Multicomponent cofs and methods of making and using same

Abstract

Provided are covalent organic frameworks (COFs). Also provided are methods of making the COFs and methods of using the COFs. The COF sheets define a plurality of pores, and stack in an eclipsed configuration to form sheets that assemble to form nanoparticles. Each COF sheet may be a co-condensate of p-phenylenediamine (PA) and (i) triformylbenzene (TFB) and triformylphloroglucinol (TP) or (ii) triformylphloroglucinol (TP). A COF of the present disclosure has the following structure: Formula (I) and / or Formula II where each X2 is Formula (III) where earch X1 is Formula (IV) Formula (V) Formula (VI) Formula (VII) Formula (VIII) Formula (IX) Formula (X) Formula (XI) Formula (XII) Formula (XIII) or any tautomer thereof, where at least one X1 is not Formula (XIV).

Description

MULTICOMPONENT COFs AND METHODS OF MAKING AND USING SAMECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 643,044, filed on May 6, 2024, the disclosure of which is hereby incorporated by reference.BACKGROUND OF THE DISCLOSURE

[0002] In the ever-evolving landscape of material science, porous materials have attracted great attention in the fields of science and technology. Specifically, covalent organic frameworks (COFs) have emerged as a flourishing class of functional solid-state materials characterized by the lightweight elements linked by strong covalent bonds.1

[0003] COFs are rapidly gaining recognition for their transformative potential across various technological applications including water treatment, energy storage, catalysis, optoelectronics and gas adsorption and separation. The appeal of COFs for these applications stems from their inherent structural features, such as crystallinity, high surface area, pore volume, accessible pore system and modular nature.

[0004] In 2D COFs, particularly imine-based COFs, the process of structure formation starts with the precipitation of an amorphous polymer from solution followed by a transformation into a crystalline framework. This transformation is facilitated by the dynamic reversibility of the imine within the precipitate.

[0005] Furthermore, the covalent connectivity of the formed layers extends exclusively in 2D, underscoring the significant role the weak interactions play between molecular sheets in achieving crystalline structures with accessible surface area and structural stability. Non-covalent interactions include both intramolecular interactions, which serves to enhance the planarity of the layers for better alignment, and intermolecular interactions that enhance 71-71 stacking. Interactions among extended pi-systems are primarily responsible for either promoting or inhibiting the stacking between layers, consequently, influencing the overall crystallization of the network. For example, introducing complementary forces to the neighboring layers of electron rich and deficient sheets results in controlling the stacking force of the formed COFs and thus their properties.

[0006] The crystalline nature of COFs ensures well-defined porosity and full access to active sites within the framework, which are indispensable properties for industrial applications such as catalysis, energy storage and gas adsorption and separation. Therefore, toenhance the crystallinity and porosity of the framework, it is imperative to consider and address the reversibility of the formed linkage and the interlayer interactions.

[0007] The quest to find high-performance COFs necessitates the ongoing progress to expand the scope of COFs by exploring and developing new linkages. This progress aims at shifting them from being mere final products in a synthetic pathway to serving as intermediates capable of transforming into otherwise inaccessible novel functional materials.

[0008] In this regard, researchers have thoroughly explored tuning variables such as linkages used and complementary interactions between layers with the aim of improving the stability and inter-layer stacking. To date, various linkages, such as boronic acid trimerization, boronate ester formation, trimerization of nitriles and Schiff base reactions, have been widely used and studied due to the availability, affordability and enhanced stability of precursors to moisture and over a wide pH range.SUMMARY OF THE DISCLOSURE

[0009] Provided are covalent organic frameworks (COFs). Also provided are methods of making the COFs and methods of using the COFs.

[0010] In an aspect, the present disclosure provides COF networks. The COF networks comprise a plurality of COF sheets or nanoparticles. The COF sheets define a plurality of pores, and stack in an eclipsed configuration to form the resulting nanoparticles or sheets. Each COF sheet may be a co-condensate of p-phenylenediamine (PA) and (i) triformylbenzene (TFB) and triformylphloroglucinol (TP) or (ii) triformylphloroglucinol (TP).

[0011] A COF sheet of the present disclosure may be made from the following monomers:benzene-1 ,4-diamine ,w|qjc|q mayreferred to as “p-phenylenediamine (PA)” and(i) benzene-1 ,3,5-tricarbaldehyde ,referre(j t0as “triformylbenzene (TFB),”2,4,6-trihydroxybenzene-1 ,3,5- tricarbaldehyde , which may be referred to as “triformylphloroglucinol (TP),” or (ii) TP. A COF sheet may be formed from a condensation between PA and TFB, or PA and TFB and TP, or PA and TP. The amount of TFB may be controlled / varied.

[0012] In an aspect, the present disclosure provides articles of manufacture. The articles may comprise one or more COF sheets and / or COF networks of the present disclosure.

[0013] The present disclosure provides various articles. For example, the article may be a fdter, membrane, flow cell, a packet, or substrate. Various fdters are contemplated. The fdter can be a screw-on fdter for a faucet or valve, an in-line fdter, an active bed in gravity fdters (a point of use fdter), a fdter for a syringe, or the like. In other examples, the COF could be formulated as a powder or granulated powder. These formulations could be used to increase the efficacy of water removal. Filters may be used for adsorption from liquid or gas samples.

[0014] In an aspect, COF networks of the present disclosure may be used to capture and / or adsorb water from a gas.BRIEF DESCRIPTION OF THE FIGURES

[0015] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0016] Figure 1. Schematic representation of the synthesis and structures of COF-TP, COF-TFB and COF-TP-X synthesized from a mixture of TP and TFB.

[0017] Figure 2. FT-IR spectra (3500-500cm-1) of COF-TP-X (maroon) compared with COF-TFB (orange), COF-TP (green) and TP (red), PA (black) and TFB (blue).

[0018] Figure 3.13C solid-state NMR spectra of COF-TFB (a), mixed linker COF (b) and COF-TP (c). PXRD patterns of COF-TP-X (d). N2 adsorption isotherms of COF-TFB (e), COF-TP-X (f) and COF-TP (g). Pore size distribution of COF-TP-X (h).

[0019] Figure 4. Effect of activation temperature (125, 180, 240, 280, 320 and 380°C) on the N2 adsorption uptake of COF-TP 0% (orange), COF-TP 37% (blue), COF-TP 43 (maroon), COF-TP 93% (red) and COF-TP 100% (green).

[0020] Figure 5. Water adsorption isotherm of COF-TP X (X=0, 37, 43, 94, 100%).

[0021] Figure 6. Change of total mass variation of COF-TP 43% during nonequilibrium adsorption and desorption over 100 cycles driven by continuous change in relative humidity between 25% and 85% RH.

[0022] Figure 7. PXRD pattern of COF_TP X (0% / 37% / 43% / 93% / 100%) after activation up to 380 °C.

[0023] Figure 8. PXRD pattern of COF_TP X (0% / 37% / 43% / 93% / 100%) after 3 cycles of water adsorption experiment.

[0024] Figure 9. PXRD pattern of COF_TP X (0% / 37% / 43 % / 93 % / 100%) soaked in water for 24 h (left) and 1 week (right).

[0025] Figure 10. PXRD of COF TP 43% freshly prepared acetone exchanged sample COF-TP 43% and after exposing the sample to over 220 water sorption cycles.

[0026] Figure 11. TGA plot for as synthesized COF-TP 0% / 20% / 35% / 75% / 100%.

[0027] Figure 12. Comparison of the 13C CP-MAS solid state NMR spectra of COFs with varying mole % of TP with COFs represented as COF-TP-X.

[0028] Figure 13. Comparison of the 13C DP-MAS solid state NMR spectra of COFs with varying mole % of TP with COFs represented as COF-TP-X.

[0029] Figure 14. Water vapor adsorption isotherms of freshly prepared acetone exchanged COF-TP X (activated at 125 °C) followed by 2 cycles (sample dried by N2 gas).

[0030] Figure 15. Water vapor adsorption isotherms of (■) freshly prepared acetone exchanged sample of COF-TP 43% and (s) after exposing the sample to over 220 water sorption cycles.

[0031] Figure 16. (left column) BET (right column) PXRD of COF TP X% (0 / 37 / 43 / 93 / 100) before and after exposure to three cycles of water adsorption experiments.

[0032] Figure 17. Pore size distribution of COF_TP X (X = 0 / 37 / 43 / 93 / 100%) after water adsorption measurements.

[0033] Figure 18. Change of total mass variation of COF-TP 43% during nonequilibrium adsorption and desorption over more than 220 cycles driven by repetitive change in relative humidity between 25% RH and 85% RH.

[0034] Figure 19. FTIR spectra of freshly prepared acetone exchanged sample of COF-TP 0% (orange), COF-TP 37% (blue), COF-TP 43% (maroon), COF-TP 93% (red), COF-TP 100% (green).

[0035] Figure 20. FTIR spectra after water exposure of COF-TP 0% (orange), COFTP 37% (blue), COF-TP 43% (maroon), COF-TP 93% (red), COF-TP 100% (green).

[0036] Figure 21. FTIR spectra of freshly prepared acetone exchanged sample COFTP 43% and after exposing the sample to over 220 water sorption cycles.

[0037] Figure 22. Water sorption analysis of COF-TP -43 at different temperatures (25°C, 35 °C and 45 °C). The filled and opened circles represent the adsorption and desorption points, respectively.

[0038] Figure 23. Water sorption properties of COF-TP -43. (a) Water sorption at 25 °C. (b) Dynamic vapor sorption properties: adsorption at 25 °C and 45, 55 and 65% RH. (c) Desorption at 65 °C and 0% RH. (d) Change of total mass variation of COF-TP -43 during non-equilibrium adsorption and desorption over 100 cycles driven by continuous change in relative humidity between 20% RH and 85% RH at 25 °C. (e) and (f) show the first and last 10 cycles respectively.

[0039] Figure 24. (a) 3 cycles of water adsorption carried at 25 °C and 45, 55 and 65% RH followed by (b) water desorption at 35 °C, 45 °C and 65 °C, and 0% RH after the material has been saturated at its perspective % RH.

[0040] Figure 25. (a) Change of total mass variation of COF-TP -43 during nonequilibrium adsorption and desorption over 1000 cycles driven by continuous change in relative humidity between 20% RH and 85% RH at 25 °C. (b) N2 adsorption measurement of COF-TP-43 before and after exposure to 1000 cycles, (c) Water adsorption at equilibrium and at 25 °C.DETAILED DESCRIPTION OF THE DISCLOSURE

[0041] Although claimed subject matter will be described in terms of certain examples, other examples, including examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, process step, and electronic changes may be made without departing from the scope of the disclosure.

[0042] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompassvariations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art accepted standard, etc. and / or with, e.g., a given confidence interval (e.g. 90%, 95%, or more confidence interval from the mean), such as, for example, variations of + / -10% or less, + / -5% or less, + / -1% or less, and + / -0. 1% or less of and from the specified value), insofar such variations in a variable and / or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value in question is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained. In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about,” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0043] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0. 1% to 5%” should be interpreted to include not only the explicitly recited values of 0. 1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particularvalue. Similarly, when values are expressed as approximations, by use of the antecedent “about, it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0044] The articles “a” and “an” are used in this disclosure to refer to one or more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.

[0045] As used herein, unless otherwise stated or indicated, “s” refers to second(s), “min” refers to minute(s), and “h” refers to hour(s).

[0046] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., has one terminus that can be covalently bonded to other chemical species), divalent, or polyvalent (i.e., has two or more termini that can be covalently bonded to other chemical species). The term “group” also includes radicals (e.g., monovalent and multivalent, such as, for example, divalent radicals, trivalent radicals, and the like).Illustrative examples of groups include:The present disclosure provides

[0047] Provided are covalent organic frameworks (COFs). Also provided are methods of making the COFs and methods of using the COFs.

[0048] In an aspect, the present disclosure provides COF networks. The COF networks comprise a plurality of COF sheets. The COF sheets define a plurality of pores, and stack in an eclipsed configuration to form the resulting nanoparticles. The networks may be referred to as nanoparticles, wherein the nanoparticles comprise a plurality of sheets. Each COF sheet may be a co-condensate of p-phcnylcncdiaminc (PA) and (i) triformylbenzene (TFB) and triformylphloroglucinol (TP) or (ii) triformylphloroglucinol (TP).

[0049] A COF sheet of the present disclosure may be made from the following monomers:benzene-1 ,4-diamine ,w|qjc|q mayreferred to as “p-phenylenediamine (PA)” and(i) benzene-1 ,3,5-tricarbaldehyde ,may oe referred to as “triformylbenzene (TFB),”2,4,6-trihydroxybenzene-1 ,3,5- tricarbaldehyde , which may be referred to as “triformylphloroglucinol (TP),” or(ii) TP. A COF sheet may be formed from a condensation between PA and TFB, or PA and TFB and TP, or PA and TP. The amount of TFB may be controlled / varied. The amount of TP present may affect the properties of the resulting network. Throughout, the amount of TP is determined by the following equation:[TP] / (TFB + TP] x 100 (equation 1).

[0050] A COF sheet of the present disclosure may have the following structure:NH2or any tautomer thereof, where at least one Xi is not ' and where each X2 isIn various examples, at least 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%.37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%. 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%. 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%. 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or y _NH2greater than 99% of the Xi groups are not '

[0051] In various examples, a COF of the present disclosure has the following structure:where each Xi isor any tautomer thereof, where at least one Xi is not

[0052] In various examples, a COF of the present disclosure has the following structure:where each Xi is independentlyand each X2 is

[0053] A COF of the present disclosure may have various structural and chemical features. For example, the resulting networks / nanoparticles may have a hexagonal P6 / m space group. The COFs and resulting sheets form nanoparticles that may be porous and have some degree of crystallinity. For example, the sheets and / or nanoparticles may be partially crystalline, substantially crystalline, or crystalline. These COFs crystallize in the hexagonal P6 / m space group forming extended hexagonal structures with slipped AA stacking of layers.

[0054] The monomers of the COF network may be mixed at various ratios when synthesizing the COF sheets. For example, the amount of PA (in moles) may be more than the amount of aldehyde (in moles) (e.g., TP or TFB and TP). In various other examples, the ratio of PA to aldehyde is 3:2 to 2:3, including all values and ranges therebetween. The amount of TFB to TP can be varied. For example, there may be no TFB present and only TP is present. In various examples at least 0.1% (e.g., at least 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%,30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%,46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%,62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%,78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%,94%, 95%, 96%, 97%, 98%, 99%, or 100%) of the total moles aldehyde is TP. In various examples, each COF sheet comprise about 40% to 45% TP (e.g., 43%).

[0055] The COF networks / nanoparticles may have various physical characteristics. For example, the specific surface area of the network may be 800 to 2200 m2g-1, including all values and ranges therebetween. The specific surface area can be adjusted by adjusting the amount of TP present in the sheet and network. Additionally, the morphology may be controlled by controlling the amount of TP present. For example, each COF’s structure varied between hollow nanospheres (TP content at 0%) with an average particle size of 610 nm (e.g., 500 to 700 nm, including all angstrom values and ranges therebetween) to a mixture of nanofibers and spheres at TP content of 37%, to nanospheres with an average size of 372 nm(e.g., 300 to 475 nm, including all angstrom values and ranges therebetween) at TP content of 43% to nanofibers at 100% TP.

[0056] The COF networks may have desirable properties and / or features. For example, the sheets and resulting networks / nanoparticles are porous. For example, the pores may have a width distribution of 0.75 nm to 2.25 nm, including all values and ranges therebetween (e.g., 1.01 nm to 1.8 nm). The networks may have a desirable pore volume. For example, the pore volume is 0.25 to 1 cm3g-1, including all values and ranges therebetween (e.g., 0.37 to 0.8 cm3g-1). The porosity (e.g., pore volume and / or pore volume) can be adjusted by adjusting the amount of TP present in the sheet and network. In various other examples, the COF sheets and COF networks have a desirable stability in water and a desirable thermal stability. For example, a COF networks and COF sheets of the present disclosure may be thermally stable up to temperatures of 400 °C. As used herein, COFs are “thermally stable” if there is minimal or no degradation of the COF sheet (e.g., at least 90% of the COF sheet has not degraded relative to a COF sheet not subjected to heat). Further, COF networks of the instant disclosure may be used to adsorb water. Without intending to be bound by any particular theory, it is considered that introducing [3-ketoenamine linkages into the COF’s backbone enhances the hydrophilicity and the hydrolytic stability of COFs. The amount of water a COF network can adsorb may be adjusted by varying the ratio of TFB to TP. The amount of water adsorbed increased as the TP content in the COF increased reaching a maximum of 70 wt% at 43% TP content. This COF also displayed the highest porosity in terms of surface area and pore volume.

[0057] Various amounts of water can be adsorbed. For example, a COF of the present disclosure can adsorb up to 45 wt% at 45-65% RH (inclusive) and then desorb completely at 35-65 °C (inclusive). Without intending to be bound by any particular theory, this underscores the COF’s its potential for use in energy-efficient adaptive water harvesting devices. Adaptive devices are of interest as they can adapt the adsorption and desorption phases of its water harvesting cycle to climate fluctuations such that its water production efficiency is continuously optimized.

[0058] In an aspect, the present disclosure provides articles of manufacture. The articles may comprise one or more COF sheets and / or COF networks of the present disclosure.

[0059] The present disclosure provides various articles. For example, the article may be a filter, membrane, flow cell, a packet, or substrate. Various filters are contemplated. The filter can be a screw-on filter for a faucet or valve, an in-line filter, an active bed in gravityfilters (a point of use filter), a filter for a syringe, or the like. In other examples, the COF could be formulated as a powder or granulated powder. These formulations could be used to increase the efficacy of water removal. Filters may be used for adsorption from liquid or gas samples.

[0060] In various examples, the article is an adaptive water-harvesting device. In an adaptive water-harvesting device, the COF sheets or COF networks may be disposed on a surface (e.g., bed). In an illustrative example, the COF network is placed in a sorption compartment, which is placed directly behind the air-intake section. The more beds / trays the compartment holds, the more COF material can be loaded and exposed to the airflow as gas moves across the face of each tray. The trays are lined with aluminum sheets, as aluminum holds high thermal conductivity, to heat the COFs quickly during the desorption step.

[0061] In an aspect, COF networks of the present disclosure may be used to capture and / or adsorb water from a gas.

[0062] The COFs of the present disclosure are recyclable. That is, water adsorbed into the COF network may be desorbed and the COF network or article comprising the COF network may be reused. The COF was tested under different conditions. The COF can be recycled by reducing the relative humidity to 20 %RH for 45 minutes at room temperature to fully desorb water. It can also desorb by heating the sample at 35-65 °C where desorbing is fastest at 65 °C (less than 10 minutes). The COF network (or article comprising the COF network) may be recycled over 500 times, while maintaining 45 wt% uptake.

[0063] The steps of the method described in the various examples disclosed herein are sufficient to carry out the methods of the present invention. Thus, in an example, the method consists essentially of a combination of the steps of the methods disclosed herein. In another example, the method consists of such steps.

[0064] The following Statements are intended to be non-limiting examples of the present disclosure.Statement 1. A covalent organic framework (COF) network / nanoparticle, comprising a plurality of COF sheets, wherein the COF sheets define a plurality of pores, and the COF sheets stacked in an eclipsed configuration and each COF nanosheet is a co-condensate of p- phenylenediamine (PA) and (i) triformylbenzene (TFB) and triformylphloroglucinol (TP) or (ii) triformylphloroglucinol (TP).Statement 2. A COF network / nanoparticle according to Statement 1, wherein the molar ratio of PA to aldehyde is 3 : 2 to 2 : 3, including all 0. 1 ratio values therebetween, wherein the aldehyde is (i) TFB and TP or (ii) TP.Statement 3. A COF network / nanoparticle according to Statement 1 or Statement 2, wherein the COF network has a longest linear dimension of about 350 to 650 nm, including all angstrom values and ranges therebetween. In various examples, the COFs’ structures varied between hollow nanospheres (TP content at 0%) with an average particle size of about 610 nm to a mixture of nanofibers and spheres at TP content of 37%, to nanospheres with an average size of about 372 nm at TP content of 43% to nanofibers at 100% TP.Statement 4. A COF network / nanoparticle according to any one of the preceding Statements, wherein each COF sheet has a pore width distribution of 0.75 nm to 2.25 nm, including all angstrom values and ranges therebetween (e.g., 1.1 nm to 1.8 nm).Statement 5. A COF network / nanoparticle according to any one of the preceding statements, wherein the COF network comprises a plurality of COF sheets, wherein the sheets align such that nanoparticles are formed.Statement 6. A COF network / nanoparticle according to any one of the preceding Statements, wherein each COF sheet comprises 0.1 to 100 mol% TP, relative to the total amount of TFB and / or TP. In various examples, each COF sheet comprises 0, 37, 43, 93 and 100 mol% TP.Statement 7. A COF network / nanoparticle according to Statement 6, wherein each COF sheet comprises 37 to 100 mol% TP, relative to the total amount of TFB and / or TP.Statement 8. A COF network / nanoparticle according to Statement 7, wherein each COF sheet comprises 37 to 50 mol% TP, relative to the total amount of moles of TFB and / or TP.Statement 9. A COF network / nanoparticle according to Statement 8, wherein each COF sheet comprises about 43 mol% TP, relative to the total amount of TFB and / or TP.Statement 10. A COF network / nanoparticle according to any one of the preceding Claims, wherein the COF network is crystalline (e.g., the COF network is crystalline).Statement 11. A COF network / nanoparticle according to Statement 10, wherein the COF network is substantially crystalline or crystalline.Statement 12. An article of manufacture comprising the COF network / nanoparticle according to any one of the preceding Statements.Statement 13. The article of manufacture according to claim 12, wherein the article is an adaptive atmospheric water harvesting device.Statement 14. A method for adsorbing water comprising contacting a COF network / nanoparticle according to any one of the preceding Statements with a sample comprising a gas.Statement 15. A method according to Statement 14, further comprising desorbing at least a portion of the captured water from the COF network / nanoparticle.Statement 16. The method according to Statement 14, further comprising repeating contacting and / or desorbing one or more times.

[0065] The following example is presented to illustrate the present disclosure. It is not intended to be limiting in any matter.EXAMPLE

[0066] This example provides a description of COF networks / nanoparticles according to the present disclosure.

[0067] Two-dimensional covalent organic frameworks (2D COFs) are steadily gaining interest due to their unique structural paradigm of well-defined pore structure, permanent porosity and thermal stability. The crystallinity and porosity of COFs are the key structural parameters in their application in science and technology. Described herein is a multicomponent reaction (MCR) approach to integrate [3-ketoenamine linkages into mixed- linker COFs, COF-TP-X, where the [3-ketoenamine formed-linkage facilitates the intralayer planarity via NH — O hydrogen bonds and promotes the n-electronic conjugation and transportation between the intralayer itself and neighboring sheets. These materials show dramatic layer-stacking -driven enhancement to surface area and pore volume. It was shown that the distribution of [3-ketoenamine and imine linkages at different molar ratios across the nodes of the sheets plays a crucial role in enhancing the inter / intra layer interactions through hydrogen bonding, hence resulting in optimized layer stacking. This is reflected in the remarkable two-fold increase in pore volume compared to the parent COFs, enhanced water stability and exceptional water uptake capacity.

[0068] To further clarify the correlation between the linkages formed and the interactions between the layers, a multicomponent reaction approach was adopted to elevate crystallinity, stability and control the hydrophilicity of the formed COFs by introducing [3- ketoenamine linkages into an isostructural imine-based COFs.

[0069] Reported herein is the synthesis of mixed linker COFs, extending through [3- ketoenamine and imine linkages, upon the condensation of primary amines and aldehydes. In this work, we present a criterion to overcome the stacking hurdles resulting in COFs with remarkable crystallinity and porosity as the percentage of [3-ketoenamine increase in the framework up to 50%. Furthermore, we illustrate the substantial effect of ketoenamine in tailoring the chemical environment of the COFs by tuning the hydrophilicity of the framework without compromising the overall water uptake capacity.

[0070] The condensation of p-phenylenediamine (PA) with either triformylbenzene (TFB) or triformylphloroglucinol (TP) forms the corresponding hexagonal 2D layered TFB- COF and TP-COF. These COFs belong to the same crystalline space group forming hexagonal sheets with eclipsed stacking. As both networks are prepared under identical reaction conditions, they represent a desirable platform to study the effect of mixing the two linkers in different ratios on the resulting COF structure.

[0071] To demonstrate this strategy, a three -component system was used in which a mixture of TFB and TP at different molar ratios (X = [TP] / ([TFB+TP]) x 100= 0, 20, 75, 35, 100) was condensed with (PA) to form mixed linker COFs denoted COF-TP-X.

[0072] COF-TP-X structures were synthesized under the same conditions applied to form the parent COFs (1.0:0.2 1,4- dioxane / acetic acid, 120 °C, 3 days). As described herein, the degree of substitution was varied from 0 to 100%, while maintaining a molar ratio of PA to total aldehyde of 2:3 (Figure 1, Table 2). A total of 5 mixtures of TP / TFB were prepared by varying the mol % of TP ranging from 0 % to 100 %. Fourier transform infrared (FT-IR) spectroscopy provides direct evidence for the complete consumption of the starting materials based on the disappearance of the N-H stretching bands of PA (3100-3300 cm'1) and the carbonyl stretching bands of TP (1635 cm'1) and TFB (1691 cm'1), while a new peak located at -1593 cm'1indicating the formation of C=N (from TFB linker) and -1577 cm'1arising from the C=C stretch present in the keto form (from TP linker). It was noted that the intensity of the peak located at 1577 cm'1corresponding to the formation of C=C bond from TP linker increases with increasing TP content, indicating the successful integration of TP linker at different monomeric feeds (Figure 2 and 19). As a result, the isolation of COF-TP-X (X defines different mole % of TP in COF) with a mixed imine and [3-ketoenamine linkages were observed for COF-TP-20 / 35 / 75. This was further confirmed by13C cross-polarization magic angle spinning (CP -MAS) solid state NMR spectroscopy (Figure 3a-c and Figure 12).13C CP-MAS NMR spectroscopy showed the appearance of the characteristic peaks of [3- ketoenamine linkage at 107 ppm and 184 ppm, which corresponds to exocyclic sp2-hybridized carbons -C=C and to the presence of keto groups (-C=O) respectively. A distinct peak at 157 ppm corresponding to the carbon atom characteristic to C=N bond formed upon the condensation of TFB with PA was observed.

[0073] CP -MAS shows comparable spectra, Figure 12, for both starting materials and the different multicomponent COFs (COF TP-X) with five peaks assignable to the respective carbon atoms in the repeating unit. A distinct peak at 107 ppm corresponding to the exocyclic sp2-hybridized carbons -C=C of the TP linker was observed, in addition to the characteristic imine carbons -C=N of the TFB linker peak at 157 ppm. Furthermore, the broad peak at -184 ppm corresponds to the presence of keto groups (-C=O) of the TP linker. All the other peaks, carbon resonances, are found between 107 ppm and 157 ppm.

[0074] As it can be clearly seen from the CP-MAS spectra of COF-TP-0, the peak at 157 ppm, which correspond to the -C=N linkages, is not observed in the spectra of the parent COF, COF-TP-100, indicating the complete replacement of the -C=N- units. In this respect, the carbon signals of the -C=C and -C=O linkages appear as intense peaks at 107ppm and 184pmm, respectively, in the spectra of the parent COF-TP-100, which are not visible in COF-TP-O spectrum, indicating the complete linkage transformation. To provide stronger evidence for the complete linkage transformation between the different multicomponent COFs, and to quantitatively determine the ratio of the two linkers in COF-TP-X, we used solid-state direct polarization13C MAS NMR spectroscopy (Figure 13). The quantitative spectra were recorded with a recycle delay of 20s (more than five times the longitudinal relaxation time T1 of all of the carbons).

[0075] Therefore, the distinct peak at 107 ppm corresponding to the exocyclic sp2hybridized carbons -C=C of the TP linker could clearly be integrated into all samples and compared with the imine -C=N peak at 157 ppm. By integrating the resonance peak intensities, TP was found to be at - 93% for COF-TP-75, at 43 % for COF-TP-35 and 37 % for COF-TP-20. These carbon integrations quantitatively confirmed the lattice components of the formed COF-TP-X. As the mole % of TP content was confirmed in each of the formed COFs, we next highlight the porosity, chemical stability and crystallinity of COF-TP-93, COF-TP-43, and COF-TP-37 and compare them to the parent COFs (TP content at 0 % and 100 %).

[0076] The permanent porosity of the isolated COF-TP-X samples was demonstrated by measuring nitrogen adsorption at 77K. The adsorption measurements revealed fully reversible type-I isotherm, characteristic of microporous materials with permanent microporosity for all COF-TP-X structures, Figure 3e-g. COF-TP-37 expresses the highestSBET surface area of 1984 m2g'1and pore volume of 0.8 cm3g'1as shown in Table 1, followed by COF-TP-43 and COF-TP-93, then COF-TP-100 and COF-TP-O. Surface area is a quantitative parameter that is highly sensitive to polymerization, crystallinity and activation conditions. The high surface area demonstrates that the COFs are microporous materials with a remarkable nitrogen uptake at low relative pressures. As the mixed linkers are similar in dimensions, it was expected that the surface area of the mixed linker COFs to lie within the range of the parent COFs. Interestingly, the measured surface area and pore volume reached optimal values with increasing TP mole % with a maximum increase of 2-fold in COF-TP-37 compared to parent COF-TP-100 and COF-TP-O.

[0077] Table 1 Surface Areas for COF-TP-X; X= 0, 37, 43, 93 and 100%.

[0078] In addition, the pore size distribution profiles, calculated using density functional theory (DFT), of the obtained COF-TP- 37 / 43 / 93 revealed a narrower pore width distribution 1.1, 1.5 nm, and 1.8 nm, where the theoretical value is 1.8 nm, compared to parent COFs. The enhanced surface area, pore volume and pore size distribution observed as the mole % of TP increases in COF-TP-X structures, reflects the role of keto forms distributed among the nodes of COF-TP-X in facilitating the intralayer planarity via the NH— — O hydrogen bonds and promotes the electronic conjugation and transportation within the layer itself and among neighboring sheets. Hence, more ordered layers are formed with accessible pore surface.

[0079] The thermal stability of the obtained COF-TP-X structures was assessed first using thermogravimetric analysis (TGA), Figure 11. All activated COFs showed thermal stability up to 430 °C. However, as TGA is less sensitive to changes in the COF’s periodic structure, COF-TP-X samples were activated at elevated temperatures of 180 °C, 240 °C, 280 °C, 320 °C and 380 °C and held under vacuum for 12 h. Then, it was followed by N2 adsorption measurements

[0080] N2 adsorption measurements were collected to study the effect of the heating temperature on the porosity and surface area of the COF. As shown in Figure 4, COF-TP- X maintain type I isotherms and preserved high structural stability as exposed to temperatures up to 380 °C. Markedly, the COF-TP 43% preserved optimal porosity after heating up to 240 °C, with a slight loss of 16% in the total surface area at 380 °C. It is also noticeable that COF-TP-X samples retained long-range periodicity at 380 °C and structure identity, Figure 7 and 21.

[0081] In light of the high porosity and the hydrophilic ketoenamine moieties dispersed in the COF’s skeleton which is expected to embark high hydrolytic stability to the framework as previously reported, it was aimed to evaluate the performance of COF-TP X under different relative humidity levels by performing water adsorption measurements.

[0082] Water Adsorption Properties of COF-TP X. Water vapor adsorption properties were carried out to examine water vapor adsorption characteristics of the COF-TP- X using IGAsorp vapor sorption analyzer from Hiden Isochema. The water vapor partial pressure was controlled automatically by mixing wet vapor feed with a N2 line, hence; N2 acts as a carrier gas for water vapor. Pretreatment of the sample was carried out by drying the sample at 125 °C in the presence of N2 dry carrier for 5h. The sample “dry mass” was measured under N2, at equilibrium (25 °C), before dosing water vapor progressively into the chamber. The stability of each of the samples collected was verified by PXRD, FTIR and N2 adsorption measurements after each run, Figure 8, 20 and 16, respectively. The adsorption isotherms, obtained at equilibrium, were collected between 0 and 98% RH at ambient temperature of 25 °C, as shown in Figure 5. Prior to exposing the samples to water adsorption measurements, acetone exchanged samples were soaked in liquid water. The stability of the sample was monitored with PXRD over the course of 24h and 1 week (Figure 9).

[0083] The water vapor adsorption isotherm of the fully activated COF-TP-X samples feature type V S-shaped (sigmoidal) adsorption and desorption branches with varying on-set pressure points depending on the mole % of TP embedded in the isolated imine COFs, where the higher content of ketoenamine moieties enhances the hydrophilicity of the framework resulting in an earlier on-set water uptake. Also observed was the effect of the ketoenamine moieties on the hysteresis loop, where it becomes more pronounced in the samples with lower ketoenamine content as the framework becomes more hydrophobic and requires larger water clusters to form before capillary condensation occur.

[0084] COF-TP-100% and COF-TP-93% exhibit water sorption isotherms with a steep pore-filling step at 20% RH (at 25 °C, Figure 5) with a relatively small hysteresis loopcompared to other COFs. The quick uptake reflects the capillary condensation of water molecules in the microporous ID channels. While COF-TP-100% reaches saturation uptake value of 41 wt % (0.41 g g'1) at 80 %RH followed by clusters agglomeration filling the interstitial spaces between micro-crystallites, COF-TP 93% displays a total water adsorption capacity of 55 wt % (0.55 g g'1) at 98 %RH, the improved capacity is due to enhanced surface area.

[0085] As for COF-TP 0%, COF-TP 37% and COF-TP 43% with lower ketoenamine content, a delayed onset was observed for all three frameworks starting at 30 %RH. COF-TP 43% exhibits an S-shaped water sorption isotherm with a pronounced hysteresis loop and a steep pore-filling step at 30 %RH (Figure 5, maroon curve). The maximal water uptake reaches 70 wt % (0.7 g g'1) at 98 %RH, one of the highest records among microporous COFs. COF-TP 34% displays a similar behavior with a slightly less steep uptake that totals at 61 wt % (0.6 g g'1) at 98 %RH. The lower water uptake capacity is due to its lower porosity. In contrast, COF-TP 0% exhibits a rather sluggish uptake between 30 and 45 %RH with a total uptake capacity of 30 wt % (0.3 g g'1) at 90 %RH.

[0086] To evaluate the recyclability and hydrolytic stability of the frameworks, each COF-TP-X was exposed to three cycles at equilibrium followed by FTIR, PXRD and N2 adsorption measurements. These COFs showed excellent recyclability as realized by the almost identical water adsorption isotherms over three cycles as shown in Figure 14. The structural integrity, as the imine and P-ketoenamine linkages are retained, of each of these COFs is maintained as shown by FTIR, Figure 20. However, COF-TP X with low ketoenamine content (COF-TP 0% / 37%) show reduced crystallinity and porosity, Figure 8 and 16, although COF-TP 37% maintains higher order and porosity compared to COF-TP 0%.

[0087] On the other hand, COFs with higher ketoenamine content (COF-TP 43% / 93% / 100%) show outstanding stability to water content Figure 14, (d, e and f) with COF-TP 43% maintaining highest water uptake due to its higher porosity. As these materials, show high water content and stability, further cyclic measurements were conducted on COF-TP 43% to evaluate the cyclic adsorption / desorption performance of the COF adsorbent.

[0088] Over 200 water vapor adsorption and desorption cycles, at room temperature and non-equilibrium conditions, were performed on COF-TP 43% (Figure 6 and 17) with adsorption at 85% RH and desorption at 25% RH. COF-TP 43% showed a high and steady cyclic water vapor adsorption operation as it maintains a high-water uptake of 45 wt %, as shown in Figure 6. The FTIR, PXRD pattern and the water adsorption isotherm (Figures 22,10, 15, and 18) collected on the extensively recycled sample confirms the hydrolytic stability of COF-TP 43% and the maintenance of its structural features and original adsorption properties.

[0089] To gain a better insight about the role of ketone groups distributed along the skeleton of the framework of COF-TP -X in enhancing the stacking between layers, a theoretical study was conducted on COF-TP 43% and compared with COF-TP 0% and COFTP 100%.

[0090] In conclusion, a series of multicomponent COFs containing phenylene diamine and two types of three -connected nodes TP and TFB, where TP was introduced at different percentages into the framework were synthesized, we employed a dual linkage system to synthesize mixed linker COFs with imine linkage and [3-ketoenamine linkage with a crystallinity and surface area far superior to the relative parent COFs.

[0091] The overall findings confirm that the crystalline hexagonal framework can be synthesized from TP and TFB at continuously variable composition, not just 1:2 or 2: 1, where the addition of TP resulted in enhanced crystallinity and porosity. It is possible that the improved materials quality is through the continuous error correction steps which the imine linkage undergoes because of the reversible nature of the bond. The incorporation of TFB into the COF structure at lower concentrations than theoretical values indicates the different kinetics of both linkers where [3-ketoenamine linkage forms at a higher rate than the imine linkage.

[0092] In addition, a high water stability and thermal stability of the obtained mixed linker COFs was observed. The combination of TP and TFB unveils new properties that are beyond the linear combination of the single components.

[0093] Powder X-ray Diffraction (PXRD) measurements were carried out at room temperature on a PANalytical Malvern Empyrean 3 diffractometer 40kV, 40mA for CuKa (X= 1.5418 A), with a scan speed of 0.03° min'1and a step size of 0.026° in 20.

[0094] Thermogravimetric analysis (TGA) was performed on a TA Instrument Hi- Res TGA Q600 with High Resolution TGA (Hi-Res TGA) capability. Experiments were performed under N2 atmosphere with balance and sample purge flow rates of 10ml min'1and 25 ml min'1, respectively. Samples were placed on 100 pl high temperature platinum crucibles and heated in Hi-Res TGA mode with a heating rate of 10 °C min'1and a resolution index of 4 and a sensitivity index of 1.

[0095] Solid-State NMR experiments were carried out on a Bruker Avance-HD 600 MHz spectrometer operating at a static field of 14.1 T using a 4.0 mm Magic Angle Spinning(MAS) probe. Powdered samples were packed into 4.0 mm zirconia rotors and were spun at 14 kHz. 1H13C CP / MAS experiments were performed using standard linearly ramped cross- polarization pulse sequence.13C chemical shifts were externally referenced to the adamantane CH2 signal at 38.48 ppm on the TMS scale. All the NMR data were processed using TopSpin software.

[0096] FTIR studies were carried out on Agilent 670-IR spectrometer in the attenuated total reflectance (ATR) mode.

[0097] Water sorption experiments were carried out at ambient conditions (25 °C) using IGAsorp vapor sorption analyzer from Hiden Isochema. The water vapor partial pressure was regulated automatically by mixing wet vapor feed with a N2 line, hence, N2 acts as a carrier gas for water vapor. The “dry mass” of the sample was measured under N2, at equilibrium (25 °C), before gradually exposing the sample in the chamber to water vapor. The adsorption isotherms, obtained at equilibrium, were collected within a range of 0% - 95% RH.

[0098] Gas adsorption measurements were performed using a Micromeritics 3-Flex Surface Characterization Analyzer at relative pressures up to 1 atm. The cryogenic temperatures were controlled using nitrogen baths at 77 K. The apparent surface area was determined from N2 adsorption isotherms collected at 77 K by applying the Brunauer- Emmet-Teller (BET) model between P / Po values of 0.05 and 0.3 for microporous COFs.

[0099] A weighed amount of the samples (20-50 mg) were first activated by washing the as-synthesized samples with 3 x 20 ml THF followed by 3 x 20 ml ethanol solvent and 3 x 20 ml acetone solvent. In a typical experiment, the activated samples will be transferred (dry) to a 12-mm flat-bottom glass sample tube after being activated at room temperature using a turbo molecular vacuum pump and then gradually heated to 125 °C, held for 16 h and cooled to room temperature. Adsorption isotherms were then measured in volumetric method with Micromeritics 3-Flex device at 77 K (maintained by liquid N2) for N2 adsorption

[0100] Table 2 Amount of TP and TFB used to synthesize COF-TP-X% solid solutions.

[0101] COF-TP-43 was selected for further water sorption studies starting by measuring the water sorption profiles at different temperatures (35 °C, and 45 °C). As shown in Figure 1, similar behavior and isotherm shape to the sample collected at 25 C was observed but with a relatively narrower gap and a slightly lower uptake.

[0102] In light of the high stability of water, further experiments were conducted, under more practical conditions, to evaluate the effect of varying the relative humidity and temperature during adsorption and desorption on the performance of the material. We determined the optimal desorption temperature by saturating the material at 45%, 55% and 65% RH at 25 °C (Figure 2b) followed by desorption at 0% RH and temperatures of 35 °C, 45 °C or 65 °C and (Figures 2c and 3). As shown in Figure 2b and 2c, the steepest uptake occurs at 65% RH, reaching saturation in less than 50 min, whereas desorption occurs very fast at 65 °C to trigger the release of 0.45 g g’1, reflecting the weak interactions between water and the framework.

[0103] Further cyclic experiments were conducted, and COF-TP-43 showed stability over 1000 cycles as shown in Figure 26a. After water adsorption, the stability of the material was confirmed N2 adsorption measurements (Figure 26b) and by measuring water adsorption at equilibrium, Figure 26c.

[0104] In summary, microporous 2D COFs with improved the performance were synthesized by incorporating [3-ketoenamine linkages using the MCR approach. By creating mixed-linker COFs that contain both imine and [3-ketoenamine linkages at varying percentages, the resulting COF-TP -37 / 43 / 93 exhibits significantly higher crystallinity and surface area than the corresponding mono-linker COFs (X = 0% or 100%). The combination of TP and TFB yields new properties surpassing the linear combination of the individual components.

[0105] Molecular dynamics simulations indicate that the superior properties of mixed-linker COFs arise from two competing density effects. COFs with a higher proportion of TP units exhibit increased density, whereas COFs with only TFB units display higher density due to smaller interlayer distances. Both effects lead to reduced gravimetric properties in the mono-linker COFs. Additionally, strong electrostatic interactions between TP linkages in neighboring layers significantly influence the stacking behavior, which is not observed with layers containing only TFB linkages.

[0106] The mixed-linker COFs also demonstrate outstanding water sorption properties and thermal stability. Specifically, COF-TP-43 shows a high-water uptake capacity of 70 wt% and maintains exceptional long-term stability over more than 200 cycles of wateradsorption-desorption experiments. Most importantly, COF-TP-43 can adsorb up to 45 wt% at 45-65% RH and desorb completely at 35-65 °C, underscoring its potential for use in energy-efficient adaptive water harvesting devices. Accordingly, COF-TP-43 is a promising adsorbent currently under evaluation for such water harvesting devices.

[0107] Although the present disclosure has been described with respect to one or more particular embodiments and / or examples, it will be understood that other embodiments and / or examples of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. A covalent organic framework (COF) network / nanoparticle, comprising a plurality of COF sheets, wherein the COF sheets define a plurality of pores, and the COF sheets stacked in an eclipsed configuration and each COF nanosheet is a co-condensate of p- phenylenediamine (PA) and (i) triformylbenzene (TFB) and triformylphloroglucinol (TP) or (ii) triformylphloroglucinol (TP).

2. The COF network / nanoparticle according to claim 1, wherein the molar ratio of PA to aldehyde is 2 : 3, wherein the aldehyde is (i) TFB and TP or (ii) TP.

3. The COF network / nanoparticle according to claim 1, wherein the COF network has a longest linear dimension of about 350 to 650 nm.

4. The COF network / nanoparticle according to claim 1, wherein each COF sheet has a pore width distribution of 0.75 nm to 2.25 nm.

5. The COF network / nanoparticle according to claim 1, wherein the COF sheets align such that a plurality of nanoparticles are formed.

6. The COF network / nanoparticle according to claim 1, wherein each COF sheet comprises 0.1 to 100 mol% TP, relative to the total amount of TFB and / or TP.

7. The COF network / nanoparticle according to claim 6, wherein each COF sheet comprises 37 to 100 mol% TP, relative to the total amount of TFB and / or TP.

8. The COF network / nanoparticle according to claim 7, wherein each COF sheet comprises 37 to 50 mol% TP, relative to the total amount of TFB and / or TP.

9. The COF network / nanoparticle according to claim 8, wherein each COF sheet comprises about 43 mol% TP, relative to the total amount of TFB and / or TP.

10. The COF network / nanoparticle according to claim 1, wherein the COF network is at least partially crystalline.

11. The COF network / nanoparticle according to claim 10, wherein the COF network is substantially crystalline or crystalline.

12. An article of manufacture comprising the COF network / nanoparticle according to claim1.

13. The article of manufacture according to claim 12, wherein the article is an adaptive atmospheric water harvesting device.

14. A method for adsorbing water comprising contacting a COF network / nanoparticle according to claim 1 with a sample comprising a gas.

15. The method according to claim 14, further comprising desorbing at least a portion of the captured water from the COF network / nanoparticle.

16. The method according to claim 15, further comprising repeating contacting and / or desorbing one or more times.

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