Highly porous solid containing membrane

Abstract

The present invention relates to a method for preparing a porous membrane comprising the steps of: a- preparing an aqueous mixture comprising a dispersion of fibers derived from an organic material in water, a solid organic binder and porous solid particles suspended in water; b- stirring the aqueous mixture comprising the fibers, the organic binder and the porous solid particles at room temperature for at least 10 minutes; c- vacuum filtering the mixture to recover the composite material; and d- pressing the composite material obtained in step c to form a porous membrane.

Description

[Technical field]

[0001] The present invention relates to the field of porous materials for capturing toxic gases such as volatile organic compounds, also called VOCs, or nitrogen oxides (NOx), which are NO or NO2. More specifically, the present invention relates to a method for preparing such materials and to membranes comprising such materials. [Background technology]

[0002] To guarantee hygiene and safety for objects and people, it is essential to be able to control the quality of the air in historical facilities and dwellings or passageways. More specifically, it is necessary to control the content of certain compounds present in the ambient air, and many methods aim at capturing volatile or gaseous compounds that are pollutants, such as volatile organic compounds (VOCs), as described in the reference application [1], NOx or other gases that can be harmful at a given concentration in the ambient air, such as CO2.

[0003] Furthermore, the materials mainly used to control the air quality of closed environments are activated carbon and zeolites. These materials have low selectivity for the adsorption of these pollutants and / or poor regeneration, more specifically, in the case of zeolites, poor regeneration for the adsorption of VOCs in the presence of water. Thus, there is a real problem of VOC adsorption efficiency in the presence of ambient humidity.

[0004] Adsorption of VOCs is known to occur from beads or granules, sometimes contained in foams, monoliths or woven fabrics. When using foams or woven fabrics, the loading of the porous solid is low, which may not be adequate for all applications, or the adsorption efficiency may be compromised, for example due to diffusion of the adsorbed material.

[0005] In the context of the present invention, the term "filling factor" defines the percentage of pores relative to the total number of available pores.

[0006] It is known to fix adsorbents to supports such as membranes or sheets or to integrate them into such supports, for example for use as filters. Methods for the production of adsorbent-loaded paper membranes already exist, but if the content of solid particles incorporated in the membrane is too high, the mechanical stability of the cellulose matrix decreases. A product designed according to one of these production methods is commercially available under the name "MicroChamber Paper™" and is intended for the preservation of cultural heritage or the conservation of archival documents. Such products have a limited zeolite loading of about 20%, the rest being a common additive for cellulose-containing fibers and papers. Its low efficiency is linked to an excessively low content of adsorbent (zeolite), and its low specificity towards the molecules actually adsorbed remains a drawback. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention aims to overcome the aforementioned drawbacks by implementing a method for the preparation of a material that integrates at least one type of fiber with sorbent particles, which should allow the integration of large amounts of these sorbents in the paper membrane, more than 50% by weight of the final weight of the paper, while retaining good mechanical stability and the same VOC capture properties as the pure sorbents.

[0008] To this end, the present invention relates to a method for the preparation of a porous membrane, a- preparing an aqueous mixture comprising a dispersion of fibers derived from organic material in water, a solid organic binder and porous solid particles suspended in water; b- allowing the resulting aqueous mixture containing the fibers, the organic binder and the porous solid particles to stand under stirring at room temperature for at least 10 minutes; c- vacuum filtering the mixture to recover the composite material; and d-- Pressing the composite material obtained in step c to form a porous membrane.

[0009] Preferably, step a) of the method for preparing a porous membrane comprises the following sub-steps: (i)-dispersing fibres derived from organic materials in water; (ii)-adding a solid organic binder; and (iii)-Adding porous solid particles suspended in water.

[0010] Preferably, instead, step a) of the method for preparing a porous membrane comprises the following sub-steps: (i)-preparing a suspension of porous solid particles in water; (ii)-Adding a dispersion of fibers derived from organic materials in water; and (iii)-Adding a solid organic binder.

[0011] In the context of the present invention, the term "solid organic binder" means a binder available in the form of a paste, a gel or a suspension in an aqueous mixture or a suspension in water (in particular a colloidal suspension). In the context of the present invention, the organic binder is used as a mixture in water with a weight content of 2 to 10% taken relative to the total weight of the binder. The term "solid organic binder" as used in the remainder of the specification corresponds to a nanoscale structuring agent comprising nanocellulose, preferably cellulose microfibrils, preferably having a length of 0.5 to 50 μm, more preferably 4.5 to 35 μm, advantageously 8 to 30 μm, or even 11 to 25 μm. The length of the fibers is determined by observation under a microscope.

[0012] The term "nanoscale structuring agent" as used in the context of the present invention is used equivalently to the expression "nanoscale and / or microscale structuring agent" and refers to the nanoscale and / or microscale structuring of an object. This nanoscale structuring agent allows to increase the number of (weakly interacting) contact points (binder-binder interactions and interactions with the porous solid particles and / or long fibers) in the composite, thus resulting in a more cohesive (less friable) and stiffer final composite compared to a composite containing only long fiber cellulose.

[0013] Preferably, the nanoscale structuring agent comprising cellulose microfibrils used in the method according to the invention is incorporated in a content of 2.5-40%, preferably 5-35%, advantageously 10-30% or 15-25% relative to the total mass of the resulting porous membrane.

[0014] The term "nanocellulose" combines different categories of cellulose nanomaterials, defined in 2011 by Klemm et al. [2]: microfibrillated cellulose (MFC), nanocrystalline cellulose (NCC) and bacterial nanocellulose (BNC). The main difference lies in their preparation methods, which subsequently result in different dimensions of these nanomaterials. BNC is obtained using aerobic bacteria and therefore is obtained from a biotechnological process, while MFC and NCC result from the breakdown of natural plant fibers. This microfibrillation is possible by hydrolysis in an acidic medium and / or mechanical treatment (generally homogenizers). The Technical Association of the Pulp and Paper Industry (also called by its English acronym TAPPI: "Technical Association of the Pulp and Paper Industry") has standardized the classification of cellulose nanomaterials by size: References [3]. Thus, microcrystalline cellulose (width: 10-15 μm, ratio L / D<2) and microfibrillated cellulose or cellulose microfibrils (MFC, length: 0.5-50 μm, width: 10-100 nm) have rather nanostructuring functions, while cellulose nanocrystals (width: 3-10 nm, L / D>5) and cellulose nanofibrils (width: 5-30 nm, L / D>50) belong rather to the field of nano objects.

[0015] In the context of the present invention, "porous solid particles" or "pore formers" are agents that impart adsorption properties for pollutant volatile or gaseous compounds. Unexpectedly, the inventors have demonstrated that such a method allows combining several types of fibers, preferably at least two types of cellulose fibers, to obtain membranes containing porous solid particles at levels in the membrane that in some cases exceed 70% by weight of the final membrane mass, while maintaining good mechanical stability and a VOC capture capacity comparable to that of the starting porous solid particles considered separately.

[0016] Depending on the porous solid particles used in the process according to the invention, these can be pre-dispersed, preferably in an aqueous solvent, advantageously in water, using an ultrasonic bath.

[0017] The term "composite material" in the sense of the present invention refers to a material that comprises at least two immiscible components.

[0018] Preferably, the composite material obtained in the penultimate step is directly shaped while being stretched under vacuum, for example by performing vacuum stretching on a support using a water tube or a vacuum pump.

[0019] Advantageously, the fibres are of biological origin. The term "biogenic" in the context of the present invention defines elements that are derived from renewable organic material (biomass) of plant or animal origin.

[0020] Preferably, the fibers are selected from among papermaking fibers of natural origin and plant fibers, such as wood fibers, softwood fibers, palm fibers, flax fibers, bamboo fibers and cotton fibers, more preferably the plant fibers include cellulose fibers. Advantageously, the fibers used in the method according to the invention are cellulose fibers, so-called cellulose-containing fibers. To improve the dispersion of the fibers, a mechanical treatment, preferably a grinding and / or an ultrasonic treatment, is advantageously carried out. Preferably, the fibers used in the method according to the invention are incorporated in a content of 30% or less, preferably 20% or less, advantageously 10% or less, or less than 5% relative to the total mass of the resulting porous membrane.

[0021] Advantageously, the porous solid particles preferably comprise pores with an average size between 0.3 and 3 nm and are selected from at least one of the following particles: zeolite particles, activated carbon particles and structured metal-organic compound particles, so-called MOFs (Metal Organic Frameworks), which MOFs comprise multidentate chelating ligands. Advantageously, the porous solid particles are suspended in an aqueous solution comprising distilled water to form an aqueous suspension which is added to the initial mixture comprising the fibres and the organic binder solids.

[0022] In the context of the present invention, the term "porous solid" refers to a solid that contains porosity, the porosity itself being defined according to the IUPAC definition (see reference [4]), which defines a porous solid as a solid that has pores (cavities, gaps, channels) whose depth is greater than their width. These pores are accessible to fluids or gases, i.e. they are in continuous communication with the outside of the solid.

[0023] In the context of the present invention, the term "MOF" defines a hybrid porous material, also referred to as "metal-organic framework", as a compound constructed from bridging organic ligands, also called "linkers" or "spacers", that remain intact throughout the synthesis and act as connectors in the network of the resulting MOF three-dimensional structure. As used herein, the term "ligand" or "linker" or "spacer" refers to a ligand coordinated to at least two metal sites, also called a "multidentate chelating ligand", that creates distance between these metal atoms and contributes to the formation of cavities or pores.

[0024] "MOFs" are solid adsorbents that can be easily regenerated by known alternating pressure or temperature adsorption techniques. Examples of MOFs are described in EP 3453450 (Reference [1]).

[0025] "Three-dimensional structure" should be understood as a three-dimensional arrangement or repetition of units and / or patterns or sub-variants in the conventional sense of the term in the field of MOF materials, which are also characterized as "organometallic polymers".

[0026] In the context of the present invention, the expression "average size of the pores" (also called "size of the pores") refers to the size of the pores (or the diameter of the pores) of porous solid particles, such as MOF particles, as conventionally used in the art, calculated by nitrogen adsorption methods. It is intended to cover the various possible pore shapes of MOF materials (e.g. tetrahedral, octahedral). Methods for measuring the size of the pores are well described in the literature: see reference [5]. For example, the size of the pores of MOFs can be determined by calculating the size distribution of the pores for nitrogen adsorption. It is also possible to estimate the maximum and limiting sizes of the pores from crystallographic data by simulating the filling of the pores by gas molecules (reference [6]), which allows the average size of the pores to be calculated. In the context of the present invention, the specific surface area BET as well as the volume of the pores were determined by N2 adsorption methods, in particular with a TriStar® II device, based on the N2 adsorption-desorption isotherms at -196 ° C (77 K).

[0027] In the context of the present invention, the term "nanoparticle" refers to a particle having a size smaller than 800 nm. In particular, the MOF adsorbent nanoparticles according to the present invention may have a diameter (or the size of the largest axis if the particle has an asymmetric shape) smaller than 800 nanometers, preferably smaller than 400 nm, more preferably smaller than 200 nm, and in some cases smaller than 100 nm.

[0028] In the context of the present invention, the term "microparticles" refers to particles with sizes between 800 nm and tens of microns.

[0029] Preferably, the porous solid particles are incorporated in a content of at least 55% relative to the total mass of the resulting porous membrane, advantageously the content is higher than 60%, more advantageously higher than 65% and even higher than 70%.

[0030] The present invention also relates to a porous membrane obtainable by the preparation method described above in the description of the invention.

[0031] More specifically, the present invention relates to a porous material, preferably a porous membrane, preferably obtained according to the method previously described in the context of the present invention, for capturing volatile organic compounds, referred to as VOCs, 50-85% porous solid particles; 15-50% cellulose matrix; The percentages are percentages by mass of the component considered relative to the total mass of the porous membrane, the porous solid particles being selected from at least one of the following particles: zeolite particles, activated carbon particles, and structured metal-organic particles, so-called MOFs, which MOFs comprise multidentate chelating ligands.

[0032] Preferably, the porous solid particle content is between 55 and 80%, advantageously said content is between 58 and 77%.

[0033] In the context of the present invention, the term "cellulose matrix" defines a matrix comprising at least two cellulose sources, preferably nanocellulose and cellulose fibers, more preferably cellulose microfibrils (MFC) combined with cellulose fibers. Advantageously, the porous solid particles cover or are interposed between the cellulose fibers, and the nanocellulose is interposed between the porous solid particles so as to create a favorable interaction with these particles. The structure of such a matrix can be observed with a scanning electron microscope (SEM).

[0034] Preferably, the porous membrane according to the invention comprises a cellulose matrix containing 0-30% MFC and 5-45% cellulose fibres, the contents being expressed as percentages by mass relative to the total mass of the porous membrane. Preferably, the MFC content is 5-25%, more preferably 8-22%. Preferably, the cellulose fibre content is 8-42%, more preferably 11.5-40.5%.

[0035] More preferably, the MFC content is higher than 15%, even higher than 17%. Unexpectedly, the inventors were able to observe that increasing the amount of MFC in the cellulose-containing fibre / MFC ratio increases the stiffness of the composite and increases the retention of particles within the composite.

[0036] Preferably, the cellulose fibers are cotton and resin fibers, the content of which is higher than 15%, even higher than 17%. Unexpectedly, the inventors have been able to observe that a relatively high cellulose fiber content, especially when it consists of the longest cellulose fibers, such as the cellulose-containing fibers of softwood and cotton, can ensure the flexibility of the material and avoid it becoming brittle.

[0037] Preferably, the MOF particles comprise at least one metal selected from among Cu, Zn, Ca, Ln, Y, Mg, Ti, Zr, V, Cr, Mn, Fe and Al, preferably the metal is an Fe, Al or Zr metal ion, advantageously consisting of a metal ion selected from among Fe metal ions.

[0038] Preferably, the polydentate chelating ligand is selected from at least one type of ligand selected from among bidentate, tridentate and tetradentate ligands, advantageously a C6-C ligand containing at least one functional group selected from among carboxylic acid, phosphonic acid, amine, alcohol, ketone and azole functional groups. 24 The polydentate chelating ligand includes aromatic compounds. Preferably, the polydentate chelating ligand is benzene-1,3,5-tricarboxylic acid (CH(COH), CAS: 554-95-0), 3,3',5,5'-azobenzenetetracarboxylic acid (C 16 H 10 N2O8, CAS: 365549-33-3), 3,5-pyrazoledicarboxylic acid (C5H4N2O4, CAS: 303180-11-2), 2,5-bistrifluoromethyl-1,4-benzenedicarboxylic acid (C 10H4F6O4, CAS: 366008-67-5), 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid (C9H5F3O4, CAS: 1483-47-2), 1,2,4-triazole (C2H3N3, CAS: 288-88-0), 2-methylimidazole (C4H6N2, CAS: 693-98-1), N,N'-piperazine(methylenephosphonic) acid (C6H 16 The ligand is selected from at least one of the following: L-aspartic acid (C4H7NO4, CAS: 56-84-8), 2,5-dihydroxydeterephthalic acid (C8O6H6, CAS: 610-92-4) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (C4O4H2, CAS: 2892-51-5).

[0039] Preferably, the porous solid particles comprise nanoparticles and / or microparticles with a diameter of 50 nm to 80 μm. Good mechanical properties (very satisfactory mechanical strength, easy handling, and high flexibility) have been observed for membranes formulated from MIL-100(Fe) nanoparticles (size smaller than 100 nm) and MOFs (Al-PDA, MIL-53-CF3) with a size of about 200 nm. MOFs with particle sizes from 800 nm (MIL-127(Fe) and UiO-66-2CF3(Zr)) to 3 μm (MIL-100(Fe)), as well as polydisperse microparticles of activated carbon with a size of 5 to 80 μm and NaY zeolite particles with a size of 700 nm also provide ideal mechanical properties. The size of the particles is determined by observing the particles under a scanning electron microscope (SEM) and measuring the size of the particles (sampling of 60 and 70 particles) using ImageJ™ software.

[0040] Preferably, the MOF is chosen from among MIL-100(Fe), MIL-127(Fe), Ca-squarate (amphiphilic), Al-PDA (also called MOF-303; hydrophilic), MIP-202(Zr) (hydrophilic), MIL-91(Ti) (hydrophilic) or from among one of the hydrophobic MOFs, i.e. UiO-66(Zr)-2CF3, MIL-53(Al)-CF3, CALF-20, ZIF-8.

[0041] Advantageously, the membrane has a thickness of 150 to 500 μm. If in the form of a monolith, the thickness can advantageously reach one to several millimeters. The membrane thickness is measured using a commercially available Vintage™ mechanical micrometer under the reference MK 0-25 mm, with an accuracy of 0.01 mm (K, USSR).

[0042] The present invention also relates to the use of the porous membranes described above in connection with the present invention for carrying out gas and vapor separations, for carrying out adsorption, for catalysis and for advantageous environmental and / or energy applications.

[0043] Preferably, the use of the porous membrane according to the invention is carried out for purifying ambient air or for purifying a storage space containing sensitive objects by VOCs. Examples of sensitive objects that need to be protected are given in reference [7].

[0044] Preferably, the porous membranes are used for the capture of CO2 in ambient air or in industrial environments, for gas separation, for gas (hydrogen, methane) storage, or for proton conduction in sustainable energy systems. Examples of such applications are given in references [8] to

[12] .

[0045] Preferably, the use of the porous membrane is carried out in the treatment of air by adsorption of water for dehumidification, fresh water production, air conditioning or heating, seasonal heat storage, decontamination of ambient air of engine exhaust gases containing NOx. Examples of such applications are given in references

[13] to

[15] .

[0046] The invention is also illustrated in the following detailed description using an experimental section detailing some embodiments using examples (given for illustrative purposes only and should not be considered limiting) and the figures which are briefly described in the following sections. [Brief description of the drawings]

[0047] [Figure 1] FIG. 1 shows X-ray diffraction patterns of the MIL-100(Fe) microparticles of Example 1 and the paper film morphology of Example 16. [Diagram 2] FIG. 1 shows the thermogravimetric analysis (in air, heating rate 5° C. / min) of the MIL-100(Fe) fine particles of Example 1 and the paper film form of Example 16. [Diagram 3] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of the MIL-100(Fe) microparticles of Example 1 and the paper membrane form of Example 16. [Figure 4a] FIG. 1 shows images of paper membrane containing 75% w / w MIL-100(Fe) microparticles of Example 16 obtained by scanning electron microscopy at different magnifications: (a) × 10,000 and (b) × 15,000. [Figure 4b] FIG. 1 shows images of paper membrane containing 75% w / w MIL-100(Fe) microparticles of Example 16 obtained by scanning electron microscopy at different magnifications: (a) × 10,000 and (b) × 15,000. [Figure 4c] FIG. 2 is a histogram showing the size distribution of MIL-100(Fe) particles and the size distribution of microfibrillated cellulose fibers obtained in Example 1. [Figure 4d] FIG. 2 is a histogram showing the size distribution of MIL-100(Fe) particles and the size distribution of microfibrillated cellulose fibers obtained in Example 1. [Diagram 5] FIG. 1 shows an X-ray diffraction pattern of MIL-100(Fe) nanoparticles of Example 2. [Figure 6] FIG. 1 shows thermogravimetric analysis (in air, heating rate 5° C. / min) of MIL-100(Fe) nanoparticles of Example 2. [Figure 7] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of MIL-100(Fe) nanoparticles of Example 2. [Figure 8] FIG. 13 is a diagram showing X-ray diffraction patterns of the MIL-127(Fe) fine particles themselves of Example 3 and the paper film form of Example 17. [Figure 9] FIG. 13 is a diagram showing thermogravimetric analysis (in air, heating rate 5° C. / min) of the MIL-127(Fe) fine particles of Example 3 and the paper film form of Example 18. [Figure 10] FIG. 13 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of MIL-127(Fe) microparticles of Example 3 and the paper membrane form of Example 17. [Figure 11] FIG. 1 shows the X-ray diffraction patterns of the Al-PDA nanoparticles themselves of Example 4 and the paper film form of Example 18. [Figure 12] FIG. 1 shows the thermogravimetric analysis (in air, heating rate 5° C. / min) of the Al-PDA nanoparticles themselves of Example 4 and the paper film form of Example 18. [Figure 13] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained for the Al-PDA nanoparticles as such in Example 4 and after activation in the form of a paper film in Example 18. [Figure 14a] 1 shows an image of a paper membrane containing 75 wt % Al-PDA nanoparticles of Example 18 relative to the total weight of the membrane. [Figure 14b] 1 shows an image of a paper membrane containing 75 wt % Al-PDA nanoparticles of Example 18 relative to the total weight of the membrane. [Figure 14c] 1 shows an image of a paper membrane containing 75 wt % Al-PDA nanoparticles of Example 18 relative to the total weight of the membrane. [Figure 14d] FIG. 1 is a histogram showing the size distribution of Al-PDA particles obtained in Example 4. [Figure 15] FIG. 13 is a diagram showing the X-ray diffraction patterns of the UiO-66(Zr)-2CF3 fine particles themselves of Example 5 and the paper film form of Example 19. [Figure 16]FIG. 13 is a diagram showing the thermogravimetric analysis (in air, heating rate 5° C. / min) of the UiO-66(Zr)-2CF3 fine particles themselves of Example 5 and the paper film form of Example 19. [Figure 17] FIG. 13 shows dinitrogen adsorption / desorption isotherms at 77 K obtained for the UiO-66(Zr)-2CF3 microparticles themselves in Example 5 and after activation in the form of a paper film in Example 17. [Figure 18] FIG. 13 shows the X-ray diffraction pattern of MIL-53(Al)-CF3 nanoparticles of Example 6. [Figure 19] FIG. 13 shows the thermogravimetric analysis (in air, heating rate 5° C. / min) of the MIL-53(Al)-CF3 nanoparticles themselves of Example 6 and of the paper film form of Example 20. [Figure 20] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained for the MIL-53(Al)-CF3 nanoparticles as such in Example 6 and after activation in the form of a paper film in Example 20. [Figure 21] FIG. 1 shows X-ray diffraction patterns of the NaY zeolite itself of Example 7 and the paper membrane form of Example 22. [Figure 22] FIG. 1 shows the results of thermogravimetric analysis (in air, heating rate 5° C. / min) of the NaY zeolite fine particles of Example 7 and the paper film form of Example 22. [Figure 23] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained for the NaY microparticles themselves of Example 7 and after activation in the form of a paper film of Example 22. [Figure 24] FIG. 13 shows experimental X-ray diffraction patterns of the activated carbon fine particles themselves of Example 8 and the paper membrane form of Example 21. [Diagram 25] FIG. 1 shows the results of thermogravimetric analysis (in air, heating rate 5° C. / min) of the activated carbon fine particles of Example 8 and the paper film form of Example 21. [Figure 26] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of the activated carbon particulates of Example 8 and the paper membrane form of Example 21. [Figure 27a] FIG. 1 shows an image of the activated carbon powder of Example 8. [Figure 27b]FIG. 13 is a histogram showing the size distribution of activated carbon particles as described in Example 8. [Figure 27c] FIG. 13 is a diagram showing an image of a paper membrane containing 75 mass % of activated carbon fine particles based on the total mass of the membrane in Example 21. [Figure 28] FIG. 13 shows the X-ray diffraction patterns of paper membranes formulated with different MIL-100(Fe) nanoparticles in Example 9. [Figure 29] FIG. 13 shows thermogravimetric analysis (in air, heating rate 5° C. / min) of different paper films loaded with MIL-100(Fe) nanoparticles of Example 9. [Diagram 30] FIG. 13 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of different paper membranes loaded with MIL-100(Fe) nanoparticles of Example 9. [Diagram 31] FIG. 1 shows the X-ray diffraction patterns of different paper films incorporating fine particles of MIL-100(Fe) and MIL-127(Fe) in Examples 10 and 11. [Diagram 32] FIG. 13 is a diagram showing the thermogravimetric analysis (in air, heating rate 5° C. / min) of different paper films incorporating MIL-100(Fe) microparticles of Example 10. [Diagram 33] FIG. 1 shows dinitrogen adsorption / desorption isotherms at 77 K obtained after activation of different paper membranes loaded with microparticles of MIL-100(Fe) and MIL-127(Fe) of Examples 10 and 11. [Diagram 34] FIG. 13 shows thermogravimetric analysis (in air, heating rate 5° C. / min) of different paper films of Example 11. [Diagram 35] FIG. 13 shows stress-strain curves obtained by tensile testing of different paper films in Example 12. [Diagram 36] FIG. 13 shows stress-strain curves obtained by tensile testing of different paper films in Example 13. [Figure 37] FIG. 13 shows stress-strain curves obtained by tensile testing of different paper films in Example 14. [Figure 38] FIG. 15 shows stress-strain curves obtained by tensile testing of different paper films of Example 15. [Figure 39]FIG. 13 shows force versus bending angle curves obtained by two-point bending tests of different membranes of Example 16. [Diagram 40] FIG. 13 shows the change in degree of polymerization of cellulose after different aging times for microparticles with or without paper membrane of Example 17. [Diagram 41] FIG. 2 shows an X-ray diffraction pattern of MIL-160(Al) particles of Example 25. [Diagram 42] FIG. 2 shows carbon dioxide (CO2) adsorption isotherm at 298 K obtained after activation of the MIL-160(Al) monolith of Example 26. [Diagram 43] FIG. 13 shows the X-ray diffraction pattern of the MIL-53(Al) solid of Example 27. [Diagram 44] FIG. 14 shows carbon dioxide (CO2) adsorption isotherm at 298 K obtained after activation of the MIL-53(Al) monolith of Example 28. [Diagram 45] FIG. 1 shows a setup for measuring VOCs. [Figure 46] FIG. 13 is a SEM (scanning electron microscope) image of the paper film having MIL-100(Fe) fine particles of Example 18. [Figure 47] FIG. 23 is a SEM image of the paper membrane having activated carbon fine particles of Example 23. [Figure 48] FIG. 23 is a SEM image of the paper membrane having activated carbon fine particles of Example 23. [Figure 49] FIG. 2 shows an SEM image of the paper membrane having zeolite microparticles of Example 24. [Figure 50] FIG. 2 shows an SEM image of the paper membrane having zeolite microparticles of Example 24.

[0048] Experimental section Analytical and experimental protocols

[0049] The crystal structure of porous solids was analyzed using a copper beam source (CuKα λ CuPowder X-ray diffraction (XRD) was performed at room temperature in air using a D8 Bruker® Advance diffractometer equipped with a 100% NMR (ΔΨ = 1.5406 Å). The resulting diffractograms are expressed in angular distances (2 theta, degrees).

[0050] Characterization of the average size of the pores of the solids was performed by dinitrogen N2 adsorption porosimetry at 77 K using a TriStar® II instrument. Samples were activated under primary vacuum overnight at temperatures between 150 and 200 °C using a Micromeritics® degasser. Dinitrogen adsorption isotherms of the solids were plotted as the amount of gas adsorbed (cm) as a function of the relative pressure P / P0. 3 .g -1 )

[0051] Thermogravimetric analysis was carried out in air using a Model Mettler Toledo™ TGA / DSC2, STAR system instrument. Samples (approximately 10 mg each) were heated at a rate of 5° C. / min. The resulting thermograms represent the mass loss Pm (in %) as a function of temperature T (in ° C.).

[0052] Observation of the surface topography of the samples was performed by scanning electron microscopy using an ESEM Quattro™ (ThermoFischer Scientific™).

[0053] The length of the cellulose microfibrils (or microfibrillated cellulose) was checked by optical microscopy (Zeiss® AX10, ×100 magnification), taking care to have an aqueous interface between the glass plate and the lamella to avoid agglomeration of the fibers. The cellulose microfibrils used are commercialized by Weidmann® and have a median length D50 between 8 and 10 μm, measured according to standard ISO 13322-2:2006-11.

[0054] The size distribution of nanoparticles and microparticles is given and measured according to the method described in references and [2]. Nanoparticles and microparticles are observed by SEM and particle size measurement is performed with ImageJ™ software.

[0055] In the context of the present invention, percentages by weight expressed in % w / w define the percentage by weight of the component used in the preparation and considered relative to the total weight of the object considered (mixture, material (such as a composite material), membrane, etc.). EXAMPLES

[0056] Part 1: Synthesis and results - Porous solids used in paper membranes

[0057] This section describes the synthesis of various metal carboxylates that are of interest in the practice of this invention.

[0058] MIL-100(Fe) or Fe3O[C6H3-(CO2)3]2.OH.nH2O

[0059] Iron carboxylate MIL-100(Fe) was synthesized to produce particles with two different particle size distributions: nanoparticles smaller than 100 nm (average size 84 nm ± 13 according to ref.

[16] ) and microparticles of 1-3 microns. The size distribution of the microparticles was calculated from five SEM images of a paper membrane containing 75% w / w MIL-100(Fe) microparticles. Approximately 70 particles (average size: 1.4 μm ± 0.4) were sized using Imagej software.

[0060] Example 1: Synthesis of MIL-100(Fe) microparticles

[0061] 3.68 g (66 mmol, Riedel de Haen®, 99%) of powdered metallic iron and 9.24 g (44 mmol, 1,3,5-benzenetricarboxylic acid or trimesic acid, 99% 1,3,5-BTC, Alfa Aesar®) are added to a 500 mL round-bottom flask, followed by 366 mL of distilled water. The round-bottom flask is stirred at room temperature and 500 rpm. Nitric acid (65%, Carlo Ferba Reagents™) is added (V=2.7 mL). The round-bottom flask is left under stirring for 1 week. The solid is collected by filtration and placed back into the reaction round-bottom flask, 400 mL of distilled water is added and left under stirring (500 rpm) for 1 h 30 min to remove the trimesic acid in the pores. The solid was filtered, resuspended in 400 mL of absolute ethanol (Carlo Ferba Reagents™) and washed a final time at 40° C. for 30 min to remove any remaining nitrate counterions (NO - ) and traces of trimesic acid are removed. The solid is recovered by hot filtration. Finally, the latter is dried at room temperature.

[0062] result

[0063] The results are summarized in Figures 1 to 3. Figure 1 shows the simulated MIL-100(Fe) solid (lower curve (a)), experimental powder (middle curve (b)) and paper membrane morphology (upper curve (c)) (particle size distribution).

number

[0064] Example 2: Synthesis of MIL-100(Fe) nanoparticles

[0065] The synthesis conditions are given in reference

[16] . 281.2 mg of trimesic acid (1.34 mmol, Alfa Aesar®, 98%) are dispersed in 100 mL of distilled water under stirring (300 rpm) and 810 mg of Fe(NO3)3.9H2O (3.35 mmol, Sigma-Aldrich®, 98%) are added. The whole is left under stirring for 48 hours. To avoid irreversible aggregation of the nanoparticles, the solution is left alone and washing is carried out after the formation of a paper film or the solid is washed with 100 mL of distilled water and then with 100 mL of absolute ethanol at 40 °C (Carlo Ferba Reagents®). The solid is then dried under vacuum at room temperature.

[0066] result

[0067] The results are summarized in Figures 5 to 7. Figure 5 shows the nanoparticle size distribution of the simulated MIL-100(Fe) solid (lower curve (a)) and the experimental one (upper curve (b)).

number

[0068] MIL-127(Fe) or FeO[C 12 N2H6(CO2)4] 3 / 2 .3H2O

[0069] Example 3: Synthesis of MIL-127(Fe) particles

[0070] The synthesis protocol was derived from that reported in the literature [4]. First, 6.4 g of sodium hydroxide (160 mmol, NaOH from Alfa Aesar®) was mixed with 40 mL of distilled water under stirring until it was completely dissolved, thus preparing a sodium hydroxide solution upstream. At the same time, a solution containing 27.13 g of ferric chloride hexahydrate (100 mmol, FeCl3·6H2O from Alfa Aesar®) and 80 mL of 2-propanol (IPA, from Carlo Ferba Reagents™) was stirred (300 rpm) at 50 °C until the ferric salt was completely dissolved. In the second step, 16.16 g of 3,3',5,5'-azobenzenetetracarboxylic acid ligand (H4TazBz, synthesis of the ligand described in part 2) is ground in a mortar and then dispersed in 100 mL of IPA in a 500 mL round-bottom flask with stirring at 50 °C until a homogenous solution is obtained. Once this step is completed, sodium hydroxide solution is added to the round-bottom flask, followed by the ferric salt solution. The round-bottom flask is placed under reflux (120 °C) and stirring (700 rpm) for 24 hours. The yellow solid is filtered and then washed twice with absolute ethanol (Carlo Ferba Reagents™) for 1 hour at room temperature. Finally, a final wash is performed with boiling water for 30 minutes to remove some of the solvent (IPA and ethanol) inside the pores. The solid is then dried under vacuum at room temperature.

[0071] result

[0072] The results are summarized in Figures 8 to 10. Figure 8 shows the simulated MIL-127(Fe) solid (lower curve (a)), experimental powder (middle curve (b)) and paper membrane morphology (upper curve (c)) (particle size distribution).

number

[0073] Al-PDA or Al(OH)(C5H2N2O4)(H2O)

[0074] The size distribution of nanoparticles was calculated from five SEM images of paper membrane containing 75% w / w Al-PDA. Approximately 70 particles (average size: 234.9 nm ± 60) were sized using Imagej™ software.

[0075] Example 4: Synthesis of Al-PDA particles

[0076] The synthesis conditions are given in reference

[17] . 1.045 g of monohydrated 3,5-pyrazole carboxylic acid (6 mmol, 3,5-PDA from Alfa Aesar®, 98%) and 0.468 g of monohydrated aluminum hydroxide (6 mmol, Al(OH)3·H2O from Sigma®) are added to 60 mL of distilled water under stirring (300 rpm), then the solution is refluxed (100 °C) for 18 h. The white solid is collected by filtration, then redispersed in 60 mL of distilled water and washed at 100 °C for 5 h. Finally, after filtration, the latter is dried at 100 °C for 2 h.

[0077] result

[0078] The results are summarized in Figures 11 to 14c. Figure 11 shows the nanoparticle size distribution for the simulated Al-PDA solid (bottom curve (a)), the experimental one for the powder (middle curve (b)).

number

[0079] UiO-66(Zr)-2CF3 or Zr6O4(OH)4(C6H22CF3C2O4)6

[0080] Example 5: Synthesis of UiO-66(Zr)-2CF3 particles

[0081] The synthesis is adapted from the synthesis of non-functionalized UiO-66 reported in the literature

[18] . 536 mg of zirconium(IV) chloride (2.3 mmol, Zr(Cl)4, Acros Organics®, 98%) and 11.2 g of benzoic acid (91.7 mmol, CH5COOH, Alfa Aesar®, 99%) were placed in a 1 L laboratory bottle, followed by the addition of 264 mL of N,N-dimethylformamide (DMF, Carlo Ferba Reagents®). The bottle was placed in an ultrasonic bath for a few minutes, then after the reagents were completely dissolved, 695 mg of 2,5-bistrifluoromethyl-1,4-benzenedicarboxylic acid (2.3 mmol H2BDC-2CF3, Angene®) were added. The mixture was stirred (300 rpm) for a few minutes until a homogeneous solution was obtained (several minutes). The bottle is closed with a cap and placed in an oven at 120° C. for 48 hours. The white solid is isolated by centrifugation (10,000 rpm for 10 minutes), washed with 150 mL of acetone, then centrifuged and dispersed in 100 mL of absolute ethanol (Carlo Ferba Reagents™). The solution is stirred at 70° C. for 24 hours to remove all traces of unreacted ligand and modulator (benzoic acid) present in the reaction medium.

[0082] Results of the zirconium carboxylate solid UiO-66(Zr)-2CF3

[0083] The results are summarized in Figures 15 to 17. Figure 15 shows the simulated UiO-66(Zr)-2CF3 solid (lower curve (a)), the experimental powder (middle curve (b)), and the particle size distribution.

number

[0084] MIL-53(Al)-CF3 or Al(OH)(C6H3CF3C2O4)

[0085] Example 6: Synthesis of MIL-53-CF3 particles

[0086] The synthesis protocol of this solid is taken from reference

[19] . 11.584 g of aluminum chloride hexahydrate (48 mmol, Al(Cl)3·6H2O, 98% Alfa Aesar), 7.5 g of 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid (32 mmol, 2-BDC-CF3, Angene™) and 2.56 g of sodium hydroxide (64 mmol, NaOH, 98% Alfa Aesar) were dispersed in 400 mL of water and the mixture was left under reflux for 16 h. The solid was isolated by centrifugation (10 min, 12,000 rpm) and the latter was dispersed in 400 mL of absolute ethanol (Carlo Ferba Reagents) and washed overnight at 70 °C. The white solid was again isolated by centrifugation (same conditions) and then dried in an oven at 90 °C for 3 h.

[0087] result

[0088] These results are summarized in Figures 18 to 20. Figure 18 shows the simulated MIL-53(Al)-CF3 solid (curve (a) at the bottom for two different pore sizes), the experimental one in powder form (curve (b) at the top), and the nanoparticle size distribution.

number

[0089] NaY type zeolite or Na2O·Al2O3·5,1SiO2

[0090] Example 7: Zeolite was commercially available and ordered from Alfa Aesar® (CAS: 1318-02-1).

[0091] result

[0092] The results are summarized in Figures 21 to 23. FIG. 21 shows the results of a simulated NaY zeolite (lower curve (a)), an experiment in powder form (middle curve (b)), and the particle size distribution (λ Cu ≈1.5406 Å), with the vertical axis being arbitrary relative intensity (arbitrary units) and the horizontal axis being 2-theta (degrees). Figure 22 shows the thermogravimetric analysis (in air, heating rate of 5°C / min) of NaY zeolite particles after washing and drying in powder form ((a) black). Mass loss Pm (unit: %) is expressed as a function of temperature T (unit: °C, horizontal axis), and vertical axis = remaining mass (unit: %). FIG. 23 shows the dinitrogen adsorption / desorption isotherms at 77 K obtained after overnight activation of powdered NaY zeolite particles (circled curve points) at 150° C., with the vertical axis representing N volume (cm 3 .g -1 ), and the horizontal axis is the relative pressure (black dots correspond to adsorption, white dots correspond to desorption; (nanoparticle size distribution) (P0 = 1 atm.)). The specific surface area (BET) of the obtained NaY zeolite powder was 845 m 2 .g -1 ±0.5 and the pore volume is 0.327 cm 3 .g -1 It is.

[0093] activated carbon

[0094] The size distribution of the particles was calculated from five SEM images of the activated carbon powder. Approximately 70 particles (average size: 23.5 μm ± 16.9) were sized using Imagej™ software.

[0095] Example 8: Activated carbon was commercially available and ordered from Fischer Scientific™ (CAS: 7440-44-0).

[0096] result

[0097] The results are summarized in Figures 24 to 27. Figure 24 shows the distribution of activated carbon particles (lower curve (a), (particle size distribution)

number

[0098] Part 2: Formulation of paper membranes using cellulose matrices and metal-organic framework-type porous solids: Influence of the cellulose matrix on the final properties

[0099] In this section, the modulation of the cellulose matrix is ​​demonstrated by comparing two types of paper fibers (cotton and softwood) with and without microfibrillated cellulose in the paper membrane.

[0100] Paper membrane with MIL-100(Fe) nanoparticles (NPs)

[0101] Example 9: Formulation of paper membranes in the presence of cellulose fibers (cotton or softwood) with or without different proportions of microfibrillated cellulose

[0102] 100 mg of cotton fibers (from a Whatman® crucible) are placed in a blade mill with 10 mL of distilled water, then the fibers are ground for 2 minutes. The fiber solution is then added to a solution containing 300 mg of synthetic MIL-100(Fe) nanoparticles to ensure their optimal dispersion within the composite. Finally, the equivalent of 100 mg of microfibrillated cellulose (MFC) (present at a mass concentration of 10% w / w, so the weight mass of added MFC is 1,000 mg, Weidmann® Celova®) is placed in the aqueous MOF solution. The mixture is left for 30 minutes and then filtered on a nylon film covering a filter paper. The resulting composite contains 60% w / w of MIL-100(Fe), 20% w / w of softwood fibers and 20% w / w of MFC. It is designated 60MIL100-NP-20R-20MFC.

[0103] Different paper films have been made with and without MFC (comparative example without MFC), by replacing cotton fibres with softwood fibres (Canson® HWBK™, Kraft Blanket™), and by increasing the proportion of MOFs up to 75% w / w.

[0104] Table 1 (Preparation of cotton fiber / MIL-100(Fe) particulate mixtures for making paper membranes) summarizes the compositions of these composites. [Table 1]

[0105] Results – Paper membrane formulated with MIL-100(Fe) nanoparticles

[0106] The results are summarized in Figures 28 to 30. FIG. 28 shows X-ray diffraction patterns of paper films containing nanoparticles of MIL-100(Fe): 60MIL100-40R (curve a), 60MIL100-20R-20MFC (curve b), 60MIL100-40C (curve c), 60MIL100-20C-20MFC (curve d), and 75MIL100-12.5R-12.5MFC (curve e).

number

[0107] Paper membrane with MIL-100(Fe) fine particles

[0108] Example 10: Formulation of paper membranes in the presence of cellulose fibers (softwood pulp) with and without microfibrillated cellulose

[0109] 62.5 mg of softwood pulp (HWBK™) is placed in a blade mill with 30 mL of distilled water, then the fibers are ground for 2 minutes. 30 mL more of distilled water is added to this suspension. The resulting solution of fibers is passed through an ultrasonic probe for 5 minutes to separate the fiber clusters cleanly (it is also possible to work with a larger amount of water to avoid this step). 62.5 mg equivalent of microfibrillated cellulose (MFC) (present at a mass concentration of 10% w / w, so the weight mass of added MFC is 625 mg, Celova® from Weidmann®) is placed in the aqueous fiber solution and the mixture is stirred for 15 minutes. At the same time, 375 mg equivalent of MIL-100(Fe) microparticles (depending on the amount of solvent contained in the pores) are dispersed in 10 mL of distilled water in an ultrasonic bath for 10 minutes. The suspension is added to the fiber solution and left under stirring for 15 minutes (300 rpm). The mixture is filtered on a nylon film covering a filter paper. The resulting paper membrane, 7 cm in diameter, contains 75% w / w MIL-100(Fe), 12.5% ​​w / w softwood fibers and 12.5% ​​MFC, and is designated 75MIL100-12.5R-12.5MFC.

[0110] Paper membranes were prepared with and without MFC (comparative example without MFC) while keeping the percentage of MIL-100(Fe) in the composite constant (75% w / w).

[0111] Table 2 (Preparation of softwood fiber / MFC / MIL-100 particulate mixtures to make paper membranes) summarizes the compositions of these membranes. [Table 2]

[0112] Results – Paper membrane formulated with MIL-100(Fe) microparticles

[0113] The results are summarized in Figures 31 to 33. FIG. 31 shows X-ray diffraction patterns of a paper film containing fine particles of MIL-100(Fe):75MIL100-25R (curve a) and 75MIL100-12.5R-12.5MFC (curve b), and fine particles of MIL-127(Fe):75MIL127-25R (curve c) and 75MIL127-12.5R-12.5MFC (curve d).

number

[0114] Paper membrane with MIL-127(Fe) fine particles

[0115] Example 11: 62.5 mg of softwood pulp (HWBK™) is placed in a blade mill with 30 mL of distilled water, then the fibers are ground for 2 minutes. 30 mL more of distilled water is added to this suspension. The resulting solution of fibers is passed through an ultrasonic probe for 5 minutes to separate the fiber clusters cleanly (it is also possible to work with a larger amount of water to avoid this step). The equivalent of 62.5 mg of microfibrillated cellulose (MFC) (present at a mass concentration of 10% w / w, so the weight mass of added MFC is 625 mg, Celova® from Weidmann®) is placed in the aqueous fiber solution and the mixture is stirred for 15 minutes. At the same time, the equivalent of 375 mg of MIL-127(Fe) microparticles (depending on the amount of solvent contained in the pores) is dispersed in 10 mL of distilled water in an ultrasonic bath for 10 minutes. The suspension is added to the fiber solution and left under stirring for 15 minutes (300 rpm). The mixture is filtered on a nylon film covering a filter paper. The resulting paper membrane, 7 cm in diameter, contains 75% w / w MIL-127(Fe), 12.5% ​​w / w softwood fibers and 12.5% ​​MFC, and is designated 75MIL127-12.5R-12.5MFC.

[0116] Paper membranes were prepared with and without MFC (comparative example without MFC) while keeping the percentage of MIL-127(Fe) in the composite constant (75% w / w).

[0117] Table 3 (Preparation of softwood fiber / MFC / MIL-100 particulate mixtures for the manufacture of paper membranes) summarizes the composition of the composites. [Table 3]

[0118] Results – Paper membrane formulated with MIL-127(Fe) microparticles

[0119] The results are summarized in FIG. 31 and FIG. 33 to FIG. FIG. 31 shows X-ray diffraction patterns of a paper film containing fine particles of MIL-100(Fe):75MIL100-25R (curve a) and 75MIL100-12.5R-12.5MFC (curve b), and fine particles of MIL-127(Fe):75MIL127-25R (curve c) and 75MIL127-12.5R-12.5MFC (curve d).

number

[0120] Part 3: Mechanical properties of paper membranes made from MOF-type porous solids

[0121] Effect of cellulose matrix modification on the mechanical properties of paper membranes. Characterization of these mechanical properties was performed by tensile strength measurements using an Adamel Lhomargy® (DY20-N™, 100 dN force sensor) universal testing machine. Each specimen had a length of 10 cm and a width of 1.5 cm. The tensile zone was positioned over a length (jaw distance) of 5 cm, the extension rate was set at 50 mm / min, and the break detection at 3%. The samples were preconditioned at 25° C. and 50% relative humidity for at least 24 hours, and the tests were also performed under the same conditions. The measurements were repeated five times for each sample.

[0122] Paper membrane with MIL-100(Fe) fine particles

[0123] Example 12: Formulation of paper films containing different ratios of cotton fibers and microfibrillated cellulose

[0124] 1.03 g of cotton fibers (from a Whatman® thimble) were dispersed in 1 L of distilled water using a blade mill, then redispersed in 4 L of distilled water and left under stirring. 11.46 g of microfibrillated cellulose (MFC) (Celova® commercialized by Weidmann®) at a concentration of 3% w / w in water were added to the mixture. Then, 4.125 g of MIL-100 microparticles (synthesis described in part 1, mass adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and placed in an ultrasonic bath for 15 minutes to properly disperse the aggregates. The resulting solution was added to the mixture of fibers and left under stirring for 15 minutes. The solution was then filtered through 1 micron canvas (Buisine®) using a Rapid Kothen™ former equipment (Frank®). The resulting paper membrane with a diameter of 20 cm is then vacuum dried for 30 minutes at 85° C. using a dryer attached to the former machine. The resulting composite material contains 75% w / w MIL-100(Fe) microparticles, 6.25% w / w cotton fiber, and 18.75% w / w MFC, and is designated as MIL100-75C-25MFC.

[0125] Different paper membranes have been prepared by varying the cotton fiber / MFC ratio.

[0126] Table 4 (Preparation of cotton fiber / MIL-100 microparticle mixtures for the manufacture of paper membranes and characterization of their mechanical properties) summarizes the composition of the composites. [Table 4]

[0127] Results - Paper membrane formulated with MIL-100(Fe) microparticles and cotton fibers

[0128] The results are shown in FIG.

[0129] FIG. 35 shows stress-strain curves obtained by tensile tests of paper membranes (a) MIL100-75C-25MFC, (b) MIL100-50C-50MFC, and (c) MIL100-25C-75MFC (vertical axis: stress (Mpa), horizontal axis: elongation (%)).

[0130] Table 5 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (vertical axis, Mpa), maximum force before break and deformation at break (vertical axis, %) for the different paper membranes MIL100-75C-25MFC, MIL100-50C-50MFC and MIL100-25C-75MFC. [Table 5]

[0131] Table 5 summarizes the mechanical data of different paper membranes using MIL-100(Fe) microparticles and cotton fibers.

[0132] Example 13: Formulation of paper films with different ratios of softwood fibers and microfibrillated cellulose

[0133] The process for preparing the paper film was the same as that described above, except that softwood pulp (HWBK™, Kraft Blanket™, from Canson®) was used instead of cotton fibers as the source of cellulose fibers.

[0134] Different paper membranes have been prepared by varying the softwood fiber / MFC ratio.

[0135] Table 6 (Preparation of fiber / MIL-100 mixtures to make paper membranes) summarizes the composition of the composites. [Table 6]

[0136] Results - Paper membranes formulated with MIL-100(Fe) particulates and softwood fibers

[0137] The results are shown in FIG.

[0138] FIG. 36 shows stress-strain curves obtained by tensile tests of paper membranes (a) MIL100-75R-25MFC, (b) MIL100-50R-50MFC, and (c) MIL100-25R-75MFC (vertical axis: stress (Mpa), horizontal axis: elongation (%)).

[0139] Table 7 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (vertical axis, Mpa), maximum force before break and deformation at break (vertical axis, %) for the different paper membranes MIL100-75R-25MFC, MIL100-50R-50MFC and MIL100-25R-75MFC. [Table 7]

[0140] Table 7 summarizes the mechanical data of different paper membranes using MIL-100(Fe) particulate and softwood fibers.

[0141] Paper membrane with MIL-127(Fe) fine particles

[0142] Example 14: Formulation of paper membranes in the presence of cotton fibers and microfibrillated cellulose at different ratios

[0143] 687 mg of softwood fibers (HWBK™, Kraft Blanket from Canson®) were dispersed in 1 L of distilled water using a blade mill, then redispersed in 4 L of distilled water and left under stirring. 22.92 g of microfibrillated cellulose (MFC) (Celova® commercialized by Weidmann®) at a concentration of 3% w / w in water were added to the mixture. Then, 4.125 g of MIL-127 microparticles (synthesis described in Example 3, mass adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and placed in an ultrasonic bath for 15 minutes to properly disperse the aggregates. The resulting solution was added to the mixture of fibers and left under stirring for 15 minutes. The solution was then filtered through 1 micron canvas (Buisine) using a Rapid Kothen™ former equipment (Frank™). The resulting paper membrane with a diameter of 20 cm is then vacuum dried for 30 minutes at 85° C. using a dryer attached to the former machine. The resulting composite material contains 75% w / w MIL-127(Fe) particulate, 12.5% ​​w / w softwood fiber, and 12.5% ​​w / w MFC, and is designated as MIL127-50R-50MFC.

[0144] Different paper membranes have been made by varying the softwood fiber / MFC ratio (comparative example without MFC). The table below summarizes the composition of these composites.

[0145] Table 8 (Preparation of softwood fiber / MIL-127 particulate mixtures for making paper membranes) summarizes the composition of the composite materials. [Table 8]

[0146] Results - Mechanical properties - Paper membranes formulated with MIL-127(Fe) particulates and softwood fibres

[0147] The results obtained are shown in FIG.

[0148] FIG. 37 shows stress-strain curves obtained by tensile tests of paper membranes (a) MIL127-100R, (b) MIL127-75R-25MFC, and (c) MIL127-50R-50MFC (vertical axis: stress (Mpa), horizontal axis: elongation (%)).

[0149] Table 9 summarizes the mechanical data estimated from the stress-strain curves corresponding to Young's modulus (vertical axis, Mpa), maximum force before break and deformation at break (vertical axis, %) for different paper membranes MIL127-100R, MIL127-75R-25MFC and MIL127-50R-50MFC. [Table 9]

[0150] Table 9 summarizes the mechanical data of different paper membranes using MIL-127(Fe) particulate and softwood fibers.

[0151] Paper membrane with MIL-100(Fe) nanoparticles

[0152] Example 15: Formulation of paper membranes with different proportions of nano MIL-100(Fe) with softwood:MFC ratio = 25:75

[0153] 0.218 g of softwood fibers (HWBK™, Kraft Blanket from Canson®) were dispersed in 1 L of distilled water using a blade mill, then redispersed in 4 L of distilled water and stirred. 21.9 g of microfibrillated cellulose (MFC) (Celova® commercialized by Weidmann®) at a concentration of 3% w / w in water were added to the mixture. Then, 2.622 g of MIL-100(Fe) nanoparticles (synthesis described in part 1, mass adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and placed in an ultrasonic bath for 15 minutes to properly disperse the aggregates. The resulting solution was added to the mixture of fibers and left under stirring for 15 minutes. The solution was then filtered through 1 micron canvas (Buisine®) using a Rapid Kothen™ former equipment (Frank®). The resulting paper membrane with a diameter of 20 cm is then vacuum dried for 30 minutes at 85° C. using a dryer attached to the former machine. The resulting composite material contains 75% w / w MIL-100(Fe) nanoparticles, 6.25% w / w softwood fibers, and 18.75% w / w MFC, and is designated as 75MIL100.

[0154] Different paper membranes were prepared with varying weight percentage of MIL-100(Fe).

[0155] Table 10 (Preparation of fiber / MIL-100 nanoparticle mixtures for making paper membranes and characterization of their mechanical properties) summarizes the composition of the composites while keeping the total mass of the composites constant (3.496 g). [Table 10]

[0156] Results - Paper membrane formulated with MIL-100(Fe) nanoparticles and softwood fibers

[0157] The results obtained are shown in FIG.

[0158] FIG. 38 shows stress-strain curves obtained by tensile tests of paper membranes (a) 60MIL100, (b) 75MIL100, and (c) 90MIL100 (vertical axis: stress (Mpa), horizontal axis: elongation (%)).

[0159] Table 11 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (vertical axis, Mpa), maximum force before break and deformation at break (vertical axis, %) for different paper membranes 60MIL100, 75MIL100 and 90MIL100. [Table 11] Table 11 summarizes the mechanical data of different paper membranes using MIL-100(Fe) nanoparticles, MFC and softwood fibers.

[0160] Part 4: Determining the optimal long fiber cellulose:MFC ratio

[0161] The influence of the adjustment of the cellulose matrix on the mechanical properties of the paper membrane, especially its flexibility, has been tested. The characterization of these mechanical properties was carried out by two-point bending resistance measurements using a Buchel Van Der Korput bending machine. The length of each sample was 5 cm and the width was 3.8 cm. The samples were preconditioned for at least 24 hours at 25 °C and 50% relative humidity and tested in these same conditions. The measurements were repeated three times for each sample. The calculation of the bending stiffness was carried out according to the standard ISO5628:2019.

[0162] Paper membrane with MIL-100(Fe) fine particles

[0163] Example 16: Formulation of paper films with different ratios of softwood fibers and microfibrillated cellulose

[0164] The steps for preparing the paper membrane, the porous solids used and the selected fibers are identical to those described in Example 13.

[0165] Different paper membranes were prepared with different softwood fiber / MFC ratios (comparative example without MFC-MIL100-100R).

[0166] Table 12 (Preparation of softwood fibre / MIL-100(Fe) particulate mixtures for making paper membranes and characterisation of their flexibility) summarises the composition of the composites. [Table 12]

[0167] Results - Paper membranes formulated with MIL-100(Fe) particulates and softwood fibers

[0168] The results obtained are shown in FIG.

[0169] FIG. 39 shows force versus bending angle curves obtained by two-point bending tests of paper membranes (a) MIL100-100R (bottom), (b) MIL100-75R-25MFC, (c) MIL100-50R-50MFC, (d) MIL100-25R-75MFC, (e) MIL100-10R-90MFC, and (f) MIL100-100MFC (top) (vertical axis: force (mN), horizontal axis: bending angle (°)).

[0170] Table 13 summarizes the mechanical data inferred from the force vs. bending angle curves corresponding to the maximum force before plastic deformation (vertical axis, N), bending stiffness at break or non-break (N.mm) for different paper membranes MIL100-100R, MIL100-75R-25MFC, MIL100-50R-50MFC, MIL100-25R-75MFC, MIL100-10R-90MFC, MIL100-100MFC. [Table 13]

[0171] Table 13 summarizes the mechanical flexibility data of different paper membranes with MIL-100(Fe) particulate and softwood fibers.

[0172] Part 5: Examining the effect of MIL-100(Fe) paper membrane on cellulose by accelerated aging

[0173] The objective of this part is to determine whether a paper membrane containing 75% w / w of MIL-100(Fe) (MIL100-50R-50MFC) has any effect on cellulose. In fact, this composite may emit volatile organic compounds (VOCs) that can alter cellulose. These tests are in accordance with the standard ISO 16245 given in ref.

[20] .

[0174] Example 17: Aging test

[0175] Unit volume 140cm 3 Five flasks made of borosilicate glass of 100 mm diameter and sealed with Silicone / Teflon® caps and septa were conditioned for at least 48 hours at 50% relative humidity and 25°C. Each of these tubes contains 250 mg of a block of cellulose paper without Whatman® 1 filler (control paper) and a humidity button that allows the control of temperature and relative humidity over time. After pretreatment (50% RH, 25°C), these samples are cut into strips and placed in a pill organizer to be evaluated for degradation after aging. Two control flasks are set up with 4.2 g of Whatman® 1 paper cut into the shape of pretreated test specimens. The control flasks are then ready to be closed. Additionally, 766 mg of paper membrane containing 75% w / w MIL-100(Fe) microparticles are cut into test specimens to prepare three pretreated flasks. The flasks are then sealed. The five flasks are placed in an oven at 80 °C for five days. After incubation, the degree of polymerization of the Whatman® 1 paper strips contained in the pill organizer is evaluated by viscosity measurements (taken from the international standard IEC 60450

[21] ) using a flow viscometer (Cannon-Fenske™ brand, Model Routine 100, Normalab Analis™).

[0176] The test was repeated with an incubation time of 3 weeks (21 days) at 80°C.

[0177] Results – Paper membrane formulated with MIL-100(Fe) microparticles

[0178] See Figure 38: Figure 38 shows the change in the degree of polymerization of cellulose (vertical axis: degree of polymerization) after various aging times (horizontal axis: aging time (days)) with or without a paper membrane, where the curve with square dots corresponds to the Whatman control and the curve with round dots corresponds to the Whatman aged in the presence of a paper membrane.

[0179] Part 6: Preparation of paper membranes from porous solids for VOC capture testing

[0180] The same characterization techniques (XRD, FTIR, ATG, and N2 adsorption / desorption at 77 K) used and described in part 1 (see also analytical section and experimental protocol) were also used for the characterization of the paper membranes formulated with the powders described in part 1.

[0181] Furthermore, the surface topography of the sample was observed using a scanning electron microscope, ESEM Quattro™ (manufactured by ThermoFischer Scientific™).

[0182] Paper membrane with MIL-100(Fe) fine particles

[0183] Example 18: Paper membrane formulation

[0184] 62.5 mg of softwood pulp (HWBK™, bleached Kraft™ pulp from Canson®) are placed in a blade mill with 30 mL of distilled water and the fibers are milled for 2 minutes. Another 30 mL are added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 minutes to neatly separate the fiber clusters (it is possible to work with a larger amount of water to avoid this step). An equivalent of 62.5 mg of microfibrillated cellulose (MFC) (present at a mass concentration of 10% w / w, so the weight mass of MFC added is 625 mg, Celova® from Weidmann®) is introduced into the aqueous fiber solution and the mixture is left under stirring for 15 minutes. At the same time, an equivalent of 375 mg of MIL-100(Fe) microparticles (depending on the amount of solvent contained in the pores) are dispersed in 10 mL of distilled water in an ultrasonic bath for 10 minutes. The suspension is added to the fiber solution and left under stirring for 15 minutes (300 rpm). The mixture is filtered onto a nylon film covering a filter paper. The resulting paper membrane, 7 cm in diameter, contains 75% w / w MIL-100(Fe), 12.5% ​​w / w softwood fiber, and 12.5% ​​w / w MFC. (After VOC capture, the paper membrane can be regenerated by soaking in distilled water for 3 days, with the water being changed 3 times a day.)

[0185] Results – Paper membrane formulated with MIL-100(Fe) microparticles

[0186] Figures 1 to 4d summarize the results obtained. Figure 1 shows the paper film morphology (upper curve (c)), (fine particle size distribution)

number

[0187] Paper membrane with MIL-127(Fe) fine particles

[0188] Example 19: Paper membrane formulation

[0189] The formulation of the paper membrane was the same as previously described for the MIL-100(Fe) microparticles, by dispersing 375 mg of dry MIL-127(Fe) in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w MIL-127(Fe), 12.5% ​​w / w softwood fibre and 12.5% ​​w / w MFC.

[0190] Results – Paper membrane formulated with MIL-127(Fe) microparticles

[0191] 8 to 10 summarize the results obtained. Figure 8 shows the paper film morphology (upper curve (c)), (fine particle size distribution)

number

[0192] Paper membrane with Al-PDA nanoparticles

[0193] Example 20: Paper membrane formulation

[0194] The formulation of the paper membrane was the same as that described above for the MIL-100(Fe) microparticles, by dispersing 375 mg of dry Al-PDA in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w Al-PDA, 12.5% ​​w / w softwood fiber and 12.5% ​​MFC.

[0195] Results – Paper membrane formulated with Al-PDA nanoparticles

[0196] 11 to 14c summarize the results obtained. Figure 11 shows the Al-PDA nanoparticles in the form of a paper film (upper curve (c)), (nanoparticle size distribution)

number

[0197] Paper membrane with UiO-66(Zr)-2CF3 particles

[0198] Example 21: Paper membrane formulation

[0199] The formulation of the paper membrane was the same as that described previously for the MIL-100(Fe) microparticles, by dispersing 375 mg of dry UiO-66(Zr)-2CF3 in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w UiO-66(Zr)-2CF3, 12.5% ​​w / w softwood fibers, and 12.5% ​​w / w MFC.

[0200] Results: Paper membrane containing UiO-66(Zr)-2CF3 microparticles

[0201] 15 to 17 summarize the results obtained. FIG. 15 shows the UiO-66(Zr)-2CF3 microparticles in the form of a paper film (upper curve (c)), (microparticle size distribution)

number

[0202] Paper membrane with MIL-53(Al)CF3 nanoparticles

[0203] Example 22: Paper membrane formulation

[0204] The formulation of the paper membrane was the same as that described above for the MIL-100(Fe) microparticles, by dissolving 375 mg of dry MIL53-CF3 in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w MIL-53-CF3; 12.5% ​​w / w softwood fiber and 12.5% ​​MFC.

[0205] Results – Paper membrane formulated with MIL-53(Al)-CF3 nanoparticles

[0206] 18 to 20 summarize the results obtained. FIG. 18 shows the MIL-53(Al)-CF3 nanoparticles in the form of a paper film (upper curve (d)), (nanoparticle size distribution)

number

[0207] Paper membrane with activated carbon particles

[0208] Example 23: Paper membrane formulation

[0209] The formulation of the paper membrane was the same as that described above for the MIL-100(Fe) microparticles, by dispersing 375 mg of dry activated carbon in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w activated carbon, 12.5% ​​w / w softwood fiber and 12.5% ​​MFC.

[0210] Results - Paper membrane containing activated carbon particles

[0211] 24 to 27 summarize the results obtained. FIG. 24 shows the activated carbon particles in the form of a paper film in Example 8 (upper curve (b)), (particle size distribution)

number

[0212] Paper membrane with zeolite particles

[0213] Example 24: Paper membrane formulation

[0214] The formulation of the paper membrane was the same as that described above for the MIL-100(Fe) microparticles, by dispersing 375 mg of dry zeolite in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting paper membrane, 7 cm in diameter, contains 75% w / w zeolite, 12.5% ​​w / w softwood fiber and 12.5% ​​MFC.

[0215] Results – Paper membrane formulated with zeolite microparticles

[0216] 21 to 23 summarize the results obtained. FIG. 21 shows the NaY zeolite in the form of a paper membrane (upper curve (c)), (fine particle size distribution)

number

[0217] MIL-160(Al) or Al(OH)[C4H2O-(CO2)2]

[0218] Example 25: Synthesis of MIL-160(Al) particles

[0219] 4.8 g of 2,5-furandicarboxylic acid (30 mmol, C6H4O5, Sikemia®) and 4.6 g of aluminum acetate (30 mmol, Al(OH)(C2H3O2)2, Alfa Aesar®) were placed in a 100 ml round-bottom flask and dispersed in 30 mL of distilled water. The stirred mixture was heated at 120° C. for 24 h. The resulting white precipitate was isolated by centrifugation and then washed with ethanol.

[0220] result

[0221] The results are summarized in Figures 41 and 42. Figure 41 shows the simulated MIL-160(Al) solid (bottom curve (a)) and the experimental powder (middle curve (b)). (Nanoparticle size distribution)

number

[0222] Monolith with MIL-160(Al)

[0223] Example 26: Monolith Formulation

[0224] 187.5 mg of softwood pulp (HWBK™, bleached Kraft™ pulp from Canson®) are added to a leaf mill with 20 mL of distilled water, then the fibers are milled for 2 min. A further 20 mL is added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 min to neatly separate the fiber clusters. An equivalent of 187.5 mg of microfibrillated cellulose (MFC) (present at a mass concentration of 3% w / w, so the weight mass of added MFC is 6.25 g, Celova® from Weidmann®) is added to the aqueous fiber solution and the mixture is stirred for 15 min. At the same time, an equivalent of 1.5 g of MIL-160(Fe) nanoparticles (depending on the amount of solvent contained in the pores) are dispersed in 30 mL of distilled water in an ultrasonic bath for 10 min. The suspension is added to the fiber solution and stirred for 30 min (300 rpm). The mixture is filtered on a filter paper. The resulting paper membrane, 3 cm in diameter and approximately 0.8 cm thick, contains 80% w / w MIL-160(Al), 10% w / w resin fibers and 10% w / w MFC.

[0225] result

[0226] The results are summarized in Figures 41 and 42. Figure 41 shows the simulated MIL-160(Al) solid (upper curve (c),

number

[0227] MIL-53(Al) or Al(OH)(C6H3C2O4) Example 27: Synthesis of MIL-53(Al) particles

[0228] 13.3 g of hexadecahydrated aluminum sulfate (20 mmol, AAl2(SO4)3.16H2O, sold by Alfa Aesar®), 3.3 g of 1,4-benzenedicarboxylic acid (20 mmol, 1,4-BDC, C8H6O4, Tokyo Chemical Industry®) and 1.2 g of urea (20 mmol, CO(NH2)2, Alfa Aesar®) were placed in a 100 mL round-bottom flask and dispersed in 40 mL of distilled water. The mixture under stirring was heated at 120 °C for 24 h. The resulting precipitate was isolated by filtration and then washed with water. The solid was dried overnight at room temperature before calcination. The powder was calcined at 330 °C for 33 h.

[0229] result

[0230] The results are summarized in Figures 43 and 44. Figure 43 shows the simulated solid MIL-53(Al) according to different pore sizes (lower curve (a)) and experimentally in powder form (middle curve (b)), (fine particle size distribution).

number

[0231] Monolith with MIL-53(Al)

[0232] Example 28: Monolith Formulation

[0233] The monolith formulation process is the same as previously described for MIL-160(Al) nanoparticles, by dispersing 1.5 g of MIL-53(Al) in an aqueous solution (taking into account the amount of solvent contained in the pores of the solid). The resulting monolith, 3 cm in diameter and about 0.8 cm thick, contains 80% w / w MIL-53(Al), 10% w / w resin fibers and 10% w / w MFC.

[0234] result

[0235] The results are summarized in Figures 43 and 44. Figure 43 shows the simulated MIL-53(Al) solid (upper curve (c), (λ Cu ≈1.5406 Å), with the vertical axis being arbitrary relative intensity (arbitrary units) and the horizontal axis being 2-theta (degrees). FIG. 44 shows the carbon dioxide (CO2) adsorption isotherm at 298 K obtained after overnight activation at 200 °C for the MIL-53(Al) monolith (curve points represented by squares), with the vertical axis representing the amount of CO2 adsorbed (mmol.g -1 ), the horizontal axis is pressure (black dots correspond to adsorption; (fine particle size distribution) (P max =14bar.)).

[0236] Part 8: VOC capture test by paper membrane

[0237] This section presents the capture efficiency of contaminants present in historical facilities that may adversely affect the collections and personal health.

[0238] To quantify the ability of the paper membrane to adsorb these vapors, a configuration that allows for the capture of organic pollutants is performed. This configuration, shown in Figure 45, is a 0.5 dm 3 It consists of a chamber 1 with a volume of 10 ... injected = 1 μL).

[0239] Measurements can be carried out with or without adsorbents so that the adsorption capacity of each material can be experimentally estimated. The measurements are divided into three steps. a) Turn on the PID detector 8 and circulate filtered air through the chamber 1 until it detects no compounds. Then close the three inlets 4, 7, 11 of the chamber 1. b) A volume of 1 μL of the VOC is injected into chamber 1 and left for 30 minutes for homogenization. c) Measure the amount of VOCs using a PID detector 8. This amount is measured by the detector at 0.5 L.min -1 The vessel is purged at a rate of 0 ppm during the measurement.

[0240] Steps a-c are carried out in the presence of an adsorbent, with 50 mg of one of the composites prepared in part 5 being pre-loaded into the chamber. The surface covered by the VOC concentration curve as a function of time during purging reflects the amount of pollutant present in the vessel. By calculating the ratio of the surface with and without the adsorbent composite, the effective adsorption rate can be estimated.

[0241] Formic acid trapping

[0242] The VOC analyzed here was formic acid, and a paper membrane (part 6) formulated with MIL-100(Fe) particulates, activated carbon and zeolite was tested.

[0243] Results - Capture Test

[0244] The results obtained are shown in Table 14.

[0245] Table 14 summarizes the results obtained, corresponding to (a) the purge time required to reach 0 ppm, (b) the maximum formic acid concentration detected by the PID, and (c) the equivalent amount of formic acid (μL) detected by the PID in the presence or absence of adsorbent for a 1 μL injection, as well as an estimate of the adsorption capacity. [Table 14]

[0246] Table 14 summarizes the data specific to the adsorption measurements performed in the presence or absence of the different composites (zeolitic activated carbon and MIL-100(Fe)), their averages, and the average formic acid adsorption percentage for each composite.

[0247] Acetic acid capture

[0248] The VOC analysed here was acetic acid, and cellulose paper and paper membranes formulated from MIL-100(Fe), MIL-127(Fe), activated carbon and zeolite particulates (see Part 6) were tested.

[0249] Results - Capture Test

[0250] The results obtained are shown in Table 15.

[0251] Table 15 summarizes the results obtained, corresponding to (a) the purge time required to reach 0 ppm, (b) the maximum acetic acid concentration detected by the PID, and (c) the equivalent amount of acetic acid (μL) detected by the PID in the presence or absence of sorbent for a 1 μL injection, as well as an estimate of the adsorption capacity. [Table 15]

[0252] Table 15 summarizes the data specific to the adsorption measurements performed in the presence or absence of cellulose paper or the different composites (zeolitic activated carbon, MIL-100(Fe) and MIL-127(Fe)) and their averages, as well as the average acetic acid adsorption percentage for each composite.

[0253] Acrylic acid capture

[0254] The VOC analysed here was acrylic acid, and cellulose paper and a paper membrane formulated from MIL-100(Fe), activated carbon and zeolite particulates (see Part 6) were tested.

[0255] Results - Capture Test

[0256] The results obtained are shown in Table 16.

[0257] Table 16 summarizes the results obtained for (a) the purge time required to reach 0 ppm, (b) the maximum acrylic acid concentration detected by the PID, and (c) the equivalent amount of acrylic acid (μL) detected by the PID in the presence or absence of sorbent for a 1 μL injection, as well as an estimation of the adsorption capacity. [Table 16]

[0258] Table 16 summarizes the data specific to the adsorption measurements performed in the presence or absence of cellulose paper or different composites (zeolitic activated carbon, MIL-100(Fe)) and their averages, as well as the average acrylic acid adsorption percentage for each composite.

[0259] Trapping furfural

[0260] The VOC analysed here was furfural, and papers containing cellulose and Al-PDA nanoparticles, as well as paper membranes formulated with MIL-100(Fe), activated carbon and zeolite particles (see Part 6) were tested.

[0261] Results - Capture Test

[0262] The results obtained are shown in Table 17.

[0263] Table 17 summarizes the results obtained for (a) the purge time required to reach 0 ppm, (b) the maximum furfural concentration detected by the PID, and (c) the equivalent amount of furfural (μL) detected by the PID in the presence or absence of adsorbent for a 1 μL injection, as well as an estimation of the adsorption capacity. [Table 17]

[0264] Table 17 summarizes the data specific to the adsorption measurements performed in the presence or absence of cellulose paper or different composites (zeolitic activated carbon, Al-PDA and MIL-100(Fe)) and their averages, as well as the average furfural adsorption percentage for each composite.

[0265] The conditions of the VOC capture test were slightly modified by increasing the contact time between the VOCs and the composite from 30 min to 1 h 30 min and dividing the mass of the composite introduced into the chamber by 10 (now 5 mg). The injection volume was kept constant (V = 1 μL).

[0266] Acetic acid capture

[0267] The VOC analysed here is acetic acid, and a paper membrane formulated with MIL-100(Fe) particulates and activated carbon (see Part 6) is being tested.

[0268] Results - Capture Test

[0269] The results obtained are shown in Table 18.

[0270] Table 18 summarizes the results obtained, corresponding to (a) the purge time required to reach 0 ppm, (b) the maximum acetic acid concentration detected by the PID, and (c) the equivalent amount of acetic acid (μL) detected by the PID in the presence of the sorbent for a 1 μL injection, as well as an estimate of the adsorption capacity. [Table 18]

[0271] Table 18 summarizes the data specific to the adsorption measurements performed in the presence of the different composites (zeolitic activated carbon, MIL-100(Fe) and MIL-127(Fe)) and their averages, as well as the average acetic acid adsorption percentage for each composite.

[0272] Acrylic acid capture

[0273] The VOC analysed here is acrylic acid, and a paper membrane (see Part 6) formulated with MIL-100(Fe) fine particles and activated carbon has been tested.

[0274] Results - Capture Test

[0275] The results obtained are shown in Table 19.

[0276] Table 19 summarizes the results obtained for (a) the purge time required to reach 0 ppm, (b) the maximum acrylic acid concentration detected by the PID, and (c) the equivalent amount of acrylic acid (μL) detected by the PID in the presence of the sorbent for a 1 μL injection, as well as an estimation of the adsorption capacity. [Table 19]

[0277] Table 19 summarizes the data specific to the adsorption measurements performed in the presence of different composite materials (zeolitic activated carbon, MIL-100(Fe)) and their averages, as well as the average acrylic acid adsorption percentage for each composite material.

[0278] Trapping furfural

[0279] The VOC analysed here was furfural, and papers containing cellulose and paper membranes formulated with Al-PDA nanoparticles, as well as activated carbon and MIL-100(Fe) particulates (see Part 6) were tested.

[0280] Results - Capture Test

[0281] The results obtained are shown in Table 20.

[0282] Table 20 summarizes the results obtained for (a) the purge time required to reach 0 ppm, (b) the maximum furfural concentration detected by the PID, and (c) the equivalent amount of furfural (μL) detected by the PID in the presence of adsorbent for a 1 μL injection, as well as an estimation of the adsorption capacity. [Table 20]

[0283] Table 20 summarizes the data specific to the adsorption measurements performed in the presence of different composites (activated carbon, Al-PDA and MIL-100(Fe)) and their averages, as well as the average furfural adsorption percentage for each composite.

[0284] Part 9: Emission test of paper membrane after VOC capture

[0285] The purpose of this part is to test the release of pollutants (pollutants tested in part 8) after capture by different paper membranes.

[0286] VOC emissions

[0287] To quantify the amount of pollutants released by the composite after the capture test, the paper membrane was placed in a sealed flask (500 cm 3 ) and left for 24 hours in the presence of a passive diffusion tube (GASTEC).

[0288] Results - Emission Test

[0289] Tables 21 to 24 summarize the data obtained.

[0290] Table 21 relates to the formic acid concentration detected in the flask, showing the potential released by the paper membrane after capture. [Table 21]

[0291] Table 21 summarizes the formic acid concentrations measured after 24 hours in flasks in the presence of paper membranes formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0292] Table 22 relates to the acetic acid concentration measured in the flask showing the potential released by the paper membrane after capture. [Table 22]

[0293] Table 22 summarizes the acetic acid concentrations measured after 24 hours in flasks in the presence of paper membranes formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0294] Table 23 relates to the acrylic acid concentration measured in the flask showing the potential released by the paper membrane after capture. [Table 23]

[0295] Table 23 summarizes the acrylic acid concentrations measured after 24 hours in flasks in the presence of paper membranes formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0296] Table 24 relates to the furfural concentration measured in the flask showing the potential released by the paper membrane after capture. [Table 24]

[0297] Table 24 summarizes the furfural concentrations measured after 24 hours in flasks in the presence of paper membranes formulated from activated carbon, Al-PDA or MIL-100(Fe).

[0298] References The table below lists the references previously cited in the text. [Table 25]

Claims

1. 1. A method for preparing a porous membrane, comprising: a- Preparing an aqueous mixture comprising a dispersion of fibers derived from organic material in water, a nanoscale structuring agent comprising cellulose microfibrils, and porous solid particles suspended in water; b- allowing the resulting aqueous mixture comprising the fibers, the nanoscale structuring agent comprising cellulose microfibrils, and the porous solid particles to stand at room temperature with stirring for at least 10 minutes; c- vacuum filtering the mixture to recover the composite material; and d - pressing the composite material obtained in step c to form a porous membrane, wherein the porous solid particles are selected from at least one of the following particles: zeolite particles, activated carbon particles and structured metal organic compounds, so-called MOFs, wherein the MOFs comprise multidentate chelating ligands and are incorporated in a content of at least 55% relative to the total mass of the obtained porous membrane.

2. 2. The method of claim 1, wherein the fibers are biological fibers, preferably cellulose fibers.

3. 3. The method according to claim 1, wherein the length of the cellulose microfibrils is between 0.5 and 50 μm.

4. 3. A porous membrane for capturing volatile organic compounds, so-called VOCs, obtained by the method according to claim 1 or 2, 50 to 85% porous solid particles; 15-50% cellulose matrix; 1. A porous membrane, wherein said percentages are weight percents of the weight of said components taken into account relative to the total weight of said porous membrane, and wherein said porous solid particles are selected from at least one of the following particles: zeolite particles, activated carbon particles, and structured metal organic compounds, so-called MOFs, said MOFs comprising multidentate chelating ligands.

5. 5. The porous membrane according to claim 4, wherein the porous solid particles are MOF particles incorporated in an amount of 55 to 80% based on the total mass of the porous membrane.

6. 5. The porous membrane of claim 4, wherein the MOF particles comprise at least one metal selected from Cu, Zn, Ca, Ln, Y, Mg, Ti, Zr, V, Cr, Mn, Fe and Al, preferably the metal is a metal ion selected from at least one metal ion of Fe, Al and Zr.

7. The polydentate chelating ligand comprises at least one carboxylic acid functional group. ６ ~C ２４ 5. The porous membrane of claim 4, comprising an aromatic compound, preferably wherein the multidentate chelating ligand is selected from at least one of the following ligands: benzene-1,3,5-tricarboxylic acid, 3,3',5,5'-azobenzenetetracarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2,5-bistrifluoromethyl-1,4-benzenedicarboxylic acid, 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid, 1,2,4-triazole, 2-methylimidazole, N,N'-piperazine(methylenephosphonic) acid, L-aspartic acid, 2,5-dihydroxydeterephthalic acid, and 3,4-dihydroxy-3-cyclobutene-1,2-dione.

8. 5. The porous membrane of claim 4, wherein the porous solid particles comprise at least one element selected from nanoparticles and microparticles having a diameter of 50 nm to 80 μm.

9. The MOFs are MIL-100(Fe), MIL-127(Fe), Ca-squarate, Al-PDA, MIP-202(Zr), MIL-91(Ti), UiO-66(Zr)-2CF ３ , MIL-53(Al)-CF ３ 5. The porous membrane of claim 4, wherein the porous membrane is selected from the group consisting of SiO2, CALF-20, and ZIF-8.

10. The porous membrane of claim 4, wherein the thickness of the membrane is 150 to 500 μm.

11. 5. Use of the porous membrane of claim 4 for purifying ambient air or for purifying a storage space containing objects sensitive to VOCs.

12. CO in ambient air or industrial environments ２ 5. Use of the porous membrane according to claim 4 for capturing carbon monoxide, for separating gases, for storing gases (hydrogen, methane), for proton conduction in sustainable energy systems, for treating air by water adsorption for dehumidification, fresh water production, air conditioning or heating, or for purifying engine exhaust gases containing NOx.

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