Polymer functionalized mesh material for carbon dioxide capture

Abstract

Compositions comprising polymer functionalized network materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are configured for carbon dioxide capture.

Description

Polymer-functionalized network materials for carbon dioxide capture

[0001] Cross-references to related applications

[0002] Pursuant to 35 USC § 119(e), this application claims priority to the filing dates of U.S. Provisional Patent Application Serial No. 63 / 587,185, filed October 2, 2023, and U.S. Provisional Patent Application Serial No. 63 / 678,968, filed August 2, 2024, the disclosure of each of which is incorporated herein by reference in its entirety. Background Technology

[0003] The unprecedented rise in atmospheric carbon dioxide (CO2) concentrations, primarily caused by human activities such as fossil fuel burning and deforestation, has become a pressing global issue due to its key role in driving climate change. This unprecedented accumulation of CO2 in the atmosphere exacerbates the greenhouse effect, leading to rising temperatures, altered precipitation patterns, and other negative environmental impacts.

[0004] In response, a large number of materials have been investigated. Polymers such as polyethyleneimine and polylysine have shown great promise in addressing the CO2 problem. However, meeting all the demanding application requirements, including high capacity, low regeneration energy, fast kinetics, and long cycle life, remains challenging. The applicability of current adsorbents (i.e., porous carbon, zeolites, hydroxides, amine solutions, and grafted amines) is limited by their low CO2 capacity, high energy consumption, and low cycle stability.

[0005] In particular, porous carbon and zeolites exhibit low carbon dioxide capacity under low pressure or dilution conditions due to their physisorption mechanisms, limiting their applicability in direct air capture and post-combustion capture from natural gas flue gas. For hydroxides, the binding between carbon dioxide and the adsorbent is too strong, requiring very high energy to regenerate the material. Amine solutions, with suitable alkalinity, exhibit high carbon dioxide adsorption capacity but suffer from amine loss, corrosion, and amine oxidation during application. Compared to amine solutions, physically grafted amines in cured resins and silica increase adsorption capacity and lower desorption temperatures, but stability and amine loss issues persist under cycling. Cyclic stability can be improved by covalently linking amines to resins or silica supports; however, most resins and silica contain only hydroxyl functional groups within their pores, limiting the possibility of post-modification reactions. Furthermore, the hydrophilic backbone of these materials adsorbs water under humid conditions, thus increasing regeneration temperatures and requiring more energy for regeneration.

[0006] Relevant literature includes: see this article. Summary of the Invention

[0007] The present invention provides methods, systems, and compositions comprising a network material including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), which can be used as a carbon dioxide adsorbent due to their highly stable pores that can be functionalized with desired functional groups.

[0008] This invention provides an innovative post-synthetic modification to functionalize network materials with polymers, which enables the adsorbent to have a strong chemisorption effect on carbon dioxide and solves the problem of polymer volatility, thereby increasing the stability of the adsorbent.

[0009] Network materials (including metal-organic frameworks and covalent organic frameworks) consist of rigid molecular building blocks linked together by strong bonds to create two-dimensional and three-dimensional extended structures. They can be used as carbon dioxide adsorbents due to their highly stable and ordered pores, which can be functionalized with desired functional groups. In this disclosure, the synthesis of polymer-functionalized network materials is described, formed through in-situ polymerization or chemical reaction between the functional groups of the polymer and functional groups inside or on the surface of the network material. The polymer-functionalized network materials exhibit high carbon dioxide adsorption capacity and cycling stability sufficient for capturing and separating carbon dioxide from air and flue gas.

[0010] In one aspect, the present invention provides a composition comprising a polymerically functionalized mesh material (e.g., COF or MOF) configured for carbon dioxide capture. In some embodiments, the composition is a COF as described herein. In some embodiments, the composition is an MOF as described herein.

[0011] In one aspect, the present invention provides polymer-functionalized mesh materials configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas.

[0012] In one aspect, the present invention provides a composition comprising a polymer-functionalized network material formed by in-situ polymerization or chemical reaction between functional groups of a polymer and functional groups inside or on the surface of the network material, wherein the polymer-functionalized network material provides sufficient carbon dioxide adsorption capacity and cycle stability for capturing and separating carbon dioxide from air or flue gas.

[0013] In one aspect, the present invention provides compositions thereof, wherein functionalization of the network material with a polymer is achieved (i) by in-situ polymerization within or on the surface of the network material; or (ii) by a chemical reaction between functional groups of the polymer and functional groups within or on the surface of the network material.

[0014] In one aspect, the present invention provides compositions described herein, wherein (i) in-situ polymerization is achieved by mixing a metal-organic framework or a covalent organic framework with a polymer monomer and subsequently carrying out a polymerization reaction.

[0015] In one aspect, the present invention provides compositions herein, wherein (ii) a chemical reaction occurs between functional groups of the polymer and functional groups inside or on the surface of the network material, wherein the network material can be functionalized by chemically reacting with the polymer to form covalent bonds.

[0016] In one aspect, the present invention provides a method for using the subject composition for carbon dioxide capture and / or separation, particularly for capturing and / or separating carbon dioxide from air or flue gas.

[0017] This invention covers all combinations of the specific embodiments listed herein, as each combination has been described in detail. Attached Figure Description

[0018] Figure 1: CO2 adsorption analysis of COF-999 (formerly known as COF-153-PEI) at 298 K.

[0019] Figure 2: Breakthrough curves of COF-999 (formerly known as COF-153-PEI) under the following conditions: 400 ppm CO2, 50% relative humidity, in N2, flow rate 60 mL / min, temperature 298 K. The shaded area is used to derive the CO2 adsorption capacity by numerical integration.

[0020] Figure 3: Design strategy and synthesis of COF-999, where each W is independently selected from -NH2, -NH(CH2)2NH2, and poly(ethyleneimine). The condensation reaction between TCPB and BPDA-N3 generates COF-999-N3, which is subsequently reduced by the azide to form COF-999-NH2. The reactive amine initiator mounted on the main chain allows for the covalent mounting of polyamines via ring-opening polymerization with aziridine, thus yielding COF-999.

[0021] Figures 4A to 4D: Characterization of the COF-999 series. Figure 4A: Experimental PXRD pattern (red), Pawley refinement pattern (black), difference pattern (pink), and Bragg position (green) of COF-999-N3. Figure 4B: N2 adsorption isotherm of COF-999-N3 measured at 77 K. Figure 4C: COF-999- 15 N3 (blue) and COF-999- 15 CP / MAS of NH2 (red) 15 NssNMR, and 15Quantitative analysis of N-labeled COF-999 (black) using multiCP / MAS 15 Comparison of N ss NMR. 15 Nitrogen atoms labeled with N are indicated by an asterisk. Signals from unlabeled nitrogen (aziridine and nitriles) are negligible due to their low natural abundance. Figure 4D: CP / MAS of COF-999-N3 (blue). 13 Quantitative multiCP / MAS analysis of C ss NMR with COF-999-NH2 (red) and COF-999 (black) 13 Comparison of C ss NMR.

[0022] Figure 5: SEM images of COF-999-N3, COF-999-NH2, and COF-999. Textured spherical morphology was observed and remained unchanged during post-synthesis modification.

[0023] Figure 6: N2 adsorption isotherm of COF-999-N3 measured at 77 K and corresponding calculated pore size distribution. The hysteresis can be attributed to the flexibility of the side chains within the pores. P, nitrogen pressure; P0 = 1 atm; STP, standard temperature and pressure.

[0024] Figure 7: Brunauer-Emmett-Teller plot (black dots) and linear fit (black line) of the N2 adsorption isotherm of COF-999-N3 measured at 77 K. P, nitrogen pressure; P0 = 1 atm; Q, amount of gas adsorbed at pressure P. STP, standard temperature and pressure.

[0025] Figure 8: N2 adsorption isotherm of COF-999-NH2 measured at 77 K and corresponding calculated pore size distribution. The hysteresis can be attributed to the flexibility of the side chains within the pores. P, nitrogen pressure; P0 = 1 atm; STP, standard temperature and pressure.

[0026] Figure 9: Brunauer-Emmett-Teller plot (black dots) and linear fit (black line) of the N2 adsorption isotherm of COF-999-NH2 measured at 77 K. P, nitrogen pressure; P0 = 1 atm; Q, amount of gas adsorbed at pressure P. STP, standard temperature and pressure.

[0027] Figure 10: N2 adsorption isotherm of COF-999 measured at 77 K. P, nitrogen pressure; P0 = 1 atm; STP, standard temperature and pressure.

[0028] Figure 11: Single-component CO2 adsorption isotherms of COF-999 measured at 15℃ (blue), 25℃ (black), and 35℃ (red).

[0029] Figure 12: Estimated isothermal values ​​of CO2 adsorption by COF-999 as a function of the amount of adsorption, determined using CO2 adsorption isotherms from 15 °C to 35 °C according to the Clausius-Clapeyron equation. The CO2 isotherm at 35 °C is at 1 mmol g −1 The inflection point near the threshold, transitioning from a sharp increase to a moderate slope, indicates a shift from chemisorption to physisorption. However, the isotherms at 15°C and 25°C maintain chemisorption at this point, making the Clausius-Clapeyron equation ineffective for adsorption amounts above 1 mmol g. −1 Not applicable at this time.

[0030] Figure 13: Single-component water vapor adsorption isotherms of COF-999 measured at 15℃ (blue), 25℃ (black), and 35℃ (red). P, water vapor pressure; 饱和 The saturated water vapor pressure at the analytical temperature.

[0031] Figure 14: Estimated isothermal value of water vapor adsorption of COF-999 as a function of adsorption amount, which was determined by the Clausius-Clapeyron equation using water vapor adsorption isotherms from 15°C to 35°C.

[0032] Figure 15: Stacked FT-IR spectra of TCPB (purple), BPDA-N3 (green), COF-999-N3 (blue), COF-999-NH2 (red), and COF-999 (black). Transmittance values ​​along the Y-axis were normalized for comparison. As shown in the figure, the transmittance at 2089 cm⁻¹ in COF-999-NH2... –1 Azide vibration (ν azide) N=N The disappearance of the stretching indicates that the Staudinger reduction is complete. 2819 cm⁻¹ in COF-999 –1 C−H vibration occurs at (ethylene ν) C−H (Stretch) indicates successful loading of polyamines.

[0033] Figure 16: PXRD spectra of COF-999-N3 (blue), COF-999-NH2 (red), and COF-999 (black). Intensity values ​​along the Y-axis were normalized for comparison. Disordered polyamines within the pores lead to a decrease in the diffraction peaks of COF-999.

[0034] Figure 17: Thermogravimetric analysis (TGA) curves of COF-999-N3 (blue), COF-999-NH2 (red), and COF-999 (black). Measurements were performed under a continuous N2 flow.

[0035] Figure 18: Quantitative analysis of COF-999 using multiCP / MAS13 Linear deconvolution of C ss NMR. The peak at 157.7 ppm is attributable to C-#15, and the region from 80 to 13 ppm is attributable to carbons on the side chains (C-#1 to C-#14). The ratio of the integrated areas of these two regions is 1.00:12.10. Line color codes: experimental data, brown; simulated peak profile, blue; sum of simulated signals, purple; simulated-experimental difference, red.

[0036] Figure 19: Quantitative analysis of COF-999 using multiCP / MAS 15 Linear deconvolution of N ss NMR. The peak at 34.4 ppm can be attributed to an amine reacting with aziridine, and the peak at 23.4 ppm can be attributed to an unreacted amine. Signals from unlabeled nitrogen (aziridine and nitriles) are negligible due to their low natural abundance. The ratio of the integrated areas of these two peaks is 0.659:0.341. Line color codes: experimental data, brown; simulated peak profile, blue; sum of simulated signals, purple; simulated-experimental difference, red.

[0037] Figures 20A to 20I: Thermodynamic and kinetic gas adsorption studies of COF-999. Figure 20A: Comparison of adsorption isotherms for single-component CO2 (red), N2 (black), O2 (yellow), and Ar (purple) measured at 25 °C. Figure 20B: Enlarged view of the CO2 adsorption isotherm from Figure 20A, highlighting the adsorption amount at ambient CO2 pressure. Figure 20C: Single-component H2O adsorption isotherm measured at 25 °C. Figure 20D: CO2 and H2O breakthrough curves in humid simulated air (400 ppm CO2 and 50% RH) at 25 °C. Figure 20E: CO2 adsorption at 400 ppm CO2 and 0%, 25%, 50%, and 75% RH. Figure 20F: CO2 adsorption kinetics in humid simulated air (400 ppm CO2 and 50% RH). Figure 20G: Comparison of CO2 desorption kinetics at 60 °C, 80 °C, and 100 °C. Figure 20H: Comparison of CO2 desorption rates at 60℃, 80℃, and 100℃. Figure 20I: CO2 adsorption capacity derived from temperature swing cycle breakthrough measurements in humid simulated air (400ppm CO2 and 50% RH), yielding an average working capacity of 2.03 mmol g. −1 cycle −1 (dotted line).

[0038] Figure 21: Schematic diagram of the permeation apparatus used for both adsorption and desorption experiments. Adsorption / desorption mode and bypass mode are controlled by a 6-way valve.

[0039] Figure 22: Dynamic breakthrough measurements of COF-999 at 400 ppm CO2, 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH, and 25°C. Breakthrough times were normalized relative to 100 mg COF-999 samples for comparison. CO2 adsorption capacities were calculated to be 0.95, 1.76, 2.02, and 2.06 mmol g, respectively. −1 .

[0040] Figure 23: Dynamic breakthrough measurements of COF-999 at 4% CO2, 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH, and 25°C. A 280 mg COF-999 sample and a 0.96 cm⁻¹ s⁻¹ were used in the measurements. −1 Gas velocity. The calculated CO2 adsorption capacities were 2.09, 2.39, 3.03, and 3.17 mmol g, respectively. −1 .

[0041] Figure 24: Dynamic breakthrough measurements of COF-999 at 15% CO2, 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH, and 25°C. A 260 mg COF-999 sample and a 0.96 cm⁻¹ s⁻¹ were used in the measurements. −1 Gas velocity. The calculated CO2 adsorption capacities were 2.34, 2.48, 2.63, and 3.24 mmol g, respectively. −1 .

[0042] Figure 25: Adsorption kinetics of COF-999 measured at 25 °C using simulated air (400 ppm CO2 and 50% RH balanced in a 4 / 1 N2 / O2 environment). A 5.0 mg COF-999 sample and a 4.8 cm⁻¹ s⁻¹ were used in the measurements. −1 Gas velocity. Then the specific CO2 adsorption capacity of the sample is obtained, which is the difference between the apparent adsorption capacity per unit mass of sample and the background adsorption capacity.

[0043] Figure 26: Desorption kinetics of COF-999 under N2 flow at 60℃ (blue), 80℃ (yellow), and 100℃ (red). A 5.0 mg COF-999 sample and a 4.8 cm⁻¹ s⁻¹ were used in the measurements. −1 Gas velocity. Prior to measurement, the sample was saturated in simulated air (400 ppm CO2 and 50% RH balanced in a 4 / 1 N2 / O2 environment). The background curve was measured without a sample in the column to eliminate the influence of residual CO2 in the gas pipeline. The amount of desorbed CO2 was calculated by integrating the downstream CO2 concentration over time.

[0044] Figure 27: A single temperature swing CO2 breakthrough cycle of COF-999. Simulated air (400 ppm CO2 and 50% RH balanced in a 4 / 1 N2 / O2 environment) was used during adsorption. In the graph of downstream CO2 concentration, the amount of CO2 adsorbed can be obtained by numerical integration of the shaded area. The detection range of the CO2 sensor is 0.6 to 984.9 ppm.

[0045] Figure 28: Ten temperature swing CO2 breakthrough cycles of COF-999. Simulated air (400 ppm CO2 and 50% RH balanced in 4 / 1 N2 / O2) was used during the adsorption process.

[0046] Figures 29A to 29D: Capture of carbon dioxide from outdoor air. Figure 29A: CO2 capture productivity (blue), corresponding outdoor ambient CO2 concentration (red), and relative humidity (black) after each adsorption cycle. All data were measured during a 20-day continuous operation using outdoor air. Figure 29B: CO2 productivity of selected cycles with corresponding outdoor ambient CO2 concentrations at an ambient RH of 37 ± 1%. The average productivity of selected cycles is shown as a dashed line. Figure 29C: Comparison of single-component CO2 adsorption isotherms (25°C) of newly synthesized COF-999 with those of a sample after 100 outdoor air cycles. Figure 29D: Comparison of CO2 breakthrough curves of newly synthesized COF-999 with those of a sample after 100 outdoor air cycles using simulated air (400 ppm CO2 and 50% RH at 25°C).

[0047] Figure 30: A temperature-oscillating CO2 breakthrough cycle of COF-999 using outdoor air as the CO2 source. In the downstream CO2 concentration graph, the CO2 adsorption amount can be obtained by numerical integration of the shaded area. The CO2 sensor's detection range is 0.6 to 984.9 ppm.

[0048] Figure 31: One hundred temperature swing CO2 penetration cycles of COF-999 using outdoor air as the CO2 source in a 20-day experiment.

[0049] Figure 32: COF-999 under dry (black) and humid (blue) conditions. 13 CO2 Dosing Experiment 13 Solid-state NMR spectroscopy. Illustrative schemes of the main adsorption products are provided to highlight signal distribution and chemical transformations of the substances. 13 C isotope-labeled sites are marked with "*". The inset shows the results of linear deconvolution of the overlapping regions. Color codes for the inserted plots: experimental data, brown; simulated peak profile, blue; sum of simulated signals, purple; simulated-experimental difference, red.

[0050] Figures 33A to 33C: CO2 adsorption structure in COF-999. Figure 33A: Formation of carbamic acid under dry conditions. Figure 33B: Formation of carbamic acid under humid conditions. Figure 33C: Formation of bicarbonate under humid conditions. All numbers represent atomic distances (in pm). C, gray; N, blue; O, red; H, white. Additional structures are shown in Figures 34 to 36.

[0051] Figures 34A to 34C: Magnified views of the optimized structures of carbamic acid / carbamate in the absence of water molecules formed during CO2 adsorption in COF-999. The corresponding reaction energy ΔE (kJ·mol⁻¹) –1 See Table 5. Figure 34A: CA1. Figure 34B: CA2. Figure 34C: CA3.

[0052] Figures 35A to 35C: Magnified views of the optimized structures of carbamic acid / carbamate in the absence of water molecules formed during CO2 adsorption in COF-999. The corresponding reaction energy ΔE (kJ·mol⁻¹) –1 See Table 6. Figure 35A: CW1. Figure 35B: CW2. Figure 35C: CW3.

[0053] Figures 36A to 36C: Magnified views of the optimized structures of carbamic acid / carbamate in the absence of water molecules formed during CO2 adsorption in COF-999. The corresponding reaction energy ΔE (kJ·mol⁻¹) –1 See Table 7. Figure 36A: BC1. Figure 36B: BC2. Figure 36C: BC3.

[0054] Figure 37: 1-Hexanol, 6-azido-, 1-(4-methylbenzenesulfonate) in CDCl3 1 1H NMR (600 MHz) spectrum.

[0055] Figure 38: BPDA-N3 in CDCl3 1 1H NMR (600 MHz) spectrum.

[0056] Figure 39: BPDA-N3 in CDCl3 13 C NMR (151 MHz) spectrum.

[0057] Figure 40: BPDA- 15 NN2 in CDCl3 1 1H NMR (600 MHz) spectrum. BPDA- 15 NN2 is α- 15 N (R‒ 15 N=N=N) and γ-15 N (R‒N=N= 15 A mixture of N-labeled compounds.

[0058] Figure 41: BPDA- 15 NN2 in CDCl3 13 C10 NMR (151 MHz) spectrum. BPDA- 15 NN2 is α- 15 N (R‒ 15 N=N=N) and γ- 15 N (R‒N=N= 15 A mixture of N-labeled compounds. Chemical shifts in the range of 51.6 to 51.3 ppm were amplified.

[0059] Figure 42: BPDA- 15 NN2 in CDCl3 15 N NMR (61 MHz) spectrum. BPDA- 15 NN2 is α- 15 N (R‒ 15 N=N=N) and γ- 15 N (R‒N=N= 15 A mixture of N-labeled compounds.

[0060] Figure 43: Aziridine in CDCl3 1 1H NMR (600 MHz) spectrum.

[0061] Figure 44: Aziridine in CDCl3 13 C NMR (151 MHz) spectrum. Detailed Implementation

[0062] Unless otherwise prohibited or stated, in these descriptions and throughout the specification, the term "a (a and an)" means one or more, and the term "or" means and / or. It should be understood that the examples and embodiments described herein are for illustrative purposes only, and various modifications or alterations thereto are to be suggested to those skilled in the art and will be included within the spirit and limits of this application and the scope of the appended claims. All publications, patents, and patent applications cited herein (including those cited herein) are incorporated herein by reference in their entirety for all purposes.

[0063] symbol Whether used as a bond or displayed perpendicular to the bond, the symbol indicates the point where the displayed portion connects to the rest of the composition. In some cases (such as the formulas described herein), the symbol indicates the point where a core connects to another repeating core.

[0064] This invention provides a polymer-functionalized network material configured as a carbon dioxide adsorbent. The various functional groups of the network material provide alternative chemical reactions for post-synthetic modification using polymers. Furthermore, thanks to the tunable pore environment and pore size, this material can be designed and configured for specific applications under different pressures and relative humidity conditions.

[0065] The polymer-functionalized network materials synthesized as disclosed herein can be used as adsorbents for CO2 captured from ambient air or after combustion from natural gas or flue gas. In the embodiments, the CO2 concentration in the feed gas is from 400 ppm to 16%, and the temperature of the feed gas is from 293 K to 373 K.

[0066] I. MOF

[0067] In the embodiments, the network materials include metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). Metal-organic frameworks are a class of compounds composed of secondary building blocks and organic linkers. The secondary building blocks are linked together by organic linkers to form two-dimensional or three-dimensional structures.

[0068] In embodiments, the metal-organic framework of the present invention comprises secondary building units composed of the following metal ions: Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ ,Sc 3+ Y 3+ La 3+ Ce 3+ Ce 4+ Ti 4+ Zr 4+ Hf 4+ V 3+ V 4+ V 5+ 、Nb 3+ 、Nb 4+ 、Nb 5+ Cr 3 + Cr 6+ Mo 3+ Mo 6+ Mn 2+ Mn 3+ Mn 6+ Fe 2+ Fe 3+ Co 2+ Co 3+ Ni 2+ Ni 3+ Cu + Cu 2+ Zn2+ Cd 2+ Al 3+ Ga 3 + In 3+ 、Ge 4+ Sn 4+ Pb 2+ Pb 4+ .

[0069] In embodiments, the metal-organic framework of the present invention comprises the following organic linkers:

[0070]

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[0075] X can be freely selected from the following groups.

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[0079]

[0080] .

[0081] II. COF

[0082] Covalent organic frameworks are a class of compounds synthesized through reactions between organic linkers to produce two-dimensional or three-dimensional structures. In the embodiments, the covalent organic frameworks disclosed in this invention comprise the following organic linkers:

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[0100]

[0101]

[0102]

[0103]

[0104] X can be freely selected from the following groups.

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[0109]

[0110] In the embodiments, the functionalization of the network material with a polymer can be achieved (i) through in-situ polymerization within or on the surface of the network material; or (ii) through a chemical reaction between the functional groups of the polymer and the functional groups within or on the surface of the network material.

[0111] Alternative strategies and examples for synthesizing polymer-functionalized network materials are described below.

[0112] In the embodiments, the in-situ polymerization method is achieved by mixing a metal-organic framework or a covalent organic framework with a polymer monomer and then carrying out a polymerization reaction.

[0113] In the embodiments, the monomer (M) of the polymer disclosed in this invention includes:

[0114]

[0115] Network materials can be functionalized by chemical reactions between the functional groups of polymers and the functional groups inside or on the surface of the network material to form covalent bonds.

[0116] In embodiments, the polymer of the present invention comprises:

[0117]

[0118] R is selected from the following groups.

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[0120]

[0121]

[0122]

[0123] .

[0124] In the embodiments, the chemical reaction between the functional groups of the polymer and the functional groups inside or on the surface of the network material of the present invention includes:

[0125]

[0126] In another aspect, the present invention provides a covalent organic framework (COF) comprising a structure according to formula (I):

[0127] (I)

[0128] Where Y is , , or ;

[0129] V is , or Z is , , or And q1, q2, and q3 are each 0, 1, or 2.

[0130] Where Z is or When Z is , then q1 + q2 = q, and where when Z is When q1 + q2 + q3 = q; each X is independently selected from , and Each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected from , , -NH(CH2)2NH2, poly(ethyleneimine), -NH(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene and poly(4-aminostyrene), and when n is 0, each Each W is independently selected from -(CH2)2NH2, poly(ethyleneimine), -(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene, and poly(4-aminostyrene), and q is 1, 2, 3, or 4.

[0131] In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V, Z, and q are as described herein, and each X is independently selected from... , and And Y is In an exemplary embodiment, COF comprises a structure according to equation (I), wherein Y, Z, and q are as described herein, and each X is independently selected from... , and And V is In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from... , and Z is , , , , , , , , , , , , or And according to Z, q is 1 or 2. In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from... , and Z is , or And q is 2. In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from... , and And Z is And q is 2. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V, Z, and Y are as described herein, and each X is independently selected from... , and And q is 1. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V, Z, and Y are as described herein, and each X is independently selected from... , and And q is 2. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V, Z, and Y are as described herein, and each X is independently selected from... , and And q is 3. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V, Z, and Y are as described herein, and each X is independently selected from... , and And q is 4.

[0132] In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V and Y are as described herein, and each X is independently selected from... , and Z is And q is 1, 2, 3, or 4. In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from... , and Z is And q1 is 0 and q2 is 1; or q1 is 1 and q2 is 0; or q1 is 1 and q2 is 1; or q1 is 2 and q2 is 0; or q1 is 2 and q2 is 1; or q1 is 2 and q2 is 2; or q1 is 1 and q2 is 2; or q1 is 0 and q2 is 2; or q1 is 3 and q2 is 0; or q1 is 3 and q2 is 1; or q1 is 1 and q2 is 3; or q1 is 0 and q2 is 3; or q1 is 4 and q2 is 0; or q1 is 0 and q2 is 4. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from , and Z is And q1 is 0 and q2 is 1; or q1 is 1 and q2 is 0; or q1 is 1 and q2 is 1; or q1 is 2 and q2 is 0; or q1 is 2 and q2 is 1; or q1 is 2 and q2 is 2; or q1 is 1 and q2 is 2; or q1 is 0 and q2 is 2; or q1 is 3 and q2 is 0; or q1 is 3 and q2 is 1; or q1 is 1 and q2 is 3; or q1 is 0 and q2 is 3; or q1 is 4 and q2 is 0; or q1 is 0 and q2 is 4. In an exemplary embodiment, COF includes a structure according to equation (I), wherein V and Y are as described herein, and each X is independently selected from , and Z is And q1 is 0, q2 is 0, and q3 is 1; or q1 is 0, q2 is 1, and q3 is 0; or q1 is 1, q2 is 0, and q3 is 0; or q1 is 1, q2 is 0, and q3 is 1; or q1 is 1, q2 is 1, and q3 is 1; or q1 is 2, q2 is 0, and q3 is 0; or q1 is 2, q2 is 1, and q3 is 0; or q1 is 2, q2 is 0, and q3 is 1 ; or q1 is 2 and q2 is 1 and q3 is 1; or q1 is 1 and q2 is 2 and q3 is 1; or q1 is 3 and q2 is 0 and q3 is 1; or q1 is 0 and q2 is 1 and q3 is 3; or q1 is 0 and q2 is 3 and q3 is 1; or q1 is 4 and q2 is 0 and q3 is 0; or q1 is 0 and q2 is 4 and q3 is 0; or q1 is 0 and q2 is 0 and q3 is 4.

[0133] In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently... or Each W is as described herein, and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and each X is independently... or Each W is as described herein, and n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and each X is independently... or Each W is as described herein, and each n is independently 2 to 8, 2 to 6, 3 to 6, 5 to 6, 5 to 7, or 4 to 8. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and X is... Each W is as described herein, and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and X is... Each W is as described herein, and each n is independently 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and X is... Each W is as described herein, and each n is independently 2 to 8, 2 to 6, 3 to 6, 5 to 6, 5 to 7, or 4 to 8. In an exemplary embodiment, COF comprises a structure according to equation (I), where V, Z, Y, and q are as described herein, and X is... Each W is as described in this paper, and each n is independently 2 to 8.

[0134] In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, each n is 0, and each X is independently [missing information]. or Each W is independently selected from -(CH2)2NH2, poly(ethyleneimine), -(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein, each n is 0, and each X is Each W is independently selected from -(CH2)2NH2, poly(ethyleneimine), -(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene and poly(4-aminostyrene).

[0135] In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from... -NH(CH2)2NH2 and poly(ethyleneimine). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y and q are as described herein, and each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from... -NH(CH(CH3))2NH2 and poly(methyl(ethyleneimine)). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y and q are as described herein, and each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from... -NH(C(CH3)2)2NH2 and poly(dimethyl(ethyleneimine)). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y and q are as described herein, and each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from... -NH(CH2)3NH2 and poly(propyleneimine). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y and q are as described herein, and each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from... Lysine and polylysine.

[0136] In some embodiments of the invention, W is an in-situ generated polymer, and therefore each core in the COF may have one or more W, which is a polymer having a different number of subunits than another W. In exemplary embodiments, the poly(ethyleneimine) as described herein has 2 to 30 subunits, 2 to 25 subunits, 2 to 20 subunits, 2 to 15 subunits, 2 to 12 subunits, 2 to 10 subunits, 2 to 9 subunits, 2 to 8 subunits, 2 to 7 subunits, 2 to 6 subunits, or 2 to 5 subunits. In exemplary embodiments, the poly(methyl(ethyleneimine)) as described herein has 2 to 30 subunits, 2 to 25 subunits, 2 to 20 subunits, 2 to 15 subunits, 2 to 12 subunits, 2 to 10 subunits, 2 to 9 subunits, 2 to 8 subunits, 2 to 7 subunits, 2 to 6 subunits, or 2 to 5 subunits. In exemplary embodiments, the poly(dimethyl(ethyleneimine)) as described herein has 2 to 30 subunits, 2 to 25 subunits, 2 to 20 subunits, 2 to 15 subunits, 2 to 12 subunits, 2 to 10 subunits, 2 to 9 subunits, 2 to 8 subunits, 2 to 7 subunits, 2 to 6 subunits, or 2 to 5 subunits. In exemplary embodiments, the poly(propyleneimine) as described herein has 2 to 30 subunits, 2 to 25 subunits, 2 to 20 subunits, 2 to 15 subunits, 2 to 12 subunits, 2 to 10 subunits, 2 to 9 subunits, 2 to 8 subunits, 2 to 7 subunits, 2 to 6 subunits, or 2 to 5 subunits. In exemplary embodiments, polylysine as described herein has 2 to 20 subunits, 2 to 15 subunits, 2 to 12 subunits, 2 to 10 subunits, 2 to 9 subunits, 2 to 8 subunits, 2 to 7 subunits, 2 to 6 subunits, 2 to 5 subunits, 2 to 4 subunits, or 2 to 3 subunits.

[0137] In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... -NH(CH2)2NH2 and poly(ethyleneimine) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is 0; and each W is independently -(CH2)2NH2 or a poly(ethyleneimine) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... -NH(CH(CH3))2NH2 and poly(methyl(ethyleneimine)) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is 0; and each W is independently -(CH(CH3))2NH2 and poly(methyl(ethyleneimine)) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... -NH(C(CH3)2)2NH2 and poly(dimethyl(ethyleneimine)) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is 0; and each W is independently -(C(CH3)2)2NH2 or poly(dimethyl(ethyleneimine)) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... -NH(CH2)3NH2 and poly(propyleneimine) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently -(CH2)3NH2 or a poly(propyleneimide) having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... Lysine and polylysine having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from... Lysine and polylysine having the subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected from... , and Each n is 0; and each W is independently a lysine or a polylysine having the subunit range described herein.

[0138] In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and Each n is an integer from 1 to 12, and each W is independently selected from... -NH(CH2)2NH2 and poly(ethyleneimine). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y and q are as described herein, and each X is independently selected from... , and Each n is 0, and each W is independently -(CH2)2NH2 or poly(ethyleneimine). In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and And each W is independently selected , , , , , , , , , and In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and And m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and And each W is or derived from A linear or branched polymer. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and And each W is independently selected , , Straight-chain or branched polymers derived from monomers, wherein the monomer is , , , , , , , , , and In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and Each W is selected independently. , , Straight-chain or branched polymers derived from monomers selected from the following: , , , , , , , and In an exemplary embodiment, the COF comprises a structure according to equation (I), wherein V, Z, Y, and q are as described herein, and each X is independently selected from... , and And each W is independently selected , and .

[0139] In an exemplary embodiment, COF comprises a structure according to equation (I), wherein Z and q are as described herein, and each X is independently selected from... , and Y is And V is In an exemplary embodiment, COF comprises a structure according to equation (I), wherein V is as described herein, and each X is independently selected from... , and Y is Z is And q is 2. In an exemplary embodiment, COF includes a structure according to equation (I), where Y is as described herein, and each X is independently selected from... , and Z is q is 2, and V is In an exemplary embodiment, COF comprises a structure according to equation (I), wherein W, n, and V are as described herein, and Y is... Z is q is 2, and each X is .

[0140] In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein Y, V, and Z are as described herein, and each X is independently selected from... , and n is 6, and each W is independently selected. -NH(CH2)2NH2 and polyethyleneimine. In an exemplary embodiment, the COF comprises a structure according to formula (I).

[0141] Where Y is V is as described in this article; Z is , or Each X is Where each n is an integer independently selected from 2 to 8; each W is independently selected from... -NH(CH2)2NH2, poly(ethyleneimine), -NH(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, and polylysine, and q is 1, 2, 3, or 4. In an exemplary embodiment, the COF comprises a structure according to formula (I), wherein Y, V, Z, and q are as described herein; each X is independently... or Each W is as described herein. In an exemplary embodiment, COF comprises a structure according to equation (I), where Y, V, Z, and q are as described herein; each X is Each W is as described herein. In an exemplary embodiment, COF comprises a structure according to equation (I), where Y is... V is Z is Each X is ; and each W is independently selected from: a) b) -NH(CH2)2NH2 or poly(ethyleneimine); -NH(CH(CH3))2NH2 or poly(methyl(ethyleneimine)); c) -NH(C(CH3)2)2NH2 or poly(dimethyl(ethyleneimine)); d) -NH(CH2)3NH2 or poly(propyleneimine); and e) Lysine or polylysine. In an exemplary embodiment, COF comprises a structure according to formula (I), wherein Y is... V is Z is Each X is And each W is independently selected -NH(CH2)2NH2 and poly(ethyleneimine).

[0142] Examples of chemical reactions between the functional groups of polymers and the functional groups inside or on the surface of network materials:

[0143]

[0144] ,

[0145] Each m is an integer independently selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.

[0146] In an exemplary embodiment, COF is synthesized as follows:

[0147]

[0148] ,

[0149] Each W is independently selected from -NH2, -NH(CH2)2NH2, and poly(ethyleneimine). In some embodiments, the poly(ethyleneimine) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0150] In an exemplary embodiment, COF is synthesized as follows:

[0151]

[0152] ,

[0153] Each W is independently selected from -NH2, -NH(CH2)3NH2, and poly(propyleneimide). In some embodiments, the poly(propyleneimide) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0154] In an exemplary embodiment, COF is synthesized as follows:

[0155]

[0156] ,

[0157] Each W is independently selected from -NH2, -NH(CH2)2NH2, and poly(ethyleneimine). In some embodiments, the poly(ethyleneimine) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0158] In an exemplary embodiment, COF is synthesized as follows:

[0159]

[0160] ,

[0161] Each W is independently selected from -NH2, -NH(CH2)3NH2, and poly(propyleneimide). In some embodiments, the poly(propyleneimide) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0162] In an exemplary embodiment, COF is synthesized as follows:

[0163]

[0164] ,

[0165] Each W is independently -(CH2)2NH2 or poly(ethyleneimine). In some embodiments, the poly(ethyleneimine) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0166] In an exemplary embodiment, COF is synthesized as follows:

[0167]

[0168] ,

[0169] Each W is independently either lysine or poly(lysine). In some embodiments, the poly(lysine) in this paragraph has 2 to 30 subunits, or 2 to 25 subunits, or 2 to 20 subunits, or 2 to 15 subunits, or 2 to 12 subunits, or 2 to 10 subunits, or 2 to 9 subunits, or 2 to 8 subunits, or 2 to 7 subunits, or 2 to 6 subunits, or 2 to 5 subunits.

[0170] In an exemplary embodiment, the COF comprises repeating nuclei, wherein the nuclei are according to the formula described herein. In an exemplary embodiment, the COF comprises nuclei (such as those according to the formula described herein). In an exemplary embodiment, the nuclei described herein (such as those according to the formula described herein) form part of an adjacent nucleus, which is part of a repeating nucleus. An example of this can be found in the lower half of FIG3, where one nucleus is shown as part of its structure forming part of an adjacent second nucleus, and the portion of the one nucleus and the portion of the adjacent second nucleus each form part of an adjacent third nucleus. In an exemplary embodiment, the COF according to the formula described herein is crystalline. In an exemplary embodiment, the structure according to the formula described herein is crystalline. In an exemplary embodiment, the COF according to the formula described herein is porous. In an exemplary embodiment, the structure according to the formula described herein is porous. In an exemplary embodiment, the structure according to the formula described herein is stable. In an exemplary embodiment, the COF according to the formula described herein is stable. In an exemplary embodiment, the structure according to the formula described herein is hydrolytically stable. In an exemplary embodiment, the COF according to the formula described herein is hydrolytically stable. In an exemplary embodiment, the structure according to the formula described herein is two-dimensional. In an exemplary embodiment, the repeating kernel described herein is two-dimensional. In an exemplary embodiment, the structure according to the formula described herein has an hcb topology. In an exemplary embodiment, the COF described herein has an hcb topology. In an exemplary embodiment, the COF is COF-999. In an exemplary embodiment, the COF is COF-999-PPI. In an exemplary embodiment, the COF is COF-998-PEI. In an exemplary embodiment, the COF is COF-998-PEI. In an exemplary embodiment, the COF is COF-997-PEI. In an exemplary embodiment, the COF is COF-997-PolyLys.

[0171] III. Methods and Systems

[0172] Carbon capture process using MOF or COF

[0173] Post-combustion capture (PCC)

[0174] In specific embodiments, the MOF described herein is used as a solid adsorbent for capturing CO2 after combustion from natural gas or coal flue gas. In specific embodiments, the COF described herein is used as a solid adsorbent for capturing CO2 after combustion from natural gas or coal flue gas. In some variations, the CO2 concentration in the feed flue gas is 4% to 16%, and the temperature of the feed flue gas is below 40°C. In some variations, the CO2 concentration in the feed flue gas is 4% to 16%, and the temperature of the feed flue gas is below 90°C.

[0175] In some variations, the MOFs or COFs described herein are used in pure form, homogeneously mixed with other materials, or loaded onto other materials as powders with a shape factor. In these variations, the powders or COFs described herein are used in packed beds, cylindrical exchangers, fluidized beds, etc.

[0176] In these cases, CO2 removal from the MOF described herein involves heating, pressure change, gas purging, washing, or a combination thereof. In these cases, CO2 removal from the COF described herein involves heating, pressure change, gas purging, washing, or a combination thereof.

[0177] In these cases, MOFs or COFs exhibiting such properties as described herein are used:

[0178] Depending on the adsorption and regeneration conditions, the combination of chemisorption (if present) and physisorption has a high working capacity difference for CO2.

[0179] For chemisorption, there are reactive functional groups, such as those in the W variable described in this paper;

[0180] For the dynamic capacity measurement of COF described in this paper, the breakthrough experiment was configured with a feed gas mixture of 4% to 50% (or 4% to 16%), and corresponding humidity and temperature.

[0181] It has sufficient affinity for CO2, allowing it to retain adequate working capacity in the presence of H2O.

[0182] Robustness: Chemically stable against H2O, O2, CO2, and impurities under both adsorption and regeneration conditions, including retention of chemical composition, crystallinity, adsorption capacity, and porosity. Thermal stability over the operating temperature range.

[0183] An open-frame structure with permanent porosity ensures efficient mass transfer.

[0184] In some variants where regeneration is achieved through heating, low heat capacity is required. In some variants where COF is in the form of a molded body or supported by other materials, tight bonding is necessary to achieve mechanical stability.

[0185] In some variations, COF is used in pure form, homogeneously mixed with other materials, or loaded onto other materials as a membrane shape factor. In these cases, the powder or molded body is used in membrane filtration, membrane exchangers, or cartridge exchangers, etc.

[0186] It has a high selective affinity for CO2, and under separation conditions, it increases the solubility of the membrane through both chemisorption (if present) and physisorption.

[0187] - For chemisorption, reactive functional groups such as -NH2 or -NHR are part of COF.

[0188] For dynamic capacity measurements of this type of COF, the breakthrough test or membrane-specific continuous test is configured with 4% to 50% (or 4% to 16%) of the feed gas mixture, and the corresponding humidity and temperature.

[0189] It has sufficient affinity for CO2, allowing it to retain adequate working capacity in the presence of H2O.

[0190] Robustness: Chemically stable against H2O, O2, CO2, and impurities under both adsorption and regeneration conditions, including retention of chemical composition, crystallinity, adsorption capacity, and porosity. Thermal stability over the operating temperature range.

[0191] In some variations where COF is loaded by other materials in the membrane, it is tightly bonded to the load to achieve mechanical stability.

[0192] In some variants where heating is used for regeneration, a low heat capacity is required.

[0193] Direct Air Capture (DAC)

[0194] In specific embodiments, MOF is used as a solid adsorbent for directly capturing CO2 from ambient air. In specific embodiments, COF is used as a solid adsorbent for directly capturing CO2 from ambient air. In most variations, the CO2 concentration in the feed flue gas is atmospheric (-400 ppm, 1 atm). In some variations, the CO2 concentration is >400 ppm (when using compressed air) or slightly higher by compression or in a closed, non-ambient chamber, and the temperature of the feed gas is ambient temperature.

[0195] In some variations, MOF is used in pure form, homogeneously mixed with other materials, or loaded onto other materials as a powder shape factor. In some variations, COF is used in pure form, homogeneously mixed with other materials, or loaded onto other materials as a powder shape factor. In some variations, MOF is used in pure form, homogeneously mixed with other materials, or loaded onto other materials as a molded body shape factor. In some variations, COF is used in pure form, homogeneously mixed with other materials, or loaded onto other materials as a molded body shape factor. In these cases, the powder or molded body is used in packed beds, cylindrical exchangers, fluidized beds, etc.

[0196] In these cases, CO2 removal from MOF involves heating, pressure changes, gas purging, washing, or a combination of some or all of these. In these cases, CO2 removal from COF involves heating, pressure changes, gas purging, washing, or a combination of some or all of these.

[0197] In these cases, MOFs or COFs exhibiting these properties are used:

[0198] Depending on the adsorption and regeneration conditions, chemisorption exhibits a high working capacity variation for CO2.

[0199] -For chemisorption, high gravimetric or bulk density of reactive functional groups such as -NH2 or -NHR.

[0200] For dynamic capacity measurements of this type of COF, the breakthrough experiment is configured with a feed gas mixture of -400 ppm, and corresponding humidity and temperature.

[0201] It has sufficient affinity for CO2, allowing it to retain adequate working capacity in the presence of H2O.

[0202] Robustness: Chemically stable against H2O, O2, CO2, and impurities under both adsorption and regeneration conditions, including retention of chemical composition, crystallinity, adsorption capacity, and porosity. Thermal stability over the operating temperature range.

[0203] An open-frame structure with permanent porosity ensures efficient mass transfer.

[0204] In some variants where heating is used for regeneration, a low heat capacity is required.

[0205] In some variations where MOF is shaped or loaded with other materials, a tight bond is achieved to obtain mechanical stability. In some variations where COF is shaped or loaded with other materials, a tight bond is achieved to obtain mechanical stability.

[0206] In exemplary embodiments, the MOF or COF described herein is configured for carbon dioxide capture. In exemplary embodiments, the MOF or COF described herein is configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas. In exemplary embodiments, the MOF or COF described herein is contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane. In exemplary embodiments, the MOF or COF described herein is contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane, located in a fluid flow path configured to allow air or a mixture to pass over, around, and / or through the matrix. In exemplary embodiments, the MOF or COF described herein comprises air or a post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and operable to collect water from the air or mixture. In an exemplary embodiment, the MOF or COF described herein is configured to capture carbon dioxide in a matrix further comprising air or a post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and operable to collect water from the air or mixture, and to provide convenient water collection as a secondary value fulfilling its function.

[0207] In another aspect, the present invention provides a system for capturing carbon dioxide from air or a mixture of post-combustion exhaust gases, comprising a matrix, such as an adsorption bed containing an MOF or COF as described herein, the matrix being configured as a solid adsorbent for capturing carbon dioxide from air or the mixture and optionally capturing water.

[0208] In another aspect, the present invention provides a method comprising using a MOF or COF as described herein as a solid adsorbent for capturing carbon dioxide from air or a post-combustion exhaust gas mixture and optionally capturing water. In exemplary embodiments, methods are provided for capturing and / or separating carbon dioxide, particularly from air or flue gas, using a MOF or COF as described herein.

[0209] Parallel water collection

[0210] In some variants, MOF or COF adsorbents exhibit high adsorption capacities for both CO2 and H2O during both PCC and DAC processes. Therefore, CO2 and H2O can be removed in the same step or in different steps under different conditions. With convenient further purification, such MOF or COF adsorbents can produce high-purity water as a byproduct of CO2 capture from air or flue gas.

[0211] In these cases, MOFs or COFs exhibiting these properties are used:

[0212] Depending on the adsorption and regeneration conditions, physical adsorption exhibits a high working capacity difference for H2O.

[0213] For dynamic capacity measurements of such MOFs or COFs, the breakthrough experiment is configured with a feed gas mixture at the desired humidity and temperature.

[0214] It has sufficient affinity for H2O, allowing it to retain adequate working capacity in the presence of CO2.

[0215] Robustness: Chemically stable against H2O, O2, CO2, and impurities under both adsorption and regeneration conditions, including retention of chemical composition, crystallinity, adsorption capacity, and porosity. Thermal stability over the operating temperature range.

[0216] An open-frame structure with permanent porosity ensures efficient mass transfer.

[0217] In some variants where heating is used for regeneration, a low heat capacity is required.

[0218] In the MOF or COF described herein, in the form of molded articles or in some variations supported by other materials, they are tightly bonded to achieve mechanical stability.

[0219] In exemplary embodiments, the MOF or COF described herein is configured for carbon dioxide capture. In exemplary embodiments, the MOF or COF described herein is configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas. In exemplary embodiments, the MOF or COF described herein is contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane. In exemplary embodiments, the MOF or COF described herein is contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane, located in a fluid flow path configured to allow air or a mixture to pass over, around, and / or through the matrix. In exemplary embodiments, the matrix described herein comprises air or a post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and operable to collect water from the air or mixture, providing convenient water collection as a secondary value function. In another aspect, the present invention provides a system for capturing carbon dioxide from air or a mixture of afterburning exhaust gases, comprising a matrix, such as an adsorption bed containing an MOF or COF as described herein, the matrix being configured as a solid adsorbent for capturing carbon dioxide from air or the mixture and optionally capturing water. In another aspect, the present invention provides a method comprising using an MOF or COF as described herein as a solid adsorbent for capturing carbon dioxide from air or a mixture of afterburning exhaust gases and optionally capturing water. In yet another aspect, the present invention provides a method for capturing and / or separating carbon dioxide, particularly from air or flue gas, using an MOF or COF as described herein.

[0220] In exemplary embodiments, the present invention is the COF described herein, configured for carbon dioxide capture. In exemplary embodiments, the present invention is the COF described herein, configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas. In exemplary embodiments, the present invention is the COF described herein, contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane. In exemplary embodiments, the present invention is the COF described herein, contained in a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger, or membrane, located in a fluid flow path configured to allow air or a mixture to pass over, around, and / or through the matrix. In exemplary embodiments, the present invention is the COF described herein, comprising air or a post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and operable to collect water from the air or mixture. In exemplary embodiments, the present invention is a system for capturing carbon dioxide from air or a mixture of afterburning exhaust gases, comprising a matrix, such as an adsorption bed containing a COF as described herein, the matrix being configured as a solid adsorbent for capturing carbon dioxide from air or the mixture and optionally capturing water. In exemplary embodiments, the present invention is a method comprising using a COF as described herein as a solid adsorbent for capturing carbon dioxide from air or a mixture of afterburning exhaust gases and optionally capturing water. In exemplary embodiments, the present invention is a method for capturing and / or separating carbon dioxide, particularly from air or flue gas, using a COF as described herein.

[0221] All publications and patent applications mentioned in this disclosure are incorporated herein by reference to the same degree, as if specifically and individually indicated that each individual publication or patent application is incorporated by reference.

[0222] No references cited herein are acknowledged to constitute prior art. The discussion of references illustrates the author's claims, and the applicant reserves the right to challenge the accuracy and relevance of the cited documents. It should be clearly understood that although numerous sources of information are referenced herein, including scientific journal articles, patent documents, and textbooks, such references do not constitute an acknowledgment that any of these documents constitutes part of common general knowledge in the art.

[0223] The discussion of the general methods presented herein is intended for illustrative purposes only. Other alternative methods and solutions will be apparent to those skilled in the art upon reading this disclosure and will be included within the spirit and scope of this application.

[0224] Further embodiments are disclosed in detail in the following examples, which are provided by way of illustration and are not in any way intended to limit the scope of this disclosure or the claims.

[0225] Example

[0226] Example 1: In-situ polymerization reaction inside or on the surface of a network material.

[0227] COF-999 (formerly known as COF-153-PEI) is synthesized via in-situ polymerization of COF-999-NH2 (formerly known as COF-153). Specifically, aziridine is polymerized in the pores of COF-999-NH2 to form polyethyleneimine (PEI).

[0228]

[0229]

[0230] Synthesis scheme of COF-999. The loading of PEI was characterized by elemental analysis of C and N, and calculated using the ratio of C to N atoms. The following results were given for COF-999-NH2 and COF-999: COF-999: C = 78.51%, N = 8.10%, C / N = 9.69; COF-999-PEI: C = 70.68%, N = 14.35%, C / N = 4.92. The decrease in the C / N ratio from 9.69 to 4.92 indicates that PEI was successfully loaded into COF.

[0231] The amine functional groups in material COF-999 exhibit strong chemisorption of CO2 at low pressure. Based on the single-component CO2 adsorption isotherm at 298 K, COF-999 absorbs 0.56 mmol / g CO2 at 0.4 mbar (conditions related to direct air capture). At 40 mbar (conditions related to post-combustion capture from natural gas flue gas), COF-999 absorbs 1.33 mmol / g CO2. At 150 mbar (conditions related to post-combustion capture from coal flue gas), the CO2 adsorption capacity is 1.55 mmol / g. Figure 1 shows the CO2 adsorption analysis of COF-999 at 298 K.

[0232] To measure the performance of COF-999 in humid air, breakthrough measurements were performed at 50% relative humidity (400 ppm CO2 in N2). Under these conditions, COF-999 adsorbed 0.83 mmol / g CO2. Figure 2 shows the breakthrough curves of COF-999 under the following conditions: 400 ppm CO2, 50% relative humidity, in N2, flow rate 60 mL / min, and temperature 298 K. The area marked in blue is used to derive the CO2 adsorption capacity through numerical integration.

[0233] Example 2: Capturing carbon dioxide from open air using a covalent organic framework

[0234] Direct air capture (DAC) plays a crucial role in achieving the vision of carbon neutrality and reducing the greenhouse effect. 6,7 Efficiently capturing CO2 from the air requires a selective material with high CO2 capacity and exhibiting rapid kinetics—all at low CO2 concentrations (around 400 ppm). Furthermore, such a material must operate at low regeneration temperatures and with high cycle stability in the presence of other air components, particularly oxygen and water. 8–10 According to reports, the use of liquid alkaline solutions... 11,12 Silica-supported amines 13–15 and metal-organic frameworks (MOFs) 16–20 It has been extensively studied as a potential candidate material for DAC applications. However, despite its promising prospects, the full-scale deployment of liquid solutions remains hampered by its energy-intensive regeneration. 8 The challenges of toxicity, and for silica-supported amines and MOFs, in cycling 21 and hydrolysis 22,23 The loss of amines remains a long-standing problem. In this paper, network chemistry... 24,25 The design principles were used to fabricate robust covalent organic frameworks (COFs) capable of capturing CO2 directly from the air under practical conditions. Specifically, a porous crystalline COF (designated COF-999) was designed that selectively captures 2.02 mmol of CO2 per gram from air containing 400 ppm CO2 at 50% relative humidity (RH). The cycling stability of this COF was demonstrated by performing 100 CO2 adsorption-desorption temperature swing cycles (ambient temperature to 60°C) in open air over a 20-day run, during which its capacity and performance were fully preserved. COF-999 surpasses the current state-of-the-art materials for DAC applications, and COF chemistry in general offers a wide range of opportunities for molecular design and the eventual deployment of such emerging materials.

[0235] Figure 3 illustrates how the molecular properties required to address the DAC challenge are incorporated into the COF. First, the use of hydrophobic building blocks in the COF construction provides hydrophobic pores capable of adsorbing a minimal amount of water, resulting in a lower CO2 regeneration temperature. 26–28 Secondly, the initiator is covalently bonded to the framework, which in turn allows for the covalent bonding of polyamines and prevents their loss during cycling. The fact that the initiator is designed to be reactive and intentionally has a large pore size provides opportunities for high polyamine loading and convenient CO2 diffusion—necessary prerequisites for achieving high capacity and rapid cycling. Thirdly, the olefinic bonds between the covalent molecules constituting the COF backbone contribute to the overall thermal and chemical stability of the structure. 29,30 This allows for the post-synthetic assembly of polyamine units and the stability of repeated CO2 cycling without compromising the porosity and integrity of the COF structure.

[0236] Synthesis and Structure of COF Series. The porous crystalline olefin-linked COF precursor COF-999-N3 was first synthesized via a Knoevenagel condensation between 3,3'-bis[(6-azidohexyl)oxy]-4,4'-biphenyldicarboxaldehyde (BPDA-N3) and 1,3,5-tris(4-cyanomethylphenyl)benzene (TCPB) (Fig. 3). Powder X-ray diffraction (PXRD) was performed to confirm the crystallinity of COF-999-N3 (Fig. 4A). The experimental PXRD pattern of COF-999-N3 in space group P6 was Pawley refined to obtain the following cell parameters: a = b = 45.524(2) Å, c = 3.94(9) Å, α = β = 90°, γ = 120°, where R p =1.81% and R wp = 3.12%. The PXRD peaks at 2.2°, 3.9°, 4.5°, 5.9°, and 6.7° are attributed to the (100), (110), (200), (210), and (300) lattice planes, respectively. These observations are consistent with the simulated structure, in which TCPB and BPDA-N3 are linked by olefinic bonds to form a honeycomb sheet with AA stacks. Scanning electron microscopy images of COF-999-N3 show a textured spherical morphology with an average particle size of approximately 5 µm (Fig. 5). The N2 adsorption isotherm of COF-999-N3 was measured at 77 K (Fig. 4B), yielding an 811 m... 2 g –1 The surface area of ​​Brunauer-Emmett-Teller (BET) pores, with an average pore size of approximately 3.3 nm (Figure 6). Using... 15 N-labeled COF-999- 15 N3 passed 15N-cross-polarized magic-angle rotation (CP / MAS) solid-state NMR (ssNMR) characterizes the azidofunctional groups within the pores (Fig. 4C). The two main peaks at 210.4 and 71.6 ppm are attributed to γ-labeled azido groups on the side chains. 15 N(R‒N=N= * N) and α- 15 N (R‒ * N=N=N).

[0237] via Staudinger reaction at room temperature 31 Further reduction of the azide group to an amine yields COF-999-NH2, which is then treated with aziridine to generate polyamines within the pores, thus obtaining COF-999 (Figure 3). Collection 15 NssNMR spectroscopy was used to demonstrate the transformation from azide to amine and then to polyamine (Figure 4C). This was achieved through... 15 The disappearance of the azido peak in the N ss NMR spectrum and the characteristic R‒ at 23.5 ppm 15 The presence of NH2 chemical shift confirms COF-999- 15 Complete reduction of N3. This can also be observed through the Fourier transform infrared spectrum of azide ν. N=N Stretching to 2089 cm –1 No vibration absorption was detected at this location (Figure 15). Notably, the crystallinity and porosity of COF-999-NH2 were retained after the reduction process (Figures 8 and 16). COF-999- 15 In-pore polymerization of NH2 with unlabeled aziridine in COF-999 15 A new peak at 35.7 ppm was observed in the NssNMR spectrum, attributed to the formation of a secondary amine linking the COF backbone and the polyethyleneimine unit. Quantitative analysis was performed. 15 MultiCP / MAS ssNMR revealed that after polymerization, 66% of the primary amine on the side chain (COF-999-NH2, Figure 3) was converted to a secondary amine (COF-999, Figure 3) (Figure 19). The degree of polymerization of COF-999 was quantitatively determined. 13 Calculations by C multiCP / MAS ssNMR (Figure 4D) and elemental analysis (Table 4) indicate that an average of 4.6 CH2CH2NH units were added to each amine side chain (see Methods section “Calculation of Degree of Polymerization”).

[0238] Gas adsorption isotherms. The adsorption capacity of COF-999 for air components was examined using gas adsorption isotherms of CO2, N2, O2, Ar, and H2O at 25 °C (Figures 20A to 20C). A sharp increase at very low CO2 pressures (Figure 20A) and a hysteresis between the adsorption and desorption isotherms indicate a strong affinity of COF-999 for CO2. Based on this data, the CO2 adsorption capacity was found to be 0.91 mmol g at 0.4 mbar (400 ppm, close to the partial pressure of CO2 in air, Figure 20B). −1 The corresponding calculated heat of adsorption is 53 kJ / mol. −1 (Figure 12). As expected, N2, O2, and Ar exhibited linear adsorption isotherms with negligible adsorption amounts, indicating that COF-999 has higher selectivity for CO2 than for other components present in ambient air. The moisture adsorption capacity of COF-999 at 50% RH was 0.09 g. 水 g COF −1 (Figure 20C), the heat of adsorption of an equal amount of water vapor is 49 kJ mol. −1 (Figure 14). This low moisture adsorption capacity has a positive impact on CO2 capture from the air by this material, as discussed further below.

[0239] The kinetics of gas adsorption from the mixture. Breakthrough experiments enabled the assessment of adsorption selectivity and dynamic behavior (Figures 20D to 20I), which is crucial for evaluating the practical performance of the adsorbent in air. Given that oxygen and water are the main components of the atmosphere, any candidate material for carbon capture must remain stable under humid and oxidizing conditions. Dynamic adsorption curves were measured at 25 °C with 400 ppm CO2 in compressed air (N2 / O2 = 4 / 1) and 50% RH to simulate environmental conditions (Figure 20D). COF-999 adsorbed both CO2 and water upon exposure to simulated air. Initially, the material rapidly reached saturation capacity for water adsorption compared to CO2, with CO2 retained in the pores, then breakthrough occurred at approximately 90 minutes and its concentration increased sharply. COF-999 eventually reached an equilibrium concentration with CO2, indicating that saturation adsorption capacity had been reached. The steep breakthrough curve indicates rapid mass transfer of CO2 in COF-999.

[0240] The effect of water on CO2 adsorption was assessed by measuring the CO2 adsorption capacity of COF-999 at 25°C and different relative humidity levels ranging from 0 to 75% (Figures 20E and 22). The cumulative CO2 adsorption capacity was calculated by numerically integrating the difference in CO2 concentration between the background and monitored outlet concentrations. Under dry conditions with 400 ppm CO2, COF-999 exhibited an adsorption capacity of 0.95 mmol g.−1 The CO2 adsorption capacity was comparable to that of its single-component CO2 adsorption. When 25% RH was introduced into the measurement, the CO2 adsorption capacity of COF-999 increased to 1.76 mmol g. −1 After increasing the RH to 50%, a further increase in capacity to 2.02 mmol g was observed. −1 Compared to dry conditions, the CO2 capacity increased significantly by 2.13 times. 2.06 mmol g was achieved at 75% RH. −1 The maximum capacity. The significant positive effect of water on CO2 adsorption is due to the formation of carbamates and bicarbonates in the pores, as demonstrated by ssNMR measurements and explained by the DFT calculations presented below. Although not the focus of this contribution, COF-999 was found to have a CO2 adsorption capacity of 3.17 mmol g under simulated natural gas flue gas (4% CO2 and 75% RH) and coal flue gas (15% CO2 and 75% RH) conditions. −1 and 3.24 mmol g −1 (Figures 23 and 24) show the CO2 capture capacity of COF-999 at different concentrations.

[0241] The adsorption kinetics of COF-999 were measured at 25 °C in simulated air (400 ppm CO2 and 50% RH) (Figures 20F and 25). Specifically, COF reached half capacity (1.01 mmol g) within 18.8 minutes. −1 It reached 80% volume (1.62 mmol g) within 61.7 minutes. −1 During the adsorption process, the maximum adsorption rate was calculated to be 0.11 mmol g. −1 minute −1 Although the reported measurements were conducted under dry conditions, this ultrafast rate is the highest rate ever measured for capturing CO2 from the air. 32 The convenient adsorption is attributed not only to the periodic pore structure of COF-999, but also to the presence of a small amount of water within the pores. 33 .

[0242] To investigate desorption and the effect of temperature on kinetics, desorption curves were measured at 60 °C, 80 °C, and 100 °C (Figures 20G, 20H, and 26). Prior to measurement, COF-999 was saturated in simulated air (400 ppm CO2 and 50% RH) at 25 °C. The temperature was then increased over 5 minutes and maintained under a nitrogen flow. At 60 °C, it took 43.1 minutes to desorb 80% of the adsorbed CO2, and the maximum desorption rate was calculated to be 0.06 mmol g. −1 minute −1Increasing the temperature to 80°C resulted in a higher maximum desorption rate of 0.12 mmol g. −1 minute −1 Furthermore, 80% of the adsorbed CO2 was desorbed after 21.5 minutes. Further heating to 100℃ yielded 0.19 mmol g. −1 minute −1 The maximum desorption rate is achieved, with 80% of the adsorbed CO2 desorbed at 15.7 minutes. The hydrophobicity of COF-999 allows CO2 desorption without requiring excessive energy input to remove water molecules, thus achieving low desorption temperature and fast desorption kinetics.

[0243] Preliminary assessment of the cycling stability of COF-999 was performed using temperature swing measurements in simulated air (400 ppm CO2 and 50% RH). After each cycle, the COF sample was regenerated at 60 °C in a nitrogen stream. Excellent stability was observed in CO2 capacity retention after 10 consecutive adsorption-desorption cycles (Figures 20I and 28).

[0244] Capturing carbon dioxide from open air. The feasibility of COF-999 under real-world conditions was tested in outdoor air for 20 consecutive days from January 18 to February 6, 2024, in Berkeley, California, USA (37°52'23.8" N, 122°15'21.2" W) (Figure 29A; see also Figures 30 and 31). Outdoor air passed through the adsorbent, where CO2 molecules were selectively adsorbed by COF-999. The breakthrough point for the adsorption process was set downstream at 300 ppm, as this represents the majority of the adsorbed CO2. The material was then regenerated at 60°C. This measurement method allows for more cycles to be run and for evaluating the adsorption-desorption cycle performance while operating at near full capacity. Throughout the experiment, the outdoor ambient CO2 concentration and relative humidity were measured before each adsorption cycle.

[0245] One hundred adsorption-desorption cycles were performed over 20 days, during which outdoor CO2 concentrations varied from 420 ppm to 517 ppm, and RH varied from 28% to 51%. After 100 consecutive cycles, the average CO2 productivity was determined to be 1.28 mmol g. –1 cycle –1 (5.63 wt.% cycle) –1 The maximum productivity was 1.48 mmol g. –1 And the minimum productivity is 1.03 mmol / g –1Notably, an increase in CO2 adsorption was observed as air humidity varied over time (Figure 29A). This positive effect of humidity on CO2 adsorption stems from the way water molecules interact with CO2 bound to the amine, as described below. CO2 productivity at a background of 37 ± 1% RH (Figure 29B) demonstrates the stability of COF-999 under these varying open-air conditions. The consistent capacity of these cycles at the same humidity further supports the chemical robustness of the COF. After completing 100 adsorption-desorption cycles, the single-component CO2 adsorption isotherm of COF-999 was measured (Figure 29C), and the dynamic breakthrough using simulated air (400 ppm CO2 and 50% RH) was measured (Figure 29D). No changes in the adsorption isotherm or breakthrough were observed, indicating the preservation of the COF structure and its normal function in CO2 capture.

[0246] The adsorption structure of CO2 in COF-999. (Using...) 13 The binding of COF-999 to CO2 molecules was studied using CssNMR spectroscopy (Figure 32). COF-999 was exposed to 1 atm at 25°C under dry conditions. 13 After CO2, 13 A strong signal was observed at 164.5 ppm in the C-ray diffraction (C-C) spectrum. This signal is attributed to the formation of carbamic acid due to the reaction of CO2 with polyamines. 34,35 Conversely, COF-999 was presaturated with water in N2 at 25°C and 80% RH, and then exposed to [unclear - possibly a specific environment or process]. 13 CO2 causes 13 Signals at 165.1 ppm and 161.7 ppm appear in the C spectrum, indicating the formation of carbamate and bicarbonate, respectively.

[0247] Periodic density functional theory calculations of the CO2 adsorption structure in COF (see "DFT Calculations" in the Methods section) show that, under dry conditions (see "Formation of Carbamic Acids / Carbamates under Dry Conditions" in the Methods section), the reaction between CO2 and primary or secondary amines is energy-favorable, and the formed carbamic acid is stabilized by hydrogen bonds with adjacent amines (e.g., Figure 33A, N···O distance of 263 pm). Upon addition of water molecules, the formed carbamic acid / carbamate is found to be stabilized by hydrogen bonds (e.g., Figure 33B, O···O). wThe distance between the amino groups is 283 pm and the N···O distance is 257 pm, which promotes the formation of bicarbonate, which is also stabilized by hydrogen bonds with adjacent amino groups (e.g., Figure 33C, N···O distances are 262 pm and 271 pm). Therefore, the stability in the presence of water explains the experimentally observed significant enhancement of CO2 adsorption capacity of COF-999 under humid conditions and its applicability for capturing carbon dioxide from open air.

[0248] This paper demonstrates how COFs with olefin-linked backbones and covalently linked adsorption sites can exhibit exceptional chemical stability, making them excellent materials for capturing CO2 from the air. These studies indicate that such application in open air represents a significant advancement towards clean air. COF-999 may be the first member of a large class of materials with a robust framework that will serve well in general carbon capture applications. By applying this strategy, other network structures can be designed, examined, and compared with COF-999 to further improve capacity and performance.

[0249] method

[0250] The general synthesis of COF according to this invention involves loading Y (approximately 0.04 mmol), Z (approximately 0.06 mmol), and a basic catalyst (NaOH, KOH, or Cs₂CO₃) or an acidic catalyst (acetic acid or trifluoroacetic acid) into a glass tube. A solvent mixture (approximately 1 mL) of dichlorobenzene, butanol, dioxane, and mesitylene can be added to the glass tube. The tube can be sealed and heated at 80°C to 140°C (typically 120°C) for 1 to 5 days (typically 3 days) to obtain a solid. The solid can then be filtered, washed with methanol (30 mL), post-treated with PPh₃, HCl, or NaOH, and dried to obtain COF.

[0251] To covalently link the polymer to the COF, approximately 50 mg of the COF from the previous step can be mixed with monomer M (approximately 100 mg) and a basic catalyst (NaOH, KOH, or Cs₂CO₃), an acidic catalyst (acetic acid or trifluoroacetic acid), or a radical catalyst (azobisisobutyronitrile). A solvent mixture of tetrahydrofuran or toluene (approximately 1 mL) can be added to the mixture. The mixture can be heated at 50°C to 120°C (typically 100°C) for 6 to 48 hours (typically 24 hours) to obtain a solid. The solid can be filtered, washed with methanol (30 mL), post-treated with HCl, NH₃, or NaOH, and dried at 120°C to obtain the polymer-functionalized COF. In an exemplary embodiment, M is... , , , , , , , , , or In an exemplary embodiment, M is... , , , , , , , or .

[0252] General synthesis of linkers

[0253]

[0254] D (approximately 1.0 equivalent) and NaN3 (approximately 1.3 equivalent) can be added to approximately 100 mL of DI water, and the reaction mixture can be refluxed at approximately 100 °C for approximately 48 hours. After cooling to room temperature, the mixture can be extracted with ethyl acetate (approximately 100 mL × 3). The organic phases can be combined, washed with water (100 mL × 3), brine (50 mL), and dried over sodium sulfate. After filtration, the solvent can be evaporated to obtain E, which can be used directly in the next step without further purification.

[0255] E can be dissolved in approximately 150 mL of DCM under a N2 atmosphere, and the solution cooled to approximately 0°C. 4-Toluenesulfonyl chloride (21.0 g, 110 mmol, 1.1 equivalents) and triethylamine (approximately 3.0 equivalents) can be added to the solution. The solution can be warmed to approximately 25°C and stirred for approximately 16 hours. After completion, approximately 100 mL of water can be added, and the organic phase can be collected, washed with water (approximately 100 mL) and brine (approximately 50 mL), and dried over sodium sulfate. The solution can be filtered and concentrated, and the resulting oil can be subjected to rapid column chromatography using silica gel with ethyl acetate / hexane (1 / 5, v / v) as eluent to obtain G. In an exemplary embodiment, D is 1-chloro-1-methanol, E is 1-azido-1-methanol, and G is 1-azidomethyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 2-chloro-1-ethanol, E is 2-azido-1-ethanol, and G is 2-azidoethyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 3-chloro-1-propanol, E is 3-azido-1-propanol, and G is 3-azidopropyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 4-chloro-1-butanol, E is 4-azido-1-butanol, and G is 4-azidobutyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 5-chloro-1-pentanol, E is 5-azido-1-pentanol, and G is 5-azidopentan 4-methylbenzenesulfonate. In an exemplary embodiment, D is 6-chloro-1-hexanol, E is 6-azido-1-hexanol, and G is 6-azidohexyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 7-chloro-1-heptanol, E is 7-azido-1-heptanol, and G is 7-azido-heptyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 8-chloro-1-octanol, E is 8-azido-1-octanol, and G is 8-azido-octyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 9-chloro-1-nonanol, E is 9-azido-1-nonanol, and G is 9-azido-nonanyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 10-chloro-1-decanol, E is 10-azido-1-decanol, and G is 10-azido-decyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 11-chloro-1-undecanol, E is 11-azido-1-undecanol, and G is 11-azido-undecanyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 12-chloro-1-dodecanool, E is 12-azido-1-dodecanool, and G is 12-azidodecanoate of 4-methylbenzenesulfonate.

[0256] General composition containing certain parts of Z:

[0257]

[0258] A (approximately 1.0 equivalent), K₂CO₃ (approximately 3.0 equivalent), and B (approximately 2.2 equivalent) can be added to approximately 30 mL of anhydrous DMF under a N₂ atmosphere. The resulting suspension can be heated to approximately 80 °C and stirred for approximately 16 hours. After cooling, the DMF can be evaporated under reduced pressure, and the remaining mixture can be extracted with water (100 mL) and DCM (100 mL). The organic phase can be collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution can be filtered and concentrated, and the resulting solid can be subjected to rapid column chromatography using silica gel with ethyl acetate / hexane (1 / 5, v / v) as eluent to obtain the product. In an exemplary embodiment, when A is... , , , , , , , , , , , or When, then the corresponding B is , , , , , , , , , , , or In an exemplary embodiment, when A is... , , , , , , , , , , , or When, then the corresponding B is , , , , , , , , , , , or In an exemplary embodiment, when A is... , , , , , , , , , , , or When, then the corresponding B is , , , , , , , , , , , or .

[0259] Synthesis of 3,3'-bis[(6-azidoalkyl)thio]-4,4'-biphenyldicarboxaldehyde

[0260]

[0261] 3,3′-dithiol-4,4'-biphenyldicarboxaldehyde (approximately 1.0 g, approximately 4.1 mmol, approximately 1.0 equivalent), K₂CO₃ (approximately 1.7 g, approximately 12 mmol, approximately 3.0 equivalent), and 1-hexanol, 6-azido-, 1-(4-methylbenzenesulfonate) (approximately 2.7 g, approximately 9.0 mmol, approximately 2.2 equivalent) were added to approximately 30 mL of anhydrous DMF under a nitrogen atmosphere. The resulting suspension was heated to approximately 80 °C and stirred for approximately 16 hours. After cooling, the DMF was evaporated under reduced pressure, and the remaining mixture was extracted with water (100 mL) and DCM (100 mL). The organic phase was collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution can be filtered and concentrated, and the resulting solid can be subjected to rapid column chromatography using silica gel and ethyl acetate / hexane (1 / 5, v / v) as eluent to obtain the product.

[0262] Synthesis of 3,3'-bis[(6-azidoalkyl)amino]-4,4'-biphenyldicarboxaldehyde

[0263]

[0264] 3,3′-diamino-4,4'-biphenyldicarboxaldehyde (approximately 1.0 g, approximately 4.1 mmol, approximately 1.0 equivalent), K₂CO₃ (approximately 1.7 g, approximately 12 mmol, approximately 3.0 equivalent), and 1-hexanol, 6-azido-, 1-(4-methylbenzenesulfonate) (approximately 2.7 g, approximately 9.0 mmol, approximately 2.2 equivalent) were added to approximately 30 mL of anhydrous DMF under a nitrogen atmosphere. The resulting suspension was heated to approximately 80 °C and stirred for approximately 16 hours. After cooling, the DMF was evaporated under reduced pressure, and the remaining mixture was extracted with water (100 mL) and DCM (100 mL). The organic phase was collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution can be filtered and concentrated, and the resulting solid can be subjected to rapid column chromatography using silica gel and ethyl acetate / hexane (1 / 5, v / v) as eluent to obtain the product.

[0265] Synthesis of COF-999-N3. TCPB (16.9 mg, 0.04 mmol), BPDA-N3 (29.6 mg, 0.06 mmol), and Cs₂CO₃ (39.1 mg, 0.12 mmol) were packed into a borosilicate glass tube with dimensions of 8 × 10 mm (inner diameter × outer diameter) and mixed in 0.5 mL of 1,2-dichlorobenzene and 0.5 mL of 1-butanol. The mixture was rapidly frozen in a liquid nitrogen bath at 77 K, evacuated to an internal pressure below 0.2 mbar, and flame-sealed. After sealing, the length of the tube was reduced to approximately 10 cm. After warming to room temperature, the mixture was heated in an oven at 120 °C for 3 days to obtain a yellow solid. The solid was filtered, washed with methanol (30 mL), and used directly in the next step without further treatment. To characterize COF-999-N3, the above-mentioned yellow solid was transferred to a Kimwipe bag and further washed with methanol in a Soxhlet extractor for 16 hours, dried with supercritical CO2, and degassed under vacuum at 30°C for 3 hours to obtain COF-999-N3 as a yellow solid (yield 81%). 23 H 21 Elemental analysis of N4O: Calculated values: C 74.77%, H 5.73%, N 15.17%; Measured values: C 74.08%, H 5.79%, N 14.01%.

[0266] Synthesis of COF-999-NH2. COF-999-N3 (100 mg), PPh3 (200 mg), and 30 mL of methanol were added to a 100 mL round-bottom flask at 25 °C. After 24 hours, the suspension was filtered and washed with methanol to remove excess PPh3. The yellow residue was transferred to another 100 mL round-bottom flask, and 24 mL of methanol and 6 mL of water were added at 25 °C. After 24 hours, the suspension was filtered in a Kimwipe bag, washed with methanol in a Soxhlet extractor for 16 hours, dried with supercritical CO2, and degassed under vacuum at 30 °C for 3 hours to give COF-999-NH2 as a yellow solid (98% yield). 23 H 23 Elemental analysis of N2O: calculated values: C 80.44%, H 6.75%, N 8.16%; measured values: C 78.51%, H 6.38%, N 8.10%.

[0267] Synthesis of COF-999. COF-999-NH2 (30 mg), toluene (2 mL), acetic acid (5 μL), and aziridine (100 μL) were added to a borosilicate glass tube with dimensions of 8 × 10 mm (inner diameter × outer diameter). The mixture was rapidly frozen in a liquid nitrogen bath at 77 K, evacuated to an internal pressure below 0.3 mbar, and flame-sealed. After sealing, the tube length was reduced to approximately 10 cm. After warming to room temperature, the reaction was heated at 100 °C for 24 h. After cooling to 25 °C, the solid was filtered through a Kimwipe bag, washed with 50 mL of 1 M NaOH in methanol, then washed with methanol in a Soxhlet extractor for 16 h, and dried under vacuum at 120 °C for 12 h to give COF-999 as a yellow solid (yield 86%). 23 H 23 N2O·(C2H5N) 3.1 Elemental analysis: Calculated values: C 73.53%, H 8.14%, N 14.98%; Measured values: C 70.19%, H 7.24%, N 14.35%.

[0268] Powder X-ray diffraction. PXRD patterns were collected in reflection geometry using Cu Kα radiation (λ = 1.54184 Å, with Ni filter) at a power of 600 W (40 kV, 15 mA). The samples were mounted on a Si (511) sample holder and leveled with a spatula. The step size was 0.02° and the exposure time per step was 0.5 s.

[0269] Solid-state nuclear magnetic resonance spectroscopy. Using a Bruker Avance I spectrometer and a 3.2 mm H / C / N magic angle rotation (MAS) probe at an external field B0 = 16.4 T ( 1 H is 700 MHz. 13 C is 176 MHz, and 15 Solid-state NMR experiments were performed at 71 MHz (N). To minimize CO2 and moisture exposure, the COF samples were fully activated and then placed in an argon-filled glove box within a 3.2 mm zirconia rotor, and Vespel was used. ® The lid was sealed. The dried or pre-humidified COF-999 sample was exposed to 1 atm of N2 and 80% RH at room temperature using a homemade gas dosing device. 13 CO2 gas (2.47 atm, Sigma Aldrich, 99% atomic) 13 C) Preparation and dosing time is 3 hours. 13 The CO2 COF sample was then evacuated to room temperature (< 0.3 mbar) for 1 minute to remove excess CO2. Unless otherwise specified, 13 C and 15 The N experiment was conducted under MAS using dry air at rotational speeds of 23 kHz and 11 kHz, respectively. 13 The C chemical shift was externally referenced using the tertiary carbon (CH) resonance of adamantane at 38.48 ppm. 15 The N chemical shift is at 33.4 ppm. 15 N-glycine was used as an external reference.

[0270] COF-999- 15 N3 and COF-999- 15 NH2 15 N-spectroscopy using MAS 1 H 15 N-cross polarization (CP / MAS) was obtained. Initially at 5.20 microseconds (48.1 kHz). 1 Following the H 90° RF pulse, a 2-millisecond CP transfer contact time is used, during which time... 15 A constant RF field of 25.3 kHz is applied to N, while 1 The H RF field amplitude linearly increased from 43.3 kHz to 48.1 kHz. 15 During N acquisition, the SPINAL-64 (64-step small phase increment alternation) decoupling scheme is used. 36 High power application 1 H decoupling, RF field amplitude set to 48.1 kHz. For COF-999- 15N3 recorded a total of 30,688 scans with a recovery delay of 2 seconds, resulting in a total experimental time of 17 hours. Regarding COF-999- 15 NH2 was recorded in a total of 896 scans with a recovery delay of 2.23 seconds, resulting in a total experimental time of 34 minutes.

[0271] Using Johnson and Schimdt-Rohr 37 The aforementioned multiple CP transfers obtained 15 Quantitative analysis of N-labeled COF-999 15 N spectrum. For each scan, a total of 4 CP transfers are used to make COF-999 15 The N signal saturates, and the initial recovery delay is 7.28 seconds (5*T1). 1 H)) and the delay between CP transfers is 2.91 seconds (2*T1( 1 H)). 1 H 15 The N CP transfer used the same parameters described previously, and a total of 1088 scans were averaged, resulting in a total experimental time of 6 hours.

[0272] COF-999-N3 13 C-spectroscopy uses 1 H 13 Obtained by CCP / MAS. Initially at 5.20 microseconds (48.1 kHz). 1 Following the H90° RF pulse, a 2-millisecond CP transfer contact time is used, during which time... 13 A constant RF field of 34.5 kHz is applied to C, while 1 The H RF field amplitude linearly increased from 43.3 kHz to 48.1 kHz. 13 During C acquisition, the SPINAL-64 decoupling scheme is used for high-power applications. 1 H-decoupling was used, and the RF field amplitude was set to 48.1 kHz. A total of 9856 scans were recorded, with a recovery delay of 1.3 seconds, resulting in a total experimental time of 3.6 hours.

[0273] Quantitative analysis of COF-999-NH2 and COF-999 using multiple CP transfer methods 13 C-spectroscopy. For each scan, a total of 10 or 14 CP transfers were used to convert COF-999-NH2 or COF-999, respectively. 13 The C signal saturates, with an initial recovery delay of 5 seconds or 4.25 seconds, and a delay between CP transfers of 2 seconds or 1.71 seconds. 1 H 13The CCP transfer used the same parameters described previously, and a total of 1940 or 3833 scans were averaged, resulting in a total experimental time of 14 hours for COF-999-NH2 or 30 hours for COF-999.

[0274] Add 13 Direct excitation experiments of CO2 with COF-999 were performed under MAS with 10 kHz and 4.12 μs 90° pulses. 13 During C acquisition, the SPINAL-64 decoupling scheme is used for high-power applications. 1 H-decoupling was used, and the RF field amplitude was set to 48.1 kHz. A total of 64 scans were averaged, with a cycle delay of 120 seconds, resulting in an experimental time of 2.2 hours.

[0275] Single-component adsorption isotherm measurements were performed. The N₂ adsorption isotherm at 77 K was measured using a Micromeritics ASAP 2420 accelerated surface area and porosity measurement system. Prior to measurement, the powder sample was activated under dynamic vacuum using the Micromeritics ASAP 2420 system. A liquid nitrogen bath was used to maintain the temperature at 77 K for each measurement. Ultra-high purity (Praxair, 99.999%) N₂ and He gases were used throughout the adsorption experiments.

[0276] CO2 adsorption isotherms were measured using a Micromeritics 3Flex adsorption analyzer. Prior to measurement, powder samples were activated under dynamic vacuum using a Micromeritics ASAP 2420 accelerated surface area and porosity measurement system. A circulating water bath was used to maintain the temperature at 15.00°C, 25.00°C, or 35.00°C for each measurement. Research-grade CO2 (Praxair, 99.998%) was used throughout the adsorption experiments.

[0277] Adsorption isotherms for O2, N2, and Ar were measured at 25 °C using a 3P micro 200 analytical station. Powder samples were activated using the 3P micro 200 activation station under dynamic vacuum at 120 °C. CryoTune 195 was used to maintain the temperature at 25.00 °C for each measurement. Research-grade O2 (TIG, 99.995%) and research-grade N2 (TIG, 99.999%) were used throughout the adsorption experiments.

[0278] H2O vapor adsorption experiments were conducted on a Belprep MAX II high-precision gas / vapor adsorption instrument. Powder samples were activated under dynamic vacuum using a Belprep VAC III before measurement. The water vapor source was degassed through five freeze-pump-thaw cycles prior to analysis. Free space correction was performed using ultra-high purity (Praxair, 99.999%) He, and an isothermal bath was used to regulate the sample temperature during measurement.

[0279] Dynamic penetration measurements were performed on a Micromeritics BTA instrument equipped with a CO2 sensor (detection range = 0.6 ppm to 984.9 ppm) and a humidity sensor. Samples were loaded into a jacketed column (4.9 mm inner diameter), and temperature was controlled using a Ministat 230 oil circulation bath. Penetration measurements were performed using ultra-high purity (Praxair, 99.999%) N2, ultra-zero grade air (Praxair), 1000 ppm CO2 balanced in air (Praxair), 1% CO2 balanced in N2 (Praxair), 20% CO2 balanced in N2 (Praxair), and research grade CO2 (Praxair, 99.998%).

[0280] Humidified air or N2 can be obtained by passing dry air or N2 through a water bath. Different CO2 concentrations and relative humidityes can be fine-tuned by adjusting the mixing ratios of different gases. Specifically, 400 ppm CO2 balanced in air is mixed with humid air, dry air, and 1000 ppm CO2 balanced in air; 400 ppm CO2 balanced in N2 is mixed with humid N2, dry N2, and 1% CO2 balanced in N2; 4% CO2 balanced in N2 is mixed with humid N2, dry N2, and 20% CO2 balanced in N2; and 15% CO2 balanced in N2 is mixed with humid N2, dry N2, and pure CO2.

[0281] Ambient air was collected from the balcony of Room 626, 6th floor, Latimer Hall (37°52'23.8"N 122°15'21.2"W), Berkeley, California, USA, between January 18, 2024 and February 6, 2024. The ambient air was pressurized to 300 kPa using a Welch 2522B-01 dry pump and then stabilized at 200 kPa using an Aldrich HPL500-2160 mini gas regulator before being introduced into the breakthrough analyzer.

[0282] In the adsorption capacity measurement experiment, 90 to 280 mg of COF-999 sample was loaded into a jacketed column. The oil bath was first heated to 80°C, resulting in a column wall temperature of 76°C and a column center temperature of 48°C. A 50 sccm N2 flow was passed through the sample until the outlet CO2 concentration was below 5 ppm. The oil bath was then cooled and maintained at 25°C, and the sample was exposed to a 10 or 50 sccm simulated gas mixture with the desired CO2 concentration (400 ppm, 4.0%, or 15.0%) and desired relative humidity (0%, 25%, 50%, or 75%) in equilibrium with N2 until the outlet CO2 concentration remained constant. The specific CO2 adsorption capacity of the sample was then obtained, which is the difference between the apparent adsorption capacity per unit mass of sample and the background adsorption capacity.

[0283] In the cyclic stability measurement experiment, 80 mg of COF-999 sample was loaded into a jacketed column. The oil bath was first heated to 64°C, resulting in a column wall temperature of 60°C and a column center temperature of 41°C. A 50 sccm N2 flow was passed through the sample until the outlet CO2 concentration was below 5 ppm. Then, the oil bath was cooled and maintained at 25°C, and the sample was exposed to 50 sccm 400 ppm CO2 equilibrated in air with 50% RH until the outlet CO2 concentration was above 395 ppm. Before each cycle, the sample was reactivated using the same procedure described above. The specific CO2 adsorption capacity of the sample was then obtained, which is the difference between the apparent adsorption capacity per unit mass of sample and the background adsorption capacity.

[0284] In the adsorption kinetics measurement experiment, 5.0 mg of COF-999 sample was loaded into a jacketed column. First, the oil bath was heated to 80°C, resulting in a column wall temperature of 76°C and a column center temperature of 48°C. A 50 sccm N2 flow was passed through the sample for 120 minutes to fully activate it. Then, the oil bath was cooled and maintained at 25°C, and the sample was humidified by exposing it to 50 sccm of CO2-free air with 50% RH for 30 minutes, followed by exposure to 50 sccm of 400 ppm CO2 equilibrated in air with 50% RH until the outlet CO2 concentration remained constant. The specific CO2 adsorption capacity of the sample was then obtained, which is the difference between the apparent adsorption capacity per unit mass of sample and the background adsorption capacity.

[0285] In the desorption kinetics measurement experiment, 5.0 mg of COF-999 sample was loaded into a jacketed column. The sample was first exposed to 400 ppm CO2 at 50 sccm in air with 50% relative humidity until the outlet CO2 concentration was constant. Then, the column was heated under a 50 sccm N2 stream until the column wall temperature reached 60°C, 80°C, or 100°C. The column temperature was maintained for 3 hours for desorption. The amount of desorbed CO2 was obtained as the integrated downstream CO2 concentration per unit mass of sample.

[0286] In the outdoor air capture measurement experiment, 73 mg of COF-999 sample was loaded into a jacketed column. For each cycle, the oil bath was first heated to 64°C, resulting in a column wall temperature of 60°C and a column center temperature of 41°C. A 50 sccm N2 flow was passed through the sample until the outlet CO2 concentration was below 20 ppm (typically 90 minutes). The oil bath was then cooled to 25°C and shut off. The background relative humidity and CO2 concentration of outdoor air (around 25°C) were measured via a bypass. The sample was then exposed to 50 sccm of ambient air until the outlet CO2 concentration was above 300 ppm. Before each cycle, the sample was reactivated using the same procedure described above. The specific CO2 adsorption capacity of the sample was then obtained, which is the difference between the apparent adsorption capacity per unit mass of sample and the background adsorption capacity. Two complete cycles were measured using simulated air before and after the experiment to evaluate the stability of the sample.

[0287] Periodic density functional theory (DFT) calculations were performed using Vienna Ab Initio Simulation (VASP version 6.1) software. 38–40 DFT calculations were performed to study CO2 adsorption in COF-999. Perdew-Burke-Ernzerhoff (PBE) exchange-correlated density functional theory was used. 41 With Grimme's D3 dispersion correction with Becke-Johnson damping (PBE-D3BJ) 42 Together, they are used in all calculations. Generally, for structural optimization of each adsorbate in COF-999, a plane-wave basis set with an energy cutoff of 400 eV is used. Each structure is optimized up to 10... –6 The energy and force convergence criteria were eV and 0.03 eV / Å. Brillouin zone sampling was performed using a 1 × 1 × 3 Γ-centered k-point grid. During each structure optimization, only atomic positions were relaxed, while the cell parameters remained constant.

[0288] The structural model of COF-999 was obtained from the COF-999-NH2 structure. First, the structure of COF-999-NH2 was optimized using DFT with the following settings: a PBE-D3BJ exchange-correlated density functional with dispersion correction and a plane-wave basis set with an energy cutoff of 520 eV. The same energy and force convergence criteria as described above were used, along with Brillouin zone sampling using a 1 × 1 × 5 Γ-centered k-point grid. Compared to subsequent structural optimizations of COF-999, the initial optimization of COF-999-NH2 used a higher energy cutoff and a denser k-point grid due to the relaxation of atomic positions and cell parameters during structural optimization. The optimized COF-999-NH2 structure was then modified to introduce 4.5 -CH2-CH2-NH- units (on average) and branched on 2 of the 6 side chains of COF-999-NH2. This model represents the polymerized polyethyleneimine unit formed in COF-999 and encompasses various CO2 adsorption sites composed of primary, secondary, and tertiary amines. This optimized structure (cell parameters: a = b = 45.084 Å, c = 3.819 Å, α = β = 90°, γ = 120°) was used to study CO2 adsorption in COF-999. Due to the conformational flexibility of the polyamine chain, several different CO2 adsorption environments composed of polyamines were investigated, and representative environments are shown here. The adsorption energy ΔE was calculated using Equation 1. 吸附 (Electron energy):

[0289]

[0290] Where E 吸附系统 It is the electronic energy of the system after adsorption, E 空COF It has the electron energy of an empty COF with a conformation similar to that of polyamines in the adsorbed state. and These are the electron energies of the separated CO2 and H2O molecules, respectively. and It represents the number of CO2 and H2O molecules adsorbed.

[0291] Chemicals. 4-Toluenesulfonyl chloride (98%), 2-chloroethylamine hydrochloride (98%), 6-chloro-1-hexanol (95%), sodium hydroxide (97%), 1,2-dichlorobenzene (99%), triphenylphosphine (99%), and sodium sulfate (99%) were purchased from AK Scientific. Potassium carbonate (99%) was purchased from Alfa Aesar. 1,3,5-Tris(4-cyanomethylphenyl)benzene (TCPB, 98%) and 3,3′-dihydroxy-4,4'-biphenyldicarboxaldehyde (97%) were purchased from Arctom Scientific. Sodium azide (Na... 15NN2,1- 15 N (98%) was purchased from Cambridge Isotope Laboratory. Cesium carbonate (Cs₂CO₃, 99.99%) was purchased from Chem-Impex International. Methanol (99.8%) was purchased from Fischer Scientific. Hexane (a mixture of isomers, enantiomeric total 98.5%) was purchased from JTBaker. Ethyl acetate (99.5%) was purchased from Macron Fine Chemicals. Dichloromethane (DCM, 99.5%), N,N-dimethylformamide (DMF, 99.9%), 1,4-dioxane (99%), triethylamine (99%), sodium azide (99%), toluene (99.5%), acetic acid (99.7%), 1-butanol (99.9%), and chloroform-d (CDCl₃, 99.8 atomic % D) were purchased from Sigma Aldrich. All reagents and solvents were used without further purification.

[0292] Solution-state nuclear magnetic resonance spectroscopy. A Bruker spectrometer equipped with an Avance-III control console was used at an external field B0 = 14.1 T ( 1 H is 600 MHz. 13 C is 151 MHz, and 15 Solution-state NMR experiments were performed at 61 MHz (N). Solvent resonance was used as the internal standard reference chemical shift (δ). 1 H: CDCl3 was 7.26 ppm; δ 13 C: CDCl3 was 77.16 ppm. Polynomial baseline correction was applied to each spectrum before integration using the Mestrelab MestReNova software.

[0293] Trace elemental analysis. Elemental analysis was performed using a PerkinElmer 2400 Series II CHNS elemental analyzer in the Trace Analysis Laboratory of the Department of Chemistry at the University of California, Berkeley.

[0294] Fourier transform infrared (FT-IR) spectroscopy. FT-IR spectra were collected on a Bruker ALPHA Platinum ATR-FT-IR spectrometer equipped with a single-reflection diamond ATR module. Spectra were collected on pure samples at room temperature (approximately 25°C). Spectra are expressed as transmittance (%) and wavenumber (cm²). –1 The relationship between the two is drawn.

[0295] High-resolution mass spectrometry (HR-MS). HR-MS measurements were performed at the QB3 / Chemical Mass Spectrometry Facility at the University of California, Berkeley. Mass is reported in m / z as molecular ion M. + [M + H] +[M + Na] + [M + K] + The corresponding intensity is expressed as a percentage (%).

[0296] Thermogravimetric analysis (TGA). TGA curves were recorded on a TA Q500 thermal analysis system under nitrogen flow, at 10°C / min. −1 Temperature was increased from room temperature (typically 25°C) to 800°C. All TGA measurements were performed using ultra-high purity N2.

[0297] Supercritical carbon dioxide dryer. Supercritical CO2 drying was performed using a Tousimis Autosamdri-931 critical point dryer. Instrument-grade CO2 (Praxair, 99.99%) was used throughout the drying process.

[0298] Scanning electron microscopy (SEM). SEM images were obtained on a Zeiss XB 550 high-resolution SEM with an accelerating voltage of 1.0 kV. Samples were dispersed on conductive carbon tape, mounted on a sample stage, and sputtered (Pd / Au) using a Tousimis sputtering coating machine located on a Bio-Rad E5400 controller.

[0299] Synthesis of linkers

[0300] Synthesis of 1-hexanol, 6-azido-, 1-(4-methylbenzenesulfonate).

[0301]

[0302] 6-Chloro-1-hexanol (13.6 g, 100 mmol, 1.0 equivalent) and NaN3 (8.5 g, 131 mmol, 1.3 equivalent) were added to 100 mL of DI water, and the reaction mixture was refluxed at 100 °C for 48 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate (100 mL × 3). The organic phases were combined, washed with water (100 mL × 3) and brine (50 mL), and dried over sodium sulfate. After filtration, the solvent was evaporated to give 6-azido-1-hexanol as a colorless oil, which could be used directly in the next step without further purification.

[0303] The above-mentioned colorless oil was dissolved in 150 mL of DCM under a nitrogen atmosphere, and the solution was cooled to 0 °C. 4-Toluenesulfonyl chloride (21.0 g, 110 mmol, 1.1 equivalents) and triethylamine (41.8 mL, 300 mmol, 3.0 equivalents) were added to the solution. The solution was warmed to 25 °C and stirred for 16 hours. After completion, 100 mL of water was added, and the organic phase was collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution was filtered and concentrated, and the resulting oil was subjected to rapid column chromatography using silica gel with ethyl acetate / hexane (1 / 5, v / v) as eluent to give a product as a colorless oil (24.2 g, total yield 81%). 1 H NMR (600 MHz, CDCl3): δ (ppm) 7.79 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.3 Hz, 2H), 4.02 (t, J = 6.3 Hz, 2H), 3.23 (t, J = 6.7 Hz, 2H), 2.45 (s, 3H), 1.65 (m, 2H), 1.54 (m, 2H), 1.33 (m, 4H).

[0304] Synthesis of 3,3'-bis[(6-azidohexyl)oxy]-4,4'-biphenyldicarboxaldehyde (BPDA-N3).

[0305]

[0306] 3,3'-dihydroxy-4,4'-biphenyldicarboxaldehyde (1.0 g, 4.1 mmol, 1.0 equivalent), K₂CO₃ (1.7 g, 12 mmol, 3.0 equivalent), and 1-hexanol, 6-azido-, 1-(4-methylbenzenesulfonate) (2.7 g, 9.0 mmol, 2.2 equivalent) were added to 30 mL of anhydrous DMF under a nitrogen atmosphere. The resulting suspension was heated to 80 °C and stirred for 16 hours. After cooling, the DMF was evaporated under reduced pressure, and the remaining mixture was extracted with water (100 mL) and DCM (100 mL). The organic phase was collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution was filtered and concentrated, and the resulting solid was subjected to rapid column chromatography using silica gel with ethyl acetate / hexane (1 / 5, v / v) as eluent to give the product as a white solid (1.52 g, 74% yield). 1H NMR (600 MHz, CDCl3): δ (ppm) 10.53 (s, 2H), 7.92 (d,J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.14 (s, 2H), 4.18 (t, J = 6.3 Hz,4H), 3.30 (t, J = 6.3 Hz, 4H), 1.91 (m, 4H), 1.65 (m, 4H), 1.57 (m, 4H), 1.50 (m, 4H). 13 C NMR (151 MHz, CDCl3) δ 189.4, 161.8, 147.9, 129.1, 124.7, 120.0,111.5, 68.7, 51.5, 29.1, 28.9, 26.6, 25.8. HR-ESI-MS: m / z: 515.2382 ([M + Na] + [C] 26 H 32 N6O4Na] + The calculated value is 515.2377.

[0307] Synthesis of 3,3'-bis(methoxymethoxy)-[1,1'-biphenyl]-4,4'-dicarboxaldehyde (BPDA-OMOM).

[0308]

[0309] Under nitrogen atmosphere, 10 mmol of 4-bromo-2-(methoxymethoxy)benzaldehyde, 10 mmol of 2-(methoxymethoxy)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)benzaldehyde, 0.1 mmol of Pd(PPh3)4, and 30 mmol of K2CO3 were added to a mixture of dioxane (150 mL) and water (50 mL). The mixture was heated to 95 °C for 18 hours. After cooling to room temperature, the solvent was evaporated, and the residue was purified by column chromatography to give 3,3'-bis(methoxymethoxy)[1,1'-biphenyl]-4,4'-dicarboxaldehyde as a white solid.

[0310] Synthesis of aziridine. 2-Chloroethylamine hydrochloride (50.0 g, 431 mmol) was slowly added to a 500 mL round-bottom flask containing an aqueous solution of sodium hydroxide (50.0 g NaOH in 200 mL DI water). The resulting solution was heated to 50 °C and stirred for 3 hours. After the reaction, aziridine was separated by distillation under vacuum (20 kPa) at 80 °C. Sodium hydroxide was added to the collected distillate for drying, and the aqueous aziridine was further purified by distillation under ambient pressure (boiling point 56 °C, 101 kPa). 1 H NMR (600 MHz, CDCl3): δ (ppm) 1.59 (s, 4H), −0.10 (s, 1H). 13 C NMR (151MHz, CDCl3) δ 18.3 ppm.

[0311] BPDA- 15 Synthesis of N3. BPDA- was synthesized according to the above method. 15 N3. Used in the reaction. 15 N-labeled sodium azide (Na) 15 NN2). BPDA- 15 N3 is α- 15 N (R‒ 15 N=N=N) and γ- 15 N (R‒N=N= 15 The mixture of N-labeled compounds is because only one terminal nitrogen atom in sodium azide is labeled. 1 H NMR (600 MHz, CDCl3): δ (ppm) 10.53 (s,2H), 7.91 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.14 (s, 2H), 4.17(t, J = 6.3 Hz, 4H), 3.30 (t, J = 6.3 Hz, 4H), 1.91 (m, 4H), 1.65 (m, 4H), 1.57 (m, 4H), 1.49 (m, 4H). 13 C NMR (151 MHz, CDCl3): δ (ppm) 189.3, 161.8,147.8, 129.1, 124.7, 119.9, 111.6, 68.7, 51.5 (d, J = 4.0 Hz), 29.1, 28.9, 26.6, 25.8. 15 N NMR (61 MHz, CDCl3): δ (ppm) 210.7 (R‒N=N=15 N), 71.7 (R‒ 15 N=N=N). HR-ESI-MS: m / z: 517.2322 ([M + Na] + [C] 26 H 32 N4 15 N2O4Na] + The calculated value is 517.2318.

[0312] Powder X-ray diffraction.

[0313] Table 1. Fractional atomic coordinates of the structural model of COF-999-N3 obtained by Pawley refinement.

[0314]

[0315] Table 2. Fractional atomic coordinates of the structural model of COF-999-NH2 obtained by Pawley refinement.

[0316]

[0317] Table 3. Fractional atomic coordinates of the COF-999 structural model obtained by geometric optimization.

[0318]

[0319] Calculation of degree of polymerization. The peak area in multiCP / MAS ssNMR (Figure 18) is proportional to the number of atoms it represents (32). Since there are 6 carbons (C-#1 to C-#6) on the side chain before polymerization, and each polyethyleneimine unit provides two additional carbons on the side chain, the average degree of polymerization per side chain can be calculated as (12.10 – 6) / 2 = 3.05. This value can also be calculated from the elemental analysis results of COF-999 (Table 4).

[0320] According to multiCP / MAS 15N ss NMR (Figure 19) showed that 65.9% of the amines on the pore walls were connected to polyethyleneimine units. Therefore, the degree of polymerization after excluding those unreacted amines can be calculated as 3.05 / (65.9%) = 4.63.

[0321] Table 4. COF-999 [C 23 H 23 N2O·(C2H5N) n The experimental elemental analysis results were compared with the calculated elemental ratios for different degrees of polymerization. The experimental C / N ratio was consistent with the calculated results for n=3.1.

[0322]

[0323] DFT calculations were performed to investigate the CO2 adsorption mechanism in COF-999 under both the absence and presence of water molecules (dry and humid conditions, respectively, for CO2 capture). Notably, the polyethyleneimine unit exhibits significant conformational flexibility, allowing the polyamine chain to be tuned to a favorable CO2 adsorption structure under both dry and humid conditions, thereby maximizing its CO2 adsorption capacity.

[0324] Under dry conditions, the formation of carbamic acid / carbamates (Table 5, CA1 to CA3) upon the reaction of CO2 molecules with polyamine groups is energy-favorable (ΔE = –75 to –101 kJ·mol⁻¹). –1 Carbamic acids are stabilized through hydrogen bonding interactions with adjacent polyamine groups (N···O distance of approximately 263 to 273 pm). Under dry conditions, carbamates are thermodynamically more favorable than adsorbed CO2 molecules.

[0325] Table 5 shows the corresponding reaction energies ΔE (kJ·mol⁻¹) for the optimized carbamic acid / carbamate structure in the absence of water molecules formed during CO₂ adsorption in COF-999. –1 O CO2 With N 胺 The hydrogen bond distance between them and the corresponding OH and N 胺 -H distance (in square brackets) is given in pm.

[0326] Table 5. ΔE (kJ·mol⁻¹) for CA1, CA2, and CA3 –1 ) and hydrogen bond distance.

[0327]

[0328] Under humid conditions, the carbamic acid / carbamates (Table 6, CW1 to CW3) formed when CO2 molecules react with polyamines interact with water molecules via hydrogen bonding (ΔE approximately –150 kJ·mol⁻¹). –1 Stable. The carbamates are each approximately 257 to 262 pm from adjacent polyamine groups (N···O [donor] distance, and approximately 281 to 317 pm from N [donor]···O distance) and water molecules (O···O). 水 Hydrogen bonds are formed between the oxygen atom of the carbamate and the adjacent polyamine group (O···H distance approximately 105 to 112 pm, and N···H distance approximately 103 to 106 pm). Thermodynamically, the formation of carbamates is more favorable under humid conditions than the formation of bicarbonates.

[0329] Table 6 shows the corresponding reaction energies ΔE (kJ·mol⁻¹) for the optimized carbamic acid / carbamate structure in the presence of water molecules formed during CO₂ adsorption in COF-999. –1 O CO2 With N 胺 The hydrogen bond distance between them and the corresponding OH and N 胺 -H distance (in square brackets) is given in pm.

[0330] Table 6. ΔE (kJ·mol⁻¹) for CW1, CW2, and CW3 –1 ) and hydrogen bond distance.

[0331]

[0332] Under humid conditions, CO2 molecules react with water molecules with the assistance of polyamine groups to form carbonates / bicarbonates (Table 7, BC1 to BC3) (ΔE = –82 to –110 kJ·mol). –1 Bicarbonate forms at least one strong hydrogen bond with the polyamine group (N···O distance approximately 254 to 263 pm), and is further stabilized by up to two additional hydrogen bonds with the adjacent polyamine (N···O distance approximately 271 to 334 pm). Bicarbonate provides up to two hydrogen bonds to the polyamine through its -OH group and accepts one hydrogen bond through its =O group. The proton is delocalized between the oxygen atom of the bicarbonate and the polyamine group (O···H distance approximately 103 to 111 pm, and N···H distance approximately 103 to 107 pm).

[0333] Table 7 shows the corresponding reaction energies ΔE (kJ·mol⁻¹) for the optimized structure of carbonate / bicarbonate in the absence of water molecules formed during CO₂ adsorption in COF-999. –1O CO2 With N 胺 The hydrogen bond distance between them and the corresponding OH and N 胺 -H distance (in square brackets) is given in pm.

[0334] Table 7. ΔE (kJ·mol⁻¹) for BC1, BC2, and BC3 –1 ) and hydrogen bond distance.

[0335]

[0336] Table 8. Absolute electron energy (in eV) and relative electron energy (kJ·mol⁻¹) of different intermediates formed during CO₂ adsorption –1 ).

[0337]

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[0381] In at least some of the previously described embodiments, one or more elements used in the embodiments may be used interchangeably in another embodiment, unless such substitution is technically not feasible. Those skilled in the art will understand that various other omissions, additions, and modifications can be made to the methods and structures described above without departing from the scope of the claimed subject matter. All such modifications and changes are intended to fall within the scope of the subject matter defined by the appended claims.

[0382] Those skilled in the art will understand that, in general, the terminology used herein, particularly in the appended claims (e.g., the text of the appended claims), is intended to be “open-ended” terms (e.g., the term “comprising” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “at least having,” the term “comprising” should be interpreted as “including but not limited to,” etc.). Those skilled in the art will also understand that if a particular number of the introduced claim statements are intended, such an intent will be explicitly stated in the claims, and if no such statements are present, such an intent does not exist. For example, to aid understanding, the following appended claims may contain the use of the introductory phrases “at least one” and “one or more” to introduce the claim statements. However, the use of such phrases should not be construed as implying that the introduction of a claim statement by the indefinite article "a / an" limits any particular claim containing such an introduced claim statement to an embodiment containing only one such statement, even when the same claim contains the introductory phrase "one or more" or "at least one" and the indefinite article "a" or "an" (e.g., "a" and / or "an" should be interpreted as meaning "one or more" or "at least one"); this also applies to the use of definite articles used to introduce claim statements. Furthermore, even when a specific number of introduced claim statements is explicitly stated, those skilled in the art should recognize that such statements should be interpreted as meaning at least the number stated (e.g., an unmodified statement of "two statements" without other modifiers means at least two statements, or two or more statements). Furthermore, in cases where conventions such as "at least one of A, B, and C" are used, generally speaking, the meaning of such a construction is the convention that should be understood by those skilled in the art (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, systems having a single A, a single B, a single C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those cases, where the convention is similar to "at least one of A, B, or C," such a construction is generally used in the sense that those skilled in the art understand the convention (e.g., "a system having at least one of A, B, or C" will include, but is not limited to, systems having a single A, a single B, a single C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). Those skilled in the art will further understand that virtually any transitional words and / or phrases presenting two or more alternative terms, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one, any, or both of these terms. For example, the phrase “A or B” will be understood as including the possibility of “A” or “B” or “A and B”.

[0383] Furthermore, when features or aspects of this disclosure are described in the form of a Markush group, those skilled in the art will recognize that this disclosure is therefore also described in the form of any single member or subgroup of a Markush group.

[0384] As those skilled in the art will understand, for any and all purposes, such as providing a written description, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any listed scope can be readily considered sufficiently descriptive and such that the same scope can be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily divided into a lower third, a middle third, and an upper third, etc. As those skilled in the art will also understand, all language, such as “up to,” “at least,” “greater than,” “less than,” etc., includes the listed numbers and refers to a scope that can subsequently be decomposed into subscopes as described above. Finally, as those skilled in the art will understand, a scope includes each individual member. Thus, for example, a group having 1-3 items means a group having 1, 2, or 3 items. Similarly, a group having 1-5 items means a group having 1, 2, 3, 4, or 5 items, and so on.

[0385] Although the foregoing invention has been described in detail by way of illustration and examples for the purpose of clarity, it will be apparent to those skilled in the art, based on the teachings of the invention, that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.

[0386] Therefore, the foregoing has merely illustrated the principles of the invention. It will be understood that those skilled in the art will be able to design various arrangements that, while not explicitly described or shown herein, embody the principles of the invention and are included within its spirit and scope. Furthermore, all instances and conditional language described herein are primarily intended to aid the reader in understanding the principles of the invention and the concepts contributed by the inventors to the field, and should be construed as not being limited to these specifically described instances and conditions. Moreover, all statements herein describing the principles, aspects, and embodiments of the invention and their specific examples are intended to cover both structural and functional equivalents. Furthermore, it is intended that such equivalents include both currently known equivalents and future-developed equivalents, i.e., any elements developed that perform the same function, regardless of structure. Furthermore, nothing disclosed herein is intended to be offered to the public, whether or not such disclosure is expressly stated in the claims.

[0387] Therefore, the scope of the invention is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of the invention are embodied in the appended claims. In the claims, 35 USC §112(f) or 35 USC §112(6) is explicitly defined as being invoked only when such limitation in the claim begins with the exact phrase “means for…” or the exact phrase “steps for…”; if such exact phrase is not used in the limitation in the claim, then 35 USC §112(f) or 35 USC §112(6) is not invoked.

Claims

1. A covalent organic framework (COF) comprising the structure according to formula (I): (I) where Y is 、 、 or V is 、 or Z is 、 、 or And q1, q2, and q3 are each 0, 1, or 2, where Z is... or When Z is , then q1 + q2 = q, and where when Z is When q1 + q2 + q3 = q; each X is independently selected from 、 and Each n is an integer independently selected from 0 to 12, and when n is an integer from 1 to 12, each W is independently selected from... -NH(CH2)2NH2, poly(ethyleneimine) 、 The following are listed: -NH(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene, and poly(4-aminostyrene), and when n is 0, each W is independently selected from -(CH 2) 2NH2, poly(ethyleneimine), -(CH(CH3))2NH2, poly(methyl(ethyleneimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethyleneimine)), -(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-1-amine, poly(but-3-en-1-amine), 4-aminostyrene and poly(4-aminostyrene); and q is 2, 1, 3 or 4.

2. The COF according to claim 1, wherein Y is 。 3. The COF according to claim 1 or 2, wherein V is 。 4. The COF according to the preceding claim, wherein Z is 、 、 、 、 、 、 、 、 、 、 、 、 or 。 5. The COF according to the preceding claim, wherein Z is 。 6. The COF according to the preceding claim, wherein q is 1 or 2.

7. The COF according to the preceding claim, wherein each n is an integer independently selected from 2 to 8.

8. The COF according to the preceding claim, wherein each X is 。 9. The COF according to the preceding claim, wherein n is 6 and each W is independently selected from... -NH(CH2)2NH2 and polyethyleneimine.

10. The COF according to the preceding claim, wherein Y is V is Z is Each X is And each W is independently selected -NH(CH2)2NH2 and polyethyleneimine.

11. The COF according to the preceding claim, configured for carbon dioxide capture.

12. The COF according to the preceding claim, configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas.

13. The COF according to the preceding claims, comprising a matrix configured as an adsorption bed, a fluidized bed, a coated heat exchanger, or a membrane.

14. The COF according to the preceding claims, comprising a matrix configured as an adsorption bed, fluidized bed, coated heat exchanger or membrane, located in a fluid flow path configured to allow air or a mixture to pass over, around and / or through the matrix.

15. The COF of claim 14, comprising air or a post-combustion exhaust mixture, wherein water is present in the air or mixture, and the material is configured and operable to collect the water from the air or mixture.

16. A system for capturing carbon dioxide from air or a mixture of post-combustion exhaust gases, comprising a matrix, such as an adsorption bed containing COF as described herein, the matrix being configured as a solid adsorbent for capturing the carbon dioxide from the air or mixture and optionally capturing water.

17. A method comprising using a COF according to the preceding claim as a solid adsorbent for capturing carbon dioxide from air or a post-combustion exhaust gas mixture and optionally capturing water.

18. A method for capturing and / or separating carbon dioxide, particularly from air or flue gas, using a COF according to the preceding claims.

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