use conditions. One or a combination of techniques, such as NMR, FT-IR, GC, GC-MS, XRD, and adsorption experiments, is used to confirm the absence of chemical decomposition, compound release (e.g., guest release from pores), or loss of crystallinity or porosity before and after the process. In many variations, COFs for recovering CO2 and HO from HO-containing gas mixtures must be stable to CO2 and HO. In other variations, where HO is not present during the preparation, storage, transportation, and recovery processes, HO stability is not necessarily required.

[0076] In certain embodiments, dynamic recovery capacity is evaluated using a breakthrough system. The system must, at a minimum, simulate the gas composition (CO, HO, O, etc.), gas flow rate, dynamic pressure, and temperature at all stages of dynamic recovery with accuracy and response time appropriate for the scale of application. The system must also be equipped with a gas analysis system to track the gases involved in the process (CO, HO, O, etc.), operating with accuracy and response time appropriate for the scale of application. An example is shown in the scheme in Figure 6. In some variations using a COF as a membrane as the active adsorbent, a membrane exchanger is used in place of the adsorbent bed in the breakthrough system or is used for testing with a separate continuous flow simulation system.

[0077] Use of COF in carbon capture processes Post-Combustion Capture (PCC) In certain embodiments, COFs are used as solid adsorbents in the capture of CO from flue gas after natural gas or coal combustion. In many variations, the CO concentration in the flue gas input is between 4% and 16%, and the temperature of the flue gas input is less than 40°C.

[0078] In some variations, the COFs are used in pure form, intimately mixed with other materials, or supported on other materials in the form of a powder. In some variations, the COFs are used in pure form, intimately mixed with other materials, or supported on other materials in the form of a compact, such as an adsorbent bed, fluidized bed, adsorbent-coated heat exchanger, or membrane.

[0079] In this case, CO2 separation from the COF is achieved by heating, pressure change, gas scavenging, or scrubbing, or by a combination of some or all of these.

[0080] In this case, a COF having the following characteristics is used:

[0081] It has a high working capacity specifically for CO2 through a combination of chemical adsorption (if applicable) and physical adsorption depending on the adsorption and regeneration conditions.

[0082] For chemical adsorption, it has reactive functional groups such as -NH2 and -NHR.

[0083] Regarding physical adsorption, it has a large surface area and polar functional groups such as -OH and -F.

[0084] Breakthrough experiments, such as dynamic capacity measurements of COF, are carried out at corresponding humidity and temperature while supplying gas mixtures at 4% to 16%.

[0085] It has sufficient CO2 affinity to retain sufficient working capacity even in the presence of H2O.

[0086] Robustness: Chemical stability to H2O, O2, CO2, and impurities under adsorption and regeneration conditions, including chemical composition, crystallinity, adsorption capacity, and porosity retention. Thermal stability over the operating temperature range.

[0087] It has a permanently porous interconnected pore structure, allowing for efficient mass transfer.

[0088] In some variations that use heating for regeneration, the heat capacity is low.

[0089] In some variations where the COF is a molded body or supported by other materials, a strong bond provides mechanical stability.

[0090] In some variations, the COFs are used in pure form, intimately mixed with other materials, or supported on other materials in the form of membranes, such as powders or compacts used in membrane filtration, membrane exchangers, or cartridge exchangers.

[0091] It has a high selective affinity for CO2, which enhances its solubility in the membrane by both chemisorption (where applicable) and physisorption under separation conditions.

[0092] For chemisorption, reactive functional groups such as -NH2, -NHR, etc. are included as part of the COF.

[0093] For physical adsorption, polar functional groups such as -OH, -F, etc. are included as part of the COF.

[0094] Breakthrough experiments or continuous testing of membranes, such as dynamic capacity measurements of COF, are carried out at corresponding humidity and temperature while supplying gas mixtures at 4% to 16%.

[0095] It has sufficient CO2 affinity to retain sufficient working capacity even in the presence of H2O.

[0096] Robustness: Chemical stability to H2O, O2, CO2, and impurities under adsorption and regeneration conditions, including chemical composition, crystallinity, adsorption capacity, and porosity retention. Thermal stability over the operating temperature range.

[0097] In some variations where the COF is supported on other materials forming a membrane, mechanical stability is provided by a strong bond to the support.

[0098] In some variations that use heating for regeneration, the heat capacity is low.

[0099] Direct Air Capture (DAC) In certain embodiments, COFs are used as solid adsorbents in the direct capture of CO from ambient air. In many variations, the CO concentration in the supplied flue gas is atmospheric (approximately 400 ppm at 1 atmosphere; in some variations, if compressed air is used, CO concentrations >400 ppm), or slightly higher than atmospheric, either by compression or in a closed, non-ambient chamber, and the temperature of the supplied gas is ambient.

[0100] In some variations, the COFs are used in pure form, intimately mixed with other materials, or supported on other materials in the form of a powder. In some variations, the COFs are used in pure form, intimately mixed with other materials, or supported on other materials in the form of a compact, such as a packed bed, cartridge exchanger, or fluidized bed.

[0101] In this case, CO2 separation from the COF is achieved by heating, pressure change, gas scavenging, or scrubbing, or by a combination of some or all of these.

[0102] In this case, a COF having the following characteristics is used:

[0103] It has a high working capacity specifically for CO2 through chemical adsorption depending on the adsorption and regeneration conditions.

[0104] With regard to chemical adsorption, the weight or volume density of reactive functional groups such as -NH2, -NHR, etc. is high.

[0105] Regarding physical adsorption, the surface area is large and the material has polar functional groups such as -OH and -F to increase affinity for CO2.

[0106] Breakthrough experiments such as dynamic capacity measurements of COF are carried out at corresponding humidity and temperature while supplying a gas mixture at about 400 ppm.

[0107] It has sufficient CO2 affinity to retain sufficient working capacity even in the presence of H2O.

[0108] Robustness: Chemical stability against H2O, O2, CO2 and impurities under adsorption and regeneration conditions, including chemical composition, crystallinity, adsorption capacity, and porosity retention. Thermal stability over the operating temperature range.

[0109] It has a permanently porous interconnected pore structure, allowing for efficient mass transfer.

[0110] In some variations that use heating for regeneration, the heat capacity is low.

[0111] In some variations where the COF is a molded body or supported by other materials, a strong bond provides mechanical stability.

[0112] Parallel moisture collection In some variations, COF adsorbents exhibit high adsorption capacities for both CO2 and HO, along with PCC or DAC. Therefore, CO2 and HO can be separated in the same process or in separate processes under different conditions. Furthermore, when using such COF adsorbents, high-purity water can be produced as a by-product of CO2 capture from air or flue gases through a simple purification process. In this case, COFs with the following properties are used:

[0113] It has a high working capacity specifically for H2O through physical adsorption according to the adsorption and regeneration conditions.

[0114] Breakthrough experiments, such as dynamic volumetric measurements of COF, are performed at desired humidity and temperature while supplying the gas mixture.

[0115] It has sufficient H2O affinity to retain sufficient working capacity even in the presence of CO2.

[0116] Robustness: Chemical stability to H2O, O2, CO2, and impurities under adsorption and regeneration conditions, including chemical composition, crystallinity, adsorption capacity, and porosity retention. Thermal stability over the operating temperature range.

[0117] It has a permanently porous interconnected pore structure, allowing for efficient mass transfer.

[0118] In some variations that use heating for regeneration, the heat capacity is low.

[0119] In some variations where the COF is a molded body or supported by other materials, a strong bond provides mechanical stability. [Example]

[0120] COF-366-F-Co COF-366-F-Co is presented as an example of a COF material to explain the definition of COF in this disclosure and to demonstrate the CO2 capture capability of COF materials. COFs are composed of the tetratopic structural unit 5,10,15,20-tetraphenylporphinatocobalt(II) and the ditopic unit 1,2,4,5-tetrafluorobenzene, linked by imine (-CH=N-) bonds. COF-366-F-Co is an extended structure with a two-dimensional sql topology. The crystallinity of this structure was confirmed by PXRD of COF-366-F-Co and GIWAXS of a COF-366-F-Co thin film on a highly oriented pyrolytic graphite (HOPG) substrate (Figure 8).

[0121] The persistent porosity of COF-366-F-Co was confirmed by N2 isothermal experiments at 77 K, which showed a BET surface area of ​​1901 m 2 The CO2 adsorption isotherms were measured at 273 K, 283 K, and 298 K (Fig. 9), and the results showed that Q st The adsorption capacity was found to be 24.2 kJ / mol. Physisorption behavior was observed for CO2 adsorption on this material at 298 K. The adsorption capacity was approximately 5 cm3 at 15% CO2 and 298 K. 3 / g, which was approximately 400 ppm, an extremely small amount at 298 K. This material is not suitable for DAC unless other methods (electrochemical reaction) are used, and its practical use in PCC is somewhat limited.

[0122] COF-316, COF-316-CONH 2 and COF-316-C(NOH)NH 2 We present COF-316, COF-316-CONH2, and COF-316-C(NOH)NH2 as examples of post-synthetic modification approaches to obtain various COFs with different functional groups, and compare their stability and CO2 capture capabilities with those of other gases. COF-316 (also known as JUC-505) is a structure consisting of the tritopic structural unit triphenylene (six bidentate extension points) and the ditopic structural unit 1,4-dicyanobenzene (four bidentate linkage points) connected by dioxin bonds. COF-316-CONH2 is synthesized by treating COF-316 with NaOH, and COF-316-C(NOH)NH2 is synthesized by treating COF-316 with NH2OH. The crystallinity and chemical identity of these COFs have been confirmed by PXRD and solid-state NMR (Figure 10).

[0123] The chemical stability of COF-316 in the presence of inorganic acids and inorganic bases was investigated by contacting COF-316 with 6M aqueous HCl and 6M aqueous NaOH solutions, respectively. PXRD, FT-IR, and N2 isotherms at 77 K were compared before and after treatment (Figure 11). The results confirmed that COF-316 largely maintained its crystallinity and porosity after contact with 6M HCl and 6M NaOH solutions. FT-IR analysis of the product after 6M NaOH treatment indicated that COF-316 was chemically unstable. This suggests that its chemical identity changed, as occurred during the synthesis of COF-316-CONH2.

[0124] The CO2, CH4, and N2 isotherms were measured for COF-316 (JUC-505) at 273 K over the pressure range of 0 to 1 bar (Figure 12). COF-316 (JUC-505) exhibited physisorption behavior for CO2 at 273 K, with significantly higher CO2 adsorption amounts than CH4 and N2 at the same (and complementary) partial pressures at CO2 concentrations higher than 0.05 bar. These results demonstrate that COF-316 (JUC-505) is capable of separating CO2 from dry binary mixtures of CO2 / N2 and CO2 / CH4 at 273 K. However, these results do not suggest practical application for PCC or DAC above 298 K or under humid conditions.

[0125] COF-701 COF-701 is presented as an example of a structure with chemically stable bonds and moisture-trapping properties at ambient temperatures. COF-701 is a structure consisting of the tritopic structural unit 1,3,5-triazine and the ditopic structural unit biphenyl linked by an unsubstituted olefin (-CH=CH-). WAXS and FT-IR measurements before and after contact with aqueous or organic solutions containing Brønsted acids, Brønsted bases, organolithium reagents, or Lewis acids demonstrated that COF-701 retained its crystallinity and chemical composition against each reagent (Figure 14).

[0126] The water vapor isotherm of COF-701 was measured at 298 K (Fig. 15). The results showed that COF-701 adsorbs water at relative humidity (RH) higher than 50%, depending on the RH value. At 70% RH, COF-701 adsorbs water at 400 cm 3 / g (29.4 wt%) of water vapor, and at 100% RH (present in some coal and natural gas exhaust gases), the 3 / g (41.2 wt%) of water vapor was adsorbed. This result suggests that this material is promising as a material for recovering HO from highly humid gas mixtures such as humid air or humid flue gas at 298 K.

[0127] References Diercks, C. S.; Lin, S.; Kornienko, N.; Kapustin, E. A.; Nichols, E. M.; Zhu, C.; Zhao, Y.; Chang, C. J.; Yaghi, O. M. Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction. J. Am. Chem. Soc. 2018, 140, 1116-1122. Zhang, B.; Wei, M.; Mao, H.; Pei, X.; Alshmimri, S. A.; Reimer, J. A.; Yaghi, O. M. Crystalline Dioxin-Linked Covalent Organic Frameworks from Irreversible Reactions. J. Am. Chem. Soc. 2018, 140, 12715-12719. Guan, X.; Li, H.; Ma, Y.; Xue, M.; Fang, Q.; Yan, Y.; Valtchev, V.; Qiu, S. Chemically Stable Polyarylether-Based Covalent Organic Frameworks. Nat. Chem. 2019, 11, 587-594. Lyu, H.; Diercks, C. S.; Zhu, C.; Yaghi, O. M. Porous Crystalline Olefin-Linked Covalent Organic Frameworks. J. Am. Chem. Soc. 2019, 141, 6848-6852.

[0128] Aspect 3: Improving moisture collection function using charged covalent organic frameworks Covalent organic frameworks (COFs) are crystalline porous materials connected by strong covalent bonds. COFs can be used as moisture adsorbents for moisture capture. Because COFs have large pore diameters, their water adsorption weight is theoretically expected to be large. However, the hydrophobic environment inside the pores of COFs hinders the formation of water clusters within the pores at low to medium relative humidity, which is a fundamental requirement for capturing atmospheric moisture.

[0129] Description of Specific Embodiments The subject COFs are composed entirely of light atoms and exhibit the highest water adsorption capacity reported to date at low RH. Unlike MOF adsorbents currently used to capture atmospheric moisture, COFs do not use heavy metals during synthesis. This avoids the additional costs associated with heavy metals as well as the potential toxicity associated with some metal cations.

[0130] In an attempt to increase the overall hydrophilicity of the pores, polar functional groups have been introduced into the COF framework. However, the addition of polar functional groups has not yet achieved sufficient hydrophilicity in COFs with large pore diameters. COFs with large pore diameters, which are expected to have a high water adsorption capacity, are of particular interest. In this invention, by using charged structures, we have succeeded in significantly increasing the interaction between water and the charged structures through strong and extensive polarization in the pores, and as a result, improving the adsorption performance.

[0131] Previous studies have reported materials incorporating salts into porous neutral matrix materials (e.g., silica gel). However, these materials have problems with salt leakage from the matrix and salt aggregation within the pores. In the present invention, counterions are immobilized in the framework through Coulomb interactions, thereby avoiding salt deliquescence and solution carryover. In the disclosed COF material, the average distance between charges is significantly larger than that of conventional desiccants in which ions are densely packed. This large distance between cations provides more space for water to form clusters, preventing ions from crystallizing into hydrated salts and effectively increasing the rate of water adsorption and desorption.

[0132] Description of Preferred Charged Structures Various strategies for generating such charged structures are described below. The introduction of charged groups into COFs can be achieved during synthesis or by post-synthetic modification. Generally, the charged backbone and counterions impart strong hydrogen bonding and ion-dipole interactions to water molecules, enhancing the hydrophilicity of COFs and improving their water adsorption capacity. The inherent hydrophilicity and generally large pore size make COFs suitable for water adsorption at low to mid-RH, while also providing excellent performance in terms of water adsorption rate.

[0133] An example of introducing a charged group during the synthesis of a COF is shown below. [ka]

[0134] An example of post-synthetic modification of COFs to introduce charged groups is shown below. [ka]

[0135] [ka]

[0136] The subject covalent organic frameworks include charged functional groups, such as those shown in Table 1, attached to the backbone. [ka]

[0137] The subject covalent organic frameworks include counterions as shown in Table 2.

[0138] Examples of inorganic counterions are shown below. [ka]

[0139] Examples of organic counterions are shown below. [ka]

[0140] The subject covalent organic frameworks include organic bonds as shown in Table 3. [ka]

[0141] The subject covalent organic frameworks include organic linkers as shown in Table 4. [ka] TIFF0007823890000012.tif212167TIFF0007823890000013.tif217164TIFF0007823890000014.tif206165TIFF0007823890000015.tif254163

Claims

1. A composition comprising a porous covalent organic framework (COF), the COF having a two-dimensional or three-dimensional (2D or 3D) topology (a 2D topology of hcb, sql, kgm, fxt, kgd, or bex, or a 3D topology of dia, ctn, bor, pts, lon, srs, ffc, or rra) for capturing atmospheric moisture, wherein the crystalline structure of the COF contains bonds selected from imine bonds, amide bonds, imide bonds, hydrazone bonds, azine bonds, imidazole bonds, benzoxazole bonds, β-ketoenamine bonds, and olefin bonds, and the bonds are formed by a combination of at least two different linkers selected from a ditopic linker, a tritopic linker, a tetratopic linker, a hexatopic linker, and an octatopic linker, and the ditopic linker has a structure selected from the group consisting of: Each R is H, F, Cl, Br, I, OH, -OCH ３ , -C(O)OCH ３ , -C(O)H, -C(O)CH ３ , -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -(CH ２ ) ２ CH ３ , -CH(CH ３ )CH ２ CH ３ , -CH ２ CH(CH ３ ) ２ , -C(CH ３ ) ３ , -CHCH ２ , -CCH, -CN, -CH ２ N = C(CH ３ ) ２ , -CH ２ N = CH(CH ３ ), -CH ２ NH C(O)CH ３ , -Ph, -OPh, -CH ２ NH CH ３ , -CH ２ NH CH ２ CH ３ , -CH ２ NH CH(CH ３ ) ２ , -CH ２ NH CH(CH ３ )CH ２ CH ３ , -CH ２ NH C(CH ３ ) ３ , -CH ２ [[ID=P86]]N = CH(Ph), -CH ２ N(CH ２ CH ３ ) ２ , -CH ２ N(CH ３ ) ２ , -CH ２ NH -Ph, -CH ２ NH CH ２ -Ph, -CH ２ NH(CH ２ ) ２ -OH、-C(O)O － 、-C(O)NHO － 、-C(NH)NHO － 、-O － 、-S － 、O － 、-OS(O) ２ O － 、-OS(O)O － 、-S(O) ２ O － 、-S(O)O － 、-OP(O)O － O － 、-OPO － O － 、-P(O)O － O － 、-OC(O － )=CHC(O)CH ３ ,NH ３ ＋ , are independently selected from

2. The composition of claim 1 , wherein the combination is a combination of a tetratopic linker and a tritopic linker.

3. The composition of claim 1 or 2, wherein the bond is an imine (-CH=N-) bond.

4. The composition comprises a tetratopic linker, 1,1,2,2-tetrakis(4-aminophenyl)ethene [ETTA, C 26 H 16 (NH 2 ) 4 ] and the tritopic linker 1,3,5-triformylbenzene [TFB, C 6 H 3 (CHO) 3 ] and exhibits the mtf topology. 3 (TFB) 4 ] イミン 2. The composition of claim 1, comprising a COF referred to as

5. 5. A device comprising the composition of any one of claims 1 to 4, wherein the device is an atmospheric moisture trap, a heat pump, a dehumidifier, an adsorption refrigerator, or a solar cooling system.

6. A method for producing the composition of any one of claims 1 to 4, comprising the step of condensing different linkers to form a crystalline structure.

7. A method of using a composition according to any one of claims 1 to 4, comprising contacting the composition with air under conditions in which the composition adsorbs moisture from the air.

8. The method described in claim 7, wherein the relative humidity in the air is 20 to 40%.

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