NANOPOROUS SPONGES FOR WATER ADSORPTION, PROCESS FOR PREPARING THE SAME AND USES THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application claims priority to U.S. Provisional Patent Application No.63/402,465, which was filed August 30, 2022, the content of which is incorporated herein by reference in their entirety. FIELD [0002] The present application is in the field of nanoporous material. More specifically, the present application relates to nanoporous carbonaceous material for water adsorption, process for their preparation and uses thereof. BACKGROUND [0003] Large populations living in parts of the world depend either on water supplied by tankers, which is expensive and intermittent, or groundwater, which is not always suitable for drinking and not always replenished by surface water. A recent UN Water Crisis Report prepared by the Food and Agriculture Organization [1] shows that there is a growing global water crisis and that more than 2 billion people living in arid regions could be threatened by a water shortage. [0004] Because an adequate supply of clean drinking water is a basic necessity for human survival, solutions to this growing crisis are required to avoid the worst. Various methods exist to generate fresh water, and most focus on using abundant seawater. Water desalination [2] is the process of removing salts and minerals from water to render it drinkable through thermal methods (multi flash distillation, multi effect distillation) or filtration methods (electrodialysis, reverse osmosis). Today, the leading process for intensive production of freshwater is reverse osmosis (RO) [3], which has become more cost effective in the past decade. However, RO requires the availability of energy (between 17 and 83 kWh per m ³ [5]) together with large bodies of saline water, a distribution infrastructure and high upfront capital cost. On the other hand, water generation from humid air corresponds to typical dehumidification devices and 1 8702004 require high energy intake to cool down humid air below dew point, from 270 to 550 kWh per cubic meter of captured water [5]. [0005] Typical water generation from humid air corresponds to typical dehumidification devices and requires energy to cool down humid air below the dew point (Figure 1, thermodynamic approach [4]). The challenge here is to generate materials on which the humidity adsorption is made to occur with no cooling below ambient temperature to limit energy requirements. Following this adsorption, there is a need to desorb the captured water with minimal energy requirement (Figure 1, sorption approach [5]). These nanostructured adsorbents are specifically designed to efficiently adsorb and desorb water from humidity using capillary condensation. In other words, the idea lies in the creation of a very efficient adsorbent based on nanostructure that would require a minimal energy input. [0006] Another method that does not rely on saline water sources is fog harvesting (Figure 1). In regions where precipitation is low or lacking, especially in remote areas such as mountains and islands in the dry season, it is feasible to set up a passive mesh system (mounted on a sturdy frame) to collect fresh water already condensed in the form of fog from the air. The mesh, which can be made from different materials, is exposed to foggy air masses, and this water-charged air is pushed through the mesh by wind currents [6]. Fog micro-droplets coalesce on the mesh to form larger drops that flow down the mesh through gravity drainage into gutters connected to a storage tank. [0007] The adsorption and desorption in porous materials for atmospheric water harvesting relies on the principle of capillary condensation. Capillary condensation is a gas to liquid phase transition of an adsorbate in a porous material and under certain conditions. Capillary condensation happens at a vapor pressure lower than the saturation pressure (i.e. dew point). Suitable conditions include the type of adsorbate and porous material, the pore diameter and pore size distribution, and the gas temperature [7]. [0008] At low vapor pressure (i.e. low relative humidity) the gas first forms a monolayer of molecules adsorbed on the inner surface of the pores, followed by the 2 8702004 growth of a metastable multilayer. The instability of the adsorbed multilayer results from a competition between the potential energy of adsorption of the substrate with the surface energy of the film and the capillary evaporation occurring simultaneously. At a critical thickness, liquid bridges can grow and form menisci whose curvature is dependent on the equilibrium vapor pressure and the surface tension of the liquid phase [8]. [0009] An important phenomenon in capillary condensation is the irreversibility between the adsorption and desorption phase, under the form of a hysteresis on the adsorption isotherms. The exact cause of this hysteresis is still debated, although several hypotheses are evoked, such as pore blocking, cavitation, irregularities in pore shape, inhomogeneity of surface chemistry or mechanical deformation of pores during condensation [9]. Hysteresis is undesirable since it prevents adsorbed water from leaving the adsorbent without addition of energy. [0010] Hysteresis can be prevented by selecting pore diameters smaller than the critical pore diameter, and a temperature above the critical temperature. These critical values are specific to the gaseous phase studied and are equal to 3.0 nm for argon at 77 K and 2.1 nm for water at 298 K (room temperature) [7]. The pore size distribution also influences the shape of the hysteresis. Recent experiments have shown that a narrow pore size distribution is favorable to obtain a smaller hysteresis compared to a wide distribution. [0011] Current research on harvesting humidity based on capillary condensation focuses on Metal Organic Frameworks (MOFs). MOFs are highly porous materials based on the coordination network of metal ions coordinated to organic ligands. The porosity is controlled via the nature of the metal ions and organic ligands as well as the synthesis parameters. MOFs are synthesized through solvothermal processes, where crystals grow slowly from hot solutions over the course of hours to days. The process is difficult to scale up and ongoing research is done to accelerate the crystal growth with microwave radiation [10]. Because MOFs are made of coordinated ions (anions or cations), they can be affected by the presence of water. An important parameter to consider MOFs for water capture application is their hydrolytic stability, i.e. the material 3 8702004 degradation in presence of water [11]. It is common to observe decrease of the performance over cycles of adsorption/desorption [11]. Some studies show MOFs with enhanced hydrolytic stability and thus better cyclability [12]. With their highly controlled porosity MOFs can have water uptakes of more than 1 kg/kg of material at high relative humidity (Figure 2) [11]. Some studies tend to go towards carbonaceous materials as adsorbent in order to overcome stability issues, lifetime and difficulty to scale up [13]. [0012] Similarly, to the MOF structure, covalent-organic frameworks (COFs) are also investigated as water adsorbents [14]. Contrary to MOFs, whose networks are coordinated by metallic ions, COFs are covalently bonded by light elements (B, C, Si, N and O) that improve their stability in contact of water. [0013] A recent study also presented a new absorbent material, the super moisture-absorbent gel (SMAG) [15]. Composed of hygroscopic polypyrrole chloride in hydrophilicity-switchable polymer made of poly N-isopropylacrylamide, the SMAG shows outstanding water uptake up to 6 g/g of material with low energy requirements for water release. No information on cyclability is available for such material. [0014] Sorbent materials, either in the form of MOF or COF, need a particular device that allows adsorption from humid air and then release it under the form of liquid water with minimal energy input. A typical set-up based on day and night cycles is shown on Figure 3 [16], from US20180171604A1, claiming several forms of heating for the desorption, such as solar irradiance, heat from the combustion of waste or biomass, a condenser with a heat sink and adsorbent materials comprising zeolites, MOF, silica gel, carbon fibers or hydroscopic salts. [0015] However, MOF adsorbents are difficult and costly to synthesize. For example, MOF-801, a common material studied in water harvesting, requires zirconium metal at the cost of 200 CAD $/kg (Zr makes up approximately 40% of the MOF-801 mass), without counting the price of the organic compounds and processing steps [17]. Moreover, some MOF-based water harvesting systems reported in the literature suffer from scalability issues and performance stability [13]. Indeed, the amount of water collected with MOF can decrease after only 5 cycles of adsorption/desorption [11]. 4 8702004 [0016] Moreover, current technologies involving thermodynamic cycles have a low coefficient of performance (COP) due to the use of refrigeration dehumidification process which cools the air below dew point to condense water vapour under the form of humidity. Subsequent reheating of the dry air consumes considerable amounts of energy. [0017] There is a need for adsorbent material that can be easily scaled up, preferably using cheap and abundant chemicals, that can be produced using a minimal amount of energy, while maintaining good water uptake and kinetics sustainably. [0018] Accordingly, there is a need for a material that would overcome at least one drawback of current technologies. SUMMARY [0019] It is advantageously shown herein that nanoporous carbonaceous material of the present application provide highly stable water adsorbent material at a low cost, requiring minimal energy to prepare and to operate. The nanoporous carbonaceous material of the present application provides for sustainably good water uptake and fast adsorption kinetics. Comparable materials and processes did not display the same properties, highlighting the advantageous results obtained with the materials and processes of the application. [0020] Accordingly, the present application includes a nanoporous carbonaceous material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. [0021] The present application also includes a nanoporous carbonaceous material for use in water adsorption, the material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized, wherein the nanoporous 5 8702004 carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. [0022] The present application further includes a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin and combinations thereof and wherein the material is optionally functionalized, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. [0023] The present application also provides a nanoporous carbonaceous material for use in water adsorption, the material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin and combinations thereof and wherein the material is optionally functionalized, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. [0024] The present application also provides a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-aldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, and combinations thereof and wherein the material is optionally functionalized, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. [0025] The present application also provides a nanoporous carbonaceous material for use in water adsorption, the material comprising at least one pyrolyzed organic compound-aldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, and combinations thereof and wherein the material is optionally functionalized, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kgwater/kgmaterial to about 2.4 kgwater/kgmaterial at 95% of relative humidity. 6 8702004 [0026] In some embodiments, the water adsorption uptake is about 0.5 kgwater/kgmaterial to about 2.2 kgwater/kgmaterial at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 1.0 kgwater/kgmaterial to about 2.0 kgwater/kgmaterial at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 1.8 kgwater/kgmaterial to about 2.2 kgwater/kgmaterial at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 0.25 kg ^water /kg ^material to about 1.5 kg ^water /kg ^material at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 0.25 kgwater/kgmaterial to about 2.2 kgwater/kgmaterial at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 0.5 kgwater/kgmaterial to about 1.8 kgwater/kgmaterial at 95% of relative humidity. In some embodiments, the water adsorption uptake is about 0.5 kgwater/kgmaterial to about 1.5 kgwater/kgmaterial at 95% of relative humidity. [0027] The present application includes a nanoporous carbonaceous material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized. [0028] The present application further includes a nanoporous carbonaceous material for use in water adsorption, the material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized. [0029] The present application also includes a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin and combinations thereof and wherein the material is optionally functionalized. In some embodiments, the organic compound is any other carbon-rich resins. [0030] The present application further provides a nanoporous carbonaceous material for use in water adsorption, the material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, other carbon-rich resins and combinations 7 8702004 thereof and wherein the material is optionally functionalized. In some embodiments, the material is optionally functionalized with oxygen, nitrogen, suflur, phosphor, carbon-based cations/anions, or mixtures thereof. [0031] The present application also includes a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is any organic compound and wherein the material is optionally functionalized. [0032] The present application further provides a nanoporous carbonaceous material for use in water adsorption, the material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is any organic compound and wherein the material is optionally functionalized. [0033] In some embodiments, the nanoporous carbonaceous material has an average pore size of about 1 to about 10 nm, or about 1 to about 5 nm, or about 1 to about 3 nm. In some embodiments, the average pore size is about 1.5 nm. [0034] In some embodiments, the nanoporous carbonaceous material has a pore size distribution is about 1.3 to about 1.9 nm, or about 1.4 to about 1.8 nm, or about 1.5 to about 1.7 nm. [0035] In some embodiments, the nanoporous carbonaceous material has a specific surface area of about 300m ² /g to about 1500 m ² /g, or about 500m ² /g to about 1400 m ² /g., or about 700m ² /g to about 1400 m ² /g. In some embodiments, the specific surface area is about 350m ² /g to about 525 m ² /g. [0036] In some embodiments, the nanoporous carbonaceous material has an average pore volume of about 0.20cm ³ /g to about 1cm ³ /g. In some embodiments, the average pore volume is about 0.3cm ³ /g to about 0.9cm ³ /g. In some embodiments, the average pore volume is about 0.4cm ³ /g to about 0.8cm ³ /g. In some embodiments, the average pore volume is about 0.6cm ³ /g. [0037] In some embodiments, the nanoporous carbonaceous material is functionalized with at least one functional group selected from hydroxyl, carbonyl, carboxyl, amino, sulfhydryl, and phosphate groups. In some embodiments, the 8 8702004 nanoporous carbonaceous material is functionalized with at least one of nitrogen- based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof. In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added prior and/or after pyrolysis in an amount from about 10% to about 50% (wt) based on total material. In some embodiments, the at least one of nitrogen-based moieties, oxygen- based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added prior and/or after in an amount of about 40% (wt) based on total material. [0038] In some embodiments, the nitrogen-based moieties are from nitrogen, or are from a heterocyclic organic compound selected from phenanthroline, pyridine, pyrrolidine, and pyrrole. [0039] In some embodiments, the oxygen-based moieties are from air, pure oxygen, hydrogen peroxide, ozone, carbon dioxide, carbon monoxide or a mixture of O2/N2. [0040] In some embodiments, the nanoporous carbonaceous material is selected from a nitrogen functionalized material, an oxygen functionalized material, a carbon functionalized material or a nitrogen-oxygen functionalized material. [0041] In some embodiments, the nanoporous carbonaceous material has an elemental content, in wt% based on total weight of the material, in carbon of about 86% to about 99%, oxygen of about 0.8% to about 9.5%, and nitrogen of about 0% to about 4.5%. [0042] In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 95%, oxygen of about 4% to about 8% and nitrogen of about 0% to about 5%. In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 88% to about 94%, oxygen of about 5% to about 8% and nitrogen of about 0% to about 4.5%. 9 8702004 [0043] In some embodiments, the nitrogen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 95% to about 97%, oxygen of about 0.5% to about 1.5% and nitrogen of about 2% to about 3%. [0044] In some embodiments, the oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 97% to about 98%, oxygen of about 2% to about 2.5% and nitrogen of about 0% to about 0.5%. [0045] In some embodiments, the nitrogen-oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 85% to about 87%, oxygen of about 9% to about 10% and nitrogen of about 3% to about 5%. [0046] In some embodiments, the nitrogen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 90% to about 94%, oxygen of about 3% to about 6% and nitrogen of about 0.5% to about 4%. [0047] In some embodiments, the oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 92% to about 94%, oxygen of about 6% to about 8% and nitrogen of about 0% to about 0.5%. [0048] In some embodiments, the nitrogen-oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 89%, oxygen of about 6% to about 8% and nitrogen of about 3% to about 5%. [0049] In some embodiments, the material may further comprises sodium, potassium, magnesium, calcium, iron, titanium in concentrations below about 1%, in wt. based on total weight of the material. [0050] In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.2 kgwater/kgmaterial at 40% of relative humidity. In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.5 kgwater/kgmaterial 10 8702004 at 90% of relative humidity. In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.3 kgwater/kgmaterial at 90% of relative humidity. [0051] In some embodiments, the water adsorption uptake is maintained through a plurality of cycles of adsorption/desorption. In some embodiments, the plurality of cycles of adsorption/desorption is at least 5, at least 10, at least 45, or at least 60. [0052] In some embodiments, the material is obtained by pyrolysis at a temperature of about 500 ^o C to about 900 ^o C. In some embodiments, wherein the pyrolysis is at a temperature of about 850 ^o C. In some embodiments, the pyrolysis is conducted at a pressure of about 0.5 to about 2 atm, or about 0.8 to about 1.2 atm. [0053] In some embodiments, the material is obtained from curing of an organic compound and formaldehyde in the presence of at least one catalyst, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. In some embodiments, the at least one catalyst is selected from alkaline salts, alkaline oxides, alkaline hydroxides, ammonia, carbonates, metal carbonyls, metal salts and mixtures thereof. [0054] In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 1:1:0.01 to about 1:4:0.5. In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 2:3:0.01. [0055] The present application also provides a process for preparing a nanoporous carbonaceous material, the process comprising: curing organic carbonaceous reagents comprising C, N and O under conditions to obtain a polymeric matrix; pyrolyzing the polymeric matrix to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material; 11 8702004 wherein the nanoporous carbonaceous material has an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%. [0056] The present application further includes a process for preparing a nanoporous carbonaceous material, the process comprising: curing an organic compound and formaldehyde under conditions to form at least one resorcinol-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, a carbon-rich resin and combinations thereof; pyrolyzing the at least one organic compound-formaldehyde resin to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material. [0057] The present application further includes a process for preparing a nanoporous carbonaceous material, the process comprising: curing an organic compound reagent and an aldehyde reagent under conditions to form at least one resorcinol-aldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin and combinations thereof; pyrolyzing the at least one organic compound-aldehyde resin to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material, wherein the curing comprises dilution of the reagents in a solvent to provide a curing solution. [0058] The present application further includes a process for preparing a nanoporous carbonaceous material, the process comprising: curing an organic compound reagent and an aldehyde reagent under conditions to form at least one resorcinol-aldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin and combinations thereof and wherein the aldehyde reagent is selected from 12 8702004 formaldehyde, hydroxymethylfurfural, terephtalaldehyde and combinations thereof; pyrolyzing the at least one organic compound-aldehyde resin to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material, wherein the nanoporous carbonaceous material has a water adsorption uptake of about 0.25 kg ^water /kg ^material to about 2.4 kg ^water /kg ^material at 95% of relative humidity. [0059] [0060] In some embodiments, it will be appreciated that the pyrolyzing step may comprise heat treatment under controlled atmosphere, thermal processing, cooking/baking, thermolysis, charring, gasification/using a gasifier, or the like. [0061] In some embodiments, the curing includes heating in the presence of at least one catalyst or a pH controlling compound. In some embodiments, the curing includes heating at a temperature of 50°C to 90°C. In some embodiments, the at least one catalyst is selected from alkaline salts, alkaline oxides, alkaline hydroxides, ammonia, carbonates, metal carbonyls, metal salts and mixtures thereof. In some embodiments, the pH controlling compound is selected from a carbonate, such as sodium carbonate, sodium bicarbonate, sodium percarbonate, calcium carbonate, potassium carbonate and ammonium carbonate; an hydroxide such as sodium hydroxide, lithium hydroxide, barium hydroxide, strontium hydroxide, potassium hydroxide and calcium hydroxide; borates such as borax, and mixtures thereof. In some embodiments, the pH controlling compound is to control the pH from about 5 to about 14, or in some embodiments from about 5 to about 8. [0062] In some embodiments, the pyrolyzing is at a temperature from about 500 ^o C to about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature of about 850 ^o C. 13 8702004 [0063] In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 1:1:0.1 to about 1:4:0.5. In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 2:3:0.01. [0064] In some embodiments, optionally functionalizing is conducted prior and/or after pyrolyzing. [0065] In some embodiments, the nanoporous carbonaceous material has an average pore size of about 1 to about 10 nm. or about 1 to about 5 nm, or about 1 to about 3 nm. In some embodiments, the average pore size is about 1.5 nm. [0066] In some embodiments, the nanoporous carbonaceous material has a pore size distribution is about 1.3 to about 1.9 nm, or about 1.4 to about 1.8 nm, or about 1.5 to about 1.7 nm. [0067] In some embodiments, the nanoporous carbonaceous material has a specific surface area of about 300m ² /g to about 1500 m ² /g, or about 500m ² /g to about 1400 m ² /g., or about 700m ² /g to about 1400 m ² /g. In some embodiments, the specific surface area is about 350m ² /g to about 525 m ² /g. [0068] In some embodiments, the nanoporous carbonaceous material has an average pore volume of about 0.20cm ³ /g to about 1cm ³ /g. In some embodiments, the average pore volume is about 0.3cm ³ /g to about 0.9cm ³ /g. In some embodiments, the average pore volume is about 0.4cm ³ /g to about 0.8cm ³ /g. In some embodiments, the average pore volume is about 0.6cm ³ /g. [0069] In some embodiments, the functionalizing comprises functionalization with at least one metal or at least one functional group selected from hydroxyl, carbonyl, carboxyl, amino, sulfhydryl, and phosphate groups. In some embodiments, the functionalizing comprises functionalization with at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof. [0070] In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added prior and/or after the pyrolysis, in an amount 14 8702004 from about 10% to about 50% (wt) based on total material. In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added in an amount of about 40% (wt) based on total material. [0071] In some embodiments, the nitrogen-based moieties are from nitrogen, or are from a heterocyclic organic compound selected from phenanthroline, pyridine, pyrrolidine, pyrrole, and other similar heterocyclic compounds. [0072] In some embodiments, the oxygen-based moieties are from air, pure oxygen, hydrogen peroxide, ozone, carbon dioxide, carbon monoxide or a mixture of O2/N2. [0073] In some embodiments, the nanoporous carbonaceous material is selected from a nitrogen functionalized material, an oxygen functionalized material, a carbon functionalized material or a nitrogen-oxygen functionalized material. [0074] In some embodiments, the nanoporous carbonaceous material has an elemental content, in wt% based on total weight of the material, in carbon of about 86% to about 99%, oxygen of about 0.8% to about 9.5%, and nitrogen of about 0% to about 4.5%. [0075] In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 95%, oxygen of about 4% to about 8% and nitrogen of about 0% to about 5%. In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 88% to about 94%, oxygen of about 5% to about 8% and nitrogen of about 0% to about 4.5%. [0076] In some embodiments, the nitrogen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 95% to about 97%, oxygen of about 0.5% to about 1.5% and nitrogen of about 2% to about 3%. [0077] In some embodiments, the oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 15 8702004 97% to about 98%, oxygen of about 2% to about 2.5% and nitrogen of about 0% to about 0.5%. [0078] In some embodiments, the nitrogen-oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 85% to about 87%, oxygen of about 9% to about 10% and nitrogen of about 3% to about 5%. [0079] In some embodiments, the nitrogen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 90% to about 94%, oxygen of about 3% to about 6% and nitrogen of about 0.5% to about 4%. [0080] In some embodiments, the oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 92% to about 94%, oxygen of about 6% to about 8% and nitrogen of about 0% to about 0.5%. [0081] In some embodiments, the nitrogen-oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 89%, oxygen of about 6% to about 8% and nitrogen of about 3% to about 5%. [0082] In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.2 kgwater/kgmaterial at 40% of relative humidity. In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.5 kgwater/kgmaterial at 90% of relative humidity. In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake of about 0.1 kgwater/kgmaterial to about 0.3 kgwater/kgmaterial at 90% of relative humidity. [0083] In some embodiments, the water adsorption uptake is maintained through a plurality of cycles of adsorption/desorption. In some embodiments, the plurality of cycles of adsorption/desorption is at least 5, at least 10, at least 45, or at least 60. [0084] Also provided is a nanoporous carbonaceous material prepared using the process of present application. 16 8702004 [0085] Included is a method to capture atmospheric water comprising; adsorbing water from ambient atmosphere using a nanoporous carbonaceous material of the present application under conditions for uptake of the water into the nanoporous carbonaceous material. [0086] Further included is a method of water-harvesting comprising; adsorbing water from ambient atmosphere using a nanoporous carbonaceous material of the present application under conditions for uptake of the water into the nanoporous carbonaceous material; applying energy to desorb water; collecting the desorbed water. [0087] Without being bound to theory, it is submitted that water is adsorbed within the material through the formation of weak links, such as inverse pyramidal structures, that can be broken up via the application of a source of energy. [0088] In some embodiments, applying energy to desorb water comprises direct or indirect heating. In some embodiments, applying energy to desorb water comprises applying heat at a temperature of from 30°C to 75°C. In some embodiments, applying energy comprises applying ultrasound or microwaves. A skilled person would appreciate that any form of energy sufficient to destabilize the weak links of the water molecules with the network structure of the nanoporous carbonaceous material may be used, and the present application is thus not limited thereto. [0089] In some embodiments, collecting the desorbed water comprises condensing vapors. [0090] Also provided is use of a nanoporous carbonaceous material of the present application for water harvesting. [0091] The present application further includes use of a nanoporous carbonaceous material of the present application for atmospheric water harvesting. [0092] Further provided is use of a nanoporous carbonaceous material of the present application for water adsorption. 17 8702004 [0093] Included is use of a nanoporous carbonaceous material of the present application for capillary condensation of water. [0094] Also included is use of a nanoporous carbonaceous material of the present application for water uptake. [0095] The present application further includes use of a nanoporous carbonaceous material of the present application for capturing atmospheric water. [0096] The present application also includes use of a nanoporous carbonaceous material of the present application in the manufacture of a nanoporous sponge for atmospheric water harvesting. [0097] Further provided is use of a nanoporous carbonaceous material of the present application for water treatment or purification. [0098] The present application also provides use of a nanoporous carbonaceous material of the present application for dehumidification or de- emulsification. [0099] The present application also provides use of a nanoporous carbonaceous material of the present application for water separation. [00100] Further included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for atmospheric water harvesting, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, and other carbon-rich resins. [00101] The present application also includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for water adsorption, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00102] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for atmospheric water harvesting, wherein the organic 18 8702004 compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00103] Further provided is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water adsorption, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00104] The present application also includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water treatment or purification, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00105] Also included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for dehumidification, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00106] Further included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for atmospheric water harvesting, wherein the organic compound is any organic compound. [00107] The present application also includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for water adsorption, wherein the organic compound is any organic compound. [00108] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for atmospheric water harvesting, wherein the organic compound is any organic compound. [00109] Further provided is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water adsorption, wherein the organic compound is any organic compound. 19 8702004 [00110] The present application also includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water treatment or purification, wherein the organic compound is any organic compound. [00111] Also included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for dehumidification, wherein the organic compound is any organic compound. [00112] Other features and advantages of the present application will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments but should be given the broadest interpretation consistent with the description as a whole. BRIEF DESCRIPTION OF DRAWINGS [00113] The embodiments of the application will now be described in greater detail with reference to the attached drawings in which: [00114] Figure 1 shows a representation of three pathways of the prior art ^[4] to capture water, fog harvesting, humidity sorption and thermodynamic approach. [00115] Figure 2 is a graph showing comparison of the water uptake of different porous materials known in the art ^[11] , at P/P0 = 0.3, 0.6 and 0.9. [00116] Figure 3 shows a representation of a device of prior art ^[16] (US20180171604) to harvest water from air with MOFs based on night and day cycles. [00117] Figure 4 shows BET isotherms for (a) NPS; (b) N-NPS; (c) O-NPS; and (d) NO-NPS measured with N2 at 77 K, according to exemplary embodiments of the application. [00118] Figure 5 shows graphs of pore size distribution of (a) NPS; (b) N-NPS; (c) O-NPS; and (d) NO-NPS obtained from N2 isotherms, the line representing the critical pore size of 2.2 nm, according to exemplary embodiments of the application. 20 8702004 [00119] Figure 6 shows a micrograph of non-functionalized NPS observed on a SEM with a scale of 10µm, according to exemplary embodiments of the application. [00120] Figure 7 shows an XPS survey for NO-NPS showing peaks for carbon C1s, nitrogen N1s and oxygen O1s, according to exemplary embodiments of the application. [00121] Figure 8 shows a graph of water uptake for the NPS samples at 90% relative humidity and 25°C, according to exemplary embodiments of the application. [00122] Figure 9 shows a graph of water adsorption over time for NO-NPS sample at 40% relative humidity and 25°C, according to exemplary embodiments of the application. [00123] Figure 10 shows a graph of water uptake of O-NPS sample over cycles of adsorption/desorption, according to exemplary embodiments of the application. [00124] Figure 11 shows adsorption and desorption isotherms for (a) NPS; (b) N- NPS; (c) O-NPS; and (d) NO-NPS, according to exemplary embodiments of the application. [00125] Figure 12 shows a graph of desorption and recovery of water from non- functionalized NPS depending on the desorption temperature, according to exemplary embodiments of the application. [00126] Figure 13 shows a photograph of NPS samples before (left) and after pyrolysis (right), according to exemplary embodiments of the application. [00127] Figure 14 shows a micrograph of NPS synthesized in concentrated conditions, according to exemplary embodiments of the application. [00128] Figure 15 shows a micrograph of O-NPS synthesized in concentrated conditions, according to exemplary embodiments of the application. [00129] Figure 16 shows water adsorption isotherms fitted with DDN model for (a) NPS; (b) N-NPS; (c) O-NPS; and (d) NO-NPS samples, according to exemplary embodiments of the application. 21 8702004 [00130] Figure 17 shows NPS isotherm recorded at 30°C in the DVS (a) and in the environmental chamber (b), according to exemplary embodiments of the application. [00131] Figure 18 shows adsorption/desorption isotherms for NPS recorded in the environmental chamber at three different temperatures, according to exemplary embodiments of the application. [00132] Figure 19 shows adsorption isotherms for NPS recorded in the environmental chamber at four different temperatures, according to exemplary embodiments of the application. [00133] Figure 20 shows a graph of adsorption/desorption cycle for NPS over time, wherein pale lines are measurements of temperature and relative humidity, while the dark line refers to the water uptake, according to exemplary embodiments of the application. [00134] Figure 21 shows a graph of mass evolution of the NPS over 61 adsorption/desorption cycles recorded at a temperature of 25°C, the cycles being recorded from different tests, according to exemplary embodiments of the application. [00135] Figure 22 shows a graph of DVS measurements on NPS showing the mass evolution depending on the targeted relative humidity, measurements performed at 30°C on a 1mg sample, according to exemplary embodiments of the application. [00136] Figure 23 shows fitting graphs of Equation 4 at the relative humidity values of (a) 5 %; (b) 35 %; (c) 65 %; and (d) 95 %, from DVS data converted from mass change to fraction water uptake, according to exemplary embodiments of the application. [00137] Figure 24 shows a graph of adsorption kinetics for NPS based on the linear driving force model, where the solid line represents the kinetics based on the average diffusion coefficient and the dotted lines take into account the upper and lower values of diffusion coefficient, according to exemplary embodiments of the application. [00138] Figure 25 shows a graph of adsorption kinetics for NPS based on the linear driving force model for different particle sizes: 1.9 µm for darker line, 5 µm for 22 8702004 middle line, 10 µm for paler line, where the solid line represents the kinetics based on the average diffusion coefficient and the dotted lines take into account the upper and lower values of diffusion coefficient, according to exemplary embodiments of the application. [00139] Figure 26 shows a graph of characteristic void size in function of the packing porosity for particle radius of 1.9, 5 and 10 micrometer, where the dashed lines correspond to the range of packing porosity found for the NPS, according to exemplary embodiments of the application. [00140] Figure 27 shows a graph of Knudsen diffusion coefficient for particles of 1.9 µm at temperatures from 300 to 380 K; where the dashed lines correspond to the range of packing porosity found for the NPS, according to exemplary embodiments of the application. [00141] Figure 28 shows a graph of water concentration evolution in the adsorbent layer at different times, according to exemplary embodiments of the application. [00142] Figure 29 shows a graph of time evolution of the water concentration at a layer position of L = 0.01 m, according to exemplary embodiments of the application. [00143] Figure 30 shows graphs of time evolution of the water concentration of the inter-particle diffusion region (a); and intra-particle diffusion region (b), according to exemplary embodiments of the application. [00144] Figure 31 shows a graph of temperature evolution in the adsorbent layer at different times, according to exemplary embodiments of the application. [00145] Figure 32 shows adsorption isotherms measured at 30ºC for the sorbents of Example 3, according to exemplary embodiments of the application. [00146] Figure 33 shows a graph of Gibbs free energy of the sorbents based on their moisture content of Example 3, according to exemplary embodiments of the application. 23 8702004 [00147] Figure 34 shows a graph of net isosteric heat of adsorption depending on the moisture content for the sorbents of Example 3, according to exemplary embodiments of the application. [00148] Figure 35 shows a graph of integral enthalpy of adsorption of the sorbents of Example 3, according to exemplary embodiments of the application. [00149] Figure 36 shows a graph of differential entropy of the sorbents of Example 3 and enhanced view of the low moisture content region, according to exemplary embodiments of the application. [00150] Figure 37 shows a graph of integral entropy of the sorbents of Example 3, according to exemplary embodiments of the application. [00151] Figure 38 shows images of the production process of the carbon gel of Example 4, according to exemplary embodiments of the application, where a) the solution at the beginning of resorcinol-formaldehyde (RF) gel synthesis, b) bubbles formation during RF gel synthesis, c) RF gel synthesis after formation of the gel layer, d) wet RF gel after demoulding, e) wet RF gel cut in pieces before drying, f) dried RF gel before grinding, g) RF resin after grinding and h) RF carbon gel after pyrolysis at 850 °C. [00152] Figure 39 shows the dynamic vapour sorption system of Example 4, according to exemplary embodiments of the application. [00153] Figure 40 shows a graph of particle size distribution for ground RF gel before pyrolysis of Example 4, according to exemplary embodiments of the application. [00154] Figure 41 shows a graph of incremental pore volume distribution by pore width from non-local density functional theory (NLDFT) analysis for NPS from formulation A pyrolyzed under argon (NPS A) or CO2 atmospheres (NPS CO2 A) and NPS from formulation B pyrolyzed under CO2 atmosphere (NPS CO2 B) of Example 4, according to exemplary embodiments of the application. [00155] Figure 42 shows a graph of a complete DVS profile for formulation A after pyrolysis with 360 SCCM of CO2 of Example 4, according to exemplary embodiments of the application. 24 8702004 [00156] Figure 43 shows a graph of a complete DVS profile for formulation A after pyrolysis with 1700 SCCM of CO2 of Example 4, according to exemplary embodiments of the application. [00157] Figure 44 shows a graph of a complete DVS profile for formulation B of Example 4, according to exemplary embodiments of the application. [00158] Figure 45 shows XPS survey scans for (a) NPS (A) pyrolyzed under argon (b) NPS CO ² (A) and (c) NPS CO ² (B) both pyrolyzed under 360 SCCM of CO ² presenting increasing concentration of sodium of Example 4, according to exemplary embodiments of the application. [00159] Figure 46 shows high resolution XPS scans of the C1s peak showing Na2CO3 peak at 289.4 eV for (a) NPS CO2 (B) and (b) NPS CO2 (A) sample of Example 4, according to exemplary embodiments of the application. DETAILED DESCRIPTION I. Definitions [00160] Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art. [00161] The term “and/or” as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that “at least one of” or “one or more” of the listed items is used or present. [00162] As used in the present application, the singular forms “a”, “an” and “the” include plural references unless the content clearly dictates otherwise. [00163] In embodiments comprising an “additional” or “second” component, such as an additional or second compound, the second component as used herein is chemically different from the other components or first component. A “third” component is different from the other, first, and second components, and further enumerated or “additional” components are similarly different. 25 8702004 [00164] As used in this application and claim(s), the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "includes") or "containing" (and any form of containing, such as "contain" and "contains"), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps. [00165] The term “consisting” and its derivatives as used herein are intended to be closed terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, and also exclude the presence of other unstated features, elements, components, groups, integers and/or steps. [00166] The term “consisting essentially of”, as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and/or steps as well as those that do not materially affect the basic and novel characteristic(s) of these features, elements, components, groups, integers, and/or steps. [00167] The term “suitable” as used herein means that the selection of the particular composition or conditions would depend on the specific steps to be performed, the identity of the components to be transformed and/or the specific use for the compositions, but the selection would be well within the skill of a person trained in the art. [00168] The present description refers to a number of chemical terms and abbreviations used by those skilled in the art. Nevertheless, definitions of selected terms are provided for clarity and consistency. [00169] The terms "about", “substantially” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±10% of the modified term if this deviation would not negate the meaning of the word it modifies or unless the context suggests otherwise to a person skilled in the art. 26 8702004 [00170] The term “sustainably” as used herein means in a way that can be sustained in time, i.e. that the results may be maintained at a certain rate or level over time. [00171] The term “aq.” as used herein refers to aqueous. [00172] The term “alkyl” as used herein, whether it is used alone or as part of another group, means a straight or branched chain, saturated, unsubstituted or substituted alkyl group. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the prefix “Cn1-n2”. For example, the term C1- 4alkyl means an alkyl group having 1, 2, 3 or 4 carbon atoms. [00173] The term “aryl” as used herein, whether it is used alone or as part of another group, refers to carbocyclic groups containing at least one aromatic ring. Aryl groups are either unsubstituted or substituted. [00174] The term “heteroaryl” as used herein, whether it is used alone or as part of another group, refers to cyclic groups containing at least one heteroaromatic ring in which one or more of the atoms are a heteroatom selected from O, S and N and the remaining atoms are C. Heteroaryl groups are either unsubstituted or substituted. [00175] The term “alkylene”, whether it is used alone or as part of another group, means a straight or branched chain, saturated, unsubstituted or substituted alkylene group, that is, a saturated carbon chain that contain substituents on two or more of its ends. The number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix “Cn1-n2”. For example, the term C1-6alkylene means an alkylene group having 1, 2, 3, 4, 5 or 6, carbon atoms. [00176] The term “alkenylene”, whether it is used alone or as part of another group, means a straight or branched chain, unsaturated, unsubstituted or substituted alkylene group, that is, an unsaturated carbon chain that contains substituents on two or more of its ends and at least one double bond. The number of carbon atoms that are possible in the referenced alkenylene group are indicated by the prefix “Cn1-n2”. For example, the term C2-6alkylene means an alkylene group having 2, 3, 4, 5 or 6, carbon atoms. 27 8702004 [00177] The term “alkynylene”, whether it is used alone or as part of another group, means a straight or branched chain, unsaturated, unsubstituted or substituted alkylene group, that is, an unsaturated carbon chain that contains substituents on two or more of its ends and at least one triple bond. The number of carbon atoms that are possible in the referenced alkynylene group are indicated by the prefix “Cn1-n2”. For example, the term C2-6alkynylene means an alkylene group having 2, 3, 4, 5 or 6, carbon atoms. [00178] The term “cycloalkylene”, whether it is used alone or as part of another group, means an unsubstituted or substituted cycloalkylene group, that is, a saturated carbocycle that contains substituents on two or more of its ends. The number of carbon atoms that are possible in the referenced cycloalkylene group are indicated by the prefix “Cn1-n2”. The cycloalkylene group is either monocyclic or polycyclic, with polycyclic rings being either bridged, fused, spirocyclic or linked by a bond. [00179] The term “arylene”, whether it is used alone or as part of another group, means an unsubstituted or substituted arylene group, that is, an unsaturated carbocycle that contains at least one aromatic ring and substituents on two or more of its ends. The arylene group is either monocyclic or polycyclic, with polycyclic rings being either bridged, fused, spirocyclic or linked by a bond. [00180] The term “heteroarylene”, whether it is used alone or as part of another group, means an unsubstituted or substituted heteroarylene group, that is, a cyclic group containing at least one heteroaromatic ring in which one or more of the atoms are a heteroatom selected from O, S and N and the remaining atoms are C, and substituents on two or more of its ends. The heteroarylene group is either monocyclic or polycyclic, with polycyclic rings being either bridged, fused, spirocyclic or linked by a bond. [00181] The term “aryl-based” in reference to a polyphosphonic acid means that the phosphonic acid groups are substituents on one or more aryl rings which, in the case of two or more aryl rings, are either fused or linked together by a linker group. [00182] The term “heteroaryl-based” in reference to a polyphosphonic acid means that the phosphonic acid groups are substituents on one or more heteroaryl 28 8702004 rings which, in the case of two or more aryl rings are either fused or linked together by a linker group. [00183] The term, “aryl- and heteroaryl-based” in reference to a polyphosphonic acid means that the phosphonic acid groups are substituents on a ring structure that comprises at least one aryl and at least one heteroaryl ring, which are either fused or linked together by a linker group. [00184] The term “substituted” as used herein means that one or more available hydrogen atoms in a referenced group are replaced with a substituent. [00185] The term “available”, as in “available hydrogen atoms”, refers to hydrogen atoms that would be known to a person skilled in the art to be capable of replacement by another atom or group. [00186] The terms “metal-organic framework” or “MOF” as used herein refer to a class of compounds comprising metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures containing potential voids (pores). [00187] The terms “resin” as used herein refers to a class of materials comprising a mixture of organic compounds convertible into polymers. [00188] As used herein, the terms “formaldehyde” or “formaldehyde reagent” may be substituted with another suitable aldehyde and aldehyde reagent, for example hydroxymethylfurfural or terephtalaldehyde. As such, the person skilled in the art would understand that “formaldehyde” and “aldehyde”, and “formaldehyde reagent” and “aldehyde reagent”, when possible, may be used interchangeably. [00189] The terms “porous” or “porosity” as used herein refer to the void (i.e. "empty") spaces in a material. [00190] The term “nanosponge” or “NPS” as used herein refer to carbonaceous material having a nanoporous structure, according to the present application. II. Materials of the Application [00191] It has been advantageously shown herein that nanoporous carbonaceous material of the present application provide highly stable water adsorbent material at a low cost, requiring minimal energy to prepare and to operate. The 29 8702004 nanoporous carbonaceous material of the present application provide for high water uptake and fast adsorption kinetics. Comparable materials and processes did not display the same properties, highlighting the advantageous results obtained with the materials and processes of the application. [00192] Accordingly, the present application includes a nanoporous carbonaceous material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized. [00193] The present application also includes a nanoporous carbonaceous material for use in water adsorption, the material comprising an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%, and wherein the material is optionally functionalized. [00194] The present application further provides a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof, wherein the material is optionally functionalized. [00195] The present application further provides a nanoporous carbonaceous material comprising at least one pyrolyzed organic compound-formaldehyde resin, wherein the organic compound is any organic compound, wherein the material is optionally functionalized. [00196] The present application also provides a nanoporous carbonaceous material for use in water adsorption, the material comprising at least one pyrolyzed resorcinol-formaldehyde resin, wherein the material is optionally functionalized. [00197] In some embodiments, the nanoporous carbonaceous material has an average pore size of about 1 to about 10 nm, or about 1 to about 5 nm, or about 1 to about 3 nm. In some embodiments, the average pore size is about 1.5 nm. 30 8702004 [00198] . In some embodiments, the nanoporous carbonaceous material has an average pore size is about 1.5 nm. A skilled person in the art would know that the pore size may vary according to different conditions. In some embodiments, the average pore size is below the critical pore size of 2.2 nm for water at room temperature, to allow for reversibility of adsorption, thus requiring minimal energy to desorb water. In some embodiments, the average pore size may allow for adsorption of CO2 or H2. [00199] In some embodiments, the nanoporous carbonaceous material has a pore size distribution of between about 1.3 nm to about 1.9 nm, or about 1.4 to about 1.8 nm, or about 1.5 to about 1.7 nm. It will be appreciated that a narrow pore size distribution is preferable for good reversibility, i.e. reversibility between the adsorption and desorption. In some embodiments, the nanoporous carbonaceous material has an average pore size of about 1.1 to about 2.5nm. [00200] In some embodiments, the nanoporous carbonaceous material has a specific surface area of about 300m ² /g to about 1500 m ² /g, or about 500m ² /g to about 1400 m ² /g., or about 700m ² /g to about 1400 m ² /g. In some embodiments, the specific surface area is about 350m ² /g to about 525 m ² /g. [00201] In some embodiments, the nanoporous carbonaceous material has an average pore volume of about 0.20cm ³ /g to about 1cm ³ /g. In some embodiments, the average pore volume is about 0.3cm ³ /g to about 0.9cm ³ /g. In some embodiments, the average pore volume is about 0.4cm ³ /g to about 0.8cm ³ /g. In some embodiments, the average pore volume is about 0.6cm ³ /g. [00202] In some embodiments, the at least one resorcinol-formaldehyde resin has a particle size distribution with a 10-percentile size of about 0.55 millimeter, a median size of about 1.2 mm and a 90-percentile size of about 2.2 mm before pyrolysis. In some embodiments, the at least one resorcinol-formaldehyde resin has a median particle size of about 0.6 mm to about 1.8 mm before pyrolysis. In some embodiments, the at least one resorcinol-formaldehyde resin has a particle size distribution with a 10- percentile size of about 0.55 millimeter, a median size of about 1.1 mm and a 90- percentile size of about 2.0 mm after pyrolysis. In some embodiments, the at least one 31 8702004 resorcinol-formaldehyde resin has a median particle size of about 0.4 mm to about 1.6 mm after pyrolysis. [00203] Without being bound to theory, it will be understood that kinetics of water adsorption are controlled by the pore size, pore size distribution, size of the adsorbent particles, such as diameter, and surface chemistry of the available surface area. The nanoporous carbonaceaous material of the present application have demonstrated fast adsorption kinetics. [00204] The nanoporous carbonaceous material may be obtained from pyrolysis, for example of a resin. However, an unfavorable effect of the pyrolysis can also be observed: most of the oxygen-based functional groups initially present in the resin are eliminated by the heat treatment, leaving a material with 95 wt% of carbon. Without being bound to theory, functional groups are beneficial to promote water nucleation on the available surface area [11] and include non-exhaustively hydroxyl, carbonyl, ketonic, carboxyl, amino, sulfhydryl, phosphate groups. As such, functionalization may be included in order to improve the amount of functional groups in the material. [00205] In some embodiments, the nanoporous carbonaceous material is functionalized with at least one functional group selected from hydroxyl, carbonyl, carboxyl, amino, sulfhydryl, and phosphate groups. In some embodiments, the nanoporous carbonaceous material is functionalized with at least one of nitrogen- based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof. [00206] In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added before or after the pyrolysis. For example, a first approach may consist in adding a molecule containing nitrogen functional groups in the original mixture before curing the resin and pyrolyzing it. A second approach may include adding oxygen functionalities through an oxidation step where the material is heated in presence of air after the initial pyrolysis. Finally, the two approaches may be combined together to introduce both N and O functionalization. Alternate functionalization approaches known in the art may be used, for example the use of 32 8702004 non-thermal plasma post-processing, acidic treatment, and this is well within the purview of a skilled person. [00207] In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added in an amount from about 10% to about 50% (wt) based on total material. In some embodiments, the at least one of nitrogen-based moieties, oxygen-based moieties, sulfur-based moieties, phosphor-based moieties, metal-based moieties or mixtures thereof are added in an amount of about 40% (wt) based on total material. [00208] In some embodiments, the nitrogen-based moieties are from phenanthroline. In some embodiments, the oxygen-based moieties are from air, pure oxygen, hydrogen peroxide, ozone, carbon dioxide, carbon monoxide or a mixture of O2/N2 at various concentrations. [00209] In some embodiments, the nanoporous carbonaceous material is selected from a nitrogen functionalized material, an oxygen functionalized material, a carbon functionalized material or a nitrogen-oxygen functionalized material. [00210] In some embodiments, the nanoporous carbonaceous material has an elemental content, in wt% based on total weight of the material, in carbon of about 86% to about 99%, oxygen of about 0.8% to about 9.5%, and nitrogen of about 0% to about 4.5%. [00211] In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 95%, oxygen of about 4% to about 8% and nitrogen of about 0% to about 5%. [00212] In some embodiments, the nanoporous carbonaceous material has a surface concentration, in wt% based on total weight of the material, in carbon of about 88% to about 94%, oxygen of about 5% to about 8% and nitrogen of about 0% to about 4.5%. 33 8702004 [00213] In some embodiments, the nitrogen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 95% to about 97%, oxygen of about 0.5% to about 1.5% and nitrogen of about 2% to about 3%. In some embodiments, the nitrogen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 90% to about 94%, oxygen of about 3% to about 6% and nitrogen of about 0.5% to about 4%. [00214] In some embodiments, the oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 97% to about 98%, oxygen of about 2% to about 2.5% and nitrogen of about 0% to about 0.5%. In some embodiments, the oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 92% to about 94%, oxygen of about 6% to about 8% and nitrogen of about 0% to about 0.5%. [00215] In some embodiments, the nitrogen-oxygen functionalized material has an elemental content, in wt% based on total weight of the material, in carbon of from about 85% to about 87%, oxygen of about 9% to about 10% and nitrogen of about 3% to about 5%. In some embodiments, the nitrogen-oxygen functionalized material has a surface concentration, in wt% based on total weight of the material, in carbon of about 87% to about 89%, oxygen of about 6% to about 8% and nitrogen of about 3% to about 5%. [00216] In some embodiments, the nanoporous carbonaceous material has a water adsorption uptake is from about 0.1 kgwater/kgmaterial to about 0.2 kgwater/kgmaterial at 40% of relative humidity. In some embodiments, the water adsorption uptake is from about 0.1 kgwater/kgmaterial to about 0.5 kgwater/kgmaterial, or about 0.1 kgwater/kgmaterial to about 0.3 kgwater/kgmaterial at 90% of relative humidity. Without being bound to theory, it will be appreciated that the presence of oxygen functionalization seems to increase the water uptake of the nanoporous carbonaceous material of the present application. [00217] An important characteristic of adsorbents to capture atmospheric water is the cyclability of the material, meaning keeping constant performance over adsorption and desorption cycles. For example, MOFs adsorbents typically show significant loss of performance after successive cycles. In some embodiments, the 34 8702004 nanoporous carbonaceous material of the present application has a water adsorption substantially constant through a plurality of cycles of adsorption/desorption. In some embodiments, the plurality of cycles of adsorption/desorption is at least 5, or at least 10, at least 45, or at least 60. In some embodiments, the plurality of cycles is about 5 to about 100 cycles, or about 5 to about 1000 cycles. [00218] In some embodiments, the material is obtained by pyrolysis at a temperature of about 500 ^o C to about 900 ^o C. In some embodiments, the pyrolysis is at a temperature of about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature from about 750 ^o C to about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature of about 850 ^o C. In some embodiments, the pyrolysis is conducted under an atmosphere of CO2, CO, N2, NH3, or a noble gas, including He, Ne, Kr, Xe, Rn. In some embodiments, the pyrolysis is conducted under a CO2 atmosphere. [00219] In some embodiments, the material is obtained from curing of an organic compound and formaldehyde in the presence of at least one catalyst. In some embodiments, the material is obtained from curing of an organic compound and formaldehyde in the presence of at least one catalyst, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. In some embodiments, the at least one catalyst is selected from alkaline salts, such as sodium carbonate, alkaline oxides and hydroxides, such as sodium hydroxide, metal carbonyls, metal salts, or ammonia: It will be appreciated that any catalyst suitable for curing may be used. [00220] In some embodiments, the ratio of organic compound:formaldehyde:catalyst is from 1:1:0.01 to 1:4:0.5. In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 2:3:0.01. III. Processes for the Application [00221] The present application provides a process for preparing a nanoporous carbonaceous material, the process comprising: curing organic carbonaceous reagents comprising C, N and O under conditions to obtain a polymeric matrix; 35 8702004 pyrolyzing the polymeric matrix to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material; wherein the nanoporous carbonaceous material has an elemental content, in wt% based on total weight of the material, in carbon of about 85% to about 99.5%, oxygen of about 0.5% to about 10%, and nitrogen of about 0% to about 5%. [00222] The present application further provides a process for preparing a nanoporous carbonaceous material, the process comprising: curing an organic compound and formaldehyde under conditions to form at least one organic compound-formaldehyde resin, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof; pyrolyzing the at least one resorcinol-formaldehyde resin to form the nanoporous carbonaceous material; and optionally functionalizing the nanoporous carbonaceous material. [00223] In some embodiments, the curing includes heating in the presence of at least one catalyst. In some embodiments, the curing includes heating at a temperature of 50°C to 90°C. [00224] In some embodiments, the components used in the curing may be added in any order. The order of addition may affect the rate of the reaction and this is well within the purview of a skilled person in the art. In some embodiments, the curing product forms a gel or a solid that is isolated to be used for further processing. In some embodiments, a solvent phase is evaporated to recuperate any curing product that may be present in the solvent phase. [00225] In some embodiments, the pyrolyzing is at a temperature from about 500 ^o C to about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature of about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature from about 750 ^o C to about 900 ^o C. In some embodiments, the pyrolyzing is at a temperature of about 850 ^o C. In some embodiments, the pyrolysis is conducted under an atmosphere 36 8702004 of CO2, CO, N2, NH3, or a noble gas, including He, Ne, Kr, Xe, or Rn. In some embodiments, the pyrolysis is conducted under a CO2 atmosphere. [00226] In some embodiments, the process further comprises crushing the polymeric matrix or resorcinol-formaldehyde resin prior to pyrolyzing. [00227] In some embodiments, the at least one catalyst is selected from sodium carbonate, In some embodiments, the ratio of organic compound:formaldehyde:catalyst is from 1:1:0.01 to 1:4:0.5. In some embodiments, the ratio of organic compound:formaldehyde:catalyst is about 2:3:0.01. [00228] In some embodiments, optionally functionalizing is conducted prior and/or after pyrolyzing. [00229] The nanoporous carbonaceous material prepared according to the process of the present application has the properties as described above. [00230] The present application also includes nanoporous material as described in any aspect or embodiment herein. In some embodiments, the nanoporous material is as prepared according to any process of any previous aspect and embodiment herein. In embodiments, the nanoporous material is as characterized according to any one of the figures. IV. Methods and Uses of the Application [00231] The processes of the application produce highly stable, ordered and nanoporous material. The nanoporous material of the present application have a wide range of applications. [00232] Accordingly, the present application includes a method to capture atmospheric water comprising; adsorbing water from ambient atmosphere using a nanoporous carbonaceous material of the present application under conditions for uptake of the water in-to the nanoporous carbonaceous material. [00233] The present application also includes a method of water-harvesting comprising; 37 8702004 adsorbing water from ambient atmosphere using a nanoporous carbonaceous material of the present application under conditions for uptake of the water in-to the nanoporous carbonaceous material; applying energy to desorb water; collecting the desorbed water. [00234] In some embodiments, applying energy to desorb water comprises heating directly or indirectly. In some embodiments, heating comprises directly applying heat to the material. In some embodiments, heating comprises indirectly increasing the temperature of the material by applying a current of hot air. In some embodiments, applying energy to desorb water comprises applying heat at a temperature of from 20°C to 75°C, or from 30°C to 75°C. In some embodiments, applying energy to desorb water comprises applying ultrasound or microwaves. [00235] In some embodiments, collecting the desorbed water comprises condensing vapors. [00236] The present application also includes use of a nanoporous carbonaceous material of the present application for water harvesting. [00237] The present application also includes use of a nanoporous carbonaceous material of the present application for atmospheric water harvesting. [00238] Also provided is use of a nanoporous carbonaceous material of the present application for water adsorption. [00239] The present application also includes use of a nanoporous carbonaceous material of the present application for capillary condensation of water. [00240] The present application further includes use of a nanoporous carbonaceous material of the present application for water uptake. [00241] The present application also provides use of a nanoporous carbonaceous material of the present application for capturing atmospheric water. 38 8702004 [00242] The present application also includes use of a nanoporous carbonaceous material of the present application in the manufacture of a nanoporous sponge for atmospheric water harvesting. [00243] The present application also includes use of a nanoporous carbonaceous material of the present application for water treatment or purification. [00244] The present application also includes use of a nanoporous carbonaceous material of the present application for dehumidification or de-emulsification. [00245] The present application also includes use of a nanoporous carbonaceous material of the present application for water separation. [00246] Also included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for atmospheric water harvesting, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00247] In some embodiments, the nanoporous carbonaceous material of the present application is used for adsorption of CO2 or H2. [00248] The present application provides use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for water adsorption, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00249] The present application also provides use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for atmospheric water harvesting, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00250] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water adsorption, wherein the organic compound is selected 39 8702004 from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00251] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water treatment or purification, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00252] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for dehumidification, wherein the organic compound is selected from resorcinol, urea, melamine, a tannin, phenol, phloroglucinol, other carbon-rich resins and combinations thereof. [00253] Also included is use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for atmospheric water harvesting, wherein the organic compound is any organic compound. [00254] The present application provides use of an organic compound/formaldehyde composition in the manufacture of a nanoporous sponge for water adsorption, wherein the organic compound is any organic compound. [00255] The present application also provides use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for atmospheric water harvesting, wherein the organic compound is any organic compound. [00256] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for water adsorption, wherein the organic compound is any organic compound. [00257] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous 40 8702004 carbonaceous material for water treatment or purification, wherein the organic compound is any organic compound. [00258] The present application further includes use of an organic compound/formaldehyde composition in the manufacture of a nanoporous carbonaceous material for dehumidification, wherein the organic compound is any organic compound. EXAMPLES [00259] The following non-limiting examples are illustrative of the present application. General Methods EXAMPLE 1 Material synthesis [00260] The nanoporous materials, or nanoporous sponges (NPS), consist of resorcinol-formaldehyde (RF) resin that undergoes heat treatments. The resin is first synthesized through wet chemistry, where resorcinol, formaldehyde and a catalyst (sodium carbonate) are dissolved in a solvent consisting of a 1:1 mixture of water and ethanol. By heating this mixture at 80°C over 24h, resorcinol and formaldehyde polymerize into a porous matrix and the solvent is evaporated. It is recognized in literature that the pore size of RF-resins is dependent on the resorcinol to formaldehyde ratio, nature of the catalyst and viscosity of the solution [18]. Trace amounts of catalysts are required for the resin to be cured. A mass ratio of resorcinol/formaldehyde/sodium carbonate of 2:3:0.01 was chosen as an exemplary embodiment. The RF resin may be used directly or ground prior to the pyrolysis step. 41 8702004

[00261] Pyrolysis in an inert atmosphere carbonizes the resin at 700 °C for 1h, forming a sample of nanoporous sponge. Pyrolysis causes the pores to shrink to the required size. However, a secondary unfavorable effect of the pyrolysis can also be observed: most of the oxygen-based functional groups initially present in the resin are eliminated by the heat treatment, leaving a material with 95 wt% of carbon. Functional groups are beneficial to promote water nucleation on the available surface [13]. In order to improve the amount of functional groups in the material under the form of nitrogen and oxygen moieties, variations in the synthesis protocol may be included. [00262] A first approach consists in adding a molecule containing N functional groups, phenanthroline, in the original mixture before curing the resin and pyrolyzing it. The phenanthroline molecule has been chosen for its molecular structure able to incorporate into the carbon matrix [19]. The mass concentration was selected at 40 wt% relative to the RF-resin. Following this technique, N-functionalized NPS (N-NPS) were produced. A second approach was to add O functionalities through an oxidation step where the material is heated at 700 °C for 1h in presence of air, resulting in O- functionalized NPS (O-NPS). Finally, the two approaches may be combined together to get N/O-functionalized NPS (NO-NPS). A third approach consisted of conducting the pyrolysis step under a CO2 atmosphere, at 800°C (NPS-CO2). Physical characterization [00263] The NPS samples were characterized for their pore size, pore volume and specific surface area through the Brunauer-Emmett-Teller (BET) technique. A Quantachrome Autosorb ^TM -1 gas sorption analyzer measured the evolution of the mass 42 8702004 uptake depending of the gas relative pressure at a temperature of 77K using N2 as the adsorbate, after degassing overnight at 200 °C under vacuum. The elemental composition of the NPS surface and bulk with X-Ray Photoelectron Spectroscopy (XPS) and elemental analysis were conducted. X-ray Photoelectron Spectroscopy was performed on a Scientific K-Alpha XPS system from Thermo Scientific with an Al X-ray source, a 400 µm spot size, and Advantage software. The elemental analysis has been performed on a Truspec ^TM Micro analyzer from LECO to determine the relative quantities of C, H, and N with infrared sensors to detect gaseous CO2 and H2O, and thermal conductivity sensor for N2. The complementary module Micro O from LECO detected CO2 with an infrared sensor to determine O concentrations. Non-functionalized NPS sample were analyzed by scanning electron microscopy (SEM) using a JEOL ^TM 7600TFE operated at 10 kV. Water adsorption [00264] The samples have been tested in a custom-made environmental chamber with humidity and temperature control. Tests are performed at 90 % of relative humidity (RH) and a temperature of 25 °C.10 to 100 mg of NPS are initially dried in the oven at 150 °C before being placed in a petri dish in the environmental chamber. The weight of the samples is measured prior the test and every 10 min to determine the mass evolution over time. Adsorption isotherms are also obtained on a dynamic vapor sorption (DVS) Intrinsic from Surface Measurement Systems Ltd., UK. Samples were equilibrated at 0% RH to determine dry mass followed by increments of 5% RH up to 95% RH, and brought back down to 0% RH for desorption measurement. The mass change is recorded at each increment once equilibrium was reached with an error of ±0.1 µg. Fitting of the adsorption isotherms [00265] The experimental adsorption isotherms have been fitted to the theoretical Do and Do equation modified by Neitsch et al (DDN) [20]–[23]. This equation describes the adsorption process of H2O on C as a two-step mechanism. The first step corresponds to the adsorption of the water molecules on the primary sites that are functional groups on the surface of the material. Water clusters grow around these primary sites via hydrogen bonds. The second step happens when cluster reach a 43 8702004 threshold of 6 molecules and break down into water pentamers that fill the micropores. It has been shown by Neitsch et al. that pentamers can be generalized into m-mers for higher accuracy [21]. The equation describing water adsorption is then the following: ^^ _^^ ∑ ^^ ^^ ^^ ^^ ^^ℎ ^^ _^^ ℎ ^^ = ^^ =1 ^^ + ^^ _{^^ ^^} 1) [00266] of surface active sites in mol/g, aµs is the saturation concentration in the micropores in mol/g, Kf is the chemisorption equilibrium constant, Kµ is the micropore equilibrium constant, N is the maximum number of water molecules adsorbed per surface site, m is the size of the water m-mers that desorb from clusters and fill the micropores, and h is the relative pressure. To fit the experimental data with the theoretical equation, the least-square method using the determination coefficient R ² as follow: ∑( ^^ _{^^ ^^ ^^} − ^^ _^ )2 ^^ ² = 1 − _{^ℎ ( ^^ − ^} ² (Equation 2) ∑ _{^^ ^^ ^^} ^̅ _^ ^{̅ ̅} _^^ ^̅ _^ ^̅ _{^ ^} ^{̅ ̅} _^) [00267] where aexp are the experimental data, ath the corresponding theoretical data, and ^̅^̅ ̅ _{^^ ^} ̅ ̅ _{^ ^} ̅ _^ the average of experimental data over the relative pressure range. [00268] The water adsorption properties of the non-functionalized NPS measured at small scale (< 100 mg) were then validated at larger scale with a custom-made water capture set-up. The moist air is generated by a boiler and controlled flow rate is passed through the porous material, until saturation of the sponge. The NPS is contained in an insulated column with glass wool. Water desorption is accomplished through mild heating from a heating tape coiled around the column to release the water. Supersaturated steam is then condensed with a water-cooling condenser. [00269] The laboratory water capture set-up was validated with well-known desiccant (silica gel) as a control adsorbent. This scaled-up prototype can accommodate tens of grams of NPS and provide the amount of water collected per adsorption and desorption cycle. 44 8702004 Results Porosity and structure [00270] Almost no hysteresis is observed between the adsorption and desorption process in the presence of N2 (isotherms are shown in Figure 4). Table 1: Summary of surface area, pore size and pore volume for the various NPS samples. Sample NPS N-NPS O-NPS NO-NPS Surface area (m ² / ) 487 347 484 527 [00271] The NPS samples exhibit a high available surface area for an average pore size of less than 2 nm (Table 1), well below the critical pore radius of 2.2 nm for water adsorption at room temperature [24]. A key aspect of reversibility between the adsorption and desorption curves for the porous material is the pore size distribution. The sponges exhibit a very narrow pore size distribution (Figure 5), preferential for reversibility. [00272] At first sight, the different treatment applied on the NPS samples in terms of N and O addition seem to have only little effect on the porosity. However, Figure 5 shows that a larger proportion of pores with a size greater than 2.2 nm are present with samples containing N. [00273] The micrometric structure of the non-functionalized NPS is shown on Figure 6. The NPS have a spherical shape with a mean diameter of 3.7 ± 1.1 µm. The micro-particles may have this specific shape due to the synthesis process where resorcinol and formaldehyde are polymerized in diluted conditions [25] or may be obtained following grinding of larger particles. The micro-particles then agglomerate through the complete evaporation of the solvent and maintain their shape through the heat treatments. Chemical composition 45 8702004 [00274] A typical XPS survey is shown on Figure 7 with the corresponding peaks of carbon C 1s, nitrogen N 1s and oxygen O 1s. The concentration for the four NPS samples is summarized on Table 2. Table 2: Summary of the carbon, oxygen and nitrogen surface concentration on the NPS C1s (at%) O1s (at%) N1s (at%) [00275] XPS results show that N is effectively added to the material structure and remains present even after the pyrolysis step. O concentration is slightly increased after the oxidation step. One can note the increase of N concentration when the oxidation step is performed for NO-NPS, explained by mass loss observed during the heat treatments. Indeed, an 80% mass loss is observed after the pyrolysis step while an additional 60% of mass loss from the remaining material is observed after the oxidation step. Phenanthroline having the ability to incorporate to a carbon matrix during pyrolysis [26], one can expect N concentration to increase after the oxidation step. The deconvolution of carbon C1s peak shows that the majority of C is graphitized through pyrolysis with more than 80% of C in the sp ² configuration. [00276] The elemental composition of the bulk of the sponges is done on a CHN analyzer. The resulting weight concentrations are then converted into atomic concentrations in order to allow the comparison with the surface composition (Table 3). Overall, the amount of O is greater on the surface rather than the bulk of the samples, because the oxidation process is a surface phenomenon. The concentration of N is similar in the bulk and on the surface, in agreement with the addition method of phenanthroline. Indeed, the molecule is initially mixed with the other compounds and is supposed to be fully incorporated in the solid. Table 3: Elemental composition of the NPS samples bulk. 46 8702004 Carbon Oxygen Nitrogen (at%) (at%) (at%) NPS water uptake in environmental chamber [00277] The oxidation step seems to play an important role in the increase of the water uptake between the different samples (Figure 8). The material almost doubles its water capture capacity after undergoing the oxidation, and almost reaches the total pore volume measured by BET analysis. At 90% RH, N addition does not appear to have a significant effect on the water uptake. Pyrolysis under CO2 at higher temperature of the unground RF resin leads to improved water uptake (0.188g/g at 60%RH, 0.211g/g at 95%RH), though water uptake is significantly improved if the RF resin is ground prior to CO2 pyrolysis (0.144g/g at 60%RH, 0.412g/g at 95%RH). As the application of water harvesting adsorbents are particularly pertinent at low RH, the two best performing samples have been tested at 40% RH. Under these conditions, O-NPS and NO-NPS show a respective water uptake of 0.14 and 0.21 g/g of NPS. At this RH, the addition of N functionalities seems to improve the overall water uptake. The adsorption kinetics at 40% RH are slower and it takes nearly 40 min to reach a plateau compared to 10 min at 90% RH (Figure 9). NPS cyclability [00278] An important aspect of using NPS to capture atmospheric water is the cyclability of the material, meaning keeping constant performance over adsorption and desorption cycles. We tested successive cycles of adsorption in the environmental chamber and desorption in the oven while recording the water uptake at each cycle (Figure 10 shows the O-NPS cyclability). Complete de-sorption at 150°C for 1h was achieved between each adsorption test. After 61 cycles, there are no significant loss of performance, phenomenon that can be observed for several MOFs adsorbents [11]. 47 8702004 Small variations between each cycles can be attributed to the powder manipulation between each of the adsorption and desorption phases. Adsorption isotherms and theoretical aspects [00279] The isotherms have been obtained with DVS for the four samples (Figure 11) to characterize water uptake over the full range of RH as well as the hysteresis between the adsorption and desorption. NPS and O-NPS have a type V isotherm (IUPAC classification) with little to no hysteresis while N-NPS and NO-NPS have a type VI isotherm with a H3 hysteresis loop. This type of hysteresis loop is generally associated with non-rigid aggregates of plate-like particles [27], [28]. From these isotherms, it seems that the presence of O in the material increases the overall water uptake. This result was already observed in the environmental chamber and comes from a high affinity between water molecules and O functionalities. N has a more com- plex role since the water adsorption happens at higher RH and the isotherms present a stronger hysteresis. One can note that the samples had higher water uptakes when measured in environmental chamber compared to the isotherms, except for the non- functionalized NPS. This difference may be due to several reasons including: (a) RH error in the environmental chamber (± 2%) that would affect particularly the samples containing N, (b) potential sources of errors leading to over-estimation of the water uptake in the environmental chamber and (c) an inhomogeneity of the functionalized materials knowing that DVS measures samples less than 1 mg. [00280] Fitting the experimental data with the DDN model led to determination coefficient higher than 0.99. The error on the different parameters was determined from several combinations of fitting parameters leading to a R ² higher than 0.99 (Table 4). Table 4: Fitting parameters of the DDN model to the water adsorption isotherms. Micropo Maximum 48 8702004 NPS 0.42 ± 0.03 5.43 ± 0.19 11 ± 1 9 ± 0 15 ± 1 1072 ± 0.992 ± 64 0002 [00281] The presence of O in the sample increases the parameters a0 and aµs while the addition of N in the NPS drastically changes the N parameter value. All of these parameters are in the range of physical meaning [29] and can help resolve fundamental differences between the structures. Table 5 summarizes the absolute concentration of functional groups from the de-convolution of high-resolution peaks of O and N. It shows a close correlation between the concentration of hydroxyl (OH) groups and the parameter a0 that corresponds to the primary ad-sorption sites. It suggests that OH groups are solely responsible of the first water molecules adsorbing on the NPS samples through hydrogen bonding, while N actually decreases the concentration of OH. The parameter aµs corresponds to the micropore filling concentration. Micropores typically have a size below 2 nm. NPS and O-NPS have 75- 80% of their pores in this region while it is only 55% for N-NPS and NO-NPS. Micropore saturation concentration aµs is lower than expected values following earlier observation between the DVS and environmental chamber measurements. Table 5: Absolute concentration of species on NPS surface al deconvolution of high- resolution XPS carbon C1s peak for non-functionalized NPS sample, converted from at% to mmol/g. O ^=C O-C C-OH N ridinic N pyrolic N quat N-O ) 49 8702004 [00282] The water cluster size m that fills the micropores has little difference between the samples, contrary to N, the maximum number of water molecules attached to a primary adsorption site. The presence of N increases the parameter value from ~10 molecules to more than 150. At low RH, the first adsorption steps are described as: (i) a first water molecule attaches to the primary ad-sorption site through hydrogen bonding (ii) water molecules turn into secondary adsorption sites (iii) additional water molecules adsorbed to the secondary adsorption sites until reaching the maximum average value N [22]. N-containing samples had lower OH concentration that were identifies as the primary adsorption sites as well as lower micro-porosity. One can suppose that the maximum N value is driven by physical blockage, i.e. pore size as well as interaction with other water clusters. Large water clusters with size up to 280 molecules are de-scribed by Ludwig et al. [30]. No clear tendencies can be drawn from the equilibrium constants Kf and Kµ respectively correlated to chemisorption and micropore filling. Scalability of the NPS [00283] A larger batch of non-functionalized NPS has been synthesized to verify the scalability of the NPS synthesis process and verify that the observed performance is maintained at larger scale. While smaller samples of RF resin before pyrolysis were easily turned under a powder form, larger scale showed a compact and glassy material that had to be crushed and powdered before heat treatment. Pyrolysis lead to smaller mass loss under these larger scale conditions, passing from 80% to 50%, probably due to the higher particle size since the composition remained identical. [00284] The resulting non-functionalized NPS weighed 30 g, compared to the 30 to 200 mg tested in the environmental chamber and less than 1 mg in the DVS. This batch was tested in a water capture set-up (described below) and water collected from condenser was weighed as a function of the desorption temperature (Figure 12). Some water remained stuck in the water-cooled condenser and the collected water weight was corrected to take it into account, by assuming a constant mass of 1.5 ± 0.1 g of water stuck on the condenser walls. Water uptakes between 0.14 and 0.16 g/g were measured and are very close to those observed at small scale. 50 8702004 [00285] The optimum range for the desorption temperature was found between 55°C and 75°C from these tests. However, measurement of the mass before and after desorption showed that no water was left in the NPS material even at room temperature, which is in agreement with the absence of hysteresis from the adsorption isotherms. At this moment, the lower water recovery observed at reduced temperature may be due to the set-up itself rather than the material. Lower temperatures generate less supersaturated vapor from the NPS leading to smaller condensation rates. Discussion [00286] Water adsorption performance of our NPS is compared to other adsorbents (Table 6), including MOFs, zeolites, mesoporous silica and carbon-based adsorbents. This comparison focuses mainly on relevant parameters for large-scale application. The water uptake loss after 5 cycles provides insight on the stability of the material over adsorption and desorption cycles. Results for the nanoporous of the present application have demonstrated constant adsorption uptake after over 60 cycles. Practical application requires thousands of cycles and thus require minimal loss from one cycle to the other. The desorption temperature corresponds to the temperature required to regenerate the material before a new adsorption cycle and is related to the amount of energy required to extract water from the adsorbent. Some recent studies show techniques to relate on solar irradiation through day and night cycles [31]. Cold and humid nights allow for efficient water adsorption while sun warmth during the day provokes water desorption. However, this system limits to a single adsorption and desorption cycle per 24 hours period. More daily cycles would require energy input for desorption, and thus the lowest regeneration temperature is recommended. One should note that vacuum is often applied in previous literature to force water desorption while our NPS samples were desorbed at ambient pressure. Table 6: Comparison of water uptake at low and high relative humidity, cyclability and desorption temperature of common adsorbent from literature Name of Water Water Water uptake u take at u take at Desorption loss after 5 Reference 51 8702004 MCM-41 0.06 0.96 225 4.2 [32] N n r 014 Thi [00287] From Table 6, NPS water uptake at low and high relative humidity is lower than reported adsorbent from literature. However, most adsorbents have low stability over 5 adsorption and desorption cycles as well as high desorption temperature. This can be explained by hydrolytic stability, where the adsorbent structure is affected by the presence of water. It is particularly pertinent for MOF structure where the metallic and organic constituents are in coordination with each other, while carbon bonds are present in the NPS as well as the porous carbon cuboids (PCC-1) [13]. From the established list, MOF-801, CAU-10, PCC-1 and our NPS follow the required criteria of low desorption temperature and stability over regeneration cycles. One of the main advantages of the MOFs is the high control in the pore size due to a large selection of molecular components of various nature and size. In contrast, NPS porosity is inherent to the material with limited control at this point. [00288] Adsorption kinetics have not been included in Table 6. The reason for such omission is the challenging comparison of kinetics from one literature study to the other. Rigorous and identical experimental conditions are required to set a comparison basis. Kinetics are highly dependent on pressure and temperature conditions, RH, 52 8702004 humid air flow rate as well as the way the adsorbent gets in contact with humid air (diffusion or feedthrough) [40], [41]. [00289] An important aspect for water adsorption at an industrial level is the ability to synthesize adsorbent at large scale. The NPS synthesis process is relatively simple and was already scaled to tens of grams in laboratory. A full-scale installation could readily deliver kilograms to tons of adsorbents, as pyrolysis is a well-established industrial process. The main primary constituents of NPS are an organic compound, such as resorcinol, and formaldehyde, which are abundant and low-cost chemicals, with respective prices of 1,700 US$ [42] and 500 US$ [43] per ton. Taking into account the base materials, solvent, and energy requirement for NPS synthesis, it is estimated that NPS material would cost from 15 to 40 US$ per kg. On the other hand, MOFs face challenges in their scalability. MOF crystallization is a slow process with highly controlled temperature and pressure conditions in batch process. For example, Furukawa et al. described a 6-hour long synthesis for 10 g of MOF-801 followed by a 7-day period of rinsing and drying the material [32]. On top of a slow synthesis process, MOF precursors can be expensive, especially because of their metallic content. As a result, MOF-801 is commercially available at 100,000$US per kg [44]. One can note that new synthesis processes are developed to help the scalability of MOFs such as electrochemistry or assistance with microwaves [45]. Conclusion [00290] Nanoporous sponges based on resorcinol-formaldehyde resins were prepared undergoing heat treatments and functionalization steps, NPS, N-NPS, O- NPS and NO-NPS. These adsorbents possess a fine and narrow pore size centered around 1.5 nm. They exhibited good performance for water adsorption, especially O- NPS, having a water uptake of 0.28 g/g of adsorbent at 90% RH and 0.14 g/g at 40% RH, stable over five regeneration cycles. The scalability of the material has been demonstrated, maintaining their performance from the tens of milligrams to the tens of grams scale. The fitting of adsorption isotherms with Do & Do theoretical model highlighted the role of the hydroxyl groups as primary adsorption sites. Oxygen addition had the tendency to improve the OH concentration and thus improve the water 53 8702004 adsorption performance. On the opposite, nitrogen addition reduced the OH groups concentration and modified the porosity itself of the material, resulting in the presence of a H3 hysteresis in the isotherms. Improvement perspectives for the NPS adsorbents include a better control of the OH groups during the synthesis process. Heat and mass transfer of water vapor through the NPS micro particles, as well as inside the pores will need to be taken into account. EXAMPLE 2 NPS synthesis [00291] The nanoporous sponges (NPS) synthesis protocol is recalled here. The NPS consist of resorcinol-formaldehyde resin that undergoes different treatments. The resin is first synthesized through wet chemistry, where resorcinol (benzene molecule with two hydroxyl groups), formaldehyde and a catalyst (sodium carbonate) are dissolved in a solvent consisting of a 1:1 mixture of water and ethanol. By heating this mixture at 80°C during 24h, resorcinol and formaldehyde polymerize into a porous matrix and the solvent is evaporated. [00292] This matrix is then pyrolyzed (heated in the absence of oxygen) to carbonize the resin, as seen on Figure 13, causing a shrinkage of the pores to the required size. A molecule containing nitrogen functional groups, phenanthroline, can also be added to the initial mixture, and an oxidation step can further be carried out at the end of the synthesis process. The purpose of these two steps is to add functional groups to the porous matrix and capture water more easily. [00293] Tests and characterization, as described in Example 1, were mostly done on small scale samples up to ~ 100 mg, while preliminary confirmation validated that a batch of 30 g had similar properties. It is important to note a difference in the synthesis process between “small” and “large” batches of the NPS. In the small batch, the precursors were highly diluted with a concentration of approximately 0.02 g/mL of solvent solution. The cured resin after solvent evaporation was highly crumbly and easily put under the form of a powder with slight manual crushing. For the synthesis of the larger batch, such dilution ratio was not applied due to the large volumes of solvent to evaporate. As such, higher precursor concentrations of 0.3 g/mL were used. The 54 8702004 resulting cured resin was a hard and brittle block that required higher effort to transform into powder with a pestle and mortar. The obtained powder was rough and finer powder could be obtained with grinders and ball milling techniques. Physical characterization [00294] The two techniques employed here to complete the already performed characterizations on the NPS are Scanning Electron Microscopy (SEM) and Dynamic Vapor Sorption (DVS). The NPS samples were analyzed by SEM using a JEOL 7600TFE instrument, operated at 10 kV, as well as a Hitachi S-4700 instrument at 3 kV, in order to observe structural differences depending on the synthesis conditions and functionalization. [00295] Dynamic vapour sorption (DVS) is a gravimetric analysis technique that determines sorption properties by measuring sample mass continuously, directly giving the rates of adsorption and desorption. A DVS system consists of a temperature- and humidity-controlled chamber, and a quartz microbalance inside the chamber upon which the sample is placed. The microbalance records sample mass continuously and the DVS system can be used either to simply measure sorption properties at a given set point or determine adsorption/desorption isotherms by varying the relative humidity in pre-determined steps. The adsorption isotherms were obtained on a DVS Intrinsic instrument from Surface Measurement Systems Ltd., UK. Environmental Chamber [00296] Due to a low availability and high maintenance time of existing DVS equipment, the environmental chamber was adapted into a fully automated gravimetric equipment. The temperature is controlled with an electrical heater that allows the chamber to go from room temperature to 38°C. Relative humidity (RH) is controlled with a commercial ultra-sonic humidifier when RH has to be increased and a normally closed solenoid valve on a dry air line when RH has to be decreased. A fan is mixing homogeneously the air in the chamber. An Arduino Uno and relay control the power inputs of heater, humidifier, solenoid valve and fan with simple on/off switches. Arduino and Python codes on the laptop enable the full automation of a given procedure that can run for several days. NPS powder sample (~ 5g) is placed in a large glass dish 55 8702004 suspended under a balance that records the sample mass in real time. As such, temperature, relative humidity and mass are collected and analyzed to determine the isotherm, kinetics and cyclability of a given sample. For isotherms, the RH is varied from 5 to 95% with 5% steps at constant temperature and letting mass equilibrate between each step. Kinetics can be studied by abruptly switching from one RH value to another one and record the time to equilibrate the mass. Cyclability is verified by reproducing the same variations from one RH value to another one over and over. Desorption study in water capture device [00297] The water adsorption properties of non-functionalized NPS measured with small scale (< 100 mg) samples were validated on a larger scale with a custom- made water capture set-up: Moist air is generated by a boiler and passed through the porous material at a controlled flow rate, until saturation occurs. The NPS is contained in a column insulated with glass wool. Desorption is accomplished through mild heating with a heating tape coiled around the column to release the water. Desorbed steam is then condensed with a water-cooled condenser. This device can accommodate tens of grams of NPS, and can quite accurately measure the amount of water collected per adsorption / desorption cycle. [00298] It is important to note that some desorbed water was always remaining on the condenser walls. The amount of irretrievable water from the condenser was estimated based on the main assumption that the condenser has the same amount of water left on the inner walls after each experiment. This assumption is reasonable since water saturates the condenser walls before droplets fall down in the beaker. This saturation was assumed to be constant with 5% error. The 30g of tested NPS were able to adsorb 4.5 g of water at 90%RH. At 60°C, all of the water was desorbed from the NPS as their weight was measured after desorption, and only 3.0 g of water was retrieved in the beaker. As a result, it was assumed that 1.5 ± 0.1 g of water remains attached to the condenser walls during the different measurements. Theoretical models DDN Model 56 8702004 [00299] As described in Example 1, the experimentally-determined adsorption isotherms have been fitted to the theoretical equation of Do and Do, modified by Neitsch et al (DDN) [20]–[23]. This equation describes the adsorption process of H2O on C as a two-step mechanism, where the first step corresponds to adsorption of water molecules on primary sites (functional groups) on the surface. Water clusters then grow around these primary sites via hydrogen bonds. The second step occurs when clusters reach a threshold size of 6 molecules and break down into water pentamers that fill the micropores. It has been shown by Neitsch et al. that pentamers can be generalized into m-mers for higher accuracy [21]. The equation describing water adsorption is: N K nh n ^ m where a is sites, aµs is the saturation concentration in the micropores (all three in units of mol/g); Kf is the chemisorption equilibrium constant, Kµ is the micropore equilibrium constant; N is the maximum number of water molecules adsorbed per surface site; m is the size of the water m-mers that desorb from clusters and fill the micropores; and h is the relative pressure. To fit experimental data with the theoretical equation, we used the least- square method with the determination coefficient R ² , as follows: (a − a ) 2 2 ^ ^e th = − ^xp 2 (Equation 2) where a exp the corresponding theoretical data, and ^̅^̅ _^ ̅ _{^ ^} ̅ ̅ _{^ ^} ̅ _^ the average of experimental data over the relative pressure range. of intra-particle diffusion [00300] The kinetics of adsorption are studied experimentally and can be modelled for spherical particles of known radius thanks to Fick’s law of diffusion (Equation 3) (see Kim et al [46]). 57 8702004 ^ C 1 ^ ^ 2 ^ C ^ = ^D ^ r ^ (Equation 3) ^ where C is the is the particle radius, and Dµ is the intra- particle diffusion coefficient. A mathematical solution to Fick’s law of diffusion has been established by Kim et al. in order to take into account fitting of actual gravimetric data (Equation 4) [46]. ^ n2 ^ 2D _^ t ^ ^ ^ ^ 1 ^ ^ ⁻ ^ 2 ^ 4) where mt/meq , parameter describing adsorption, and being equal to 0 at t = 0s, and equal to 1 once the equilibrium water uptake has been reached. The intra-particle diffusion coefficient can be determined over a range of relative humidity and temperature, based on DVS data. Once determined, a simple kinetics profile based on the linear driving force model (Equation 5) can predict the adsorption or desorption rate over the time [47]. The solution to the linear driving force model is provided in Equation 6. ^ C ^ 15 = D _^ − C _^ ) (Equation 5) where Cµ is the in the particle, and Ceq is the equilibrium vapor concentration. f ⁽ t ^{) =1−} e ^{−kL t} (Equation 6) where f(t) corresponds to the FWU previously defined and kL = 15Dµ/rc2. The particle radius size is extracted from the electron microscopy data. Mass and energy transport in packed adsorbent [00301] While the isotherms provide resourceful and fundamental information on the developed adsorbents, it is important to predict how the fundamental properties can translate into design parameters in an industrial scaled equipment. As such, a 58 8702004 model described with high details by Kim et al [46] and summarized here is applied and solved in the present case. It consists of the equations of mass and energy transport in a packed adsorbent layer of known thickness (Equations 7 and 8). This model takes into account the water vapour diffusion between the particle (inter-particle diffusion) and the ability of the particles to adsorb and retain water (intra-particle diffusion). The equations are solved by finite differences technique. ^ C (1 ₋ ^ ) C = ^ ^D ^ C − ^{^} _{^ 8)} where C is layer [mol/m3], T is the temperature in the packed adsorbent [K], Dv is the inter-particle diffusion coefficient, ε is the packed porosity, ∂Cµ/∂t is the adsorption/desorption rate provided by the gravimetric data [mol/m ³ ·s], ρ is the locally averaged density, cp is the specific heat capacity of the adsorbent [J/K·kg], k is the thermal conductivity [W/m·K] and had is the enthalpy of adsorption [J/mol]. [00302] The specific heat capacity and thermal conductivity are estimated for the moment based on the values for carbon material, and powder samples at 750 J/K·kg and 0.1 W/m·K. It is planned to measure experimentally these values. The enthalpy of adsorption can be determined from thermodynamic model based on isotherms recorded for at least three different temperatures. The packed porosity is measured experimentally following the formula given by Equation 9. ^ ^ =1 − ads ^ powder (Equation 9) where ρads is the apparent density of the adsorption layer and ρpowder is the density of the powder itself. ρads can be easily determined by weighing a known volume of adsorbent. ρpowder requires to fill the void volume between the particle with a known volume of water, before weighing the mixture water-powder and measuring its volume. 59 8702004 It can be noted that the minimum packing porosity for spherical particles is obtained for hexagonal closed-packed configuration and equal to 0.25. [00303] The inter-particle diffusion coefficient Dv is given in Equation 10. − 1 ^ 1 1 ^ ^ _{3/ 2} ^ ^ (Equation 10) where Dvap is the in air, and equal to 2.82·10-5 m ² /s at 298 K, and DK is the Knudsen diffusion coefficient [m ² /s], typical of tight spaces where the collision between the water molecules and the material walls are frequent. The Knudsen diffusion coefficient relation is given in Equation 11. d p 8 _RT D = (Equation 11) where d p is the [m], or the average distance between two particles in other terms, R is the gas constant [m ³ ·atm/mol·K], T is the temperature [K], M is the molecular mass of vapor [kg/mol]. The characteristic void size is obtained based on a probability distribution that depend on the packing porosity, and given in Equation 12. ^ (1− ^)(1 − ^ ^ − HCP ) (1+ 3 ^(1− ^)( ^{^} _^ ^{^} ^) − 1 ^{^ ^} _^ P( ^)=3(1 + ^ ) 2 1 − ^ HCP ) e ^ ( ^ − ^ ^HCP ) ^ (Equation 12) ( ^ − ^ HCP ) where εHCP is the packing porosity of hexagonal closed-packed configuration (0.25). The characteristic void size is calculated from Equation 13: d _p ^{= 2 r} _c ^{^} _{av (Equation 13)} where rc is the particle χav is calculated from the probability distribution in Equation 14: 1 ^ ^ _av ⁼ ^ ^P( ^ ) d ^ (Equation 14) 60 8702004 Results NPS morphology [00304] The micrometric structure of non-functionalized NPS, shown on Figure 6, reveals spherically shaped particles with a mean diameter of 3.7 ± 1.1 µm. These micro-particles are thought to have this specific shape on account of the synthesis process, whereby resorcinol and formaldehyde are polymerized in dilute solutions [25]. The micro-particles agglomerate through complete evaporation of the solvent, and they maintain their shape in the course of heat treatments. These spherical micro-spheres are observed when the precursors are diluted in the water/ethanol solvents (concentrations lower than 0.1 mol/L). When synthesizing larger batches of NPS samples, the precursors have been more concentrated in order to decrease the solvent volume to evaporate, with precursor concentrations around 1 mol/L. The spherical microstructure was not observed anymore (Figure 14). The synthesis under concentrated conditions lead to large macrometric blocks (Figure 15) that were crushed into finer powder. Desorption of the NPS in the water capture device [00305] A larger batch of non-functionalized NPS was synthesized in order to verify whether the NPS synthesis process could readily be scaled up, and the observed performance maintained. While smaller samples of RF resin were easily turned into powder before pyrolysis, larger batches formed a compact, glassy material that had to be crushed into powder before heat treatment. Pyrolysis of the latter led to smaller mass loss, going from 80% to 50%, probably due to the larger particle size since the composition remained identical. [00306] The resulting scaled-up batch of non-functionalized NPS weighed 30 g, compared with 30 to 200 mg batches tested in the environmental chamber, and less than 1 mg in the DVS. This larger batch was tested in the water capture device and desorbed water collected from the condenser was weighed as a function of time, depending on the desorption temperature (Figure 12). Some water remained adhering to the walls of the water-cooled condenser. The weight of collected water was 61 8702004 corrected to take this into account, by assuming a constant mass, 1.5 ± 0.1 g, of irretrievable water on the condenser walls. Water uptakes were found to be between 0.14 and 0.16 g/g, very close to those observed at small scale. [00307] Based on these tests, the optimum desorption temperature was found to range between 55°C and 75°C. The water recovery rates have to be taken with caution due to the water left on the condenser walls. Mass measurements before and after desorption showed no residual water in the NPS material, even at room temperature, in agreement with the observed non-hysteretic adsorption isotherms. Without being bound to theory, it is believed that the lower percentage of water recovery at reduced temperature in Figure 12 may be due to the experimental set-up itself rather than a material intrinsic property. Lower temperatures could reduce the desorption kinetics of the NPS, generating less concentrated water vapor in air, making the vapor liquefaction by the water-cooled condenser less efficient. As a result, for the same amount of desorbed water, less water would be condensed at lower temperature. NPS isotherms [00308] Isotherms of the four sample types were obtained with the DVS instrumentation (Figure 11), to characterize water uptake from 0 to 95% RH, along with hysteresis between the adsorption and desorption portions. NPS and O-NPS are seen to display a type V isotherm (IUPAC classification) with little to no hysteresis, while N- NPS and NO-NPS have type VI isotherms with a H3 hysteresis loop. This type of loop is generally associated with non-rigid aggregates of plate (oblate spheroid)-like particles [27], [28]. On a practical aspect, it means that NPS and O-NPS will adsorb most of the water at low RH (40-60% RH) while N-NPS and NO-NPS require high RH to reach their maximum water uptake, which can have interest in high humidity environments. On top of that, the higher hysteresis for N-NPS and NO-NPS can be related to a higher energy requirement for desorbing water. [00309] From these isotherms, it appears that O in the material increases overall water uptake, a result already observed with the environmental chamber and resulting from affinity between water molecules and highly polar O functionalities (attractive dipole-dipole interactions, hydrogen bonding). On the other hand, N seems to have a 62 8702004 more complex role since water adsorption occurs at higher RH and the isotherm presents stronger hysteresis. One can also note that samples had higher water uptake values when measured in the environmental chamber, except for the case of non- functionalized NPS. Reasons for this difference may include RH error in the environmental chamber (± 2%) that would particularly affect samples containing N. Indeed, at 90% RH, a small variation of RH will lead to a greater variation of water uptake for the N-functionalized NPS compared to the others. Other causes for this difference include potential over-estimation of water uptake in the environmental chamber, and inhomogeneity of the functionalized materials, knowing that sample mass of less than 1mg are analyzed with DVS. [00310] Fitting the experimental data with the DDN model resulted in a strong mathematic fit, namely R ² > 0.99, as seen on Figure 16. The error on the different parameters was determined from several combinations of fitting parameters leading to the mentioned R ² values higher than 0.99 (see Table 4 above, Example 1). [00311] The presence of bonded O in a sample is seen to increase the values of parameters a0 and aµs, while that of N in the NPS drastically changes the N parameter’s value. All of these parameters are in ranges that possess plausible physical meanings [29], and this fact can help resolve observed fundamental differences between the various structures. Table 5 in Example 1 summarizes the absolute concentrations of diverse functional groups, obtained by deconvoluting high-resolution XPS peaks of O 1s and N 1s. It shows a close correlation between the concentration of hydroxyl (OH) groups and the parameter a0 that corresponds to the primary adsorption sites. This strongly suggests that OH groups are responsible as adsorption sites for the first water molecules, via hydrogen bonding; in contrast, the presence of N is seen to actually decrease the concentration of OH. The parameter aµs corresponds to the micropore filling concentration; micropores typically have sizes below 2 nm. NPS and O-NPS have 75-80% of their pores in this size range, while it is only 55% for N-NPS and NO- NPS. Micropore saturation concentration aµs is lower than expected for N-NPS, O-NPS and NO-NPS, when compared to the values obtained in the environmental chamber. 63 8702004 This observation fits with the abovementioned discrepancy between the DVS and environmental chamber measurements. [00312] The water cluster size m that can fill the micropores differs little between the samples, contrary to N, the maximum number of water molecules that can attach to a primary adsorption site. The presence of N increases this parameter value from N ~10 molecules to more than 150. At low RH, the initial adsorption steps can be described as follows: (i) a first water molecule attaches to the primary adsorption site through hydrogen bonding; (ii) subsequent water molecules become secondary adsorption sites; (iii) additional water molecules adsorb onto the secondary adsorption sites until reaching the maximum value N [22]. In Table 5, it can be observed that the N-containing samples have lower OH concentration. A lower concentration of hydroxyls, thus a reduced number of primary adsorption sites, allows for more physical space around each site enabling a larger amount of water molecules to be attached. This is also reflected in the observation of larger pores for N-containing samples. One can suppose that the maximum N value results from physical blockage, governed by pore size as well as interaction with other water clusters. Indeed, large water clusters with sizes up to 280 molecules have been reported by Ludwig et al. [30]. No clear tendencies can be drawn from the equilibrium constants Kf and Kµ, respectively correlated to chemisorption and micropore filling. [00313] Isotherms for NPS are also obtained in the environmental chamber, that are further discussed in the next section. A comparison of the isotherms between the DVS, done on a small batch and the environmental chamber, on a larger batch of NPS is shown in Figure 17. This comparison offers the validation of the environmental chamber compared to an actual DVS equipment while supporting the scalability of the NPS. One can note minor differences in the maximum water uptake and hysteresis that can be attributed to experimental error and intrinsic differences between the small and larger batch of NPS. NPS isotherms – temperature dependence [00314] The influence of the atmospheric temperature on the adsorption and desorption behavior of the NPS has been assessed in the environmental chamber, by 64 8702004 recording isotherms at three different temperatures (Figure 18). While the adsorption part is highly similar in the range 22.4 – 34.6°C (Figure 19), the hysteresis between the adsorption and desorption is shrinking when the temperature is increased. It shows that the desorption is facilitated at relatively higher temperature, confirming the observation done in Figure 12. [00315] NPS cyclability [00316] Cycles of adsorption and desorption are studied in the environmental chamber by varying the relative humidity from 5 to 95% at constant temperature. A typical cycle is presented on Figure 20, while repetitions of these cycles are shown on Figure 21. It confirms that the NPS performance remain constant over cycles. The kinetics of adsorption have been fitted with a simple exponential function under the form: F( ^t ) ^{= F} ₀ (1 ^{−e − kt} ) (Equation 15) Values for F0 and k were found at 0.146 kg/kg and 1.95 h ^-1 and remained constant over the different cycles. Diffusion models Intra-particle diffusion [00317] The solution to Fick’s law of diffusion (Equation 4) is used to determine the coefficient of intra-particle diffusion. This diffusion coefficient is dependent on temperature and relative humidity. Thus, it is possible to estimate an average value for a certain range of experimental conditions. As seen on Figure 22, kinetics data are available from DVS at each step from 5 to 95% RH, based on measurement from small batch of NPS whose spherical particle have a radius of 1.9 µm. The Equation 4 is fitted for each adsorption step, with several examples shown on Figure 23. The summary of the diffusion coefficients over the entire range of relative humidity is provided in Table 7. It can be deduced that the average diffusion coefficient at 30°C and from 5 to 95% RH is equal to 7.3 ± 4.3·10-16 m ² /s. 65 8702004 Table 7: Summary of the diffusion coefficient based on the DVS data. 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 .3 6.5 [00318] Based on the average diffusion coefficient previously obtained, it is possible to predict the overall kinetics of adsorption to pass from a specific RH value to another. The linear driving force model is employed for NPS at 30°C for an adsorption step from 5 to 95%. The resulting kinetics are shown on Figure 24, taking into account the uncertainty range. It can be seen that it takes up to an hour to fully adsorb water in a single particle having a radius of 1.9 µm. [00319] Assuming the diffusion coefficient would remain identical for any particle size, the effect of the particle radius on the adsorption kinetics was investigated, shown on Figure 25. While it took up to 1h to fully adsorb water for a single NPS particle having a radius of 1.9 µm, this time increased to 8h and 25h for particle radiuses of 5 and 10 µm. [00320] While smaller particle radius is more favorable for intra-particle diffusion, it is important to recall that smaller particles have a more limited inter-particle diffusion since the resistance to flow increases. As such, an optimal point must be found in the particle radius to take into account of both the intra- and inter-particle diffusion, based on the mass and energy transport model discussed in the following section. Mass and energy transport [00321] Before resolving the equation of mass and energy transport in an adsorption layer, several parameters have to be determined following the equations described in the methodology section. The packing porosity of the NPS adsorbent layer is determined by measurement of the apparent and powder densities and is equal to 0.46 ± 0.05. The characteristic void size is calculated based on several particle radiuses, identical to those considered in the intra-particle diffusion (1.9, 5 and 10 µm) and is shown on Figure 26. The Knudsen coefficient is calculated for a specific particle 66 8702004 size and different temperatures, on Figure 27. For a particle radius of 1.9 µm, at a temperature of 300 K and a packing porosity of 0.46, the Knudsen coefficient is equal to 8.67·10 ^-5 m ² /s, resulting in an inter-particle diffusion coefficient of 6.64·10 ^-6 m ² /s. [00322] The mass and energy transport equations are solved for a 1 cm thick NPS layer. The water concentration profiles are shown on Figure 28. It is important to mention that the water concentration corresponds to the concentration in the air, meaning that when the concentration reaches equilibrium at the maximum value, there is no more diffusion nor adsorption occurring, happening around 2000 s, from the graph. [00323] In order to extract kinetics data, a position at the extremity of the layer (L = 0.01 m) is arbitrarily chosen and the water concentration is plotted in function of time, as shown on Figure 29. The water concentration is increasing quickly in the first seconds before increasing slowly and reaching the maximum value. This difference in the water concentration increase is due to the intra- and inter-particle diffusion phenomena which have different time scales. To better visualize the contribution from the two effects, Figure 30 shows zoomed-in sections of the two regions. The region in the first seconds is dominated by inter-particle diffusion, where the water molecules quickly diffuse between the particles. After that, the slowest phenomenon corresponds to the intra-particle diffusion where the water molecules need to diffuse in the 1.5 nm pores of the NPS. Finally, when the NPS particle have adsorbed their maximum water uptake, the water concentration is equilibrated, at approximately 2000 s. [00324] In the specific case of spherical particles having a radius of 1.9 µm, it can be concluded that the main phenomenon driving the kinetics is the intra-particle diffusion. Additional calculations need to be done to study these kinetics when the particle radius is reduced. [00325] The temperature profiles in the adsorbent layer are depicted on Figure 31. It can be seen that the temperature barely increases in the layer due to the adsorption. The heat generated by the water adsorption occurs over a relatively long time (2000 s), meaning the heating power is very low at a specific time. On top of that, carbon powder has a thermal conductivity allowing to dissipate the heat before it 67 8702004 accumulates in the NPS material. The measured value for thermal conductivity was 0.1 W/m.K. Having a material with a temperature barely increasing during the adsorption is important for the material performance. LaPotin et al. mentioned that porous adsorbents, and more specifically MOFs have low thermal conductivity that can be compared to insulating materials [41]. As a result, heat can be trapped in the adsorbent particles, reducing the amount of water that can be adsorbed and obtaining overall poor performance. To overcome this issue with MOFs, thermal binders can be added, such as metallic foam or carbon particles [41]. Conclusion [00326] In conclusion, further characterization and understanding of the NPS material in the water adsorption application were obtained. Through experimental and theoretical work, it has become possible to draw several conclusions and confirmations from preliminary results: [00327] Validation of the scalability of the synthesis protocol: The water uptake of 0.15 kg/kg in the NPS material is maintained from 100 mg to 30g samples. The main difference lies in the morphology of the particles, where they are spherical for the small batch with diameters below 4 µm while particles with diameters of tens of µm are observed for larger batches. This difference can be compensated through fine crushing of the largest particles. [00328] Validation of the cyclability of the NPS: The water uptake and kinetics of adsorption are maintained over 10 adsorption/desorption cycles. [00329] Mechanism of the NPS adsorption: Literature is providing the mechanism steps of the adsorption of water on carbon-based material, through the Do & Do model. Recording adsorption isotherms and application of the theoretical model led to the identification of the primary adsorption sites, the hydroxyl groups. [00330] Kinetics of the water adsorption in the NPS: Through mass and energy transport equations in a packed adsorbent layer, it is possible to simulate the required time to reach equilibrium for a given adsorbent configuration. For NPS particle radius 68 8702004 of 1.9 µm in an adsorbent layer of 1 cm, it takes approximately 2000 s to reach equilibrium. [00331] These conclusions confirm the applicability of the nanoporous sponges of the present application in industrial applications. As such, the scalability may be extended to even larger batches of NPS samples, in order to build a prototype of water capture device. Additional cycles, up to 100, may be recorded to further confirm the cyclability. The NPS are mostly composed of carbon sp ² , and are, by nature, a very stable material over the time. In order to increase the maximum water uptake of the NPS, initial composition and functionalization of the synthesized material may be studied, with the objective to increase hydroxyl group concentration on the surface of the NPS. Several methods are considered, such as modifying the nature of the initial precursors, or addition of hydroxyl groups through heat treatments with water or peroxide precursors or eventually by acid or plasma treatment. A secondary objective to study the composition and functionalization of the NPS is to reduce the mass loss occurring during synthesis to lower the production cost of the material. Experimental work showed potential temperature dependant property in the water adsorption. This phenomenon needs to be studied. Thermodynamic properties of the NPS may also be further investigated. The mass and energy transport model may be continued to better define the kinetics of the water adsorption in the NPS. The objective is to determine the optimal particle size in a packed layer that maximize both inter-particle diffusion and water adsorption to increase the number of adsorption/desorption cycles per day. The diffusion model may be confronted to a forced flow model, where the water vapor is pushed through a layer or a column of adsorbent. All of this information may provide some design tools to adapt the NPS technology as an industrial scale. EXAMPLE 3 – Sorbents materials analysis [00332] The thermodynamic properties are assessed for five samples. They consist of nanoporous sponges (NPS), oxidized nanoporous sponges (O-NPS), silica gel and two metal–organic frameworks (MOFs): MOF-801-P and Cr-MIL-101. NPS and O-NPS were obtained were obtained as described above. 69 8702004 [00333] Silica gel (type A, Dry-Packs®) was purchased from Amazon. Finer powders of silica gel were obtained by grinding of the gel beads for 20 s in a Simplicite automatic grinder. Cr-MIL-101 and MOF-801-P were respectively chromium- and zirconium-based MOFs that were already described in literature [48-51]; both were purchased from Nanoshel-UK LTD. A simplification of the surface chemistry of the different sorbents studied is shown below in Scheme 1. Environmental Chamber [00334] Water adsorption isotherms were measured for each sorbent, at three temperatures: 25, 30 and 35ºC. The measurement of these isotherms was performed in a custom-made and fully automated environmental chamber employing a gravimetric method. In this method, the weight of the sample is continuously measured while the relative humidity varies and the temperature remains constant. A 3–5 g 70 8702004 sample of sorbent was dispersed on a thin layer in a 71 cm ² glass dish suspended under an AB204-S analytical balance from Mettler Toledo. [00335] Relative humidity (RH) was controlled by a humidifier and a solenoid valve connected to a dry air inlet. Temperature was controlled with a heater for the duration of the experiment. Also, a fan kept the conditions homogeneous in the entire volume of the environmental chamber. The humidifier, solenoid valve, heater and fan were controlled by an Arduino ^TM via a Python interface. Prior to isotherm measurement, the samples were left to dry in the environmental chamber for several hours until mass equilibration was reached. The adsorption isotherm protocol involved increasing the RH in 5 % steps from 5 to 95 % RH, and each step was maintained (1– 4 h) until the sorbent mass could equilibrate. Thermodynamic equations [00336] Water adsorption isotherms were fitted applying the Stineman’s algorithm [52] using the KaleidaGraph 4.5 (Synergy) software package. This fitting allowed extrapolating 100 data points based on the experimental isotherms. [00337] Gibbs molar free energy was estimated using Equation 16: (Equation 16) where T [K] is the absolute temperature, R [J/mol⋅K] is the universal gas constant and aw (=RH/100) [-] is the water activity. [00338] To calculate the differential enthalpy or isosteric heat, the methodology reported by Flores-Andrade et al. was applied [53]. First, Othmer’s equation (Equation 17) was used to determine the changes in differential enthalpy at the water–solid interface at different stages of adsorption [54]: (Equation 17) 71 8702004 [00339] Where M [g H2O/100 g dry sorbent] is the air moisture, H _v (T) [J/mol] is the isosteric heat for water sorption, Hv ⁰ (T) [J/mol] is the heat of condensation for pure water and C1 is a constant of adsorption, Pv [Pa] is the partial vapor pressure of water in the system and P _v ⁰ [Pa] is the standard state vapor pressure. By plotting ln(P _v ) vs. ln(P _v ⁰ ), a straight line can be obtained if the ratio H _v (T)/ H _v ⁰ (T) is constant for the studied range of temperature. The differential adsorption molar enthalpy ΔHdiff [J/mol] or net isosteric heat of adsorption was then computed with Equation 18: (Equation 18) previously calculated were used to calculate the change in the molar differential entropy ΔS _diff [J/mol], following the methodology reported by Flores-Andrade et al. [53] using Equation (19): (Equation 19) [00341] The molar integral enthalpy (ΔH _int ) _T [J/mol] was calculated by maintaining diffusion pressure (ϕ) constant, as reported by Flores-Andrade et al. [53] using Equation 20. The diffusion pressure is the available work to adsorb humidity. Rowley and Innes defined it as the total reversible work involved in the formation of an interface between the condensed water and the gas [55]. (Equation 20) where Hv,int(T) [J/mol] is the integral molar heat of water adsorbed in the material, H _v ⁰ (T) [J/mol] is the heat of condensation for pure water and can by determined with the Wexler equation (Equation 21), valid between 0 and 100 ^º C [56]: 72 8702004 (Equation 21) [00342] The diffusion pressure ϕ can be found via Equations 22 and 23: where μap [J/mol] is the chemical potential of the pure adsorbent, μa [J/mol] is the chemical potential of the adsorbent in the condensed phase, W _ap [kg/mol] is the molecular weight of the adsorbent, and Wv [kg/mol] is the molecular weight of water. [00343] The changes in the molar integral entropy (ΔSint)T [J/mol] were calculated as reported by Pascual-Pineda et al. and Acosta-Domínguez et al. in Equation 24 [57,58]: (Equation 24) where S ₁ = S/N ₁ [J/mol⋅K] is the integral entropy of the water adsorbed; S [J/ K] is the total entropy of water adsorbed in the adsorbent; N ₁ [mol] is the moles of water adsorbed in the adsorbent, and S _L [J/mol⋅K] is the molar entropy of the pure liquid water in equilibrium with the vapor. Results Sorbent surface chemistry [00344] The five studied sorbents presented various surface chemistry and physical properties and were thus expected to have different thermodynamic properties (Table 8). Simplified surface chemistry is illustrated in Scheme 1. [00345] Silica gel can be considered as a polymeric form of silicic acid in an amorphous network of SiO4 tetrahedra. The surface is terminated by either siloxane (- 73 8702004 Si-O-Si-) or silanol groups (-Si-OH) and thus exhibits high oxygen concentration, rendering it hydrophilic [61]. On average, 3.1 –OH groups per nm ² are present on the surface, with irregular distribution [62]. For the rest of the sorbents, the hydroxyl surface concentration was estimated based on available atomic O concentration from XPS, and surface area measurement from BET. NPS and O-NPS were derived from the pyrolysis of resorcinol–formaldehyde resin pyrolysis (with an oxidation step added for O-NPS) and are thus mostly composed of carbon sp ² , with slightly more oxygen for O- NPS compared to NPS. Among the oxygen moieties contained on the carbon-based sorbents, –OH groups were identified as primary adsorption sites using the Do & Do model [23]. NPS and O-NPS contained respectively 0.5 and 0.8 –OH groups per nm ² . Cr-MIL-101 was synthesized from Cr(NO3)3⋅9H2O salt and trimesic acid. The resulting sorbent material contained a high oxygen concentration on its surface. However, most of these oxygen atoms were involved in the MOF structure where they were linked to Cr atoms, and thus only a few oxygen atoms from carboxylic moieties would be able to participate in the water adsorption process. [00346] From surface analysis data in [49,60], it was estimated there were 1.5 – OH groups per nm ² . Many derivatives of Cr-MIL-101 could be found in the literature by functionalizing the organic linkers with various groups such as –NH2, –NO2 or SO3H [49]. MOF-801-P was synthesized from ZrOCl2⋅8H2O salt and fumaric acid. Similar to Cr-MIL-101, most oxygen atoms participated in the MOF structure, and it was estimated that only 1.8 –OH groups per nm ² were available for water adsorption. Table 8 - Physical properties and surface chemistry of the sorbents 74 8702004

[00347] Adsorption isotherms at 30ºC for the five studied sorbents are presented in Fig.32. NPS and silica gel exhibited decreasing equilibrium moisture content when increasing temperature at constant water activity due to the exothermic nature of the adsorption process [56]. O-NPS, MOF-801-P and Cr-MIL-101 had several regions of the isotherms where the opposite phenomenon was observed, and the equilibrium water constant increased with increasing temperature. [00348] NPS, O-NPS and Cr-MIL-101 isotherms presented a type V shape, according to the classification proposed by the International Union of Pure and Applied Chemistry (IUPAC); this is an S-shaped isotherm commonly found on various charcoals, carbon black and more generally hydrophobic materials [63]. Non-porous carbons with a void or small presence of Oxygen Functional Groups (OFGs) such as graphite or Graphitized Carbon Black (GCB) would present a Type III isotherm instead [64]. Silica gel was in good agreement with the experimental isotherms from literature [59]. However, it was observed that the isotherm from the commercial MOF-801-P deviated from literature reports, especially at low water activity, where the isotherms from literature exhibit a sharp increase [31]. Due to the constituency and adequacy of the other isotherms, it was concluded that this behavior came from the sample itself, and that scale-up of the MOF-801-P sorbent synthesis might have altered its adsorption properties. Gibbs free energy 75 8702004 [00349] Gibbs free molar energy of the different sorbents are shown in Fig.33 as a function of moisture (M, gH2O / 100 g of dried sorbent). Free energy increased with increasing water activity; thus, the process was less spontaneous as the sorbent moisture increased. It was also observed that at low moisture content and with increasing temperature, adsorption was less spontaneous since more energy was required for adsorption to occur [71]. At higher moisture, the reverse phenomenon happened for sorbents that had higher water uptakes at higher temperatures. [00350] Gibbs free energy was also used to compare the hygroscopicity of the sorbents, i.e. the facility for a sorbent to adsorb water vapor from its surrounding environment. The lowest energy values were correlated to the most hygroscopic materials. Silica gel appeared to be the most hygroscopic material, followed by the two MOFs, Cr-MIL-101 and MOF-801-P, and then the carbon-based samples, NPS and O- NPS. This behavior aligns with the –OH concentration on the sorbents’ active surface area, and more generally with the surface chemistry. Both NPS and O-NPS samples reached a “plateau” rapidly at around -2000 J/mol during the adsorption process, which suggested that water was adsorbed with homogenous spontaneity over a considerable range of RH. Enthalpy of adsorption [00351] The net isosteric heat of adsorption or differential enthalpy at 30ºC are presented in Figure 34. At low water activities, the differential enthalpy was higher than the enthalpy of vaporization of pure water for all the samples, indicating that the interactions between the water molecules and the surface of the sorbent material were higher than the intermolecular forces of water molecules in the liquid state (bulk). The net isosteric heat of adsorption decreased exponentially when increasing the water activity, evidence that the highly active sites (–OH groups) were being occupied as the adsorption process evolves. After that, differential enthalpy slightly oscillated close to the reference (pure water), meaning that the enthalpy of adsorption was practically the same as the heat of vaporization of water at each specific temperature (~44 kJ/mol). Liu et al. (2017) concluded that during the main pore filling in porous carbons, the isosteric heat was close to the heat of condensation because the water adsorption was 76 8702004 governed by water-water interactions [62]. One should note that the NPS sample presented an equivalent behavior to the commercial Cr-MIL-101 adsorbent, i.e., relatively low water-absorbent interactions when compared to silica gel and MOF-801- P. The weak interactions on the NPS and O-NPS became advantageous for water harvesting applications since less energy would be required to dry the sorbent before using it again in a cyclical adsorption–desorption process. [00352] The integral enthalpy of the different sorbents at 30ºC are shown in Fig. 35. This property represents the average energetic state of the adsorbed water on the surface of the material. That is, the average interactions between water molecules and adsorbent at a specific moisture content [52]. Integral enthalpy was directly correlated to the amount of energy released during water adsorption. The highest amount of energy was released for the first water molecules being adsorbed, which had the highest water-sorbent interaction. This behavior could be employed to better understand energy release during the adsorption step and optimize the energy management in a water capture set-up, where heat was demonstrated to be a limiting step in certain cases [41,72]. [00353] The moisture content was defined as a percentage of the maximum water uptake %Mmax. For example, 30%Mmax of silica gel would correspond to 11.5gH2O/100gsorbent. Taking into account the heat of vaporization for pure water at 30ºC, adsorbing water from 0%Mmax to 30%Mmax for silica gel would release an average energy of 63.5 kJ/mol, compared to 51.5 kJ/mol to adsorb water from 0%Mmax (dry sorbent) to 100%Mmax, due to high water-adsorbent interaction at low moisture content. The summary of the released heat of adsorption for different cases applied on all sorbents iss shown in Table 9. These simple cases show that the samples with the lowest water-sorbent interactions at higher water activity, i.e. NPS and Cr-MIL-101, released lower amounts of energy than silica gel and MOF-801-P, which have higher water-sorbent interactions. In other words, the amount of energy released during the adsorption, and by analogy the required energy for desorption, could be controlled in an actual water capture set-up by setting the moisture content levels during cycles of adsorption–desorption. O-NPS was considered as an intermediate in terms of water- 77 8702004 sorbent interactions between NPS and Cr-MIL-101 on one side and silica gel and MOF- 801-P on the other side. Table 9 – Heat of adsorption released during three adsorption cases for the sorbents [00354] The enthalpy of adsorption for silica gel has already been characterized in the literature. Chakraborty et al. determined that silica gel type RD had an enthalpy of adsorption at 30ºC of 2,550 kJ/kg, i.e.46.0 kJ/mol [65]. Ng et al. reported a value of 2,380 kJ/kg, i.e.42.8 kJ/mol for silica gel type 3A [66] and 45.2 kJ/mol for silica gel type RD. Chua et al. reported values of 48.8 and 48.5 kJ/mol for silica gel of respectively type A and type RD [67]. The enthalpy of adsorption varied from a silica gel type to another, but variations were also observed for the same type of silica gel, depending on the studies. It appears that the present study slightly overestimated the enthalpy of adsorption compared to available literature data. Explanations for this could include the material itself, purchased from a large-scale commercial supplier, and experimental errors that make difficult the precise determination of moisture content at low water activity and potentially causing variations in the thermodynamic properties. Enthalpy of adsorption was also studied in literature for MOF-801-P. Kim et al. determined values of 55 kJ/mol for this sorbent at 30ºC [68] while Furukawa et al. reported enthalpy of adsorption of 60 kJ/mol at similar temperature [32]. Entropy 78 8702004 [00355] Differential and integral entropy are respectively presented in Figure 36 and Figure 37. Statistical thermodynamics describes entropy as the distribution of the system energy in a number of possible microscopic states at thermodynamic equilibrium [69]. Applied to water adsorption, entropy corresponds to the energy spreading or dispersing by adsorbed water molecules, and the impact of intermolecular interaction between the water molecules and the sorbent surface on the energy dispersal within the system. It is important to point out that the differential adsorption molar entropy does not represent the energy spreading of the entire system, instead it shows the contribution to the energy spreading when the last molecules of water are adsorbed at a specific water level [52]. As such, this property allows the determination of the water content for which new arriving molecules do not affect the energy spreading of the system for each sample. This is valuable information for the design and scale-up of sorbent technologies for water recovery, since it allows to predict the minimal drying conditions for the sorbent before it is used again to adsorb water in a cyclical system. Indeed, new arriving water molecules that do not contribute to the energy spreading would practically arrange in an equivalent way as they would do in pure water. This implies that extraction conditions will then be equivalent as in pure water. An equivalent shape or behavior of the differential entropy has been observed in a MOF [70]. It can be observed that, for the NPS and the Cr-MIL-101 samples, differential entropy rapidly reaches a value of 0, indicating that additional molecules of water being adsorbed become equal to the molar entropy of liquid water in equilibrium with gaseous water. Even though the energy dispersal for the MOF-801-P sample is affected at low water contents, it also becomes stable close to 0 at around 13g H2O/100g of MOF-801-P. Silica gel was the sample where the energy dispersal is least affected by the new arriving molecules due to the higher energy sites and higher water- sorbent interactions. [00356] Integral entropy represents the average entropy of the entire system and is shown in Figure 37. This property is defined as the integral entropy of the water in the adsorbed state minus the molar entropy of the pure liquid water in equilibrium with the vapor (S1-SL). It then allowed the observation that, for most of the sorbent the adsorption process, the energy of the water molecules spreads in an equivalent way 79 8702004 as it would in pure liquid water. Overall, NPS and Cr-MIL-101 saw their integral entropy rapidly converge to 0, showing the energy of the adsorbed water rapidly reached the same distribution of microscopic states than pure water. The integral entropy of MOF- 801-P also converged towards 0, but the water molecules remained in a lower energy dispersal before fully filling the sorbent. Water molecules in silica gel did not reach the entropy of pure water and the strong interactions with sorbent surface maintained a lower energy dispersal. This also shows that it is entropically advantageous to adsorb water up to the maximum uptake, especially for NPS and Cr-MIL-101. It is not necessary to completely dry the samples before using them again in a cyclical process since a more negative entropy is correlated with higher difficulty to remove them from the sorbent. From a practical point of view, this implies that NPS and Cr-MIL-101 should maintain a moisture content of 3–5 gH2O/100 g of dried sorbent between cycles to ensure that the system keeps an entropy close to that of pure water. This condition could be achieved by performing adsorption–desorption steps with a lower limit at 20– 35%RH. [00357] The five studied sorbents exhibited various levels of –OH concentration on their active surface area, as shown in Table 8 [23]. The different thermodynamic properties were correlated with these surface chemistries. Gibbs free energy confirmed the hygroscopicity of the sorbents. At low RH, the carbon-based sorbents, NPS and O-NPS, were the least hygroscopic samples while silica gel had the highest hygroscopicity. In terms of integral enthalpy, the sorbents with the lowest –OH surface concentration had the highest enthalpy adsorption at low moisture content, due to a higher water-sorbent interaction. However, the adsorption enthalpy for these samples converged more rapidly towards the heat of vaporization of pure water than for the samples with higher water-sorbent interactions. Similar trends were observed with the integral entropy, where NPS, O-NPS and Cr-MIL-101 had lower values of entropy at low moisture content, indicating a higher number of possible microscopic states of the first adsorbed molecules. The integral entropy of these samples was converged rapidly towards 0, equivalent of the entropy of pure water. In contrary, silica gel and MOF-801- P kept lower integral entropies for higher moisture content, due a higher water- sorbent interaction and preventing the dominance of water-water interactions. 80 8702004 [00358] Despite a general good agreement between the –OH concentration and thermodynamic behaviors, some discrepancies were still observed for enthalpy and entropy. This illustrates that water adsorption is a more complex phenomenon, and several additional parameters should be considered. For example, even if –OH groups were identified as primary adsorption sites for NPS and O-NPS, surface chemistry could be more complex with other moieties having various repulsive or attractive behavior towards water. On top of the surface chemistry, water adsorption also depends on the pore size and geometry. For example, sudden variations in the pore diameter could locally lead to pore blocking, one of the potential causes for hysteresis between adsorption and desorption [9]. The present example focused mainly on the thermodynamic properties of the sorbent during the adsorption step. While hysteresis during desorption is likely to affect the thermodynamic behavior of the sorbent, one should expect only minor differences between adsorption and desorption integral properties. This is because the thermodynamic properties of interest are mainly extracted in the low humidity region (water activity = 0 – 0.2) where the sorbent surface – water molecules interactions are the strongest and the hysteresis is minimal. Conclusion [00359] The thermodynamic properties of five sorbents (Cr-MIL-101, MOF-101, silica gel, NPS and O-NPS) have been assessed based on their adsorption isotherms at three temperatures. The thermodynamic properties of silica gel were in good agreement with those found in literature. Gibbs free energy gave insight on the spontaneity of the adsorption process and on the hygroscopicity of the sorbent’s surface, which was correlated with the surface chemistry and more specifically the – OH surface concentration. Enthalpy of adsorption demonstrated that the highest amount of released energy occurred for the first adsorbed water molecules that had the highest water-sorbent interaction. The changes in adsorption enthalpy between the analyzed sorbents could be mostly correlated with the surface chemistry; other parameters could potentially affect the thermodynamic properties, such as pore size distribution and surface heterogeneity. Based on the enthalpy of adsorption, it could be possible to optimize the amount of released energy by performing incomplete desorption between adsorption steps, particularly for the most hydrophobic sorbents, 81 8702004 namely NPS and Cr-MIL-101. Entropy provided information on the distribution of microscopic states in adsorbed water molecules, which is related to the energy spreading or dispersing within the system. While the most hydrophobic sorbents rapidly reached a similar entropy to that of pure liquid water, silica gel maintained a lower entropy due to higher water-sorbent interactions. It showed that it was entropically advantageous to entirely use the materials to adsorb water and set conditions to avoid complete desorption. EXAMPLE 4 – Sorbent synthesis with CO ₂ activation Material [00360] Resorcinol flakes FG (CAS 108-46-3) at >98% purity were purchased from Sigma-Aldrich. Anhydrous sodium carbonate certified ACS powder (CAS 497-19- 8) with >99.5% purity and 37% by weight formaldehyde (CAS 50-00-0) solution (F79P- 4) were purchased from Fisher Chemical. Ethyl alcohol (95% VOL) was purchased from Greenfield global. CO2 (99,8% pure) and argon (99,999% pure) were purchased form Air Liquide. Resin synthesis [00361] Batches of RF gel were synthesized in a 4 L beaker on a hot plate (Figure 38a) set at 120 °C. Resorcinol flakes were poured in the beaker followed by sodium carbonate. Both reagents were thoroughly mixed with a spatula. Formaldehyde was quickly poured to provide turbulent mixing and ethyl alcohol was added last. The solution was continuously heated without agitation for approximately 1 to 2 hours on the hot plate until the bottom half of the beaker formed a gel layer and no bubbles were able to get through the gel (Figure 38b and c). [00362] The dark supernatant liquid on top of the gel was poured in a separate container. The gel was cut in 2-3 cm pieces and completely dried before further processing (Figure 38d, e and f). The dried gel was ground with a Paderno conical bur grinder Model No. CGR034 at its largest setting (Figure 38g). Two formulations explored are presented in Table 10. 82 8702004 Table 10 Gel formulations Formulation A Formulation B Reagent Weight (g) Weight Ratio Weight (g) Weight Ratio (%) (%) Resorcinol 560 18 840 25 Sodium Carbonate 14 0.5 21 0.6 Formaldehyde 840 27 1260 38 Ethyl Alcohol 1720 55 1200 36 Pyrolysis [00363] The pyrolysis tests were performed in an MTI GSL-1500X-50 horizontal tube furnace in a quartz tube (O.D.50.8 mm I.D.47.6 mm). The gas flow at the inlet of the furnace was controlled with a mass flow controller. The outlet was connected to ventilation. The furnace was heated at a rate of 12 °C/min until 850 °C. CO2 was introduced from the beginning of the process. Three different flowrates of CO2 were tested: 170 SCCM, 360 SCCM and 720 SCCM. After 3 hours at 850 °C the furnace’s heating system was turned off and allowed to cool naturally. Meanwhile, CO2 flow was discontinued, and the line was left to drain while argon was added in the reactor at a flow rate of 360 SCCM. Characterization Dynamic vapour sorption [00364] Sorption measurements were performed on a custom-built computer- controlled dynamic vapour sorption system (DVS). The system consisted of a glovebox coupled with an analytical balance, a humidity sensor, a temperature sensor, a humidifier, a source of dry air, a fan and a heater (Figure 39). The process was controlled and programmed from a LabView interface. [00365] A complete DVS analysis was performed by placing a sample of approximately 500 mg of dried NPS in the system and subjecting it cyclically to relative humidity (RH) increased from 0 to 95% RH and decreasing from 95% to 0% RH in 5% RH increments. The RH step was changed only when the weight of the sample completely stabilized. The temperature in the system was kept constant at 30℃. 83 8702004 [00366] During the cycle, the weight of the sample was recorded every 5 seconds. The water uptake, which is described by the following equation (Equation 25), was estimated at the completion of the cycle for each RH by calculating the average during the last 5 minutes of its step. ^^ ^^ ^^ ^^  ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ −  ^^ ^^ ^^  ^^ ^^ ^^ ^^  ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ ( ^^/ ^^)  =   ^{( )} ^^ ^^ ^^  ^^ ^^ ^^ ^^  ^^ ^^  ^^ ^^ ^^ (Equation 25) [00367] BET (Brunauer, Emmett and Teller) tests were performed on a Micromeritics Gemini VII under nitrogen. Samples were degassed before the tests at 300 °C over 12 hours and their final weight was between 0.15 g and 0.2 g. Non-local density functional theory (NLDFT) was used to characterize the micropore size distribution of the samples. A NPS sample pyrolyzed under an argon atmosphere served as a reference. X-ray photoelectron spectroscopy [00368] The surface composition of pyrolyzed carbon gel were characterized by X-ray photoelectron spectroscopy (XPS) with a Thermo Scientific K-Alpha. The X-ray source was an aluminum-kα with a spot size of 400 µm. Survey scans were performed with a pass energy of 200 eV and step size of 1 eV. High resolution spectra of O1s and C1s peaks were performed with a pass energy of 50 eV and step size of 0.1 eV. Binding energies were compared to references from the literature [19]. Bulk density [00369] Samples of NPS were poured into a graduated cylinder until they occupied a volume ranging from 5 to 10 mL. The final mass and volume of the samples were then used in the following equation (Equation 26) to evaluate the bulk density: ^^ ^^ ^^ ^^  ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ ^^  =   ^^ ^^ ^^ ^^ ^^ ^^  ^^ ^^ ^^ ^^ ^^ ^^ ^^ ^^  ^^ ^^  ^^ ^^ ^^ (Equation 26) 84 8702004 [00370] Size distribution of NPS before and after pyrolysis were measured with a Mastersizer 3000 from Malvern Panalytical with a hydro cell. The particles were dispersed in water for the test. Results and Analysis [00371] After pyrolysis, the carbon gel particles have a dark shiny surface (Figure 38h). The yield of carbon gel after pyrolysis was between 30% and 35%. The resulting particles had a bulk density of 0.40 g/cm³ for formulation A and 0.28 g/cm³ for formulation B. [00372] During pyrolysis, the CO2 acts as an oxidizer just like oxygen in previous experiments. At high flow rate (720 SCCM), the sample was completely consumed during the pyrolysis process. Further characterization was only performed on samples using the low (170 SCCM) and normal (360 SCCM) flow rate. [00373] The particle size distribution of ground dried RF gel and the carbon gel particle after pyrolysis are presented in Table 11. The particles are mostly millimeter- sized with a narrow distribution as presented in Figure 40. Pyrolysis caused an approximately 13% shrinkage of the average particle size. Table 11 Particle size distribution of RF gel before pyrolysis and carbon gel after pyrolysis Ground RF gel Carbon gel after before pyrolysis pyrolysis Dx10 [µm] 561 551 Dx50 [µm] 1239 1075 Dx90 [µm] 2173 1946 [00374] BET and NLDFT analyses for NPS from formulation A pyrolyzed under argon or CO2 atmospheres and NPS from formulation B pyrolyzed under CO2 atmosphere are presented in Table 12 and in Figure 41. Without being bound to theory, it is submitted that CO2 pyrolysis increased the area of functional surfaces available and the total volume of the micropores. NLDFT analysis also confirm that the pore size is below the critical pore size required for water nucleation by capillary condensation to minimize hysteresis (2.2 nm at 298 K). NPS synthesized under CO2 using 85 8702004 formulation A shows an increased amount of porosity below this critical threshold, which correlates with increased water uptake. Table 12 Results from the BET analysis for NPS from formulation A pyrolyzed under argon or CO2 atmospheres and NPS from formulation B pyrolyzed under CO2 atmosphere NPS (A) NPS CO2 (A) NPS CO2 (B) BET surface area [m²/g] 509 1301 884 T-plot micropore volume [cm³/g] 0,224 0,480 0,328 T-plot micropore area [m²/g] 446 956 654 T-plot external surface area [m²/g] 63,0 344,6 229,6 Table 13 Water uptake for NPS (A), NPS CO2 (A) and NPS CO2 (B) as function of water activity NPS (A) NPS CO ₂ (A) NPS CO ₂ (B) Water activity Water uptake [%] [g/g] 95 0.13 0.33 0.71 60 0.11 0.16 0.22 30 0.02 0.01 0.02 [00375] Without being bound to theory, the presence of a CO ² atmosphere during pyrolysis appears to slow down the sodium carbonate thermal decomposition [21] leading to a higher residual content of sodium carbonate (Figure 45a and b). The CO2 also act as an oxidizer to help the carbonization of the RF gel into carbon gel. The higher concentration of sodium carbonate after pyrolysis in the NPS CO2 (B) sample (Figure 46) comes from the higher initial concentration of sodium carbonate due to the lower dilution in formulation B. The presence of sodium carbonate combined with the oxidizing effect of CO ² leads to higher water uptake for NPS CO ² (A) and NPS CO ² (B). The sodium carbonate in the system acts as a deliquescent salt that condense liquid water. That liquid water is then filling the pore through the capillary forces in addition to traditional capillary condensation previously observed in NPS. The higher residual concentration of sodium carbonate on the surface of NPS CO2 (B) samples allow them to capture more water them the NPS CO2 (A) samples (Figure 5 and Figure 86 8702004 7). On the contrary, the lower CO2 pressure from the low flow rate pyrolysis resulted in a lower residual concentration of sodium carbonate and reduced oxidation leading to lower water uptake (Figure 43). Conclusion [00376] Pyrolysis of RF gel under a CO2 atmosphere significantly improves the water harvesting capability of the resulting carbon gel. The presence of a CO2 atmosphere during pyrolysis preserves a portion of the sodium carbonate from thermal degradation. Sodium carbonate in the carbon gel then act as a deliquescent salt boosting the water uptake capability of carbon gel. Further tests are planned to evaluate the effect of different catalyst during the production of RF gel and the resulting water harvesting capabilities of the carbon gel. [00377] While the applicant's teachings described herein are in conjunction with various embodiments for illustrative purposes, it is not intended that the applicant's teachings be limited to such embodiments as the embodiments described herein are intended to be examples. 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