Polymer-functionalized reticular materials for carbon dioxide capture

Abstract

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

Description

Polymer-functionalized Reticular Materials for Carbon Dioxide CaptureCross-Reference to Related Applications

[0001] Pursuant to 35 U.S.C. § 119(e), this application claims priority to the filing dates of United States Provisional Patent Application Serial Nos. 63 / 587,185 filed October 2, 2023, and 63 / 678,968 filed August 2, 2024, the disclosure of each of which is herein incorporated by reference in their entirety.Introduction

[0002] The unprecedented rise in atmospheric carbon dioxide (CO2) concentrations, largely attributed to anthropogenic activities such as fossil fuel combustion and deforestation, has become an urgent global issue because of its key role in driving climate change. The unprecedented accumulation of CO2in the atmosphere has exacerbated the greenhouse effect, leading to increased temperatures, altered precipitation patterns, and other negative environmental impacts.

[0003] In response, a significant number of materials have been investigated. Polymers, such as polyethylenimine and polylysine, have demonstrated significant promise in addressing the CO problem. However, it is challenging to meet all the demanding application requirements, which include high capacity, low regeneration energy, quick kinetics, and long cycling lifetime. The applicability of the current desiccants, namely porous carbon, zeolites, hydroxides, amine liquids, and grafted amines, is limited by low carbon dioxide capacity, high energy consumption, and low cycle stability.

[0004] In particular, porous carbon and zeolites display low carbon dioxide capacity under low pressure or diluted conditions because of the physisorption mechanism, which limits their applicability in direct air capture and post combustion capture from natural gas flue gas. For hydroxides, the binding between carbon dioxide and adsorbent is too strong, thus requiring very high energy to regenerate the material. Amine liquids have suitable basicity and show high carbon dioxide uptake, but face the problems of amine loss, corrosion, and amine oxidation during application. Physically grafted amines in solidified resins and silica increase the uptake and decrease the desorption temperature compared to amine liquids, but still have stability and amine loss issues under cycling. By covalently linking amines to resins or silica supports, the cycle stability would increase; however, most resins and silica contain only hydroxyl functionalities inside the pore, which limits the possibility of post-modification reactions of the material. Meanwhile, the hydrophilic backbones of those materials also adsorb water underhumid conditions, thus raising their regeneration temperature and costing more energy to regenerate.

[0005] Relevant Literature includes: see herein.Summary of the Invention

[0006] The invention provides methods, systems and compositions comprising reticular materials, including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), that can be employed as carbon dioxide adsorbents because of their highly stable pores which can be functionalized with desired functional groups.

[0007] The invention provides innovative post-synthetic modifications to functionalize reticular materials with polymers, which enables the sorbent to have strong chemisorption of carbon dioxide, and addresses the volatility of polymers, increasing the stability of the sorbent.

[0008] Reticular materials (including metal-organic frameworks and covalent organic frameworks) are composed of rigid molecular building blocks linked together through strong bonds to generate two- and three-dimensional extended structures. They can be employed as carbon dioxide adsorbents because of their highly stable and ordered pores which can be functionalized with desired functional groups. In this disclosure, the synthesis of polymer- functionalized reticular materials formed by in situ polymerization or chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material is described. The polymer-functionalized reticular materials show high carbon dioxide uptake and cycling stability sufficient to be useful for carbon dioxide capture and separation from air and flue gas.

[0009] In an aspect the invention provides a composition comprising a polymer-functionalized reticular material (e.g. COF or MOF) configured for carbon dioxide capture. In certain embodiments, the composition is a COF described herein. In certain embodiments, the composition is a MOF described herein.

[0010] In an aspect the invention provides polymer-functionalized reticular 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.

[0011] In an aspect the invention provides a composition comprising a polymer-functionalized reticular material, formed by in situ polymerization or chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material, wherein the polymer-functionalized reticular material provides carbon dioxide uptake and cycling stability sufficient for carbon dioxide capture and separation from air or flue gas.

[0012] In an aspect the invention provides a composition herein, wherein the functionalization of the reticular materials with polymers is accomplished (i) through in situ polymerization reactions within or on the surface of the reticular material; or (ii) through chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material.

[0013] In an aspect the invention provides a composition herein, wherein (i) the in situ polymerization is achieved by mixing metal-organic frameworks or covalent organic frameworks with the monomer of polymers, followed by polymerization reactions.

[0014] In an aspect the invention provides a composition herein, wherein (ii) the chemical reactions occur between the functional groups of the polymer and the functional groups within or on the surface of the reticular materials, wherein reticular materials can be functionalized through chemical reactions with polymers to form covalent bonds.

[0015] In an aspect the invention provides methods of using the subject compositions for carbon dioxide capture and / or separation, especially from air or flue gas.

[0016] The invention encompasses all combinations of the particular embodiments recited herein, as if each combination had been laboriously recited.Brief Description of the Drawings

[0017] FIG. 1: CO2sorption analyses of COF-999 (previously known as COF-153-PEI) under 298 K.

[0018] FIG. 2: Breakthrough curve of COF-999 (previously known as COF-153-PEI) under 400 ppm CO2at 50% relative humidity in N2, flow rate 60 mL / min, temperature 298 K. The shaded area was used for deriving the CO2uptake through numerical integration.

[0019] FIG. 3: Design strategy and synthesis of COF-999 wherein each W is independently selected from -NH2, -NH(CH2)2NH2, and poly (ethyleneimine). The condensation reaction between TCPB and BPDA-N3 results in COF-999-N3, followed by the reduction of azides to form COF-999-NH2. The reactive amine initiators mounted on the backbone allow for the covalent installation of polyamines through a ring-opening polymerization reaction with aziridine, yielding COF-999.

[0020] FIGS. 4A-4D: Characterization of COF-999 series. FIG. 4A: Experimental PXRD pattern (red), Pawley refined pattern (black), difference pattern (pink), and Bragg positions (green) of COF-999-N3. FIG. 4B: N2 sorption isotherm of COF-999-N3measured at 77 K. FIG. 4C: Comparison of CP / MAS15N ssNMR of COF-999-15N3(blue) and COF-999-15NH2(red),and quantitative multiCP / MAS15N ssNMR of15N labeled COF-999 (black).15N labeled nitrogen atoms are marked with asterisks. Signals from unlabeled nitrogen (aziridine and nitrile) can be neglected due to their low natural abundance. FIG. 4D: Comparison of CP / MAS13C ssNMR of COF-999-Ns (blue), and quantitative multiCP / MAS13C ssNMR of COF-999-NH2(red) and COF-999 (black).

[0021] FIG. 5: SEM images of COF-999-N3, COF-999-NH2, and COF-999. The textured spherically shaped morphology was observed and remained unchanged during the post-synthetic modification process.

[0022] FIG. 6: N2sorption isotherm of COF-999-N3measured at 77 K and corresponding calculated pore size distribution. The hysteresis can be attributed to the flexibility of side chains within the pores. P, nitrogen pressure; Po - 1 atm; STP, standard temperature and pressure.

[0023] FIG. 7: Brunauer-Emmett-Teller plot (black dots) and linear fitting (black line) of N2sorption isotherm of COF-999-N3measured at 77 K. P, nitrogen pressure; Po = 1 atm; Q, quantity of gas adsorbed at pressure P. STP, standard temperature and pressure.

[0024] FIG. 8: N2sorption isotherm of COF-999-NH2measured at 77 K and corresponding calculated pore size distribution. The hysteresis can be attributed to the flexibility of side chains within the pores. P, nitrogen pressure; Po = 1 atm; STP, standard temperature and pressure.

[0025] FIG. 9: Brunauer-Emmett-Teller plot (black dots) and linear fitting (black line) of N2sorption isotherm of COF-999-NH2measured at 77 K. P, nitrogen pressure; Po = 1 atm; Q, quantity of gas adsorbed at pressure P. STP, standard temperature and pressure.

[0026] FIG. 10: N2sorption isotherm of COF-999 measured at 77 K. P, nitrogen pressure; Po = 1 atm; STP, standard temperature and pressure.

[0027] FIG. 11: Single-component CO2sorption isotherms of COF-999 measured at 15 °C (blue), 25 °C (black), and 35 °C (red).

[0028] FIG. 12: Estimated isosteric heat of CO2adsorption of COF-999 plotted as a function of uptake determined through the Clausius-Clapeyron equation using CO2sorption isotherms at 15 °C to 35 °C. The CO2isotherm at 35 °C showed a turning point from a steep increase to a moderate slope at around 1 mmol g-1, indicating the transformation from chemisorption to physisorption. However, the isotherm at 15 °C and 25 °C maintained chemisorption at this point, making the Clausius-Clapeyron equation not applicable when uptake is higher than 1 mmol g-1.

[0029] FIG. 13: Single-component water vapor sorption isotherm of COF-999 measured at 15 °C (blue), 25 °C (black), and 35 °C (red). P, water vapor pressure;sat, saturation water vapor pressure at the analysis temperature.

[0030] FIG. 14: Estimated isosteric heat of water vapor adsorption of COF-999 plotted as a function of uptake determined through the Clausius-Clapeyron equation using water vapor sorption isotherms at 15 °C to 35 °C.

[0031] FIG. 15: Stacked FT-IR spectra of TCPB (violet), BPDA-N3(green), COF-999-N3(blue), COF-999-NH2(red), and COF-999 (black). The transmittance values along the Y-axis were normalized for comparison. As shown in the figure, the disappearance of the azide vibration at 2089 cm-1(azide VN=N stretch) in COF-999-NH2indicated the completion of Staudinger reduction. The emergence of C-H vibration at 2819 cm-1(ethylene VC-H stretch) in COF-999 indicated the successful loading of poly amine.

[0032] FIG. 16: PXRD spectra of COF-999-N3(blue), COF-999-NH2(red), and COF-999 (black). The intensity values along the Y-axis were normalized for comparison. The disordered polyamines inside the pores lead to weakened diffraction peaks of COF-999.

[0033] FIG. 17: Thermogravimetric analysis (TGA) curve COF-999-N3(blue), COF-999-NH3(red), and COF-999 (black). Measurements were conducted under a continuous flow of N2.

[0034] FIG. 18: Linear deconvolution of quantitative multiCP / MAS13C ssNMR of COF-999. The peak at 157.7 ppm can be assigned to C-#15, and the region from 80 to 13 ppm can be assigned to carbons on the side chain (C-#l to C-#14). The ratio of the integrated area of those two regions was 1.00: 12.10. Color code for lines: experimental data, brown; simulated peak profiles, blue; sum of simulated signals, violet; simulation-experiment difference, red.

[0035] FIG. 19: Linear deconvolution of quantitative multiCP / MAS15N ssNMR of COF-999. The peak at 34.4 ppm can be assigned to the amines reacted with aziridine, and the peak at 23.4 ppm can be assigned to unreacted amines. Signals from unlabeled nitrogen (aziridine and nitrile) can be neglected due to their low natural abundance. The ratio of the integrated area of those two peaks was 0.659:0.341. Color code for lines: experimental data, brown; simulated peak profiles, blue; sum of simulated signals, violet; simulation-experiment difference, red.

[0036] FIGS. 20A-20I: Thermodynamic and kinetic gas sorption studies of COF-999. FIG. 20A: Comparison of single-component CO2(red), N2 (black), O2 (yellow), and Ar (violet) sorption isotherms measured at 25 °C. FIG. 20B: Zoomed-in view of the CO2sorption isotherm taken from FIG. 20A highlighting the uptake at the ambient CO2pressure. FIG. 20C: Singlecomponent H2O sorption isotherm measured at 25 °C. FIG. 20D: CO2and H2O breakthroughprofiles under humid simulated air (400 ppm of CO2with 50% RH) at 25 °C. FIG. 20E: CO2uptake under 400 ppm of CO2with 0, 25, 50, and 75% RH. FIG. 20F: CO2adsorption kinetics under humid simulated air (400 ppm of CO2with 50% RH). FIG. 20G: Comparison of CO2desorption kinetics at 60, 80, and 100 °C. FIG. 20H: Comparison of CO2desorption rates at 60, 80, and 100 °C. FIG. 201: CO2uptake under humid simulated air (400 ppm of CO2with 50% RH) derived from the temperature-swing cycling breakthrough measurements, giving an average working capacity of 2.03 mmol g-1cycle-1(dotted line).

[0037] FIG. 21: Schematic diagram of the breakthrough instrument used to perform both adsorption and desorption experiments. The adsorption / desorption mode and bypass mode were controlled by a 6-port valve.

[0038] FIG. 22: Dynamic breakthrough measurements of COF-999 at 400 ppm of CO2with 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH at 25 °C. The breakthrough time was normalized to 100 mg of COF-999 sample for comparison. The CO2uptakes were calculated to be 0.95, 1.76, 2.02, and 2.06 mmol g-1, respectively.

[0039] FIG. 23: Dynamic breakthrough measurements of COF-999 at 4% of CO2with 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH at 25 °C. 280 mg COF-999 sample and 0.96 cm s-1gas velocity were used in the measurement. The CO2uptakes were calculated to be 2.09, 2.39, 3.03, and 3.17 mmol g-1, respectively.

[0040] FIG. 24: Dynamic breakthrough measurements of COF-999 at 15% of CO2with 0% (red), 25% (yellow), 50% (blue), and 75% (purple) RH at 25°C. 260 mg COF-999 sample and 0.96 cm s-1gas velocity were used in the measurement. The CO2uptakes were calculated to be 2.34, 2.48, 2.63, and 3.24 mmol g-1, respectively.

[0041] FIG. 25: Adsorption kinetics measurement of COF-999 using simulated air (400 ppm of CO2balanced in 4 / 1 N2 / O2 with 50% RH) at 25 °C. 5.0 mg COF-999 sample and 4.8 cm s-1gas velocity were used in the measurement. The specific CO2uptake of the sample was then obtained as the difference between the apparent and background uptakes per unit mass of the sample.

[0042] FIG. 26: Desorption kinetics measurement of COF-999 under N2 flow at 60 °C (blue), 80 °C (yellow), and 100 °C (red). 5.0 mg COF-999 sample and 4.8 cm s-1gas velocity were used in the measurement. The sample was saturated with simulated air (400 ppm of CO2balanced in 4 / 1 N2 / O2 with 50% RH) before the measurement. The background curve was measured without the sample in the column to eliminate the impact of the remaining CO2in thegas line. The amount of desorbed CO2was calculated by the integration of downstream CO2concentration over time.

[0043] FIG. 27: One temperature-swing CO2breakthrough cycle conducted on COF-999. Simulated air (400 ppm of CO2balanced in 4 / 1 N2 / O2 with 50% RH) was used in the adsorption process. In the plot of the downstream CO2concentration, the CO2uptake can be derived through numerical integration of the shaded area. The detection range of the CO2sensor is 0.6 to 984.9 ppm.

[0044] FIG. 28: Ten temperature- swing CO2breakthrough cycles conducted on COF-999. Simulated air (400 ppm of CO2balanced in 4 / 1 N2 / O2 with 50% RH) was used in the adsorption process.

[0045] FIGS. 29A-29D: Carbon dioxide capture from open air. FIG. 29A: CO2capture productivity after each adsorption cycle (blue), corresponding ambient outdoor CO2concentration (red), and relative humidity (black). All data was measured over the course of 20 continuous days of operation using outdoor air. FIG. 29B: CO2productivity of selected cycles with an ambient RH of 37+1%, with corresponding ambient outdoor CO2concentration. The average productivity of selected cycles is shown as the dotted line. FIG. 29C: Comparison of single-component CO2sorption isotherms (25 °C) of as-synthesized COF-999 and sample after 100 outdoor air cycles. FIG. 29D: Comparison of CO2breakthrough curves using simulated air (400 ppm of CO2with 50% RH at 25 °C) run on as-synthesized COF-999 and sample after 100 outdoor air cycles.

[0046] FIG. 30: One temperature-swing CO2breakthrough cycle conducted on COF-999 by using outdoor air as the CO2source. In the plot of the downstream CO2concentration, the CO2uptake can be derived through numerical integration of the shaded area. The detection range of the CO2sensor is 0.6 to 984.9 ppm.

[0047] FIG. 31: One hundred temperature-swing CO2breakthrough cycles conducted on COF- 999 by using outdoor air as the CO2source over a 20-day experiment.

[0048] FIG. 32:13C solid-state NMR spectra of13CO2dosing experiments performed on COF- 999 under dry (black) and humid (blue) conditions. Illustrative schemes of major sorption products are provided to highlight the assignments of signals and chemical conversion of species. Isotopic labeling sites are marked with for13C. Inset shows the result of linear deconvolution of the overlapping region. Color code for inserted graph: experimental data, brown; simulated peak profiles, blue; sum of simulated signals, violet; simulation-experiment difference, red.

[0049] FIGS. 33A-33C: CO2adsorption structures in COF-999. FIG. 33A: Formation of carbamic acid under dry conditions. FIG. 33B: Formation of carbamic acid under humid conditions. FIG. 33C: Formation of bicarbonate under humid conditions. All numbers represent atom distances in pm. C, gray; N, blue; O, red; H, white. Additional structures are shown in FIGS. 34-36.

[0050] FIGS. 34A-34C: Zoomed-in view of optimized structures of carbamic acid / carbamates in the absence of water molecules formed during CO2adsorption in COF-999. Corresponding reaction energies AE (kJ-mol-1) are in Table 5. FIG. 34A: CAI. FIG. 34B: CA2. FIG. 34C: CA3.

[0051] FIGS. 35A-35C: Zoomed-in view of optimized structures of carbamic acid / carbamates in the absence of water molecules formed during CO2adsorption in COF-999. Corresponding reaction energies AE (kJ-mol-1) are in Table 6. FIG. 35A: CW1. FIG. 35B: CW2. FIG. 35C: CW3.

[0052] FIGS. 36A-36C: Zoomed-in view of optimized structures of carbamic acid / carbamates in the absence of water molecules formed during CO2adsorption in COF-999. Corresponding reaction energies AE (kJ-mol-1) are in Table 7. FIG. 36A: BC1. FIG. 36B: BC2. FIG. 36C: BC3.

[0053] FIG. 37: 'H NMR (600 MHz) spectrum of 1 -hexanol, 6-azido-, l-(4- methylbenzenesulfonate) in CDCh.

[0054] FIG. 38: ' H NMR (600 MHz) spectrum of BPDA-N3 in CDCI3.

[0055] FIG. 39:13C NMR (151 MHz) spectrum of BPDA-N3 in CDCI3.

[0056] FIG. 40: ’H NMR (600 MHz) spectrum of BPDA-15NN2in CDCI3. BPDA-15NN2is a mixture of a-15N (R-15N=N=N) and y-15N (R-N=N=15N) labeled compounds.

[0057] FIG. 41:13C NMR (151 MHz) spectrum of BPDA-15NN2in CDCI3. BPDA-15NN2is a mixture of a-15N (R-15N=N=N) and y-15N (R-N=N=15N) labeled compounds. The chemical shift ranging from 51.6 to 51.3 ppm is magnified.

[0058] FIG. 42:15N NMR (61 MHz) spectrum of BPDA-15NN2in CDCh. BPDA-15NN2is a mixture of a-15N (R-15N=N=N) and y-15N (R-N=N=15N) labeled compounds.

[0059] FIG. 43: 'H NMR (600 MHz) spectrum of aziridine in CDCI3.

[0060] FIG. 44:13C NMR (151 MHz) spectrum of aziridine in CDCI3.Description of Particular Embodiments of the Invention

[0061] Unless contraindicated or noted otherwise, in these descriptions and throughout this specification, the terms “a” and “an” mean one or more, the term “or” means and / or. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein, including citations therein, are hereby incorporated by reference in their entirety for all purposes.

[0062] The symbolwhether utilized as a bond or displayed perpendicular to a bond, indicates the point at which the displayed moiety is attached to the remainder of the composition. In certain instances, such as a Formula described herein, the symbol indicates the point at which the core is attached to another repeating core.

[0063] The invention provides polymer- functionalized reticular materials configured as carbon dioxide adsorbents. The various functionalities of reticular materials provide alternative chemical reactions for post-synthetic modifications with polymers. At the same time, benefiting from the adjustable pore environment and pore size, the material can be design-configured for specific applications under different pressures and relative humidities.

[0064] Polymer functionalized reticular materials synthesized as disclosed herein can be utilized as CO2adsorbents in ambient air or post-combustion capture from natural gas or flue gas. In embodiments, the CO2concentration in the feed gas is 400 ppm to 16%, and the temperature of the feed gas is 293 K to 373 K.I. MOFs

[0065] In embodiments the reticular materials include metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). Metal-organic frameworks are a class of compounds consisting of secondary building units and organic linkers. The secondary building units are linked together with organic linkers to form two- or three-dimensional structures.

[0066] In embodiments the metal-organic frameworks of this invention comprise secondary building units consisting of the following metal ions: Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, La3+, Ce3+, Ce4+, Ti4+, Zr4+, Hf14, V3+, V4+, V5+, Nb3+, Nb4+, Nb5+, Cr3+, Cr6+, Mo3+, Mo6+, Mn2+, Mn3+, Mn6+, Fe2+, Fe3+, Co2+, Co3+, Ni2+, Ni3+, Cu+, Cu2+, Zn2+, Cd2+, Al3+, Ga3+, In3+, Ge4+, Sn4+, Pb2+, Pb4+.

[0067] In embodiments the metal-organic frameworks of this invention comprise the following organic linkers:wherein X is selected from the group consisting ofIL COFs

[0068] Covalent organic frameworks are a class of compounds that are synthesized through reactions between organic linkers resulting in two- or three-dimensional structures. In embodiments the covalent organic frameworks disclosed of this invention comprise the following organic linkers:

[0069] In embodiments the functionalization of the reticular materials with polymers can be accomplished: (i) through in situ polymerization reactions within or on the surface of the reticular material; (ii) through chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material.

[0070] Alternative strategies and examples for the synthesis of polymer functionalized reticular materials are described below.

[0071] In embodiments the in situ polymerization method is achieved by mixing metal-organic frameworks or covalent organic frameworks with the monomer of polymers, followed by polymerization reactions.

[0072] In embodiments the monomers (M) of polymers disclosed in this invention include:

[0073] Reticular materials can be functionalized through chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material to form covalent bonds.

[0074] In embodiments the polymers of this invention include:Poly(ethyleneimine), branched Poly(ethylenimine), linearwherein R is selected from the group consisting of

[0075] In embodiments the chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material of this invention include:

[0076] In another aspect, the invention provides a covalent organic framework (COF) comprising a structure according to Formula (I):q2, and q3 are each 0, 1 , or 2then ql + q2 = q, and wherein whenthen ql + q2 + q3 = q; each X is independently selected from, , and, wherein 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(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), - NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene), and when n is 0, each W is independently selected from -(CH2)2NH2, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4- aminostyrene), and q is 1, 2, 3, or 4.

[0077] In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V, Z, and q are as described herein, each X is independently selected fromembodiment, the COF comprises a structure according to Formula (I), wherein Y, Z, and q are as described herein, each X is independently selected from , andIn an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromcomprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromexemplary embodiment, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected from and q is 2.In an exemplary embodiment, the COF comprises a structure according to Formula (1), whereinV, Z, and Y are as described herein, each X is independently selected fromand q is 1 . In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V, Z, and Y are as described herein, each X is independently selected from, and q is 2. In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V, Z,and Y are as described herein, each X is independently selected from, , and q is 3. In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V, Z, and Y are as described herein, each X is independently selected fromand q is 4.

[0078] In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromexemplary embodiment, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromand and q1 is 0 and q2 is 1; or q1 is 1 and q2 is 0; or q1 is 1 and q2 is1 ; 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 ql 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, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromand 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 ql 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, the COF comprises a structure according to Formula (I), wherein V and Y are as described herein, each X is independently selected fromand q1 is 0 and q2 is 0 and q3 is1 ; or q1 is 0 and q2 is 1 and q3 is 0; or q1 is 1 and q2 is 0 and q3 is 0; or q1 is 1 and q2 is 0 and q3 is 1 ; or q1 is 1 and q2 is 1 and q3 is 1 ; or q1 is 2 and q2 is 0 and q3 is 0; or q1 is 2 and q2 is 1 and q3 is 0; or q1 is 2 and 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 ql is 0 and q2 is 0 and q3 is 4.

[0079] 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, 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, the COF comprises a structure according to Formula (I), wherein V, Z, Y, and q are as described herein, each X is independently, 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, the COF comprises a structure according to Formula(I), wherein V, Z, Y, and q are as described herein, each X is independently, each W is as described herein, and each n is independently from 2 to 8, from 2 to 6, from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V, Z, Y, and q are as described herein,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, the COF comprises a structure according toFormula (I), wherein V, Z, Y, and q are as described herein, 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, the COF comprises a structure according to Formula (I), wherein V, Z, Y, and q are as described herein, X is, each W is as described herein, and each n is independently from 2 to 8, from 2 to 6, from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. Inan exemplary embodiment, the COF comprises a structure according to Formula (I), wherein V,Z, Y, and q are as described herein, X iseach W is as described herein, and each n is independently from 2 to 8.

[0080] In an exemplary embodiment, the 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 independentlyor , each W is independently selected from - (CH2)2NH2poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(CH2))2NH2, poly(dimethyl(ethylenimine)), - (CH2)3NH2, poly (propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l- amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, the 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 selectedfrom -(CH2)2NH2, poly( (ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CH2)3NH2, poly (propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene).

[0081] 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 fromeach 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 fromNH(CH2)2NH2, and poly(ethylenimine). 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 fromn, , an , 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(ethylenimine)). Inan 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, 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(ethylenimine)). In an exemplary embodiment, the COF comprises a structureaccording to Formula (I), wherein V, Z, Y, and q are as described herein, each X is independently selected from, , each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 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, each X is independently selected fromeach 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 fromysine, and polylysine.

[0082] In certain embodiments of the invention, W is a polymer which is generated in situ and thus each core in the COF may have one or more W which are a polymer with a different number of subunits than another W. In an exemplary embodiment, poly(ethylenimine), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(methyl(ethylenimine)), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(dimethyl(ethylenimine)), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(propylenimine), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, polylysine, as described herein, has from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, from 2 to 5 subunits, from 2 to 4 subunits, or from 2 to 3 subunits.

[0083] 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; each n is an integer independently selectedfrom 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from-NH(CH2)2NH2, and poly(ethylenimine) having a 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, each n is 0; and each W is independently -(CH2)2NH2or poly(ethylenimine) having a subunit range described herein. In an exemplary embodiment, the COF comprises a structure according to Formula (1), wherein V, Z, Y, and q are as described herein; each X is independently selected fromeach 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(ethylenimine)) having a 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 fromeach n is 0; and each W is independently -(CH(CH3))2NH2, and poly(methyl(ethylenimine)) having a 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; 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 (ethylenimine)) having a 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 fromeach n is 0; and each W is independently -(C(CH3)2)2NH2or poly(dimethyl(ethylenimine)) having a 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 from10, 11, or 12; and each W is independently selected from-NH(CH2)3NH2, and poly(propyleneimine) having a subunit range described herein. In an exemplary embodiment, the COF comprises a structure accordingto Formula (I), wherein V, Z, Y, and q are as described herein; each X is independently selected fromeach n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently -(CfhhNFh or poly(propyleneimine) having a 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; 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 a 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; 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 a 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 fromeach n is 0; and each W is independently lysine or polylysine having a subunit range described herein.

[0084] 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, 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, each X is independently selected fromeach n is 0, and each W is independently -(CFhhNFh orpoly(ethyleneimine). In an exemplary embodiment, 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, prises a structure according to Formula (I), wherein V, Z, Y, and q are as described herein, each X is independently selected from, , , and m is 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, or 12. 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 W isor a linear or branched polymer derived fromIn an exemplary embodiment, theCOF 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 W is independently selected from, , , a linear or branched polymerembodiment, 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 W is independently selected from , a linear orbranched polymer derived from a monomer selected fromexemplary 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

[0085] In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein Z and q are as described herein, each X is independently selected fromexemplary embodiment, the COF comprises a structure according to Formula (I), wherein V is as described herein, each X is independently selected fromexemplary embodiment, the COF comprises a structure according to Formula (I), wherein Y is as described herein, each X is independently selected fromCN In an exemplary embodiment, the COF comprises a structure according W, n, and V are as described herein,ach

[0086] In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein Y, V, and Z are as described herein, each X is independently selected fromF comprises a structure according to Formula (I),from 2 to 8; each W is independently selected from, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly (propyleneimine), lysine, and poly-lysine, 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 independentlywherein each W is as described herein. 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 iswherein each W is as described herein. In an exemplary embodiment, the COF comprises a structure according to Formula (I), wherein Y isNH(CH(CH3))2NH2, or poly(methyl(ethylenimine)); c) -NH(C(CH3)2)2NH2, orpoly(dimethyl(ethylenimine)); d) -NH(CH2)3NH2, or poly (propyleneimine); and e)lysine, or polylysine. In an exemplary embodiment, the COF comprises a structureX isand each W is independently selected from , -NH(CH2)2NH2, andpoly (ethyleneimine) .

[0087] Example chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material:wherein each m is an integer independently selected from 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.

[0088] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently selected from -NH2, -NH(CH2)2NH2, and poly (ethyleneimine). In certain embodiments, the poly(ethyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0089] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently selected from -NH2, -NH(CH2)2NH2, and poly (propyleneimine). In certain embodiments, the poly(propyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0090] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently selected from -NH2, -NH(CH2)NH2, and poly (ethyleneimine). In certain embodiments, the poly(ethyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0091] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently selected from -NH2, -NH(CH2)3NH2, and poly (propyleneimine). In certain embodiments, the poly(propyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0092] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently -(CH2)2NH2or poly (ethyleneimine). In certain embodiments, the poly(ethyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0093] In an exemplary embodiment, the COF is synthesized as described below:wherein each W is independently lysine or poly(lysine). In certain embodiments, the poly(lysine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0094] In an exemplary embodiment, the COF comprises a repeating core, wherein a core is according to a Formula described herein. In an exemplary embodiment, the COF comprises a core (such as according to a Formula described herein). In an exemplary embodiment, a core described herein (such as according to a Formula described herein) forms part of an adjacent core which is part of the repeating core. An example of this can be found in the lower half of FIG 3, where one core is shown as having a portion of its structure forming a portion of an adjacent second core, and portions of the one core and the adjacent second core each form a portion of an adjacent third core. In an exemplary embodiment, the COF according to a Formula described herein is crystalline. In an exemplary embodiment, the structure according to a Formula described herein is crystalline. In an exemplary embodiment, the COF according to a Formula described herein is porous. In an exemplary embodiment, the structure according to a Formula described herein is porous. In an exemplary embodiment, the structure according to a Formula described herein is stable. In an exemplary embodiment, the COF according to a Formula described herein is stable. In an exemplary embodiment, the structure according to a Formula described herein is hydrolytically stable. In an exemplary embodiment, the COF according to a Formula described herein is hydrolytically stable. In an exemplary embodiment, the structure according to a Formula described herein is two-dimensional. In an exemplary embodiment, the repeating core described herein is two-dimensional. In an exemplary embodiment, the structure according to a Formula described herein has a hcb topology. In an exemplary embodiment, the COF described herein has a 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.III. Methods and SystemsUtilization of MOFs or COFs for Carbon Capture Processes Post-combustion capture (PCC)

[0095] In specific embodiments, a MOF described herein is used as a solid adsorbent in the post-combustion capture of CO2from natural gas or coal flue gas. In specific embodiments, aCOF described herein is used as a solid adsorbent in the post-combustion capture of CO2from natural gas or coal flue gas. In some variations, the CO2concentration in the feed flue gas is from 4% to 16%, and the temperature of the feed flue gas is below 40 °C. In certain variations, the CO2concentration in the feed flue gas is from 4% to 16%, and the temperature of the feed flue gas is below 90 °C.

[0096] In some variations, a MOF or COF described herein is used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of powders. In some variations, a MOF or COF described herein is used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of shape bodies. In these scenarios, the powder or shape bodies are used in packed bed, cartridge exchanger, fluidized bed, etc.

[0097] In these scenarios, removal of CO2from a MOF described herein involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them. In these scenarios, removal of CO2from a COF described herein involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them.

[0098] In these scenarios, a MOF or COF described herein exhibiting such properties are used:

[0099] High working capacity difference toward CO2from the combination of chemisorption (if present) and physisorption depending on the adsorption condition and regeneration condition;

[0100] For chemisorption, bearing reactive functional groups such as those in the W variable described herein;

[0101] For the dynamic capacity measurement of COFs described herein, breakthrough experiments are configured with feed gas mixture of 4%-50% (or from 4%- 16%), corresponding humidity and temperature.

[0102] Adequate affinity to CO2such that enough working capacity is retained in the presence of H2O.

[0103] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0104] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0105] In some variations where heating is used for regeneration, low heat capacity. In some variations where the COF is in shape body or supported by other materials, tight binding for mechanical stability.

[0106] In some variations, COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of membranes. In these scenarios, the powder or shape bodies are used in membrane filtration, membrane exchanger, or cartridge exchanger, etc.

[0107] High, selective affinity toward CO2that increases the solubility of the membrane, through both chemisorption (if present) and physisorption at the separation condition.

[0108] -For chemisorption, reactive functional groups such as -NH2or -NHR are part of the COF.

[0109] For the dynamic capacity measurement of such COFs, breakthrough experiments or membrane-specific continuous tests are configured with feed gas mixture of 4%-50% (or from 4%-16%), corresponding humidity and temperature.

[0110] Adequate affinity to CO2such that enough working capacity is retained in the presence of H2O.

[0111] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0112] In some variations where the COF is supported by other materials in the membrane, tight binding with the support for mechanical stability.

[0113] In some variations where heating is used for regeneration, low heat capacity.Direct air capture (DAC)

[0114] In a specific embodiment, MOFs are used as solid adsorbent in the direct capture of CO2from ambient air. In a specific embodiment, COFs are used as solid adsorbent in the direct capture of CO2from ambient air. In most variations, the CO2concentration in the feed flue gas is atmospheric concentration (-400 ppm, 1 atm. In some variations, CO2concentration > 400 ppm when compressed air is used) or slightly higher through compression or in a closed, nonambient chamber, and the temperature of the feed gas is ambient temperature.

[0115] In some variations, MOFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of powders. In some variations,COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of powders. In some variations, MOFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of shape bodies. In some variations, COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of shape bodies. In these scenarios, the powder or shape bodies are used in packed bed, cartridge exchanger, fluidized bed, etc.

[0116] In these scenarios, removal of CO2from MOFs involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them. In these scenarios, removal of CO2from COFs involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them.

[0117] In these scenarios, MOFs or COFs exhibiting such properties are used:

[0118] High working capacity difference toward CO2from chemisorption depending on the adsorption condition and regeneration condition.

[0119] -For chemisorption, high gravimetric or volumetric density of reactive functional groups such as -NH2or -NHR.

[0120] For the dynamic capacity measurement of such COFs, breakthrough experiments are configured with feed gas mixture of -400 ppm, corresponding humidity and temperature.

[0121] Adequate affinity to CO2such that enough working capacity is retained in the presence of H2O.

[0122] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0123] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0124] In some variations where heating is used for regeneration, low heat capacity.

[0125] In some variations where the MOF is in shape body or supported by other materials, tight binding for mechanical stability. In some variations where the COF is in shape body or supported by other materials, tight binding for mechanical stability.

[0126] In an exemplary embodiment, the MOF or COF described herein is configured for carbon dioxide capture. In an exemplary embodiment, 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 an exemplary embodiment, theMOF or COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the MOF or COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the MOF or COF described herein comprises an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture. In an exemplary embodiment, the MOF or COF described herein is configured for carbon dioxide capture in a matrix which further comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture, and provides facile collection of water as a second value-delivering function.

[0127] In another aspect, the invention provides a system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the MOF or COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture.

[0128] In another aspect, the invention provides a method comprising using the MOF or COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture. In an exemplary embodiment, the method of using the MOF or COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.Parallel Water Harvesting

[0129] In some variations, the MOF or COF adsorbent exhibit high uptake of both CO2and H2O at the same time of PCC or DAC. The CO2and H2O can be therefore removed in the same step, or in different steps through different conditions. Through facile further purification, such MOF or COF adsorbent can produce high-purity water as a side-product of CO2capture from air or from flue gas.

[0130] In these scenarios, MOFs or COFs exhibiting such properties are used:

[0131] High working capacity difference toward H2O from physisorption depending on the adsorption condition and regeneration condition.

[0132] For the dynamic capacity measurement of such MOFs or COFs, breakthrough experiments are configured with feed gas mixture at the desired humidity and temperature.

[0133] Adequate affinity to H2O such that enough working capacity is retained in the presence of CO2.

[0134] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0135] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0136] In some variations where heating is used for regeneration, low heat capacity.

[0137] In some variations where the MOF or COF described herein is in shape body or supported by other materials, tight binding for mechanical stability.

[0138] In an exemplary embodiment, the MOF or COF described herein is configured for carbon dioxide capture. In an exemplary embodiment, 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 an exemplary embodiment, the MOF or COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the MOF or COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the matrix described herein is comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture, and provides facile collection of water as a second value-delivering function. In another aspect, the invention provides a system for capturing carbon dioxide from air or a postcombustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the MOF or COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture. In another aspect, the invention provides a method comprising using the MOF or COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture. In another aspect, the invention provides a method of using the MOF or COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.

[0139] In an exemplary embodiment, the invention is a COF described herein, configured for carbon dioxide capture. In an exemplary embodiment, the invention is a COF described herein configured for carbon dioxide capture and separation, including direct air capture from ambientair and post-combustion capture from natural gas or flue gas. In an exemplary embodiment, the invention is a COF described herein, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the invention is a COF described herein, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the invention is a COF described herein, comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture. In an exemplary embodiment, the invention is a system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture. In an exemplary embodiment, the invention is a method comprising using the COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture. In an exemplary embodiment, the invention is a method of using the COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.

[0140] All publications and patent applications mentioned in this disclosure are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

[0141] No admission is made that any reference cited herein constitutes prior art. The discussion of the references states what their authors assert, and the Applicant reserves the right to challenge the accuracy and pertinence of the cited documents. It will be clearly understood that, although a number of information sources, including scientific journal articles, patent documents, and textbooks, are referred to herein; this reference does not constitute an admission that any of these documents forms part of the common general knowledge in the art.

[0142] The discussion of the general methods given herein is intended for illustrative purposes only. Other alternative methods and alternatives will be apparent to those of skill in the art upon review of this disclosure, and are to be included within the spirit and purview of this application.

[0143] Additional embodiments are disclosed in further 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.EXAMPLESExample 1: in situ polymerization reactions within or on the surface of the reticular material.

[0144] COF-999 (previously known as COF-153-PEI) is synthesized by in situ polymerization reaction of COF-999-NH2(previously known as COF-153). Particularly, aziridine polymerized to polyethylenimine (PEI) in the pore of COF-999-NH2.

[0145] Synthetic scheme of COF-999. The loading of PEI is characterized by elemental analysis for C, N, and calculated by the ratio of C and N atoms. COF-999-NH and COF-999 give the following results. 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 C / N ration from 9.69 to 4.92 indicates the successful loading of PEI in the COF.

[0146] The amine functionalities in the material, COF-999 shows strong chemisorption to CO2at low pressure. From the single-component CO2sorption isotherm under 298 K, COF-999 takes up 0.56 mmol / g CO2at 0.4 mbar (condition relevant to direct air capture). At 40 mbar (relevant to post combustion capture from natural gas flue gas), COF-999 absorbs 1.33 mmol / g CO2. At 150 mbar (condition relevant to post combustion capture from coal flue gas), the CO2uptake is 1.55 mmol / g. FIG 1. shows CO2sorption analyses of COF-999 under 298 K.

[0147] In order to measure the performance of COF-999 under humid air, breakthrough measurements were conducted under 50% relative humidity (400 ppm CO2in N2). COF-999 takes up 0.83 mmol / g CO2under this condition. FIG. 2 shows a breakthrough curve of COF-999 under 400 ppm CO2at 50% relative humidity in N2, flow rate 60 mL / min, temperature 298 K. The area marked in blue was used for deriving the CO2uptake through numerical integration.Example 2: Carbon dioxide capture from open air using covalent organic frameworks

[0148] Direct air capture (DAC) plays a crucial role in achieving the vision of carbon neutrality and reducing the greenhouse effect6’7. Efficient capture of CO2from air requires a material to be selective, have a high capacity for CO2, and exhibit fast kinetics — all under low CO2concentration (-400 ppm). Furthermore, such a material must be operated with low regeneration temperature and high cycling stability in the presence of other air components, especially oxygen and water8-10. Extensive research has been reported for using liquid alkaline solutions11 12, silica- supported amines13-15, and metal-organic frameworks (MOFs)16-20as potential candidates for DAC applications. However, despite their promise, the full deployment of liquid solutions has been challenged by their energy-intensive regeneration8and toxicity, while for silica-supported amines and MOFs, loss of amines upon cycling21and hydrolysis22,23remain persistent problems. Herein, the design principles of reticular chemistry24,25are used to make robust covalent organic frameworks (COFs) capable of capturing CO2directly from the air under practical conditions. Specifically, a porous, crystalline COF (termed COF-999) was designed that selectively captures 2.02 mmol of CO2per gram from air containing 400 ppm of CO2at 50% relative humidity (RH). The cycling stability of this COF is shown by performing 100 CO2adsorption-desorption temperature- swing cycles (ambient temperature-60 °C) over 20 days of operation in open air, with full retention of its capacity and performance. COF-999exceeds the current state-of-the-art materials in DAC applications, and COF chemistry in general presents extensive opportunities for molecular design and ultimately deployment of this emerging class of materials.

[0149] FIG. 3 shows how the molecular attributes needed to address the DAC challenges are incorporated into the COF. First, the use of hydrophobic building units in the construction of the COF provides for hydrophobic pores into which a minimum amount of water could be adsorbed, leading to a lower CO2regeneration temperature26-28. Second, the initiators are covalently bound to the framework and in turn, allow the covalent attachment of polyamine and prevent their loss during the cycling. The fact that the initiators are designed to be reactive and the pores are intentionally large, provides for opportunities to have a high loading of polyamines and facile diffusion of CO2— necessary prerequisites for achieving high capacity and rapid cycling. Third, the olefin linkage between covalent molecules making up the COF backbone leads to the overall thermal and chemical stability of the structure2930to allow the post-synthetic installation of the polyamine units and repeated CO2cycling stability without compromising the porosity and integrity of the COF structure.

[0150] Synthesis and structure of the COF series. A porous, crystalline olefin-linked COF precursor, COF-999-N3, was first synthesized through Knoevenagel condensation between 3,3’- bis[(6-azidohexyl)oxy]-4,4'-biphenyldicarbaldehyde (BPDA-N3) and l,3,5-tris(4- cyanomethylphenyl)benzene (TCPB) (FIG. 3). Powder X-ray diffraction (PXRD) was carried out to confirm the crystallinity of COF-999-Ni (FIG. 4A). Pawley refinement was conducted with the experimental PXRD pattern of COF-999-Ns in the space group of P6 to yield unit cell parameters of a = b = 45.524(2) A, c = 3.94(9) k, a = fi = 90°, y = 120° with Rp= 1.81% and Rwp= 3.12%. The PXRD peaks at 2.2°, 3.9°, 4.5°, 5.9°, and 6.7° were assigned to the (100), (1 10), (200), (210), and (300) lattice planes, respectively. These observations are consistent with the simulated structure, where TCPB and BPDA-N3 are connected through olefin linkages to form honeycomb sheets with AA stacking. Scanning electron microscopy image of COF-999-N3 showed a textured spherically shaped morphology with an average particle size of -5 pm (FIG. 5). The N2sorption isotherm of COF-999-N3was measured at 77 K (FIG. 4B), giving a Brunauer- Emmett-Teller (BET) surface area of 811 m2g-1, with an average pore size of -3.3 nm (FIG. 6). The azide functional groups within the pore were characterized by15N cross- polarization magic-angle spinning (CP / MAS) solid-state NMR (ssNMR) using15N labeled COF-999-15N3 (FIG. 4C). Two dominant peaks at 210.4 and 71.6 ppm were attributed to labeled y-15N (R-N=N=*N) and a-15N (R-*N=N=N) on the azide groups of the sidechain.

[0151] Further reduction of its azide groups to amines by Staudinger reaction31under room temperature afforded COF-999-NH2, which was then treated with aziridine to produce polyamines within the pore to obtain COF-999 (FIG. 3).15N ssNMR spectra were collected to prove the conversion of azide to amine to polyamine (FIG. 4C). The complete reduction of COF-999-15N2was confirmed by the disappearance of the azide peaks and the emergence of characteristic R-15NH2chemical shift at 23.5 ppm in15N ssNMR spectra. This can also be monitored by the absence of vibrational absorbance bands at 2089 cm-1for azide VN=N stretch from Fourier-transform infrared spectroscopy (FIG. 15). Notably, the crystallinity and porosity of COF-999-NH2were retained upon performing the reduction process (FIGS. 8 and 16). The in-pore polymerization of COF-999-15NH2with unlabeled aziridine gave a new peak at 35.7 ppm in the15N ssNMR spectrum of COF-999, which was assigned to the formation of secondary amines connecting the COF backbone and polyethylenimine units. Quantitative15N multiple- CP / MAS (multiCP / MAS) ssNMR revealed that 66% of the primary amines on the side chain (COF-999-NH2, FIG. 3) were converted to secondary amines (COF-999, FIG. 3) upon polymerization (FIG. 19). The degree of polymerization for COF-999 was calculated from quantitative13C multiCP / MAS ssNMR (FIG. 4D) and elemental analysis (Table 4), indicating an average of 4.6 CH2CH2NH units was added to each amine side chain (see Methods section “Calculation of Degree of Polymerization’’).

[0152] Gas sorption isotherms. The uptake of air components by COF-999 was examined using gas sorption isotherm measurements for CO2, N2, O2, Ar, and H2O at 25 °C (FIGS. 20A- 20C). A steep increase at very low CO2pressures was observed (FIG. 20A), as well as the hysteresis between the adsorption and desorption isotherms, indicating the strong affinity of COF-999 for CO2. From this data, it was found that the uptake for CO2is 0.91 mmol g-1at 0.4 mbar (400 ppm, condition close to the CO2partial pressure in air, FIG. 20B), and the corresponding calculated isosteric heat of adsorption is 53 kJ mol-1(FIG. 12). As expected, N2, O2, and Ar exhibited linear-shaped sorption isotherms with negligible uptake, indicating that COF-999 possesses a high selectivity for CO2over other components present in ambient air. The water uptake of COF-999 was 0.09 gwater gcoF-1at 50% RH (FIG. 20C), with an isosteric heat of water vapor adsorption of 49 kJ mol-1(FIG. 14). This low water uptake has positive implications for CO2capture from air by this material as discussed further below.

[0153] Kinetic uptake of gas from mixtures. Breakthrough experiments enable the assessment of sorption selectivity and dynamic behavior (FIGS. 20D-20I), which are critical for evaluating the sorbent’s practical performance in air. Given that oxygen and water are major components in the atmosphere, any candidate material for carbon capture must be stable under humid andoxidizing conditions. Dynamic sorption curves were measured under 400 ppm of CO2balanced in compressed air (N2 / C>2=4 / 1) with 50% RH at 25 °C to simulate ambient conditions (FIG. 20D). COF-999 adsorbed both CO2and water after being exposed to the simulated air. Initially, the material quickly reached the saturated capacity for water adsorption compared to CO2, which is retained in the pores before it breaks through at approximately 90 min with a steep concentration increase. COF-999 eventually reached the equilibrium concentration with CO2, indicating the saturated adsorption capacity was reached. The sharp breakthrough curve suggests the rapid mass transfer of CO2in COF-999.

[0154] The impact of water on CO2adsorption was evaluated by measuring the CO2uptake of COF-999 under varying relative humidity levels from 0 to 75% at 25 °C (FIG. 20E and FIG. 22). The cumulative CO2uptake was calculated through numerical integration of the CO2concentration difference between the background and the monitored outlet concentrations.Under dry conditions with 400 ppm of CO2, COF-999 exhibited a CO2uptake of 0.95 mmol g-1, which is comparable to its single-component CO2sorption result. When 25% RH was introduced into the measurement, the CO2adsorption capacity of COF-999 increased to 1.76 mmol g-1. A further increase to 2.02 mmol g-1in the capacity was observed upon increasing RH to 50%. This is a remarkable 2.13-fold increase in CO2capacity over the dry condition. A maximum capacity of 2.06 mmol g-1is achieved at RH of 75%. The dramatic positive impact of water on CO2uptake is due to the formation of carbamates and bicarbonates in the pores as proven by ssNMR measurements and explained by DFT calculations presented below. Although not the emphasis of this contribution, under simulated natural-gas flue (4% of CO2with 75% RH) and coal flue gas (15% of CO2with 75% RH) conditions, the CO2uptake capacity of COF- 999 was found to be 3.17 mmol g-1and 3.24 mmol g-1, respectively (FIG. 23 and FIG. 24), indicating the CO2capture ability of COF-999 under various concentrations.

[0155] The adsorption kinetics of COF-999 was measured under simulated air (400 ppm of CO2with 50% RH) at 25 °C (FIG. 20F and FIG. 25). Specifically, the COF reached half capacity (1.01 mmol g-1) within 18.8 minutes and 80% capacity (1.62 mmol g-1) within 61.7 minutes. During the adsorption process, the maximum adsorption rate was calculated to be0.11 mmol g-1min-1. This ultra- fast rate is the highest measured for CO2capture from air, albeit the reported measurements were done under dry conditions32. The facile 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 pore33.

[0156] To investigate the desorption and the impact of temperature on kinetics, desorption curves were measured at 60, 80, and 100 °C (FIGS. 20G, H and FIG. 26). Prior to themeasurement, COF-999 was saturated with simulated air (400 ppm of CO2with 50% RH) at 25 °C. The temperature was then ramped within 5 min and maintained under nitrogen flow. At 60 °C, 43.1 min was needed to desorb 80% of the adsorbed CO2, and the maximum desorption rate was calculated to be 0.06 mmol g-1min-1. Increasing the temperature to 80 °C resulted in a higher maximum desorption rate of 0.12 mmol g-1min-1, and at 21.5 min, 80% of the adsorbed CO2was desorbed. Further elevating the temperature to 100 °C yielded a maximum desorption rate of 0.19 mmol g-1min-1, with 80% of the adsorbed CO2desorbed at 15.7 min. The hydrophobic nature of COF-999 allows for CO2desorption without requiring a large amount of excessive energy input to remove water molecules, resulting in a low desorption temperature and fast desorption kinetics.

[0157] An initial assessment of the cycling stability of COF-999 was done by a temperatureswing measurement in simulated air (400 ppm of CO2with 50% RH). The COF sample was regenerated under 60 °C in nitrogen flow after each cycle. The retention of CO2capacity after 10 consecutive adsorption-desorption cycles showed excellent stability (FIG. 201 and FIG. 28).

[0158] Carbon dioxide capture from open air. The viability of COF-999 under practical conditions was tested in outdoor air by conducting the experiment continuously for 20 days in Berkeley, California, United States (37°52'23.8" N, 122°15’21.2" W), from January 18 to February 6, 2024 (FIG. 29A; see also FIGS. 30, 31). Outdoor air was passed through the sorbent, where CO2molecules were selectively adsorbed by COF-999. The breakthrough point of the adsorption process was set to be 300 ppm downstream because this represents most of the CO2adsorbed. Afterwards, the material was regenerated at 60 °C. In this measurement approach, it is possible to run a higher number of cycles and to assess the adsorption-desorption cycling performance, while operating at near full capacity. Throughout the experiment, the ambient outdoor CO2concentration and relative humidity were measured before each adsorption process.

[0159] One hundred adsorption-desorption cycles were performed over the 20 days during which outdoor CO2concentration varied from 420 to 517 ppm and the RH from 28% to 51%. The average CO2productivity was determined to be 1.28 mmol g-1cycle-1(5.63 wt.% cycle-1) over 100 consecutive cycles, with a maximum productivity of 1.48 mmol g-1and minimum productivity of 1.03 mmol g-1. Remarkably, it was observed that as the humidity in the air varies over time, so does the enhancement of CO2uptake (FIG. 29A). This positive impact of humidity on CO2uptake is rooted in the manner in which water molecules interact with the CCU-bound to the amines as elaborated below. The CO2productivity of cycles with a background of 37+1% RH (FIG. 29B) demonstrates the stability of COF-999 under these varying open-air conditions.The chemical robustness of the COF is further supported by the consistent capacity found for those cycles carried out under the same humidity. Single-component CO2sorption isotherm (FIG. 29C) and dynamic breakthrough using simulated air (400 ppm of CO2with 50% RH) (FIG. 29D) of COF-999 were measured after the completion of the 100 adsorption-desorption cycles. No changes in either sorption isotherm or breakthrough were observed, indicating retention of the COF structure and its proper functioning in CO2capture.

[0160] Adsorption structures of CO2in COF-999.13C ssNMR spectroscopy (FIG. 32) was employed to study the binding of CO2molecules by COF-999. Upon exposing COF-999 to 1 atm13CO2at 25 °C under dry conditions, an intense signal at 164.5 ppm in the13C spectrum was observed. This signal was assigned to the formation of carbamic acid as the result of CO2reaction with the polyamine34,35. In contrast, pre-saturation with water of COF-999 at 80% RH in N2 at 25 °C, followed by exposure to13CO2, led to the appearance of signals at 165.1 and 161.7 ppm in the13C spectrum, indicating the formation of carbamate and bicarbonate, respectively.

[0161] Periodic density functional theory calculations (see Methods section “DFT Calculations”) of the CO2adsorption structures in the COF suggested that under dry conditions (see Methods section “Formation of carbamic acid / carbamate under dry conditions”), the reaction between CO2and primary or secondary amines is energy favored, and the formed carbamic acid is stabilized by hydrogen bonds with adjacent amines (for example, FIG. 33A, N- • ■ O distance of 263 pm). Upon addition of water molecules, it was found that the formed carbamic acid / carbamate are stabilized through hydrogen bonds (for example, FIG. 33B, O- • • Owdistance of 283 pm and N • O distance of 257 pm), and promoted the formation of bicarbonates, which are also stabilized by hydrogen bonds with adjacent amine groups (for example, FIG. 33C, N -O distances of 262 and 271 pm). Thus, the stabilization in the presence of water explains the experimentally observed significant enhancement of CO2uptake by COF-999 under humid conditions and its suitability for open-air carbon dioxide capture.

[0162] Herein, it is shown how COFs with an olefin-linked backbone and covalently attached sorption sites, bringing ultra-high chemical stability, can serve as excellent materials for capturing CO2from the air. These studies demonstrate that this application in open air is a significant advance towards achieving clean air. COF-999 is perhaps the first member of a large class of materials with a robust framework backbone which will serve the general purpose of carbon capture very well. By applying this strategy, other reticular structures may be designed, examined, and compared to COF-999 to further improve capacity and performance.Methods

[0163] General Synthesis of COFs of the invention. A glass tube can be charged with Y (approx. 0.04 mmol), Z (approx. 0.06 mmol), and alkaline (NaOH, KOH, or CS2CO3) or acidic (acetic acid or trifluoroacetic acid) catalyst. A solvent mixture (approx. 1 mL) of dichlorobenzene, butanol, dioxane, and mesitylene can be added to the glass tube. The tube can be sealed and heated at 80 to 140 °C (typically 120 °C) for 1 to 5 days (typically 3 days) to yield a solid. The solid can then be filtered, washed with methanol (30 mL), post-treated with PPI13, HC1, or NaOH and dried to yield the COF.

[0164] To covalently link polymers to the COF, approx. 50 mg of the COF from the previous paragraph can be mixed with monomers M (approx. 100 mg) and alkaline (NaOH, KOH, or CS2CO3) or acidic (acetic acid or trifluoroacetic acid) or free radical (azobisisobutyronitrile) catalyst. A solvent mixture (approx. 1 mL) of tetrahydrofuran or toluene can be added to the mixture. The mixture can be heated at 50 to 120 °C (typically 100 °C) for 6 to 48 hours(typically 24 hours) to yield a solid. The solid can be filtered, washed with methanol (30 mL), post-treated with HC1, NH3, or NaOH, and dried under 120 °C to yield polymer functionalizedGeneral Synthesis of linkers

[0165] D (approx. 1.0 equiv.) and NaNs (approx. 1.3 equiv.) can be added to approx 100 mL DI water and the reaction mixture can be refluxed under approx. 100 °C for approx. 48 h. Aftercooling to room temperature, the mixture can be extracted with ethyl acetate (approx 100 mL x 3). The organic phase can be combined, washed with water (100 mL x 3), brine (50 mL), and dried over sodium sulfate. After filtration, the solvent can be evaporated to afford E, which was used directly for the next step without further purification.

[0166] E can be dissolved into approx. 150 mL DCM under N2 atmosphere, and the solution can be cooled to approx. 0 °C. 4-toluenesulfonyl chloride (21.0 g, 110 mmol, 1.1 equiv.) and triethylamine (approx. 3.0 equiv.) can be added to the solution. The solution can be warmed to approx. 25 °C and stirred for approx. 16 h. Approx. 100 mL water can be added upon completion, and the organic phase can be collected, washed with water (approx. 100 mL) and brine (approx. 50 mL), and dried over sodium sulfate. The solution can be filtered and concentrated, and the resulting oil can be subjected to flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford 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-l- ethanol, and G is 2-azidoethyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 3- chloro- 1 -propanol, E is 3-azido-l -propanol, and G is 3-azidopropyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 4-chloro- 1 -butanol, E is 4-azido-l -butanol, and G is 4- azidobutyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 5-chloro-l -pentanol, E is 5-azido-l -pentanol, and G is 5-azidopentyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 6-chloro-l -hexanol, E is 6-azido-l -hexanol, and G is 6-azidohexyl 4- methylbenzenesulfonate. In an exemplary embodiment, D is 7-chloro-l -heptanol, E is 7-azido- 1 -heptanol, and G is 7-azidoheptyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 8-chloro-l -octanol, E is 8-azido-l -octanol, and G is 8-azidooctyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 9-chloro-l -nonanol, E is 9-azido-l -nonanol, and G is 9- azidononyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 10-chloro-l-decanol, E is 10-azido-l -decanol, and G is 10-azidodecyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 11 -chloro- 1 -undecanol, E is 11 -azido- 1 -undecanol, and G is 11- azidoundecyl 4-methylbenzenesulfonate. In an exemplary embodiment, D is 12-chloro-l -dodecanol, E is 12- azido-1 -dodecanol, and G is 12-azidododecyl 4-methylbenzenesulfonate.General synthesis of certain moieties comprising Z:An is from 1 to 12

[0167] A (approx 1.0 equiv.), K2CO3 (approx 3.0 equiv.) and B (approx 2.2 equiv.) can be added to approx 30 mL anhydrous DMF under N2 atmosphere. The resulting suspension can be heated to approx 80 °C and can be stirred for approx 16 h. After cooling down, DMF can be evaporated under reduced pressure, and the remaining mixture can be extracted by 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 flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product. In an exemplary embodiment,Synthesis of 3,3'-bis[(6-azidoalkyl)thio]-4,4'-biphenyldicarbaldehyde

[0168] 3,3' -dithiol-4,4'-biphenyldicarboxaldehyde (approx 1.0 g, approx 4.1 mmol, approx 1.0 equiv.), K2CO3 (approx 1.7 g, approx 12 mmol, approx 3.0 equiv.) and 1-hexanol, 6-azido-, 1- (4-methylbenzenesulfonate) (approx 2.7 g, approx 9.0 mmol, approx 2.2 equiv.) can be added to approx 30 mL anhydrous DMF under N2 atmosphere. The resulting suspension can be heated to approx 80 °C and can be stirred for approx 16 h. After cooling down, DMF can be evaporated under reduced pressure, and the remaining mixture can be extracted by 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 flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product.Synthesis of 3,3'-bis[(6-azidoalkyI)amino]-4,4'-biphenyIdicarbaldehyde

[0169] 3,3' -diamino-4,4’-biphenyldicarboxaldehyde (approx 1.0 g, approx 4.1 mmol, approx 1.0 equiv.), K2CO3 (approx 1.7 g, approx 12 mmol, approx 3.0 equiv.) and 1-hexanol, 6-azido-, 1- (4-methylbenzenesulfonate) (approx 2.7 g, approx 9.0 mmol, approx 2.2 equiv.) can be added to approx 30 mL anhydrous DMF under N2 atmosphere. The resulting suspension can be heated to approx 80 °C and can be stirred for approx 16 h. After cooling down, DMF can be evaporated under reduced pressure, and the remaining mixture can be extracted by 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 flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product.

[0170] Synthesis of COF-999 -N3. A borosilicate glass tube measuring 8 x 10 mm (i.d. x o.d.) was charged with TCPB (16.9 mg, 0.04 mmol), BPDA-N3 (29.6 mg, 0.06 mmol) and CS2CO3(39.1 mg, 0.12 mmol) were mixed in 0.5 mL 1 ,2-dichlorobenzene and 0.5 mL 1-butanol. The mixture was flash frozen at 77 K in a liquid nitrogen bath, evacuated to an internal pressure below 0.2 mbar, and flame sealed. The length of the tube was reduced to around 10 cm upon sealing. After warming to room temperature, the mixture was heated at 120 °C for 3 days in an oven to yield a yellow solid. The solid was filtered, washed with methanol (30 mL), and was used directly for the next step without further treatment. To characterize COF-999-N3, the yellow solid described above was transferred into a Kimwipe bag and further washed with methanol for 16 h in a Soxhlet extractor, dried with supercritical CO2, and degassed at 30 °C for 3 h under vacuum to yield COF-999-N3 as a yellow-colored solid (yield 81%). Elemental analysis for C23H21N4O: Calcd. C 74.77%, H 5.73%, N 15.17%; Found C 74.08%, H 5.79%, N 14.01%.

[0171] Synthesis of COF-999-NH2. To a 100 mL round bottom flask, COF-999-Ns (100 mg), PPI13 (200 mg), and 30 mL methanol were added under 25 °C. After 24 h, the suspension was filtered and washed with methanol to remove excess PPI13. The yellow residue was transferred to another 100 mL round bottom flask, and 24 mL methanol and 6 mL water were added under 25 °C. After 24 h, the suspension was filtered in a Kimwipe bag, washed in methanol for 16 h in a Soxhlet extractor, dried with supercritical CO2, and degassed at 30 °C for 3 h under vacuum to yield COF-999-NH2as a yellow-colored solid (yield 98%). Elemental analysis for C23H23N2O: Calcd. C 80.44%, H 6.75%, N 8.16%; Found C 78.51 %, H 6.38%, N 8.10%.

[0172] Synthesis of COF-999. COF-999-NH2(30 mg), toluene (2 mL), acetic acid (5 pL), and aziridine (100 pL) were added to a borosilicate glass tube measuring 8 x 10 mm (i.d. x o.d. The mixture was flash frozen at 77 K in a liquid nitrogen bath, evacuated to an internal pressure below 0.3 mbar, and flame sealed. The length of the tube was reduced to around 10 cm upon sealing. After warming to room temperature, the reaction was heated at 100 °C for 24 h. After cooling down to 25 °C, the solid was filtered in a Kimwipe bag, washed with 50 mL 1 M NaOH in methanol, then washed with methanol for 16 h in a Soxhlet extractor, and dried at 120 °C for 12 h under vacuum to yield COF-999 as a yellow-colored solid (yield 86%). Elemental analysis for C23H23N2O- (C2H5N)3.1: Calcd. C 73.53%, H 8.14%, N 14.98%; Found C 70.19%, H 7.24%, N 14.35%.

[0173] Powder X-ray Diffraction. PXRD patterns were collected using a Rigaku Miniflex 600 X-ray diffractometer in reflection geometry employing Cu Ka radiation (Z = 1.54184 A, with a Ni filter) at a power of 600 W (40 kV, 15 mA). Samples were mounted on Si (511) sampleholders and leveled with a spatula. The step size was 0.02° with an exposure time of 0.5 s per step.

[0174] Solid-state Nuclear Magnetic Resonance Spectroscopy. Solid-state NMR experiments were conducted at an external field Bo= 16.4 T (700 MHz for1H, 176 MHz for13C, and 71 MHz for15N) using a Bruker Avance I spectrometer and a 3.2 mm H / C / N magic angle spinning (MAS) probe. To reduce CO2and moisture exposure, COF samples were fully activated then packed in 3.2 mm zirconia rotors and closed using Vespel® caps in an argon-filled glovebox.13CO2dosed COF samples were conducted by exposing dry or pre-humidified (by N2 with 80% RH) COF-999 samples to 1 atm13CO2gas (2.47 atm, Sigma Aldrich, 99% atom13C) with a home-built gas dosing apparatus for 3 h at room temperature, followed by evacuation (< 0.3 mbar) at room temperature for 1 min to remove excess CO2. Unless specified differently,13C and15N experiments were performed under MAS at a spinning rate of 23 and 11 kHz using dry air, respectively.13C chemical shifts were externally referenced using the tertiary carbon (CH) resonance of adamantane at 38.48 ppm.15N chemical shifts were externally referenced to15N- glycine at 33.4 ppm.

[0175] 15N spectra of COF-999-15N3 and COF-999-15NH2were obtained using1H-15N cross- polarization under MAS (CP / MAS). After an initial1H 90° radio-frequency pulse of 5.20 ps (48.1 kHz), a CP transfer contact time of 2 ms was used, during which a constant RF-field equal to 25.3 kHz was applied on15N, while the 'H RF-field amplitude was linearly ramped from 43.3 to 48.1 kHz. During15N acquisition, high-power]H decoupling was applied using the SPINAL- 64 (Small Phase Incremental Alternation with 64 steps) decoupling scheme36with an RF-field amplitude set to 48.1 kHz. For COF-999-15N3, a total of 30688 scans were recorded with a recovery delay of 2 s, leading to overall experimental times of 17 h. For COF-999-15NH2, a total of 896 scans were recorded with a recovery delay of 2.23 s, leading to overall experimental times of 34 min.

[0176] Quantitative15N spectra of15N labeled COF-999 were obtained using multiple CP transfers as described by lohnson and Schimdt-Rohr37. For each scan, a total of 4 CP transfers were used to saturate the15N signals of COF-999, with an initial recovery delay of 7.28 s (5*T1(1H)) and a delay of 2.91 s (2*T1(1H)) in between CP transfers. The1H→15N CP transfer used the same parameters described previously and in total, 1088 scans were averaged, leading to an overall experimental time of 6 h.

[0177] 13C spectra of COF-999-N3were obtained using1H→-15C CP / MAS. After an initial1H 90° radio-frequency pulse of 5.20 ps (48.1 kHz), a CP transfer contact time of 2 ms was used,during which a constant RF-field equal to 34.5 kHz was applied on13C, while the1H RF-field amplitude was linearly ramped from 43.3 to 48.1 kHz. During13C acquisition, high-power!H decoupling was applied using the SPINAL-64 decoupling scheme with an RF-field amplitude set to 48.1 kHz. A total of 9856 scans were recorded with a recovery delay of 1.3 s, leading to overall experimental times of 3.6 h.

[0178] Quantitative13C spectra of COF-999-NH2and COF-999 were obtained using multiple CP transfers. For each scan, a total of 10 or 14 CP transfers were used to saturate the13C signals of COF-999-NH2or COF-999, respectively, with an initial recovery delay of 5 s or 4.25 s and a delay of 2 s or 1.71 s in between CP transfers. The]H^-13C CP transfer used the same parameters described previously and in total, 1940 or 3833 scans were averaged, leading to an overall experimental time of 14 h or 30 h for COF-999-NH2or COF-999, respectively.

[0179] Direct excitation experiments of13CO2-dosed COF-999 were performed under MAS at 10 kHz with a 90° pulse of 4.12 ps. During13C acquisition, high-power 'H decoupling was applied using the SPINAL-64 decoupling scheme with an RF-field amplitude set to 48.1 kHz. In total, 64 scans were averaged with a recycle delay of 120 s, leading to an experimental time of 2.2 h.

[0180] Single-component Sorption Isotherm Measurements. N2 sorption isotherms at 77 K were measured using a Micromeritics ASAP 2420 Accelerated Surface Area and Porosimetry System. Powder samples were activated under a dynamic vacuum using a Micromeritics ASAP 2420 Accelerated Surface Area and Porosimetry System before measurement. A liquid nitrogen bath was used to maintain a temperature of 77 K for each measurement. Ultra-high-purity (Praxair, 99.999%) N2 and He gases were used throughout the adsorption experiments.

[0181] CO2sorption isotherms were measured using a Micromeritics 3Flex Adsorption Analyzer. Powder samples were activated under a dynamic vacuum using a Micromeritics ASAP 2420 Accelerated Surface Area and Porosimetry System before measurement. A water circulation bath was used to maintain a temperature of 15.00, 25.00, or 35.00 °C for each measurement. Research-grade CO2(Praxair, 99.998%) was used throughout the adsorption experiments.

[0182] O2, N2, and Ar sorption isotherms at 25 °C were measured using a 3P micro 200 analysis station. Powder samples were activated under a dynamic vacuum at 120 °C using the activation station of 3P micro 200. A cryoTune 195 was used to maintain a temperature of 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.

[0183] H2O vapor sorption experiments were carried out on a Belsorp MAX II high-precision gas / vapor adsorption measurement instrument. Powder samples were activated under a dynamic vacuum using Belprep VAC III before measurement. The water vapor source was degassed through five freeze-pump-thaw cycles before the analysis. Ultra-high-purity (Praxair, 99.999%) He was used for free space corrections, and an isothermal bath was employed to adjust the sample temperature during the measurements.

[0184] Dynamic Breakthrough Measurements. Dynamic breakthrough experiments were carried out on a Micromeritics Breakthrough Analyzer (BTA) equipped with a CO2sensor (detection range = 0.6 to 984.9 ppm), and a humidity sensor. The samples were packed in a jacked column (4.9 mm i.d.) and the temperature was controlled by a Ministat 230 oil circulation bath. Ultra-high-purity (Praxair, 99.999%) N2, ultra-zero-grade air (Praxair), 1000 ppm CO2balanced in air (Praxair), 1% CO2balanced in N2 (Praxair), 20% CO2balanced in N2 (Praxair), and research-grade CO2(Praxair, 99.998%) were used for breakthrough measurements.

[0185] The humidified air or N2 can be obtained by passing the dry air or N2 through a water bath. Different CO2concentrations and relative humidities can be fine-tuned by adjusting the blend ratio of different gases. Specifically, 400 ppm CO2balanced in air was mixed by humid air, dry air, and 1000 ppm CO2balanced in air; 400 ppm CO2balanced in N2 was mixed by humid N2, dry N2, and 1% CO2balanced in N2; 4% CO2balanced in N2 was mixed by humid N2, dry N2, and 20% CO2balanced in N2; 15% CO2balanced in N2 was mixed by humid N2, dry N2, and pure CO2.

[0186] Ambient air was collected from the 6lh-floor (room 626) balcony of Latimer Hall, Berkeley, California, United States (37°52'23.8"N 122°15'21.2"W) between January 18, 2024 and February 6, 2024. The ambient air was pressurized by a Welch 2522B-01 dry pump to 300 kPa and was then stabilized at 200 kPa by an Aldrich HPL500-2160 mini gas regulator before being introduced into the breakthrough analyzer.

[0187] In the adsorption capacity measurement experiments, 90 to 280 mg of COF-999 sample was packed in the jacked 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 seem N2 flow was passed through the sample until the outlet CO2concentration was less than 5 ppm. Then, the oil bath was cooled and maintained at 25 °C, and the sample was exposed to 10 or 50 seem simulated gas mixture with desired CO2concentration (400 ppm, 4.0%, or 15.0%) balanced in N2 with desired relative humidity (0%, 25%, 50%, or 75%) until the outlet CO2concentration was constant. The specific CO2uptake of the sample was then obtained as the difference between the apparent and background uptakes per unit mass of the sample.

[0188] In the cycling stability measurement experiments, 80 mg of COF-999 sample was packed in the jacked 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 seem N2 flow was passed through the sample until the outlet CO2concentration was less than 5 ppm. Then, the oil bath was cooled and maintained at 25 °C, and the sample was exposed to 50 seem 400 ppm of CO2balanced in air with 50% RH until the outlet CO2concentration was higher than 395 ppm. The sample was reactivated through the same procedure described above before each cycle. The specific CO2uptake of the sample was then obtained as the difference between the apparent and background uptakes per unit mass of the sample.

[0189] In the adsorption kinetics measurement experiments, 5.0 mg of COF-999 sample was packed in the jacked 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 seem N2 flow was passed through the sample for 120 min to fully activate the sample. Then, the oil bath was cooled and maintained at 25 °C, and the sample was humidified by exposing it to 50 seem CO -free air with 50% RH for 30 min, followed by 50 seem 400 ppm CO2balanced in air with 50% RH until the outlet CO2concentration was constant. The specific CO2uptake of the sample was then obtained as the difference between the apparent and background uptakes per unit mass of the sample.

[0190] In the desorption kinetics measurement experiments, 5.0 mg of COF-999 sample was packed in the jacked column. The sample was first exposed to 50 seem 400 ppm CO2balanced in air with 50% relative humidity until the outlet CO2concentration was constant. Then, the column was heated under 50 seem N2 flow until the column wall temperature reached 60, 80, or 100 °C. The column temperature was maintained for 3 h for desorption. The amount of desorbed CO2was obtained as the integrated downstream CO2concentration per unit mass of the sample.

[0191] In the outdoor air capture measurement experiments, 73 mg of COF-999 sample was packed in the jacked 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 seem N2 flow was passed through the sample until the outlet CO2concentration was less than 20 ppm (typically 90 min). Then, the oil bath was cooled to 25 °C and turned off. Background relative humidity and CO2concentration of the outdoor air were measured through the bypass (at around 25 °C). The sample was then exposed to 50 seem ambient air until the outlet CO2concentration was higher than 300 ppm. The sample was reactivated through the same procedure described above before each cycle. The specific CO2uptake of the sample was then obtained as the difference between the apparent and background uptakes per unit mass of the sample. Two fullcycles were measured before and after this experiment using simulated air to assess the stability of the sample.

[0192] Periodic density functional theory (DFT) calculations. DFT calculations were performed in the Vienna Ab Initio Simulation (VASP version 6.1) software38-40to investigate CO2adsorption in COF-999. The Perdew-Burke-Ernzerhoff (PBE) exchange-correlation density functional41was used along with Grimme’s D3 dispersion corrections with Becke-Johnson damping (PBE-D3BJ)42for all the calculations. Generally, for the structural optimization of each adsorbed species in COF-999, a plane-wave basis set with an energy cutoff of 400 eV was employed. Each structure was optimized until the energy and force convergence criteria of 10-6eV and 0.03 eV / A were achieved. A 1 X 1 X 3 Γ-centered k-point grid was used for the Brillouin zone sampling. During each structural optimization, only the atom positions were relaxed while the unit cell parameters were held constant.

[0193] A structural model for COF-999 was obtained from the COF-999-NH2structure. First, the structure of COF-999-NH2was optimized using DFT with the following settings. The PBE- D3BJ exchange-correlation density functional with dispersion corrections and a plane- wave basis set with an energy cutoff of 520 eV were employed. The same energy and force convergence criteria as described above were used while a 1 x 1 x 5 / ’-centered k-point grid was used for the Brillouin zone sampling. A higher energy cutoff and denser k-point grids were used for the initial optimization of COF-999-NH2as compared to subsequent structure optimizations of COF-999 since the positions of the atoms as well as unit cell parameters were relaxed during the structure optimization. The optimized COF-999-NH2structure was then modified to introduce 4.5 -CH2-CH2-NH- units (on average) with branching on 2 out of the 6 sidechains in COF-999-NH2. Such a model is representative of the polymeric polyethyleneimine units formed in COF-999 and encompasses the varied CO2adsorption sites constituted by primary, secondary, and tertiary amines. This optimized structure (unit cell parameters: a = b = 45.084 A, c = 3.819 A, α = β = 90°, y = 120°) was used for investigating CO2adsorption in COF-999. Due to the conformational flexibility of the polyamine chains, several different CO2adsorption environments constituted by polyamines were investigated and representative of these are shown here. The adsorption energy, ΔEadsorption, (electronic energy) was calculated using Equation 1 :ΔEadsorptio n =Eadsorbed system - Eem pty COF-n CO2· Eisolated CO2-nH2O · Eisolated H2O ( 1 ) where Eadsorbed systemis the electronic energy of the system upon adsorption, Eempty COF is the electronic energy of the empty COF having a similar conformation of the polyamines as in theadsorbed state, Eisoiated Co2and ^isolated H2O are the electronic energies of an isolated CO2and H2O molecule respectively, and nCO2and nH2o are the number of adsorbed CO2and H2O molecules.

[0194] Chemicals. 4-Toluenesulfonyl chloride (98%), 2-chloroethanamine hydrochloride (98%), 6-chloro- 1 -hexanol (95%), sodium hydroxide (97%), 1 ,2-di chlorobenzene (99%), triphenylphosphine (99%), sodium sulfate (99%) were purchased from AK Scientific. Potassium carbonate (99%) was purchased from Alfa Aesar. l,3,5-tris(4-cyanomethylphenyl)benzene (TCPB, 98%), 3,3'-dihydroxy-4,4’-biphenyldicarboxaldehyde (97%) were purchased from Arctom Scientific. Sodium azide (Na15NN2, 1-1SN, 98%) was purchased from Cambridge Isotope Laboratories. Cesium carbonate (CS2CO3, 99.99%) was purchased from Chem-Impex International. Methanol (99.8%) was purchased from Fischer Scientific. Hexane (mixture of isomers, 98.5% sum of enantiomers) was purchased from J.T.Baker. Ethyl acetate (99.5%) was purchased from Macron Fine Chemicals. Methylene chloride (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%), chloroform-d (CDCI3, 99.8 atom % D) were purchased from Sigma Aldrich. All reagents and solvents were used without further purification.

[0195] Solution-state Nuclear Magnetic Resonance Spectroscopy. Solution-state NMR experiments were conducted at an external field Bo= 14.1 T (600 MHz for]H, 151 MHz for13C, and 61 MHz for15N) using a Bruker spectrometer equipped with an Avance-III console. Chemical shifts were referenced using the solvent resonances as internal standards (δ1H: 7.26 ppm for CDCI3; δ13C: 77.16 ppm for CDCI3). A polynomial baseline correction was applied to each spectrum before integration using Mestrelab MestReNova software.

[0196] Elemental Microanalysis. Elemental analysis was performed in the Microanalytical Laboratory of the College of Chemistry at UC Berkeley, using a Perkin Elmer 2400 Series II CHNS elemental analyzer.

[0197] Fourier- transform infrared (FT-IR) Spectra. 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 the neat samples and at room temperature (~25 °C). Spectra are plotted in transmittance (%) against the wavenumbers (cm-1).

[0198] High Resolution Mass Spectra (HR-MS). HR -MS measurements were performed by the QB3 / Chemistry Mass Spectrometry Facility at UC Berkeley. Masses are reported in m / zunits as the molecule ion M+, [M + H]+, [M + Na]+, [M + K]+, with the corresponding intensities in %.

[0199] Thermogravimetric Analyses (TGA). TGA curves were recorded on a TA Q500 thermal analysis system under nitrogen flow, ramping at 10 °C min-1from room temperature (typically 25 °C) to 800 °C. Ultrahigh-purity-grade N2was used for all TGA measurements.

[0200] Supercritical Carbon Dioxide Dryer. The supercritical CO2drying was performed by Tousimis Autosamdri-931 critical point dryer. Instrument grade CO2(Praxair, 99.99%) was used throughout the drying process.

[0201] Scanning Electron Microscopy (SEM). SEM images were obtained on a Zeiss XB 550 high-resolution SEM with an accelerating voltage of 1.0 kV. The samples were dispersed on conductive carbon tape, mounted on stubs, and sputter coated (Pd / Au) with a Tousimis sputter coater on top of a Bio-Rad E5400 controller.Synthesis of LinkersSynthesis of 1-hexanol, 6-azido-, l-(4-methylbenzenesulfonate).

[0202] 6-Chloro- 1-hexanol (13.6 g, 100 mmol, 1.0 equiv.) and NaN3(8.5 g, 131 mmol, 1.3 equiv.) were added to 100 mL DI water and the reaction mixture was refluxed under 100 °C for 48 h. After cooling to room temperature, the mixture was extracted with ethyl acetate (100 mL x 3). The organic phase was combined, washed with water (100 mL x 3), brine (50 mL), and dried over sodium sulfate. After filtration, the solvent was evaporated to afford 6-azido- 1-hexanol a colorless oil, which was used directly for the next step without further purification.

[0203] The above colorless oil was dissolved into 150 mL DCM under N2 atmosphere, and the solution was cooled to 0 °C. 4- toluenesulfonyl chloride (21.0 g, 110 mmol, 1.1 equiv.) and triethylamine (41.8 mL, 300 mmol, 3.0 equiv.) were added to the solution. The solution was warmed to 25 °C and stirred for 16 h. 100 mL water was added upon completion, 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 flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product as a colorless oil (24.2 g, overall yield 81%).1H NMR (600 MHz, CDCL): 3 (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).Synthesis of 3,3'-bis[(6-azidohexyl)oxy]-4,4'-biphenyldicarbaldehyde (BPDA-N3).

[0204] 3,3'-dihydroxy-4,4’-biphenyldicarboxaldehyde (1.0 g, 4.1 mmol, 1.0 equiv.), K2CO3 (1.7 g, 12 mmol, 3.0 equiv.) and 1 -hexanol, 6-azido-, 1 -(4-methylbenzenesulfonate) (2.7 g, 9.0 mmol, 2.2 equiv.) were added to 30 mL anhydrous DMF under N2atmosphere. The resulting suspension was heated to 80 °C and stirred for 16 h. After cooling down, DMF was evaporated under reduced pressure, and the remaining mixture was extracted by 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 flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product as a white solid (1.52 g, yield 74%). H NMR (600 MHz, CDCh): 5 (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).13C NMR (151 MHz, CDCh) 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-ESLMS: m / z: 515.2382 ([M+ Na]+, calcd. for [C26H32N6O4Na]+515.2377).Synthesis of 3,3'-bis(methoxymethoxy)-[l,l'-biphenyl]-4,4'-dicarbaldehyde (BPDA- OMOM).

[0205] 4-Bromo-2-(methoxymethoxy)benzaldehyde (10 mmol), 2-(methoxymethoxy)-4- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)benzaldehyde (10 mmol), Pd(PP3)4(0.1 mmol), K2CO3 (30 mmol) were added to a mixture of dioxane (150 mL) and water (50 mL) under nitrogen. The mixture was heated to 95 °C for 18 h. After cooling down to room temperature, the solvent was evaporated and the residue was purified through column chromatography to yield 3,3’-Bis(methoxymethoxy)[l,l ’-biphenyl]-4,4’-dicarboxaldehyde as a white solid.

[0206] Synthesis of aziridine. To a 500 mL round bottom flask containing sodium hydroxide aqueous solution (50.0 g NaOH in 200 mL DI water), 2-chloroethanamine hydrochloride (50.0 g, 431 mmol) was slowly added. The resultant solution was heated to 50 °C and stirred for 3 h.After the reaction, aziridine was separated by distillation at 80 °C under vacuum (20 kPa). Sodium hydroxide was added to the collected distillate for drying and the water-containing aziridine was further purified by distillation under ambient pressure (boiling point 56 °C at 101 kPa). ’H NMR (600 MHz, CDCh): 5 (ppm) 1.59 (s, 4H), -0.10 (s, 1H).13C NMR (151 MHz, CDCh) 5 18.3 ppm.

[0207] Synthesis of BPD A -15N3. BPDA-15N3 was synthesized according to the method described above.15N labeled sodium azide (Na15NN2) was used in the reaction. BPDA-15N3 is a mixture of a-15N (R-15N=N=N) and y-15N (R-N=N=15N) labeled compounds since only one of the terminal nitrogen atoms is labeled in the sodium azide.]H NMR (600 MHz, CDCh): 6 (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).13C NMR (151 MHz, CDCh): 8 (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, 25.8.15N NMR (61 MHz, CDCh): 8 (ppm) 210.7 (R-N=N=15N), 71.7 (R-15N=N=N). HR-ESI-MS: m / z: 517.2322 ([M+ Na]+, calcd. for [C26H32N4lsN2O4Na]+517.2318).Powder X-ray Diffraction.Table 1. Fractional atomic coordinates of the structural model of COF-999-N3, resulting fromPawley refinement.Table 2. Fractional atomic coordinates of the structural model of COF-999-NH2, resulting from Pawley refinement.Table 3. Fractional atomic coordinates of the structural model of COF-999, resulting from geometric optimization.

[0208] Calculation of Degree of Polymerization. The area of the peak in multiCP / MAS ssNMR (FIG. 18) is proportional to the number of atoms that it represents (32). Since there are 6 carbons (C-#l to C-#6) on the side chain before the polymerization reaction, and each polyethylenimine unit provides two additional carbons on the side chain, the average degree of polymerization can be calculated as (12.10 - 6) / 2 = 3.05 per side chain. This number can also be calculated from the elemental analysis results of COF-999 (Table 4).

[0209] From multiCP / MAS15N ssNMR (FIG. 19), 65.9% of the amines on the pore wall were linked with polyethylenimine units, so the degree of polymerization after excluding those nonreacted amines can be calculated as 3.05 / (65.9%) = 4.63.Table 4. Comparison of the experimental elemental analysis result of COF-999[C23H23N2O- ( C2H5N ) n ] with calculated elements ratio of different degrees of polymerization. The experimental C / N ratio matches with the calculated result of n=3.1.

[0210] DFT Calculations. DFT calculations were performed to investigate the mechanism of CO2adsorption in COF-999 both in the absence and presence of water molecules (dry and humid conditions for CO2capture respectively). It is noted that the polyethyleneimine units can exhibit significant conformational flexibility, which allows the polyamine chains to adjust to favored CO2adsorption structures under dry and wet conditions and thus, maximize their CO2uptake.

[0211] Under dry conditions, the formation of carbamic acid / carbamate (Table 5, CA1-CA3) upon the reaction of the CO2molecules with the polyamine groups is energy-favorable (AE = - 75 to -101 kJ-mol-1). Carbamic acid is stabilized through H-bond interactions with adjacent polyamine groups (N- -- 0 distances about 263-273 pm). Carbamates are thermodynamically favored over adsorbed CO2molecules under dry conditions.

[0212] Table 5 shows the corresponding reaction energies, AE (kJ- mol ') of optimized structures of carbamic acid / carbamates in the absence of water molecules formed during CO2adsorption in COF-999. The hydrogen bond distances between Ocoz and Namine as well as the corresponding O-H and Namine-H distances (within square brackets) are given in pm.Table 5. AE (kJ- mol-1) and hydrogen bond distances for CAI, CA2 and CA3.

[0213] Under humid conditions, carbamic acid / carbamate (Table 6, CW1-CW3) formed upon the reaction of CO2molecules with polyamines are stabilized through hydrogen bond interactions with the water molecules (AE about -150 kJ- mol-1). The carbamates form hydrogen bonds each with an adjacent polyamine group (N- • ■ Ofdonor] distances about 257-262 pm and Nfdonor]- ■ • O distances about 281-317 pm) and a water molecule (O- • ■ Owaterdistances about 266-283 pm). The proton is delocalized between the oxygen atom of carbamate and the adjacent polyamine group (O-- -H distances about 105-112 pm and N- --H distances about 103-106 pm). The formation of carbamates under humid conditions is thermodynamically more favorable than the formation of bicarbonates under humid conditions.

[0214] Table 6 shows the corresponding reaction energies, AE (kJ- mol ') of optimized structures of carbamic acid / carbamates in the presence of water molecules formed during CO2adsorption in COF-999. The hydrogen bond distances between Oco2 and Namine as well as the corresponding O-H and Namine-H distances (within square brackets) are given in pm.Table 6. AE (kJ-mol-1) and hydrogen bond distances for CW1, CW2 and CW3.

[0215] Under humid conditions, a CO2molecule can form carbonic acid / bicarbonate (Table 7, BC1-BC3) upon reaction with a water molecule assisted by the polyamine group (AE = -82 to - 110 kJ- mol-1). The bicarbonates form at least one strong hydrogen bond with the polyamine groups (N- • • O distances about 254-263 pm) and are further stabilized through up to two additional hydrogen bonds with the adjacent polyamines (N- • • O distances about 271-334 pm). The bicarbonates donate up to two hydrogen bonds to the polyamines through its -OH groups and accept one hydrogen bond through its =0 group. The proton is delocalized between theoxygen atom of bicarbonate and the polyamine group (O- H distances about 103-111 pm and N -H distances about 103-107 pm).

[0216] Table 7 shows corresponding reaction energies, AE (kJ-mol-1) of optimized structures of carbonic acid / bicarbonates in the absence of water molecules formed during CO2adsorption in COF-999. The hydrogen bond distances between Oco2and Namineas well as the corresponding O-H and Namine-H distances (within square brackets) are given in pm.Table 7. AE (kJ-mol ') and hydrogen bond distances for BC1, BC2 and BC3.Table 8. Absolute electronic energies (in eV) and relative electronic energies (kJ-mol-1) of different intermediates formed upon CO2adsorption.References(1) H. Lyu, O. I. Chen, N. Hanikel, M. I. Hossain, R. W. Flaig, X. Pei, A. Amin, M. D. Doherty, R. K. Impastato, T. G. Glover, D. R. Moore, O. M. Yaghi. Carbon Dioxide Capture Chemistry of Amino Acid Functionalized Metal-Organic Frameworks in Humid Flue Gas. J. Am. Chem. Soc., 2022, 144, 2387-2396.(2) H. Lyu, H. Li, N. Hanikel, K. Wang, O. M. Yaghi. Covalent Organic Frameworks for Carbon Dioxide Capture from Air. J. Am. Chem. 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[0217] In at least some of the previously described embodiments, one or more elements used in an embodiment can interchangeably be used in another embodiment unless such a replacement is not technically feasible. It will be appreciated by those skilled in the art that various other omissions, additions and modifications may 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, as defined by the appended claims.

[0218] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations.However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and / or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). It will befurther understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0219] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0220] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like include the number recited and refer to ranges which can be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 articles refers to groups having 1, 2, or 3 articles. Similarly, a group having 1-5 articles refers to groups having 1, 2, 3, 4, or 5 articles, and so forth.

[0221] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.

[0222] Accordingly, the preceding merely illustrates the principles of the invention. It will be appreciated that those skilled in the art will be able to devise various arrangements which, although not explicitly described or shown herein, embody the principles of the invention and are included within its spirit and scope. Furthermore, all examples and conditional language recited herein are principally intended to aid the reader in understanding the principles of the invention and the concepts contributed by the inventors to furthering the art, and are to be construed as being without limitation to such specifically recited examples and conditions. Moreover, all statements herein reciting principles, aspects, and embodiments of the invention as well as specific examples thereof, are intended to encompass both structural and functionalequivalents thereof. Additionally, it is intended that such equivalents include both currently known equivalents and equivalents developed in the future, i.e., any elements developed that perform the same function, regardless of structure. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.

[0223] The scope of the present invention, therefore, is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of present invention is embodied by the appended claims. In the claims, 35 U.S.C. § 112(f) or 35 U.S.C. §112(6) is expressly defined as being invoked for a limitation in the claim only when the exact phrase "means for" or the exact phrase "step for" is recited at the beginning of such limitation in the claim; if such exact phrase is not used in a limitation in the claim, then 35 U.S.C. § 112 (f) or 35 U.S.C. §112(6) is not invoked.

Claims

CLAIMS1. A covalent organic framework (COF) comprising a structure according to Formula (I):each X is independently selected fromwherein 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(ethylenimine) J-NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), - NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly (4- aminostyrene), and when n is 0, each W is independently selected from -(CH2)2NH2, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CH2)3NH2, poly(propyleneimine), lysine, polylysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene); and q is 2, 1, 3, or 4.

3. The COF of claim 1 or 2, wherein V is5. The COF of a preceding claim, wherein6. The COF of a preceding claim, wherein q is 1 or 2.

7. The COF of a preceding claim, wherein each n is an integer independently selected from 2 to8.

8. The COF of a preceding claim, wherein each X is9. The COF of a preceding claim, wherein n is 6 and each W is independently selected from, -NH(CH2)2NH2, and polyethyleneimine.

10. The COF of a preceding claim, whereineach X is; and each W is independently selected from-NH(CH2)2NH2, and polyethyleneimine.

11. The COF of a preceding claim, configured for carbon dioxide capture.

12. The COF of a 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 of a preceding claim, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane.

14. The COF of a preceding claim, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix.

15. The COF of claim 14, comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture.

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

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

18. A method of using the COF of a preceding claim for carbon dioxide capture and / or separation, especially from air or flue gas.

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