Membrane having a high porous solid content

Abstract

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

Description

[0001] Description

[0002] Title of the invention:

[0003] High solid porous membrane

[0004] [1]The present invention relates to the field of porous materials for trapping volatile organic compounds, also known as VOCs, or toxic gases such as nitrogen oxides (NOx) such as NO or NO2; and more particularly relates to a process for preparing such a material and a membrane comprising such a material.

[0005] State of the art

[0006] [2]It is important to be able to control the air quality in heritage institutions and in residential or transit areas to ensure hygiene and safety for property and people. More specifically, the control of the content of certain compounds present in the ambient air must be controlled, and many methods aim to capture volatile or gaseous polluting compounds such as volatile organic compounds (VOCs), as described in the application in reference [1], NOx, or other gases which can be harmful in a certain concentration in the ambient air, such as CO2.

[0007] [3]Furthermore, the materials mainly used for air quality control in confined environments are activated carbons and zeolites. These materials are not very selective for the adsorption of these pollutants and / or are poorly regenerable, and more particularly in the context of the adsorption of VOCs, in the presence of water for zeolites. There is therefore a real problem of efficiency of VOC adsorption in the presence of ambient humidity.

[0008] [4]VOC adsorption is known from beads or granules, sometimes included in foams, monoliths or textiles. In the case of the use of foams or textiles, the filling rates in porous solids are low, and are not compatible with all uses, or lead to problems of adsorption efficiency, caused by the diffusion of adsorbed materials for example.

[0009] [5]In the context of the invention, the term “filling rate” defines the percentage of occupied pores relative to the total number of pores available.

[0010] [6]It is known to use supports such as membranes or sheets for the adsorbent material, or to integrate the adsorbent material into such a support, in order to be able to use them, for example, as filters. Methods for manufacturing paper membranes with adsorbents already exist, however if the content of solid particles integrated into the membrane is too high, the mechanical stability of the cellulose matrix deteriorates. A product designed according to one of these manufacturing methods is commercially available under the reference "MicroChamber paper™", it is intended for the conservation of cultural property or for the preservation of archival documents.Such a product is limited to a load of about 20% zeolite, the rest being cellulose fibers and common additives for paper, its lack of efficiency being linked to the too low content of adsorbent (Zeolite) and its lack of specificity for the molecules actually adsorbed remains a disadvantage.

[0011] Description of the invention

[0012] [7]The present invention aims to overcome the aforementioned drawbacks, by implementing a process for preparing a material integrating at least one type of fiber with adsorbent particles, which process must make it possible to integrate these adsorbents in significant contents in a paper membrane, beyond 50% by mass of the final mass of the paper, while retaining good mechanical stability and VOC capture properties identical to those of the pure adsorbent.

[0013] [8]For this purpose, the present invention relates to a method for preparing a porous membrane comprising the following steps: 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- leaving the obtained aqueous mixture comprising the fibers, the organic binder and the porous solid particles stirring for at least 10 minutes at room temperature; c- vacuum filtering the mixture and recovering a composite material; and d- pressing said composite material obtained in step c- to form a porous membrane.

[0014] [9]Preferably, step a) of the process for preparing a porous membrane comprises the following sub-steps:

[0015] (i) - dispersing the fibers from an organic material in water;

[0016] (ii) - add the solid organic binder; and

[0017] (iii) - add the porous solid particles suspended in water.

[0018]

[0010] Preferably, and alternatively to the above, step a) of the process for preparing a porous membrane comprises the following sub-steps:

[0019] (i) - prepare a suspension of porous solid particles in water;

[0020] (ii) - adding a dispersion of fibers derived from organic matter in water; and

[0021] (iii) - add the solid organic binder.

[0022]

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

[0023]

[0012] The term "nanoscale structuring agent" used in the context of the invention is used in an equivalent manner to the expression "nanoscale and / or microscale structuring agent" and qualifies the structuring of an object at the nanoscale and / or microscale. This nanoscale structuring agent makes it possible to increase the contact points (by weak interactions) within the composite (inter-binder interactions as well as with the particles of porous solids and / or the long fibers) and thus have a final composite with more cohesion (less powderiness) and more rigid compared to a composite comprising only long cellulose fibers.

[0024]

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

[0025]

[0014] The term "nanocellulose" covers different categories of cellulosic nanomaterials defined in 2011 in [2] by Klemm et al: microfibrillated cellulose (MFC), nanocrystalline cellulose (NCC) and bacterial nanocellulose (BNC). The main difference lies in their method of preparation, which consequently results in distinct dimensions of these nanomaterials. BNC is obtained using aerobic bacteria, therefore from a biotechnological process, whereas MFC and NCC result from the destructuring of natural plant fibers. This microfibrillation is possible by hydrolysis in an acid medium and / or mechanical treatment (generally a homogenizer).The Technical Association of the Pulp and Paper Industry (TAPPI) has standardized the classification of cellulosic nanomaterials according to their size: reference [3], Thus, microcrystalline cellulose (width: 10-15um, L / D ratio <2) and microfibrillated cellulose or cellulose microfibril (MFC, length: 0.5-50 μm and width: 10-100 nm) have a nanostructuring function, while cellulose nanocrystals (width: 3-10nm, L / D>5) and cellulose nanofibrils (width: 5-30nm, L / D>50) are more in the domain of nano-objects.

[0015] In the context of the present invention, the “porous solid particles”, or “porogenic agents”, are agents which confer the properties of adsorption of volatile or gaseous polluting compounds.The inventors have unexpectedly shown that such a process makes it possible to combine several types of fibers, and preferably at least two types of cellulose fibers, and to obtain membranes comprising levels of porous solid particles in a membrane in certain cases beyond 70% by mass of the final mass of the membrane, while retaining good mechanical stability and a capacity to capture VOCs equal to those of the starting porous solid particles, taken separately.

[0026]

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

[0027]

[0017] The term “composite material” within the meaning of the invention qualifies a material comprising at least two immiscible components.

[0028]

[0018] Preferably, the composite material obtained in the penultimate step is directly shaped while it is being vacuum-drawn, for example by applying a vacuum to a support with a water pump, or even with a vacuum pump.

[0029]

[0019] Advantageously, the fibers are bio-sourced fibers.

[0030] The term “biosourced” in the context of the invention defines elements derived from renewable organic matter (biomass), of plant or animal origin.

[0031]

[0020] Preferably, the fibers are selected from paper fibers of natural origin and plant fibers such as wood fibers, softwood fibers, coconut fibers, flax fibers, bamboo fibers, and cotton fibers, and more preferably the plant fibers comprise cellulose fibers. Advantageously, the fibers used in the method according to the invention are cellulose fibers, also referred to as cellulosic fibers. A mechanical treatment, preferably grinding, and / or an ultrasonic treatment, is advantageously carried out to improve the dispersion of said fibers. Preferably, the fibers used in the method according to the invention are taken in a content less than or equal to 30% relative to the total mass of the porous membrane obtained, and preferably less than or equal to 20%, advantageously less than or equal to 10%, or even less than 5%.

[0032]

[0021] Advantageously, the porous solid particles preferably comprise pores whose average size is from 0.3 to 3 nm, and are selected from at least one of the following particles: a zeolite particle, an activated carbon particle, and a particle of structured metal-organic compound, referred to as MOF (Metal Organic Framework), which MOF comprises polydentate chelating ligands. The porous solid particles are advantageously suspended in an aqueous solution comprising distilled water to form an aqueous suspension which is added to the initial mixture comprising the fibers and the solid organic binder.

[0033]

[0022] In the context of the present invention, the term "porous solid" qualifies a solid comprising porosity, which porosity is itself defined according to the IUPAC definition (see reference [4]), which defines a porous solid as a solid having pores (cavities, interstices, channels) whose depth will be greater than the width. These pores will be accessible to a fluid or a gas, that is to say pores having continuous communication with the exterior of the solid.

[0034]

[0023] In the context of the present invention, the term "MOF" defines hybrid porous materials, also referred to as "metalorganic framework", as compounds constructed from bridging organic ligands, also referred to as "linkers" or "spacers", which remain intact throughout the synthesis, these ligands acting as connectors in the network of the resulting three-dimensional MOF structure. As used herein, the term "ligand" or "linker" or "spacer" refers to a ligand coordinated to at least two metal sites, and also referred to as a "polydentate chelating ligand", which participates in providing the distance between these metal atoms and in forming empty spaces or pores.

[0035]

[0024] MOFs are solid adsorbents that can be easily regenerated by known pressure swing adsorption or temperature swing adsorption techniques. Examples of MOFs are described in application EP3453450 (reference [1]).

[0036]

[0025] By "three-dimensional structure" is meant a three-dimensional sequence or repetition of units and / or patterns, or even sub-variants, in the conventional sense of the term in the field of MOF materials, which are also characterized as "organometallic polymers".

[0037]

[0026] In the context of the present invention, the expression "average pore size", which will also be referred to as "pore size", refers to the size (or pore diameter) of the pores of the porous solid particles, for example MOF particles, as conventionally used in the art, calculated by the nitrogen adsorption method. It is intended to encompass the different possible pore geometries of the MOF material (for example, tetrahedron, octahedron). Methods for measuring pore size are well documented in the literature: see reference [5]. For example, the MOF pore size can be determined by calculating the nitrogen adsorption pore size distribution. The maximum and limiting pore size can also be estimated from crystallographic data by simulating the filling of the pores with gas molecules (reference [6]) which allows the calculation of average pore sizes.In the context of the present invention, the BET specific surface area as well as the pore volume were determined by the N2 adsorption method, on the basis of the N2 adsorption-desorption isotherms at -196°C (77K), and in particular with a TriStar® II device.

[0038]

[0027] In the context of the present invention, the term "nanoparticle" designates a particle whose size is less than 800 nm. In particular, the MOF adsorbent nanoparticles according to the invention may have a diameter (or size of the largest axis if the particles are of asymmetrical shape) of less than 800 nanometers, preferably less than 400 nm, more preferably less than 200 nm and even less than 100 nm.

[0039]

[0028] In the context of the present invention, the term "microparticle" designates a particle whose size is from 800 nm to several tens of microns.

[0029] Preferably, the porous solid particles are taken in a content greater than or equal to 55% relative to the total mass of the porous membrane obtained, and advantageously the content is greater than 60%, more advantageously greater than 65%, or even greater than 70%.

[0040]

[0030] The present invention also relates to a porous membrane capable of being obtained by the above-mentioned preparation method of the description of the invention.

[0041] [3 l]The present invention relates more particularly to a porous material, and preferably a porous membrane, preferably obtained according to the method previously described in the context of the present invention for the capture of volatile organic compounds qualified as VOCs, comprising:

[0042] 50 - 85% of a porous solid particle;

[0043] 15-50% of a cellulose matrix; the percentages being mass percentages of the mass of the ingredient considered relative to the total mass of the porous membrane; the porous solid particle being selected from at least one of the following particles: a zeolite particle, an activated carbon particle, and a particle of structured metallo-organic compound, called MOF, which MOF comprises polydentate chelating ligands.

[0044]

[0032] Preferably, the content of porous solid particles is from 55 to 80%, and advantageously said content is from 58 to 77%.

[0045]

[0033] In the context of the present invention, the term "cellulose matrix" defines a matrix comprising at least two sources of cellulose, preferably nanocellulose and cellulose fibers, and more preferably cellulose microfibrils (CMF) combined with cellulose fibers. Advantageously, the porous solid particles cover the cellulose fibers, or are intercalated between the cellulose fibers, and the nanocellulose is intercalated between the porous solid particles so as to create privileged interactions with these particles. Such a structure of the matrix can be observed by scanning electron microscopy (SEM).

[0046]

[0034] Preferably, the porous membrane according to the invention comprises a cellulosic matrix containing from 0 to 30% of MFC and from 5 to 45% of cellulose fibers, the contents being expressed as a mass percentage relative to the total mass of the porous membrane. Preferably, said MFC content is from 5 to 25%, and more preferably it is from 8 to 22%. Preferably, the cellulose fiber content is from 8 to 42%, and more preferably it is from 11.5 to 40.5%.

[0047]

[0035] More preferably, the MFC content is greater than 15%, and even greater than 17%. The inventors were able to observe unexpectedly that an increase in the quantity of MFC in the cellulose fiber / MFC ratio results in an increase in the rigidity of the composite, as well as an increase in the retention of particles within the composite.

[0048]

[0036] Preferably, the cellulose fibers are cotton and softwood fibers taken in a content greater than 15%, and even greater than 17%. The inventors were able to observe unexpectedly that a relatively higher cellulose fiber content, and in particular when it comes to the longest cellulose fibers as is the case with softwood and cotton cellulose fibers, made it possible to guarantee flexibility of the material and to prevent it from becoming brittle.

[0049]

[0037] Preferably, the MOF particle comprises 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 of Fe, Al or Zr, and advantageously it is a metal ion selected from Fe metal ions.

[0050]

[0038] Preferably, the polydentate chelating ligand is selected from at least one type of ligand chosen from a bidendate ligand, a tridentate ligand and a tetradentate ligand, and advantageously comprises C6-C24 aromatic compounds comprising at least one function selected from a carboxylic acid, phosphonic acid, amine, alcohol, ketone and azole function;preferably the polydentate chelating ligand is selected from at least one of the ligands: benzene-1,3,5-tricarboxylic acid (C6Fh(CO2H)3, CAS: 554-95-0), 3,3',5,5'-azobenzenetetracarboxylic acid (C16H10N2O8, CAS: 365549-33-3), 3,5-pyrazoledicarboxylic acid (C5H4N2O4, CAS: 303180-11-2), 2,5-bistrifluoromethyl-1-1,4-benzenedicarboxylic acid (C1OFLFÔCL, CAS: 366008-67-5), 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid (C9H5F3O4, CAS: 366008-67-5), 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid (C9H5F3O4, CAS: 366008-67-5), : 1483-47-2), 1,2,4-triazole (C2H3N3, CAS: 288-88-0), 2-methylimidazole (C4H6N2, CAS: 693-98-1), N,N'-piperazine(methylenephosphonic acid) (C6H16N2O6P2, CAS: 89280-71-7), L-aspartic acid (C4H7NO4, CAS: 56-84-8), 2,5-dihydroxydeterephthalic acid (C8H6O4, CAS: 610-92-4) and 3,4-dihydroxy-3-cyclobutene-l,2-dione (C4O4H2, CAS: 2892-51-5).;

[0051]

[0039] Preferably, the porous solid particle comprises nanoparticles and / or microparticles of 50 nm to 80 11 m in diameter. Good mechanical properties (very satisfactory mechanical strength, easy to handle and highly flexible) have been observed for membranes formulated from MIL-100(Fe) nanoparticles (size less than 100 nm) as well as MOFs of size of approximately 200 nm (Al-PDA, MIL-53-CF3). MOFs with particle sizes from 800 nm (MIL-127(Fe) and UiO-66-2CF3(Zr)) down to 3 μm (MIL-100(Fe)) as well as polydisperse activated carbon microparticles with sizes from 5 to 80 μm and NaY zeolite particles with sizes of 700 nm, also offer ideal mechanical properties. The particle size is determined by a method consisting of observing the particles by scanning electron microscopy (SEM) and measuring the particle size (a sampling of 60 and 70 particles) using Image J™ software.

[0052]

[0040] Preferably, the MOF is selected from MIL-100(Fe), MIL-127(Fe), Ca-Squarate (amphiphilic), Al-PDA (also called MOF-303; hydrophilic character), MIP-202(Zr) (with hydrophilic character), MIL-91(Ti) (with hydrophilic character) or from one of the hydrophobic MOFs: UiO-66(Zr)-2CF3, MIL-53(A1)-CF3, CALF-20, ZIF-8.

[0053]

[0041] The thickness of the membrane is advantageously 150-500 µm. When it is in the form of a monolith, the thickness can advantageously reach 1, or even several millimeters. The thickness of the membrane is measured using a Vintage™ mechanical micrometer marketed under the reference MK 0-25mm, with a precision of 0.01mm (K, USSR).

[0042] The present invention also relates to the use of a porous membrane as described previously in the context of the present invention; with a view to carrying out the separation of gases and vapors; to carrying out adsorption; to carrying out catalysis, advantageously for an application linked to the environment and / or energy.

[0054]

[0043] Preferably, the use of the porous membrane according to the invention is implemented with a view to purifying the ambient air or purifying a storage space containing objects sensitive to VOCs. An example of the sensitive objects which must be preserved is described in reference [7],

[0055]

[0044] Preferably, the porous membrane is used to capture CO2 from ambient air or in an industrial environment, separate gases, store gases (hydrogen, methane) or for proton conductivity in sustainable energy systems. Examples of such applications are described in reference [8] to

[0012] ,

[0056]

[0045] Preferably, the use of the porous membrane is implemented to treat air by water adsorption for the purpose of dehumidification, fresh water production, air conditioning or heating, inter-seasonal heat storage, decontamination in the ambient air of engine exhaust gases comprising NOx. Examples of such applications are described in reference

[0013] to

[0015] ,

[0057]

[0046] The present invention is also described in the detailed description which follows, using the experimental part which details certain embodiments using examples, given solely for illustrative purposes and which should not be considered as limiting, and the figures briefly described in the part which follows.

[0058] Brief description of the figures

[0059]

[0047] [Fig. l ] - Figure 1 represents the X-ray diffractograms of the MIL-100(Fe) microparticles of Example 1 and in the form of a paper membrane of Example 16;

[0060]

[0048] [Fig .2 ] - Figure 2 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-100(Fe) microparticles of Example 1 and in the form of a paper membrane of Example 16;

[0049] [Fig g.3] - Figure 3 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the MIL-100(Fe) microparticles of Example 1 and in the form of a paper membrane of Example 16;

[0061]

[0050] [Fig.4a]-[Fig.4b]-[Fig.4c]-[Fig.4d] - Figures 4a and 4b represent the images of the paper membrane containing 75% w / w of MIL-100(Fe) microparticles of Example 16, obtained by scanning electron microscopy at different magnifications: (a) x10 000 and (b) x15 000; and Figures 4c and 4d represent the histograms illustrating the size distribution of the MIL-100(Fe) particles obtained in Example 1 and the size distribution of the microfibrillated cellulose fibers;

[0062]

[0051] [Fig.5] - Figure 5 represents the X-ray diffractograms of the MIL-100(Fe) nanoparticles of example 2;

[0063]

[0052] [Fig .6 ] - Figure 6 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-100(Fe) nanoparticles of example 2;

[0064]

[0053] [Fig.7] - Figure 7 represents the adsorption-desorption isotherm of dinitrogen at 77K obtained after activation of the MIL-100(Fe) nanoparticles of example 2;

[0065]

[0054] [Fi g.8] - Figure 8 represents the X-ray diffractograms of the MIL-127(Fe) microparticles as such from Example 3; and in the form of a paper membrane from Example 17;

[0066]

[0055] [Fi g.9] - Figure 9 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-127(Fe) microparticles of Example 3 and in the form of a paper membrane of Example 18;

[0067]

[0056] [Fig. 10] - Figure 10 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the MIL-127(Fe) microparticles of Example 3 and in the form of a paper membrane of Example 17;

[0068]

[0057] [Fig. 11] - Figure 11 represents the X-ray diffractograms of the Al-PDA nanoparticles as such from Example 4 and in the form of a paper membrane from Example 18;

[0058] [Fig. 12] - Figure 12 represents the thermogravimetric analysis (in air, at a heating rate of 5°C / minute) of the Al-PDA nanoparticles as such from Example 4 and in the form of a paper membrane from Example 18;

[0069]

[0059] [Fig. l 3] - Figure 13 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the Al-PDA nanoparticles as such from Example 4 and in the form of a paper membrane from Example 18;

[0070]

[0060] [Fig. 14a]-[Fig. 14b]-[Fig. 14c]-[Fig. 14d] - Figures 14a, 14b and 14c represent the images of the paper membrane containing 75% by mass, relative to the total mass of the membrane, of Al-PDA nanoparticles of Example 18 and Figure 14d represents the histogram illustrating the size distribution of the Al-PDA particles obtained in Example 4;

[0071]

[0061] [Fig. l 5] - Figure 15 represents the X-ray diffractograms of the UiO-66(Zr)-2CF3 microparticles as such from Example 5 and in the form of a paper membrane from Example 19;

[0072]

[0062] [Fig. 16] - Figure 16 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the microparticles of UiO- 66(Zr)-2CF; as such from Example 5 and in the form of a paper membrane from Example 19;

[0073]

[0063] [Fig. l 7] - Figure 17 represents the adsorption-desorption isotherm of dinitrogen at 77K obtained after activation of the microparticles of UiO- 66(Zr)-2CF; as such from Example 5 and in the form of a paper membrane from Example 17;

[0074]

[0064] [Fig. l 8] - Figure 18 represents the X-ray diffractograms of the MIL-53(A1)-CF3 nanoparticles of Example 6;

[0075]

[0065] [Fig. 19] - Figure 19 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-53(A1)-CF3 nanoparticles as such from Example 6 and in the form of a paper membrane from Example 20;

[0076]

[0066] [Fig.2O] - Figure 20 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the MIL-53(A1)-CF3 nanoparticles as such from Example 6 and in the form of a paper membrane from Example 20;

[0077]

[0067] [Fig.21] - Figure 21 represents the X-ray diffractograms of the NaY zeolite as such from Example 7 and in the form of a paper membrane from Example 22;

[0078]

[0068] [Fig .22] - Figure 22 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the NaY zeolite microparticles as such from Example 7 and in the form of a paper membrane from Example 22;

[0079]

[0069] [Fig.23] - Figure 23 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the NaY microparticles as such from Example 7 in the form of a paper membrane from Example 22;

[0080]

[0070] [Fig.24] - Figure 24 represents the experimental X-ray diffractograms of the activated carbon microparticles as such from Example 8 and in the form of a paper membrane from Example 21;

[0081]

[0071] [Fig.25] - Figure 25 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the activated carbon microparticles as such from Example 8 and in the form of a paper membrane from Example 21;

[0082]

[0072] [Fig.26] - Figure 26 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the activated carbon microparticles of Example 8 and in the form of a paper membrane of Example 21;

[0083]

[0073] [Fig. 27a]-[Fig. 27b]-[Fig. 27c] - Figure 27a represents the image of the activated carbon powder of Example 8, Figure 27b represents the histogram illustrating the size distribution of the activated carbon particles described in Example 8 and Figure 27c represents the image of the paper membrane containing 75% by mass, relative to the total mass of the membrane, of the activated carbon microparticles of Example 21;

[0084]

[0074] [Fig.28] - Figure 28 represents the X-ray diffractograms of the paper membranes formulated with the different MIL-100(Fe) nanoparticles of Example 9;

[0075] [Fig.29] - Figure 29 represents the thermogravimetric analyses (in air, heating rate of 5°C / minute) of the different paper membranes formulated with the MIL-100(Fe) nanoparticles of Example 9;

[0085]

[0076] [Fig.3O] - Figure 30 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the different paper membranes formulated with the MIL-100(Fe) nanoparticles of example 9;

[0086]

[0077] [Fig.31] - Figure 31 represents the X-ray diffractograms of the different paper membranes formulated with the microparticles of MIL-100(Fe) and MIL-127(Fe) of examples 10 and 11;

[0087]

[0078] [Fig.32] - Figure 32 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the different paper membranes formulated with the MIL-100(Fe) microparticles of example 10;

[0088]

[0079] [Fig.33] - Figure 33 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the different paper membranes formulated with the microparticles of MIL-100(Fe) and MIL-127(Fe) of examples 10 and 11;

[0089]

[0080] [Fig .34] - Figure 34 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the different paper membranes of example 11;

[0090]

[0081] [Fig.35] - Figure 35 represents the stress-strain curves obtained by tensile tests of the different paper membranes of example 12;

[0091]

[0082] [Fig .36] - Figure 36 represents the stress-strain curves obtained by tensile tests of the different paper membranes of example 13;

[0092]

[0083] [Fig .37] - Figure 37 represents the stress-strain curves obtained by tensile tests of the different paper membranes of example 14;

[0093]

[0084] [Fig.38] - Figure 38 represents the stress-strain curves obtained by tensile tests of the different paper membranes of Example 15;

[0085] [Fig. 39] - Figure 39 the force vs. bending angle curves obtained by two-point bending tests of the different membranes of Example 16;

[0094]

[0086] [Fig.4O] - Figure 40 represents the evolution of the degree of polymerization of the cellulose after different aging times of the microparticles with or without paper membrane of example 17;

[0095]

[0087] [Fig.41 ] - Figure 41 represents the X-ray diffractograms of the MIL-16O(A1) particles of Example 25;

[0096]

[0088] [Fig.42] - Figure 42 represents the adsorption isotherm of carbon dioxide (CO2) at 298K obtained after activation of the MIL-16O(A1) monolith of Example 26;

[0097]

[0089] [Fig.43] - Figure 43 represents the X-ray diffractograms of the solid MIL-53(A1) of example 27;

[0098]

[0090] [Fig.44] - Figure 44 represents the adsorption isotherm of carbon dioxide (CO2) at 298K obtained after activation of the MIL-53(A1) monolith of Example 28;

[0099]

[0091] [Fig.45] - Figure 45 represents a setup intended for measuring VOCs;

[0100]

[0092] [Fig.46] - SEM (scanning electron microscope) image of paper membranes with the MIL-100(Fe) microparticles of example 18;

[0101]

[0093] [Fig.47]-[Fig.48] - SEM image of paper membranes with the activated carbon microparticles of example 23; and

[0102]

[0094] [Fig.49]-[Fig.5O] - SEM image of paper membranes with zeolite microparticles from example 24.

[0103] Experimental Part

[0104] 195] Analyses and experimental protocols

[0105]

[0096] The analysis of the crystal structure of the porous solids was carried out by powder X-ray diffraction (XRD) using a Bruker® Advance D8 diffractometer equipped with a copper source (CuKa radiation Xcu=1.5406 Å), at room temperature, in air. The diffractograms obtained are represented in angular distances (2 theta, in degrees).

[0106]

[0097] The characterization of the average pore size of the solids was carried out by adsorption porosimetry of dinitrogen N2 at 77K with a TriStar® II apparatus. The samples were activated under primary vacuum using a Micromeritics® degasser overnight at temperatures between 150 and 200°C. The dinitrogen adsorption isotherm of the solids represents the amount of gas adsorbed (in cm 3 . g 1 ) according to the relative pressure P / Po.

[0107]

[0098] Thermogravimetric analysis was carried out in air using a Model Mettler Toledo™ TGA / DSC2, STAR system. The samples (approximately 10 mg of each) were heated at a rate of 5°C / minute. The resulting thermogram represents the mass loss Pm (in %) as a function of temperature T (in °C).

[0108]

[0099] Observation of the surface topography of the samples was carried out by scanning electron microscopy using an ESEM Quattro™ (marketed by ThermoFischer Scientific™).

[0109]

[0100] The length of the cellulose microfibrils (or microfibrillated cellulose) was checked by optical microscopy (Zeiss® AX10, magnification 100) ensuring that there was an aqueous interface between the glass plate and the coverslip to avoid aggregation of the fibers. The cellulose microfibrils used are marketed by Weidmann® and have a median length D50 of between 8 and 10 μm measured according to ISO 13322-2:2006-11.

[0110]

[0101] The size distribution of nanoparticles and microparticles is that given and measured according to the method described in reference and [2]; the nano and microparticles were observed by SEM and the particle size measurements are carried out with the ImageJ™ software.

[0111]

[0102] In the context of the invention, a mass percentage expressed in % m / m, defines the percentage by mass of an ingredient used in the preparation and taken in relation to the total mass of the object considered: a mixture, a material (composite, etc.), a membrane, etc.

[0112] Examples

[0103] Part 1: synthesis and results - porous solids used in paper membranes

[0113]

[0104] This part describes the synthesis of various metal carboxylates of interest for the implementation of the present invention.

[0114]

[0105] MIL-100(Fe) or Fe3O[C 6H 3-- (CO2)3]2.OH.nH2O

[0115]

[0106] The iron carboxylate MIL-100(Fe) was synthesized with two different particle sizes: nanoparticles smaller than 100 nm (average size: 84 nm + / - 13 according to ref.

[0016] ) and microparticles of 1 to 3 microns. The size distribution of the microparticles calculated from 5 SEM images of the paper membranes containing 75% w / w of MIL-100(Fe) microparticles. Size determined with Image j software on approximately 70 particles (average size: 1.4μm + / - 0.4).

[0116] [ 1071Example 1: Synthesis of MIL-100(Fe) microparticles

[0117]

[0108] 3.68 g of powdered metallic iron (66 mmol, marketed by Riedel de Haën®, 99%) and 9.24 g of 1,3,5-benzenetricarboxylic acid or trimesic acid (44 mmol, 1,3,5-BTC marketed by Alfa Aesar®, 99%) are added to a 500 mL flask followed by 366 mL of distilled water. The flask is stirred at 500 rpm at room temperature. Nitric acid (65%, marketed by Carlo Ferba Reagents™) is added (V=2.7 mL). The flask is left stirring for 1 week. The solid is recovered by filtration and then reinserted into the reaction flask with the addition of 400 mL of distilled water under stirring (500 rpm) for 1 hour 30 minutes in order to remove the trimesic acid in the pores. The solid is filtered and resuspended in 400 mL of absolute ethanol (sold by Carlo Ferba Reagents™) for a final wash for 30 minutes at 40°C to remove the remaining nitrate counterions (NO3) and traces of trimesic acid.The solid is recovered by hot filtration. Finally, it is dried at room temperature.

[0118]

[0109] Results

[0119]

[0110] The results are summarized in Figures 1-3: Figure 1 represents the X-ray diffractograms of the simulated MIL-100(Fe) solid (curve (a) at the bottom), experimental powder (middle curve (b)) and paper membrane form (curve (c) at the top) (microparticle particle size) (Xcu~1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 2 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-100(Fe) microparticles after washing and drying in the powder state ((a) in black) and in the paper membrane form ((b) in gray), the mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %);Figure 3 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the solid MIL-100(Fe) in powder (microparticle particle size) (isotherm a, points of the curve represented by black circles) and in the form of a paper membrane (isotherm b, points of the curve represented by black squares) as well as of the regenerated paper membranes after adsorption of acetic acid (isotherm c, points of the curve represented by gray triangles), acrylic acid (called d, points of the curve represented by gray squares) and furfural (called e, points of the curve represented by gray diamonds) (Po=latm.) at 150°C overnight, ordinates: volume N2 (cm; 3 . g -1 ), abscissa: Relative Pressure (the black circles correspond to adsorption, the white circles to desorption; (microparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the MIL-100(Fe) powder is 1835 m 2 .g -1+ / - 4.4 and a pore volume of 0.795 cm 3 . g 1 .

[0120] [111 Example 2: Synthesis of MIL-100(Fe) nanoparticles

[0121]

[0112] The synthesis conditions are given in reference

[0016] , 281.2 mg of trimesic acid (1.34 mmol, marketed by Alfa Aesar®, 98%) were dispersed in 100 mL of distilled water under stirring (300 rpm) then addition of 810 mg of Fe(NO3)s.9H2O (3.35 mmol, marketed by Sigma-Aldrich®, 98%). The whole is left under stirring for 48 hours. Either the solution is kept as is in order to avoid irreversible aggregation of the nanoparticles and the washings are done after formation of the paper membrane, or the solid is washed with a volume of 100 mL of distilled water then 100 mL of absolute ethanol at 40°C (marketed by Carlo Ferba Reagents™). And the solid is dried under vacuum at room temperature under vacuum.

[0122]

[0113] Results

[0123]

[0114] The results are summarized in Figures 5-7: Figure 5 represents the X-ray diffractograms of the simulated (curve (a) at the bottom) and experimental (curve (b) at the top, (nanoparticle particle size) (λcu≈1.5406 A)) solid MIL-100(Fe), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 6 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-100(Fe) nanoparticles after washing and drying. The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 7 represents the adsorption-desorption isotherm of dinitrogen at 77K obtained after activation of MIL-100(Fe) nanoparticles at 150°C overnight, ordinate: volume N2 (cm 3 . g" 1), abscissa: Relative Pressure (the black circles correspond to adsorption, the white circles to desorption; (nanoparticle granulometry) (Po= latin.)). The BET specific surface obtained for the MIL-100(Fe) powder is 1668 m 2 .g"* + / - 4 is a pore volume of 1.2 cm 3 . g 1 .

[0124] [ 1151MIL-127(Fe) or Fe3O[C 12 N2H6(CO2)4]3 / 2.3H2O

[0125] [1161 Example 3: Synthesis of MIL-127(Fe) particles

[0126]

[0117] The synthesis protocol was taken from a protocol reported in the literature [4]. First, a sodium hydroxide solution was prepared upstream by mixing, with stirring, 6.4 g of sodium hydroxide (160 mmol, NaOH marketed by Alfa Aesar®) in 40 mL of distilled water until complete dissolution. At the same time, a solution containing 27.13 g of iron chloride hexahydrate (100 mmol, FeCl3.6H2O marketed by Alfa Aesar®) and 80 mL of 2-propanol (IPA, marketed by Carlo Ferba Reagents™) was stirred (300 rpm) at 50°C until complete dissolution of the ferric salt. In a second step, 16.16g of 3,3',5,5'-azobenzenetetracarboxylic acid ligand (H4TazBz, ligand synthesis presented in part 2) were ground in a mortar and then dispersed in 100mE of IPA in a 500mL flask with stirring at 50°C until a homogeneous solution was obtained.At the end of this step, the sodium hydroxide solution is added to the flask, followed by the ferric salt solution. The flask is placed under reflux (120°C) and stirred (700 rpm) for 24 hours. The yellow solid is filtered and then washed twice with absolute ethanol (sold by Carlo Ferba Reagents™) at room temperature for 1 hour. Finally, a final wash is carried out with boiling water for 30 minutes to remove some of the solvents (IPA and ethanol) inside the pores. The solid is then dried under vacuum at room temperature.

[0127] 1118]Results

[0128]

[0119] The results are summarized in Figures 8-10:

[0129] Figure 8 shows the X-ray diffractograms of the simulated MIL-127(Fe) solid (curve (a) at the bottom), experimental powder (curve (b) middle) and paper membrane (curve (c) at the top) (microparticle particle size) (Xcu~L5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 9 shows the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-127(Fe) microparticles after washing and drying in the powder state ((a) in black) and in the paper membrane form ((b) in gray).The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 10 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the microparticles of MIE-127(Fe) in powder form (points of the curve represented by circles) and in the form of a paper membrane (points of the curve represented by squares) at 150°C overnight, ordinates: volume N2 (cm. 3 . g 1 ), abscissa: Relative Pressure (the black circles correspond to adsorption, the white circles to desorption; (microparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the MIE-127(Fe) powder is 1427 m 2 .g -1 + / - 0.63 is a pore volume of 0.579 cm 3 . g -1 . [ 1201A1-PDA or A1(OH)(C5H2N2O4)(H2O)

[0130]

[0121] The size distribution of nanoparticles calculated from 5 SEM images of paper membranes containing 75% m / m Al-PDA. Size determined with Image J™ software on approximately 70 particles (average size: 234.9 nm + / - 60).

[0131]

[0122] Example 4: Synthesis of Al-PDA particles

[0132]

[0123] The synthesis conditions are given in reference

[0017] , 1.045 g of 3,5-pyrazolecarboxylic acid monohydrate (6 mmol, 3,5-PDA marketed by Alfa Aesar®, 98%) and 0.468 g of aluminum hydroxide monohydrate (6 mmol, A1(OH)3.H2O marketed by Sigma®) were added to 60 mL of distilled water with stirring (300 rpm) and then the solution was refluxed (100°C) for 18 hours. The white solid was recovered by filtration and then redispersed in 60 mL of distilled water and washed for 5 hours at 100°C. Finally, after filtration, the latter was dried at 100°C for 2 hours.

[0133]

[0124] Results

[0134]

[0125] The results are summarized in Figures 1 l-14c:

[0135] Figure 11 represents the X-ray diffractograms of the simulated Al-PDA solid (curve (a) at the bottom), experimental powder (curve (b) middle), (nanoparticle particle size) (Xcu~1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 12 represents the thermogravimetric analysis (in air, at a heating rate of 5°C / minute) of the Al-PDA nanoparticles after washing and drying in the powder state ((a) in black). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 13 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of powdered Al-PDA nanoparticles (points of the curve represented by circles) at 200°C for 5h, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the Al-PDA powder is 1152 m 2 .g -1 + / - 1.2 and a pore volume of 0.527 cm 3 . g -1 .

[0136] [ 1261UiO-66(Zr)-2CF3or Zr6O4(OH)4(C6H22CF3C2O4)6

[0137] [ 1271Example 5: Synthesis of UiO-66(Zr)-2CF3 particles

[0138]

[0128] This synthesis was adapted from a synthesis of non-functionalized UiO-66 reported in the literature

[0018] , 536 mg of zirconium (IV) chloride (2.3 mmol, Zr(Cl)4 marketed by Acros Organics®, 98%) and 11.2 g of benzoic acid (91.7 mmol, C6H5COOH marketed by Alfa Aesar®, 99%) were inserted into a laboratory bottle of IL then 264 mL of N,N-dimethylformamide were added (DMF marketed by Carlo Ferba Reagents™). This bottle is placed for a few minutes in an ultrasonic bath then after complete dissolution of the reagents, 695 mg of 2,5-Bistrifluoromethyl-1,4-benzenedicarboxylic acid (2.3 mmol of H2BDC- 2CF3 marketed by Angène™). The mixture is stirred (300 rpm) for a few minutes until a homogeneous solution is obtained (a few minutes). The bottle is closed with a stopper and placed in the 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 re-centrifuged and dispersed in 100 mL of absolute ethanol (sold by Carlo Ferba Reagents™). The solution is stirred for 24 hours at 70°C to remove all traces of unreacted ligand and modulator (benzoic acid) present in the reaction medium.

[0139]

[0129] Results for the solid zirconium carboxylate UiO-66(Zr)-2CF3

[0130] The results are summarized in Figures 15-17:

[0140] Figure 15 represents the X-ray diffractograms of the simulated solid UiO-66(Zr)-2CF3 (bottom curve (a)), experimental powder (middle curve (b)) (microparticle particle size) (Xcu~ 1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 16 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the microparticles of UiO-66(Zr)-2CF3 after washing and drying in the powder state ((a) in black). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 17 represents the adsorption-desorption isotherm of dinitrogen at 77K obtained after activation of UiO-66(Zr)-2CF3 microparticles in powder form at 150°C overnight, ordinate: volume N2 (cm 3.g“ '), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the UiO-66-2CF3(Zr) powder is 977 m 2 .g -1 + / - 0.4 and a pore volume of 0.41 cm 3 . g -1 .

[0141]

[0131] MIL-53(AD-CF3OU A1(OH)(C6H3CF3C2O4)

[0142]

[0132] Example 6: Synthesis of MIL-53-CF3 particles

[0143]

[0133] The synthesis protocol of this solid is taken from reference

[0019] , 11.584g of aluminum chloride hexahydrate (48 mmol, A1(C1)3.6H2O marketed by Alfa Aesar®, 98%), 7.5g of 2-(trifluoromethyl)-1,4-benzenedicarboxylic acid (32 mmol, 2-BDC-CF3 marketed by Angène™) and 2.56g of sodium hydroxide (64 mmol, NaOH marketed by Alfa Aesar, 98%) were dispersed in 400 mL of water and the mixture was placed under reflux for 16h. The solid was isolated by centrifugation (10 minutes, 12000 rpm) and the latter was dispersed in 400 mL of absolute ethanol (marketed by Carlo Ferba Reagents) for washing overnight at 70°C. The white solid was isolated again by centrifugation (same conditions) and then dried at 90°C for 3 hours in an oven.

[0144]

[0134] Results

[0145]

[0135] These results are summarized in Figures 18-20: Figure 18 represents the X-ray diffractograms of the simulated MIL-53(A1)-CF3 solid (two curves for two different pore sizes (a) at the bottom), experimental in the powder state (curve (b) at the top, (nanoparticle particle size) (Xcu~1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 19 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the MIL-53(A1)-CF3 nanoparticles after washing and drying in the powder state ((a) in black). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 20 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of MIL-53(A1)-CF3 powder nanoparticles (points of the curve represented by circles) at 150°C overnight, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the MIL-53-CF3 powder is 763.7 m 2 .g -1 + / - 0.6 and a pore volume of 0.351 cm 3 . g 1 .

[0146] [ 1361 Zeolite NaY or Na2O.Al2O3.5,1SiO2

[0147]

[0137] Example 7: Zeolith is a commercial product and was ordered from Alfa Aesar® (CAS: 1318-02-1).

[0148]

[0138] Results

[0149]

[0139] The results are summarized in Figures 21-23: Figure 21 represents the X-ray diffractograms of the simulated NaY zeolite (curve (a) at the bottom), experimental in the powder state (curve (b) in the middle), (microparticle particle size) (Xcu~1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 22 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the NaY zeolite microparticles after washing and drying in the powder state ((a) in black). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 23 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the microparticles of NaY zeolite powder (points of the curve represented by circles) at 150°C overnight, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the NaY zeolite powder is 845 m 2 .g“ 1 + / - 0.5 and a pore volume of 0.327 cm 3 . g -1 .

[0140] Activated carbon

[0150]

[0141] The size distribution of microparticles calculated from 5 SEM images of activated carbon powder. Size determined with ImageJ™ software on approximately 70 particles (average size: 23.5μm + / - 16.9).

[0151]

[0142] Example 8: Activated carbon is a commercial product and was ordered from Fischer Scientific™ (CAS: 7440-44-0)

[0152]

[0143] Results

[0153]

[0144] The results are summarized in Figures 24-27: Figure 24 represents the experimental X-ray diffractograms of the powdered activated carbon microparticles, (curve (a) at the bottom), (microparticle particle size) (λcu≈ 1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 25 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the activated carbon microparticles of Example 8 after washing and drying in the powder state ((a) in black). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 26 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the microparticles of activated carbon in powder form (points of the curve represented by circles) 150°C overnight, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface area obtained for the activated carbon powder is 1556 m 2 .g“ 1 + / - 0.7 and a pore volume of 1.2 cm 3 . g -1 . Figure 27a represents the image of the activated carbon powder obtained by scanning electron microscopy at a magnification of x650 and Figure 27b represents the histogram illustrating the size distribution of the activated carbon particles, in ordinate: number, abscissa: particle size (pm).

[0145] Part 2: formulation of paper membranes using a cellulose matrix and porous solids such as Metal-Organic Frameworks: impact of the cellulose matrix on the final properties

[0154]

[0146] This part shows the adjustment of the cellulose matrix by comparing two types of paper fibers (cotton and resinous) with or without microfibrillated cellulose within the paper membranes.

[0155] [ 1471 Paper membranes with nanoparticles (NPs) of MIL-100(Fe)

[0156]

[0148] Example 9: formulation of paper membranes in the presence of cellulose fibers (cotton or resinous) with or without microfibrillated cellulose at different ratios

[0157]

[0149] 100 mg of cotton fibers (from crucibles marketed by Whatman®) are inserted into a blade mill with 10 mL of distilled water and then the fibers are ground for 2 minutes. The fiber solution is then added to the solution containing 300 mg of MIL-100(Fe) nanoparticles from synthesis in order to ensure optimal dispersion of the latter within the composite. Finally, the equivalent of 100 mg of microfibrillated cellulose (MFC) (weighed mass of 1000 mg of MFC added because present at a mass concentration of 10% m / m, Celova® marketed by Weidmann®) is inserted into the aqueous MOF solution. The mixture is left for 30 minutes and then filtered through a nylon film covering a paper filter. The resulting composite contains 60% w / w MIL-100(Ee), 20% w / w softwood fibers and 20% w / w MEK. It is annotated 60MIL100-NP-20R-20MFC.

[0158]

[0150] Different paper membranes were developed by inserting or not (comparative examples without MFC) MFC and by replacing the cotton fibers with softwood fibers (HWBK™, bleached kraft™ marketed by the company Canson®). In addition, the proportion of MOF was increased to 75% m / m.

[0159]

[0151] Table 1 (preparation of cotton fiber / MIL-100(Fe) microparticle mixtures for the production of paper membranes) summarizes the compositions of these composites.

[0160] [Table 1]

[0161]

[0152] Results - paper membranes formulated with MIL-100(Fe) nanoparticles

[0162]

[0153] The results are summarized in Figures 28-30: Figure 28 represents the X-ray diffractograms of the paper membranes formulated with the MIL-100(Fe) nanoparticles: 60MIL100-40R (curve a), 60MIL100-20R-20MFC (curve b), 60MIL100-40C (curve c), 60MIL100-20C-20MFC (curve d), 75MIL100-12.5R-12.5MFC (curve e), (Xcu~1.5406 Â), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 29 represents the thermogravimetric analyses (in air, heating rate of 5°C / minute) of these paper membranes formulated with MIL-100(Fe) nanoparticles. The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 30 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the paper membranes formulated with MIL-100(Fe) nanoparticles at 150°C overnight, ordinate: volume N2 (cm 3 . g -1), abscissa: Relative Pressure (solid circles correspond to adsorption, circles to desorption; (nanoparticle granulometry) (Po=latm.)).

[0163]

[0154] Paper membranes with microparticles of MIL-100(Fe) [ 1551Example 10: formulation of paper membranes in the presence of cellulose fibers (softwood pulp) with or without microfibrillated cellulose

[0164]

[0156] 62.5 mg of softwood pulp (HWBK™) are inserted into a blade mill with 30 mL of distilled water and then the fibers are ground for 2 minutes. An additional 30 mL of distilled water are added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 minutes in order to properly separate the fiber clumps (it is also possible to work in a larger volume of water in order to eliminate this step). The equivalent of 62.5 mg of microfibrillated cellulose (MFC) (weighed mass of 625 mg of MFC added because present at a mass concentration of 10% m / m, Celova® marketed by Weidmann®) is inserted into the aqueous fiber solution and the mixture is stirred for 15 minutes. At the same time, the equivalent of 375 mg of MIL-100(Fe) microparticles (depending on the amount of solvent contained in the pores) is dispersed in an ultrasonic bath in 10 mL of distilled water for 10 minutes.The suspension is added to the fiber solution and left stirring for 15 minutes (300 rpm). The mixture is filtered through a nylon film covering a paper filter. The resulting 7 cm diameter paper membrane contains 75% m / m MIL-100(Fe), 12.5% ​​m / m softwood fibers and 12.5% ​​MFC. It is annotated 75MIL100-12.5R-12.5MFC.

[0165]

[0157] Paper membranes were produced with or without MFC (comparative examples without MFC) while ensuring that the proportion of MIL-100(Fe) within the composite was kept constant (75% m / m).

[0166]

[0158] Table 2 (Preparation of resinous fiber / MFC / MIL-100 microparticle mixtures for the production of paper membranes) summarizes the compositions of these membranes.

[0167] [Table 2]

[0159] Results - paper membranes formulated with MIL-100(Fe) microparticles

[0168]

[0160] The results are summarized in Figures 31-33: Figure 31 represents the X-ray diffractograms of the paper membranes formulated with the microparticles of MIL-100(Fe): 75MIL100-25R (curve a) and 75MIL100-12.5R-12.5MFC (curve b) as well as with the microparticles of MIL-127(Fe): 75MIL127-25R (curve c) and 75MIL127-12.5R-12.5MFC (curve d) (Xcu~1.5406 A), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 32 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the paper membranes formulated with the microparticles of MIL-100(Fe): 75MIL100-25R (curve a) and 75MIL100-12.5R-12.5MFC (curve b).The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 33 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the paper membranes formulated with the microparticles of MIL-100(Fe): 75MIL100-25R (isotherm a) and 75MIL100-12.5R-12.5MFC (isotherm b) as well as with the microparticles of MIL-127(Fe): 75MIL127-25R (isotherm c) and 75MIL127-12.5R-12.5MFC (isotherm d) at 150°C overnight, ordinates: volume N2 (cm. 3 . g 1 ), abscissa: Relative Pressure (solid circles correspond to adsorption, circles to desorption; (microparticle granulometry) (Po=latm.)).

[0169] [161 IMembranes papers with microparticles of MIL-127(Fe)

[0170]

[0162] Example 11: 62.5 mg of softwood pulp (HWBK™) are inserted into a blade mill with 30 mL of distilled water and then the fibers are ground for 2 minutes. An additional 30 mL of distilled water are added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 minutes in order to properly separate the fiber clusters (it is also possible to work in a larger volume of water in order to eliminate this step). The equivalent of 62.5 mg of microfibrillated cellulose (MFC) (weighed mass of 625 mg of MFC added because present at a mass concentration of 10% m / m, Celova® marketed by Weidmann®) is inserted into 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 an ultrasonic bath in 10 mL of distilled water for 10 minutes.The suspension is added to the fiber solution and left stirring for 15 minutes (300 rpm). The mixture is filtered through a nylon film covering a paper filter. The resulting 7 cm diameter paper membrane contains 75% m / m MIL-127(Fe), 12.5% ​​m / m softwood fibers and 12.5% ​​MFC.

[0171] It is annotated 75MIL127-12.5R-12.5MFC.

[0172]

[0163] Paper membranes were produced with or without MFC (comparative examples without MFC) while ensuring that the proportion of MIL-127(Fe) within the composite was kept constant (75% m / m).

[0173]

[0164] Table 3 (Preparation of resin fiber / MFC / MIL-100 microparticle mixtures for the production of paper membranes) summarizes the compositions of the composites.

[0174] [Table 3]

[0175] [ 1651 Results - paper membranes formulated with microparticles of

[0176] MIL-127(Fe)

[0177]

[0166] The results are summarized in Figures 31 and 33-34: Figure 31 represents the X-ray diffractograms of the paper membranes formulated with the microparticles of MIL-100(Fe): 75MIL100-25R (curve a) and 75MIL100-12.5R-12.5MFC (curve b) as well as with the microparticles of MIL-127(Fe): 75MIL127-25R (curve c) and 75MIL127-12.5R-12.5MFC (curve d) (Xcu~L5406 A), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 33 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the paper membranes formulated with the microparticles of MIL-100(Fe): 75MIL100-25R (isotherm a) and 75MIL100-12.5R-12.5MFC (isotherm b) as well as with the microparticles of MIL-127(Fe): 75MIL127-25R (isotherm c) and 75MIL127-12.5R-12.5MFC (isotherm d) at 150°C overnight, ordinates: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (solid circles correspond to F adsorption, circles to desorption; (microparticle particle size) (Po=latm.)); Figure 34 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the paper membranes formulated with the microparticles of MIL-127(Fe) 75MIL127-25R (curve a) and 75MIL127-12.5R-12.5MFC (curve b). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %).

[0178] [ 1671 Part 3: mechanical properties of paper membranes made from porous solids such as MOFs

[0179]

[0168] The impact of cellulosic matrix adjustment on the mechanical properties of paper membranes. The characterization of these mechanical properties was carried out by tensile strength measurements using an Adamel Lhomargy® tensile testing machine (DY20-N™, 100 dN force sensor). Each specimen had a length of 10 cm and a width of 1.5 cm. The tensile zone was located over a length of 5 cm (jaw-to-jaw distance) with an elongation rate of 50 mm / min and a break detection set at 3%. The samples were preconditioned for at least 24 hours at 25°C and 50% relative humidity and the tests were carried out under these same conditions. The measurement was repeated 5 times for each sample.

[0180] [ 1691 Paper membranes with MIL-100(Fe) microparticles

[0181]

[0170] Example 12: formulation of the paper membrane with cotton fibers and microfibrillated cellulose at different ratios

[0182]

[0171] 1.03 g of cotton fibers (from thimbles marketed by Whatman®) were dispersed using a blade mill in 1 L of distilled water and then redispersed in a volume of 4 L of distilled water and stirred. 11.46 g of microfibrillated cellulose (MFC) with a concentration equal to 3% m / m in water (Celova® marketed by Weidmann®) was added to the mixture. Then, 4.125 g of MIL-100 microparticles (synthesis explained in part 1, the mass was adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and put in an ultrasonic bath for 15 minutes in order to satisfactorily disperse the aggregates. The solution obtained is added to the fiber mixture and left stirring for 15 minutes. The solution is then filtered through a 1 micron cloth (marketed by Buisine®) using a Rapid Kôthen™ sheet-forming device (manufactured by Frank®).The resulting 20 cm diameter paper membrane is then vacuum dried at 85°C for 30 minutes using a dryer attached to the forming machine. The resulting composite contains 75% m / m of MIL-100(Fe) microparticles, 6.25% m / m of cotton fibers and 18.75% m / m of MFC and is denoted MIL100-75C-25MFC.

[0183]

[0172] Different paper membranes have been developed by varying the cotton / MFC fiber ratio.

[0184]

[0173] Table 4 (Preparation of cotton fiber / MIL-100 microparticle blends for the production of paper membranes and the characterization of their mechanical properties) summarizes the compositions of the composites. [Table 4]

[0185]

[0174] Results - paper membranes formulated with MIL-100(Fe) microparticles and cotton fibers

[0186]

[0175] Figure 35 and Table 5 show the results obtained.

[0187]

[0176] Figure 35 shows the stress-strain curves obtained by tensile tests of the paper membranes (a) MIL100-75C-25MFC, (b) MIL100-50C-50MFC and (c) MIL100-25C-75MFC (ordinate: stress (Mpa), Abscissa: elongation (%)).

[0177] Table 5 summarizes the mechanical data deduced from the stress-strain curves corresponding to the Young's modulus (ordinate, Mpa), the maximum force before rupture and the strain at rupture (ordinate, %) of the different paper membranes MIL100-75C-25MFC, MIL100-50C-50MFC and MIL100-25C-75MFC; [Table 5]

[0188]

[0178] Table 5 summarizes the mechanical data of the different paper membranes with MIL-100(Fe) microparticles and cotton fibers.

[0189] [ 1791Example 13: formulation of the paper membrane with softwood fibers and microfibrillated cellulose at different ratios

[0190]

[0180] The steps for preparing the paper membranes are identical to those presented above, but softwood pulp (HWBK™, bleached kraft™ supplied by Canson®) was used as the source of cellulose fibers instead of cotton fibers.

[0191]

[0181] Different paper membranes have been developed by varying the ratio of resinous fibers to MFC.

[0192]

[0182] Table 6 (Preparation of fiber / MIL-100 mixtures for the production of paper membranes) summarizes the compositions of the composites.

[0193] [Table 6]

[0194]

[0183] Results - paper membranes formulated with MIL-100(Fe) microparticles and resinous fibers

[0195]

[0184] Figure 36 and Table 7 show the results obtained.

[0196]

[0185] Figure 36 represents the stress-strain curves obtained by tensile tests of the paper membranes (a) MIL100-75R-25MFC, (b) MIL 100-50R-50MFC and (c) MIL100-25R-75MFC, (ordinate: stress (Mpa), Abscissa: elongation (%)).

[0197]

[0186] Table 7 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (ordinate, Mpa), maximum force before rupture and strain at rupture (ordinate, %) of the different paper membranes MIL100-75R-25MFC, MIL100-50R-50MFC and MIL100-25R-75MFC;

[0198] [Table 7]

[0187] Table 7 summarizes the mechanical data of the different paper membranes with MIL-100 microparticles and fibers of conifers.

[0199] [ 1881 Paper membranes with MIL-127(Fe) microparticles

[0200] [ 1891Example 14: formulation of the paper membrane in the presence of cotton fibers and microfibrillated cellulose at different ratios

[0201]

[0190] 687mg of resinous fibers (HWBK™, bleached kraft™ marketed by Canson®) were dispersed using a blade mill in 1L of distilled water and then redispersed in a volume of 4L of distilled water and stirred. 22.92g of microfibrillated cellulose (MFC) with a concentration equal to 3% m / m in water (Celova® marketed by Weidmann®) was added to the mixture. Then, the equivalent of 4.125g of MIL-127 microparticles (synthesis explained in Example 3, the mass was adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and put in an ultrasonic bath for 15 minutes in order to satisfactorily disperse the aggregates. The resulting solution is added to the fiber mixture and left stirring for 15 minutes. The solution is then filtered through a 1 micron mesh (sold by Buisine) using a Rapid Kôthen™ sheet-forming device (sold by Frank™).The resulting 20 cm diameter paper membrane is then vacuum dried at 85°C for 30 minutes using a dryer attached to the form machine. The resulting composite contains 75% m / m of MIL-127(Fe) microparticles, 12.5% ​​m / m of softwood fibers and 12.5% ​​m / m of MFC and is denoted MIL127-50R-50MFC.

[0202]

[0191] Different paper membranes were developed by varying the ratio of resin fibers to MFC (comparative examples without MFC). The table below summarizes the compositions of these composites.

[0203]

[0192] Table 8 (Preparation of resin fiber / MIL-127 microparticle mixtures for the production of paper membranes) summarizes the compositions of the composites.

[0204] [Table 8]

[0205] [ 1931 Results - mechanical characteristics - paper membranes formulated with MIL- 127(Tc) microparticles and resinous fibers

[0206]

[0194] Figure 37 and Table 9 show the results obtained.

[0207]

[0195] Figure 37 represents the stress-strain curves obtained by tensile tests of the paper membranes (a) MIL127-100R, (b) MIL127-75R-25MFC and (c) MIL 127-50R-50MFC (ordinate: stress (Mpa), Abscissa: elongation (%));

[0208]

[0196] Table 9 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (ordinate, Mpa), maximum force before rupture and strain at rupture (ordinate, %) of the different paper membranes MIL127-100R, MIL127-75R-25MFC, MIL127-50R-50MFC;

[0209] [Table 9] Paper membranes with MIL-127(Fe) microparticles and resinous fibers [ 1981Paper membranes with MIL-100(Fe) nanoparticles

[0210]

[0199] Example 15: formulation of the paper membrane with a resinous ratio:MFC=25:75 at different percentages of nano-MIL- 1 OO

[0211]

[0200] 0.218 g of softwood fibers (HWBK™, bleached kraft™ marketed by Canson®) were dispersed using a blade mill in 1 L of distilled water and then redispersed in a volume of 4 L of distilled water and stirred. 21.9 g of microfibrillated cellulose (MFC) with a concentration equal to 3% m / m in water (Celova® marketed by Weidmann®) was added to the mixture. Then, 2.622 g of MIL-100(Fe) nanoparticles (synthesis explained in part 1, the mass was adjusted according to the amount of solvent contained in the pores) were placed in 250 mL of distilled water and put in an ultrasonic bath for 15 minutes in order to satisfactorily disperse the aggregates. The resulting solution is added to the fiber mixture and left stirring for 15 minutes. The solution is then filtered through a 1 micron mesh (sold by Buisine®) using a Rapid Kôthen™ sheet-forming device (manufactured by Frank®).The resulting 20 cm diameter paper membrane is then vacuum dried at 85°C for 30 minutes using a dryer attached to the forming machine. The resulting composite contains 75% m / m of MIL-100(Fe) nanoparticles, 6.25% m / m of softwood fibers and 18.75% m / m of MFC and is rated 75MIL100.

[0212]

[0201] Different paper membranes were developed by varying the mass percentage of MIL-100(Fe).

[0213]

[0202] Table 10 (Preparation of MIL-100 fiber / nanoparticle mixtures for the production of paper membranes and the characterization of their mechanical properties), summarizes the compositions of the composites, taking care to keep the total mass of the composite constant (3.496g).

[0214] [Table 10]

[0215]

[0203] Results - paper membranes formulated with MIL-100(Fe) nanoparticles and resinous fibers

[0216]

[0204] Figure 38 and Table 11 show the results obtained.

[0217]

[0205] Figure 38 represents the stress-strain curves obtained by tensile tests of the paper membranes (a) 60MIL100, (b) 75MIL100 and (c) 90MIL100 (ordinate: stress (Mpa), Abscissa: elongation (%)).

[0218]

[0206] Table 11 summarizes the mechanical data deduced from the stress-strain curves corresponding to Young's modulus (on the ordinate, Mpa), to the maximum force before rupture and the deformation at rupture (on the ordinate, %) of the different paper membranes 60MIL100, 75MIL100 and 90MIL100;

[0219] [Table 11]

[0220] Table 11 summarizes the mechanical data of the different paper membranes with MIL-100(Fe) nanoparticles, MFC and resinous fibers.

[0221]

[0207] Part 4: Determination of an optimal ratio of long cellulose fiber:MFC

[0222]

[0208] The impact of the adjustment of the cellulose matrix on the mechanical properties and more precisely the flexibility of the paper membranes was studied. The characterization of these mechanical properties was carried out by two-point bending strength measurements using a Büchel Van Der Korput bending machine. Each sample had a length of 5 cm and a width of 3.8 cm. The samples were preconditioned for at least 24 hours at 25°C and 50% relative humidity and the tests were carried out under these same conditions. The measurement was repeated 3 times for each sample. The bending stiffness calculations were carried out following the ISO5628:2019 standard.

[0223] 1209]Paper membranes with MIL-100(Fe) microparticles

[0224] [21 OIExample 16: formulation of the paper membrane with softwood fibers and microfibrillated cellulose at different ratios

[0225] [21 l]The steps for preparing the paper membranes, porous solid used and fibers chosen are identical to those presented in example 13.

[0226]

[0212] Different paper membranes were developed by varying the resin fiber / MFC ratio (comparative example without MFC - MIL100-100R).

[0227]

[0213] Table 12 (Preparation of resin fiber / MIL-100(Fe) microparticle mixtures for the production of paper membranes and the characterization of their flexibility), summarizes the compositions of the composites. [Table 12]

[0214] Results - paper membranes formulated with MIL-100(Fe) microparticles and resinous fibers

[0228]

[0215] Figure 39 and Table 13 show the results obtained.

[0229]

[0216] Figure 39 shows the force vs. bending angle curves obtained by two-point bending tests of the 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) (ordinate: force (mN), Abscissa: bending angle (°)).

[0230]

[0217] Table 13 summarizes the mechanical data deduced from the force vs. bending angle curves corresponding to the bending stiffness (N.mm), the maximum force before plastic deformation (ordinate, N), and the rupture or not of the different paper membranes MIL100-100R, MIL100-75R-25MFC, MIL 100-50R-50MFC, MIL100-25R-75MFC, MIL100-10R-90MFC, MIL100-100M FC;

[0231] [Table 13]

[0232]

[0218] Table 13 summarizes the mechanical flexibility data of the different paper membranes with MIL-100(Fe) microparticles and resinous fibers.

[0219] Part 5: Study of the impact of MIL-100(Fc) paper membranes on cellulose by accelerated aging

[0233] The objective of this section is to determine whether the paper membrane containing 75% w / w MIL-100(Fe) (MIL100-50R-50MEC) would have an effect on cellulose. Indeed, this composite would be likely to release volatile organic compounds (VOCs) that could alter cellulose. These tests were adapted from ISO 16245, given in reference

[0020] ,

[0234]

[0220]

[0235] [221 Example 17: aging tests

[0236]

[0222] Five borosilicate glass bottles with a unit volume of 140 cm 3and can be hermetically sealed using a silicone / Teflon® cap and septum were conditioned for at least 48 hours at 50% relative humidity and a temperature of 25°C. Each of these tubes contains a mass of Whatman® 1 unfilled cellulose paper (control paper) equal to 250mg and a hygro-button to control the temperature and relative humidity over time. These samples were preconditioned (50% RH and 25°C) then cut into thin strips and placed in a pillbox, their degradation will be assessed after aging. Two control bottles are established by inserting 4.2g of Whatman® 1 paper cut into the shape of preconditioned test tubes. The control bottles are then ready to be closed. In addition, three other vials are prepared with 766 mg of paper membranes containing 75% w / w of MIL-100(Ee) microparticles cut into test tubes and preconditioned. The vials are then hermetically sealed.The five bottles are placed in an oven at 80°C for 5 days. After incubation, the degree of polymerization of the Whatman® 1 paper strips contained in the pillboxes is evaluated by viscosimetry (adapted from the international standard IEC 60450

[0021] ) using a flow viscometer (Cannon-Eenske™ brand, Routine 100 model) marketed by Normalab Analis™).

[0223] The test was repeated with an incubation time at 80°C equal to 3 weeks (21 days).

[0237]

[0224] Results - paper membranes formulated with MIL-100(Fe) microparticles

[0238]

[0225] See Figure 38: Figure 38 represents the evolution of the degree of polymerization (ordinate: degree of polymerization) of the cellulose after different aging times (abscissa: aging time in days) with or without paper membrane, the curve with the square points corresponds to the Whatman control, and the curve with the round points corresponds to the Whatman aged in the presence of the paper membrane.

[0239]

[0226] Part 6: Development of paper membranes from porous solids for VOC capture tests

[0240]

[0227] The same characterization techniques (DRX, FTIR, ATG and Adsorption / Desorption N2 at 77K) used and described in part 1 (see also the analysis and experimental protocols section) were used to characterize the paper membranes formulated with the powders described in part 1.

[0241]

[0228] Furthermore, the observation of the surface topography of the samples was carried out by scanning electron microscopy using an ESEM Quattro™ (marketed by ThermoFischer Scientific™).

[0242]

[0229] Paper membranes with MIL-100(Fe) microparticles

[0243] [23 OIExample 18: formulation of the paper membrane

[0244]

[0231] 62.5 mg of softwood pulp (HWBK™, bleached kraft pulp™ supplied by Canson®) are inserted into a blade mill with 30 mL of distilled water and then the fibers are ground for 2 minutes. An additional 30 mL are added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 minutes in order to properly separate the fiber clumps (it is also possible to work in a larger volume of water in order to eliminate this step). The equivalent of 62.5 mg of microfibrillated cellulose (MFC) (weighed mass of 625 mg of MFC added because present at a mass concentration of 10% m / m, Celova® marketed by Weidmann®) is inserted into the aqueous fiber solution and the mixture is stirred for 15 minutes. At the same time, the equivalent of 375 mg of MIL-100(Fe) microparticles (depending on the amount of solvent contained in the pores) is dispersed in an ultrasonic bath in 10 mL of distilled water for 10 minutes.The suspension is added to the fiber solution and left stirring for 15 minutes (300 rpm). The mixture is filtered through a nylon film covering a paper filter. The resulting 7 cm diameter paper membrane contains 75% m / m of MIL-100(Fe), 12.5% ​​m / m of softwood fibers and 12.5% ​​m / m of MFC. (After VOC capture, the paper membranes can be regenerated by placing them in distilled water for 3 days, making sure to change the water 3 times a day).

[0245] 12321 Results - paper membranes formulated with MIL-100(Fe) microparticles

[0246]

[0233] Figures 1-4d compile the results obtained: Figure 1 represents the X-ray diffractograms in the form of a paper membrane (cur©(c) at the top) (microparticle granulometry) (Xcu~L5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta deg.); Figure 2 represents the thermogravimetric analysis (in air, at a heating rate of 5°C / minute) of the MIL-100(Fe) microparticles after in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 3 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the MIL-100(Fe) microparticles in the form of paper membrane example 16 (points of the curve represented by squares) at 150°C all night, ordinate: volume N2 (cm 3 . g -1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (microparticle granulometry) (Po=latm.)). The BET specific surface obtained from the MIL-100(Fe) paper membrane is 1416 m 2 .g -1 + / - 1.5; Figures 4a and 4b represent the images of the paper membrane containing 75% w / w of MIL-100(Fe) microparticles by scanning electron microscopy at different magnifications: (a) xl0 000 and (b) xl5 000 and Figure 4c and 4d represent the histograms illustrating the size distribution of MIL-100(Fe) particles as well as the size distribution of fibers, in ordinate: number, abscissa: size of particles (or fibers) (iim).

[0247] 1234]Paper membranes with MIL-127(Fe) microparticles

[0248] [235 Example 19: formulation of the paper membrane

[0249]

[0236] The method of formulating the paper membrane is identical to that described above for the MIL-100(Fe) microparticles, by dispersing in an aqueous solution, 375 mg of dry MIL-127(Fe) (and taking care to take into account the quantity of solvent contained in the pores of the solid). The resulting 7 cm diameter paper membrane contains 75% m / m of MIL-127(Fe), 12.5% ​​m / m of softwood fibers and 12.5% ​​m / m of MFC.

[0250]

[0237] Results - paper membranes formulated with MIL-127(Fe) microparticles

[0251]

[0238] Figures 8-10 compile the results obtained: Figure 8 represents the RX diffractograms in the form of a paper membrane (curve (c) at the top) (microparticle granulometry) 1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 9 represents the thermogravimetric analysis (in air, at a heating rate of 5°C / minute) of MIL-127(Fe) microparticles after being in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 10 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of MIL-127(Fe) microparticles in the form of a paper membrane example 17 (points of the curve represented by squares) at 150°C overnight, ordinates: volume N2 (cm 3 . g -1 ), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (microparticle granulometry) (Po=latm.)). The BET specific surface obtained from the MIL-127(Fe) paper membrane is 1100.5 m 2 .^ 1+ / - 0.4 ;

[0252]

[0239] Paper membranes with Al-PDA nanoparticles [2401Example 20: formulation of the paper membrane

[0253]

[0241] The process for formulating the paper membranes is identical to 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 7 cm diameter paper membrane contains 75% m / m Al-PDA, 12.5% ​​m / m softwood fibers and 12.5% ​​MFC.

[0254]

[0242] Results - paper membranes formulated with Al-PDA nanoparticles

[0255]

[0243] Figures 1 l-14c compile the results obtained:

[0256] Figure 11 represents the X-ray diffractograms of Al-PDA nanoparticles in the form of a paper membrane (curve (c) at the top), (nanoparticle particle size) (Xcu~1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 12 represents the thermogravimetric analysis (in air, at a heating rate of 5°C / minute) of Al-PDA nanoparticles after in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 13 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of Al-PDA nanoparticles in the form of paper membrane example 18 (points of the curve represented by squares) at 200°C for 5h, ordinates: volume N2 (cm 3 . g -1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)). The BET specific surface obtained from the Al-PDA paper membrane is 794 m 2 .g -1 + / - 0.83; Figures 14a, 14b and 14c represent the images of the paper membrane containing 75% w / w Al-PDA nanoparticles obtained by scanning electron microscopy at different magnifications: (a) x800, (b) x6500 and (c) x250000 and Figure 14d represents the histogram of Al-PDA particle size distribution, ordinate: number, abscissa: particle size (nm).

[0257] 1244]Paper membranes with UiO-66(Zr)-2CF3 microparticles

[0258] [245 Example 21: formulation of the paper membrane

[0259]

[0246] The method of formulating the paper membrane is identical to that described above for the MIL-100(Fe) microparticles, by dispersing in an aqueous solution, 375 mg of dry UiO-66(Zr)-2CF3 (taking into account the quantity of solvent contained in the pores of the solid). The resulting 7 cm diameter paper membrane contains 75% m / m of UiO-66(Zr)-2CF3, 12.5% ​​m / m of softwood fibers and 12.5% ​​m / m of MFC.

[0260]

[0247] Results - paper membranes formulated with UiO-66(Zr)-2CF3 microparticles

[0261]

[0248] Figures 15-17 compile the results obtained: Figure 15 represents the X-ray diffractograms of UiO-66(Zr)-2CF3 microparticles in the form of a paper membrane (curve (c) at the top), (microparticle particle size) (λcu≈ 1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 16 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of UiO-66(Zr)-2CF3 microparticles in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 17 represents the adsorption-desorption isotherm of dinitrogen at 77K obtained after activation of UiO-66(Zr)-2CF3 microparticles in the form of a paper membrane (points of the curve represented by squares) at 150°C overnight, ordinate: volume N2 (cm 3 . g -1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)) The BET specific surface obtained from the UiO-66-2CF3(Zr) paper membrane is 685 m 2 .g -1 + / - 0.3 ;

[0262] [2491Paper membranes with MIL-53(A1) CF3 nanoparticles [25 OIExample 22: formulation of the paper membrane

[0263] [25 l]The formulation process of the paper membrane is identical to that described above for the microparticles of MIL-100(Fe), in an aqueous solution, 375 mg of MIL53-CF3sec (taking into account the quantity of solvent contained in the pores of the solid). The resulting paper membrane of 7 cm diameter contains 75% m / m of MIL-53-CF;, 12.5% ​​m / m of softwood fibers and 12.5% ​​of MFC.

[0264]

[0252] Results - paper membranes formulated with MIL-53(A1)-CF3 nanoparticles

[0265]

[0253] Figures 18-20 compile the results obtained: Figure 18 represents the X-ray diffractograms of MIL-53(A1)-CF3 nanoparticles in the form of a paper membrane (curve (d) at the top), (nanoparticle particle size) (Xcu~1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 19 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of MIL-53(A1)-CF3 nanoparticles in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 20 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the MIL-53(A1)-CF3 nanoparticles as such from Example 6 in the form of a paper membrane from Example 20 (points of the curve represented by squares) at 150°C overnight, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (black dots correspond to adsorption, white dots to desorption; (nanoparticle granulometry) (Po=latm.)) The BET specific surface obtained from the MIL-53-CF3(Al) paper membrane is 513 m 2 . g -1 + / - 0.766;

[0266]

[0254] Paper membranes with activated carbon microparticles

[0267] [255 Example 23: formulation of the paper membrane

[0268]

[0256] The method of formulating the paper membrane is identical to that described above for the MIL-100(Fe) microparticles, by dispersing in an aqueous solution, 375 mg of dry activated carbon (taking care to take into account the quantity of solvent contained in the pores of the solid). The resulting paper membrane of 7 cm in diameter contains 75% m / m of activated carbon, 12.5% ​​m / m of softwood fibers and 12.5% ​​of MFC.

[0269] 1257]Results - paper membranes formulated with activated carbon microparticles

[0270]

[0258] Figures 24-27 compile the results obtained: Figure 24 represents the experimental X-ray diffractograms of the activated carbon microparticles of Example 8 in the form of a paper membrane (curve (b) at the top, (microparticle particle size) (Xcu~1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 25 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the activated carbon microparticles of Example 8 in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 26 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of the activated carbon microparticles of Example 8 in the form of a paper membrane (points of the curve represented by squares) 150°C overnight, ordinates: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (the black dots correspond to adsorption, the white dots to desorption; (nanoparticle granulometry) (Po=latm.)) The BET specific surface obtained from the activated carbon paper membrane is 1118 m 2 .g -1 + / - 0.5; Figure 27b shows the image of the paper membrane containing 75% m / m of the activated carbon microparticles of Example 8 obtained by scanning electron microscopy at a magnification of x 10000.

[0271] [2591Paper membranes with zeolite microparticles 12601Example 24: formulation of the paper membrane

[0272]

[0261] The method of formulating the paper membrane is identical to that described above for the MIL-100(Fe) microparticles, by dispersing in an aqueous solution, 375 mg of dry zeolite (taking care to take into account the quantity of solvent contained in the pores of the solid). The resulting paper membrane of 7 cm in diameter contains 75% m / m of zeolite, 12.5% ​​m / m of resinous fibers and 12.5% ​​of MFC.

[0273] [2621Results - paper membranes formulated with zeolite microparticles

[0274]

[0263] Figures 21 to 23 compile the results obtained. Figure 21 represents the X-ray diffractograms of the NaY zeolite in the form of a paper membrane (curve (c) at the top), (microparticle particle size) (Xcu~L5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 22 represents the thermogravimetric analysis (in air, heating rate of 5°C / minute) of the NaY zeolite microparticles in the form of a paper membrane ((b) in gray). The mass loss Pm (in %) is represented as a function of the temperature T (in °C, on the abscissa): on the ordinate = remaining mass (in %); Figure 23 represents the adsorption-desorption isotherms of dinitrogen at 77K obtained after activation of powdered NaY microparticles (points of the curve represented by circles) at 150°C overnight, ordinate: volume N2 (cm 3 . g 1), abscissa: Relative Pressure (the black dots correspond to adsorption, the white dots to desorption; (nanoparticle granulometry) (Po=latm.)) The BET specific surface obtained from the zeolite paper membrane is 607 m 2 .g -1 + / - 0.3 ;

[0275] Part 7: Formulation of monoliths using porous solids of the Metal-Organic Frameworks type.

[0276] This section aims to extend the previously proposed formulation process by increasing the thickness of the paper membrane in order to form a monolith. The characterizations of the textural properties of the MOF powders and monoliths were carried out by carbon dioxide CO2 adsorption porosimetry at 298K either with a Micromeritics™ Triflex® device when the maximum pressure was 1 bar or with a Hiden Isoschema™ Intelligent Gravimetric Analyzer® (IGA) when the maximum pressure was 14 bar. The samples were activated under primary vacuum using a Micromeritics® degasser overnight at temperatures between 150 and 200°C. The CO2 adsorption isotherm of the solids represents the amount of gas adsorbed (in mmol.g 1 ) according to the pressure P in CO2.

[0277]

[0264] MIL-16O(A1) or A1(OH)[C4H2O-(CO2)2]

[0278]

[0265] Example 25: Synthesis of MIL-16O(A1) particles

[0279]

[0266] 4.8g of 2,5-furanedicarboxylic acid (30mmol, CÔFLOS marketed by Sikémia®) and 4.6g of aluminum acetate (30mmol, A1(OH)(C2H3O2)2 marketed by Alfa Aesar®) were placed in a 100mL round-bottomed flask and dispersed in 30 mL of distilled water. The stirred mixture was heated for 24h at 120°C. The white precipitate obtained was isolated by centrifugation and then washed with ethanol.

[0280]

[0267] Results

[0281]

[0268] The results are summarized in Figures 41-42: Figure 41 represents the X-ray diffractograms of the simulated MIL-16O(A1) solid (curve (a) at the bottom), experimental in the powder state (curve (b) in the middle, (nanoparticle particle size) (Xcu~1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 42 represents the adsorption isotherm of carbon dioxide (CO2) at 298K obtained after activation of the MIL-16O(A1) powder (points of the curve represented by circles) at 150°C overnight, ordinate: Quantity of CO2 adsorbed (mmol.g 1 ), abscissa: Pressure (the black dots correspond to adsorption); (nanoparticle granulometry) (P m ax=lbar.)).

[0282]

[0269] Monolith with the MIL-16O(A1)

[0283]

[0270] Example 26: Formulation of the monolith

[0284]

[0271] 187.5 mg of softwood pulp (HWBK™, bleached kraft pulp™ supplied by Canson®) are inserted into a blade mill with 20 mL of distilled water and then the fibers are ground for 2 minutes. An additional 20 mL are added to this suspension. The resulting fiber solution is passed through an ultrasonic probe for 5 minutes in order to properly separate the fiber clusters. The equivalent of 187.5 mg of microfibrillated cellulose (MFC) (weighed mass of 6.25 g of MFC added because present at a mass concentration of 3% m / m, Celova® marketed by Weidmann®) is added to the aqueous fiber solution and the mixture is stirred for 15 minutes. At the same time, the equivalent of 1.5g of MIL-160(Fe) nanoparticles (depending on the amount of solvent contained in the pores) is dispersed in an ultrasonic bath in 30 mL of distilled water for 10 minutes. The suspension is added to the fibrous solution and left stirring for 30 minutes (300 rpm).The mixture is filtered through a paper filter. The resulting paper membrane, 3 cm in diameter and approximately 0.8 cm thick, contains 80% m / m MIL-16O(A1), 10% m / m softwood fibers, and 10% m / m MFC.

[0285]

[0272] Results

[0286]

[0273] The results are summarized in Figures 41-42: Figure 41 represents the X-ray diffractograms of the simulated MIL-16O(A1) solid (curve (c) at the top), λcu≈ 1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 42 represents the carbon dioxide (CO2) adsorption isotherm at 298K obtained after activation of the MIL-16O(A1) monolith (points of the curve represented by squares) at 150°C overnight, ordinate: Quantity of CO2 adsorbed (mmol.g 1 ), abscissa: Pressure (the black dots correspond to adsorption); (nanoparticle granulometry) (P m ax=lbar.)).

[0287] MIL-53(A1) or Al(OH)(C6H3C2O4)

[0288]

[0274] Example 27: Synthesis of MIL-53(A1) particles

[0289]

[0275] 13.3g of aluminum sulfate hexadecahydrate (20 mmol, A12(SO4)3.16H2O marketed by Alfa Aesar®), 3.3g of 1,4-benzenedicarboxylic acid (20 mmol, 1,4-BDC, C8H6O4 marketed by Tokyo Chemical Industries®) and 1.2g of urea (20mmol, CO(NH2)2, marketed by Alfa Aesar®) were placed in a 100mL flask and dispersed in 40mL of distilled water. The stirred mixture was heated for 24h at 120°C. The precipitate obtained was isolated by filtration and then washed with water. The solid was dried at room temperature overnight before calcination. The powder was calcined at 330°C for 33h.

[0290]

[0276] Results

[0291]

[0277] The results are summarized in Figures 43-44: Figure 43 represents the X-ray diffractograms of the solid MIL-53(A1) simulated according to the different pore sizes (curve (a) at the bottom), experimental in the powder state (curve (b) in the middle, (microparticle granulometry) (Xc u ~1.5406 Â)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 44 represents the adsorption isotherm of carbon dioxide (CO2) at 298K obtained after activation of MIL-53(A1) powder (points of the curve represented by circles) at 200°C overnight, ordinate: Quantity of CO2 adsorbed (mmol.g' 1 ), abscissa: Pressure (the black dots correspond to adsorption); (microparticle granulometry) (P m ax=14bar.)).

[0292] [278 IMonolith with the MIL-53(A1)

[0293]

[0279] Example 28: Formulation of the monolith

[0294]

[0280] The monolith formulation process is identical to that described above for the MIL-16O(A1) nanoparticles, by dispersing 1.5g of MIL-53(A1) 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 approximately 0.8 cm thick, contains 80% m / m of MIL-53(A1), 10% m / m of softwood fibers and 10% m / m of MFC.

[0295] [281 (Results

[0296]

[0282] The results are summarized in Figures 43-44: Figure 43 represents the X-ray diffractograms of the simulated MIL-53(A1) solid (curve (c) at the top), (λcu≈1.5406 A)), on the ordinate: arbitrary relative intensity (au), abscissa: 2-theta (deg.); Figure 44 represents the carbon dioxide (CO2) adsorption isotherm at 298K obtained after activation of the MIL-53(A1) monolith (points of the curve represented by squares) at 200°C overnight, ordinate: Quantity of CO2 adsorbed (mmol.g1 ), abscissa: Pressure (the black dots correspond to adsorption); (microparticle granulometry) (P m ax=14bar.)).

[0297] 1283]Part 8: Tests for the capture of VOCs by paper membranes

[0298]

[0284] This section shows the effectiveness of capturing certain pollutants that may be present in heritage institutions and harmful to the objects in the collections as well as to the health of individuals.

[0299]

[0285] A setup for trapping organic pollutants is produced in order to quantify the capacity of paper membranes to adsorb these vapors. This setup, shown in Figure 45, comprises a chamber 1 with a volume of 0.5 dm 3, placed in a thermostatic bath 2 (T=25°C). The thermostatic bath 2 comprises three separate inlets, each of which can be opened or closed using a tap 3. A first inlet 4 constitutes the arrival of outside air 5 passing through a first activated carbon filter 6 in order to guarantee clean air during the measurement. A second inlet 7 makes the connection between the chamber and the measuring instrument, a photoionization PID detector 8 (PID ppbRAE 3000+™ marketed by Honeywell®). The laboratory air 9 is filtered by a second activated carbon filter 10. The detector 8 makes it possible to accurately detect VOCs at concentrations ranging from 1 ppb to 15,000 ppm. Thus, it is possible, thanks to this device, to quantify the presence of VOCs in the chamber during the experiments carried out and thus to be able to compare the effectiveness of the adsorbents tested. A third inlet 11 has an injection cap which allows the injection of the VOC using a syringe (Vmjected = 1 uL).

[0300]

[0286] A measurement can be made with or without adsorbent in order to be able to experimentally estimate the adsorption capacity of each material. The measurement is broken down into three steps: a) the PID 8 detector is switched on in order to circulate filtered air in chamber 1 until it no longer detects any compound. The three inlets 4, 7, 11 of chamber 1 are then closed; b) a volume of 1 uL of VOC is injected into chamber 1, and left for 30 minutes for homogenization; c) the quantity of VOC is measured using the PID 8 detector, this quantity decreases throughout the measurement until reaching 0 ppm because the detector purges the container at a rate of 0.5 L.min 1 .

[0301]

[0287] In the presence of an adsorbent, steps ac are carried out, and 50 mg of one of the composites prepared in part 5 are previously inserted into the chamber. The surface area covered by the VOC concentration curve as a function of time during purging reflects the quantity of pollutant present in the container. Calculating the ratio of the surfaces obtained with and without adsorbent composite makes it possible to deduce the effective percentage of adsorption.

[0302] [288 ICapture of formic acid

[0303]

[0289] The VOC analyzed here is formic acid and the paper membranes formulated (part 6) from microparticles of MIL-100(Le), activated carbon and zeolite were tested.

[0304]

[0290] Results - capture tests

[0305]

[0291] Table 14 shows the results obtained.

[0306]

[0292] Table 14 summarizes the results obtained corresponding to (a) the purge time necessary to reach Oppm, (b) the maximum concentration of formic acid detected by the PID and (c) the equivalent volumes of formic acid detected (pL) by the PID in the presence or absence of an adsorbent for I pL injected as well as the deduction of the adsorption capacities

[0307] [Table 14]

[0308]

[0293] Table 14 summarizes the data inherent in the adsorption measurements carried out in the presence or absence of the different composites (activated carbon zeolite and MIL-100(Fe)), their average as well as the average percentages of formic acid adsorption for each composite.

[0309] 12941Capture of acetic acid

[0310]

[0295] The VOC analyzed here is acetic acid, cellulose paper and paper membranes formulated (see part 6) from microparticles of MIL-100(Fe), MIL-127(Fe), activated carbon and zeolite were tested.

[0311]

[0296] Results - capture tests

[0312]

[0297] Table 15 shows the results obtained.

[0313]

[0298] Table 15 summarizes the results obtained corresponding to (a) the purge time necessary to reach Oppm, (b) the maximum concentration of acetic acid detected by the PID and (c) the equivalent volumes of acetic acid detected (pL) by the PID in the presence or absence of an adsorbent for I pL injected as well as the deduction of the adsorption capacities.

[0314] [Table 15]

[0315]

[0299] Table 15 summarizes the data inherent in the adsorption measurements carried out in the presence or absence of cellulose paper or the different composites (zeolithe activated carbon, MIL-100(Fe) and MIL-127(Fe)) and their average as well as the average percentages of acetic acid adsorption for each composite.

[0316] [3001Capture of acrylic acid

[0317]

[0301] The VOC analyzed here is acrylic acid, cellulose paper and paper membranes formulated (see part 6) from microparticles of MIL-100(Fe), activated carbon and zeolithe were tested.

[0318]

[0302] Results - capture tests

[0319]

[0303] Table 16 shows the results obtained.

[0320]

[0304] Table 16 summarizes the results obtained (a) at the purge time required to reach Oppm, (b) at the maximum acrylic acid concentration detected by the PID and (c) at the equivalent volumes of acrylic acid detected (pL) by the PID in the presence or absence of an adsorbent for I pL injected as well as the deduction of the adsorption capacities.

[0321] [Table 16]

[0322]

[0305] Table 16 summarizes the data inherent in the adsorption measurements carried out in the presence or absence of cellulose paper or the different composites (zeolithe activated carbon, MIL-100(Fe)) and their average as well as the average percentages of acrylic acid adsorption for each composite.

[0323] 13061Capture of furfural

[0324]

[0307] The VOC analyzed here is furfural, cellulose paper and paper membranes formulated (see part 6) from Al-PDA nanoparticles as well as microparticles of MIL-100(Fe), activated carbon and zeolite were tested.

[0325]

[0308] Results - capture tests

[0326]

[0309] Table 17 shows the results obtained.

[0327]

[0310] Table 17 summarizes the results obtained (a) at the purge time necessary to reach Oppm, (b) at the maximum furfural concentration detected by the PID and (c) at the equivalent volumes of furfural detected (μL) by the PID in the presence or absence of an adsorbent for 1 μL injected as well as at the deduction of the adsorption capacities.

[0328] [Table 17]

[0329]

[0311] Table 17 summarizes the data inherent to the adsorption measurements carried out in the presence or absence of cellulose paper or the different composites (zeolite activated carbon, Al-PDA and MIL-100(Fe)) and their average as well as the average percentages of furfural adsorption for each composite.

[0312] The conditions of the VOC capture tests were slightly modified by increasing the contact time between the VOC and composite from 30 minutes to 1h30 and by dividing the mass of composite inserted into the chamber by 10 (5 mg at present). The injected volume is left constant (V=1pL).

[0330] [313 ICapture of acetic acid

[0331]

[0314] The VOC analyzed here is acetic acid and the paper membranes formulated (see part 6) from microparticles of MIL-100(Fe), and activated carbon were tested.

[0332]

[0315] Results - capture tests

[0333]

[0316] Table 18 shows the results obtained.

[0334]

[0317] Table 18 summarizes the results obtained corresponding to (a) the purge time required to reach 0 ppm, (b) the maximum concentration of acetic acid detected by the PID and (c) the equivalent volumes of acetic acid detected (pL) by the PID in the presence of an adsorbent for 1 pL injected as well as the deduction of the adsorption capacities.

[0335] [Table 18]

[0336]

[0318] Table 18 summarizes the data inherent to the adsorption measurements carried out in the presence of the different composites (zeolite activated carbon, MIL-100(Fe) and MIL-127(Fe)) and their average as well as the average percentages of acetic acid adsorption for each composite. [3191Capture of acrylic acid

[0337]

[0320] The VOC analyzed here is acrylic acid and the paper membranes formulated (see part 6) from microparticles of MIL-100(Fe), and activated carbon were tested.

[0338]

[0321] Results - capture tests

[0339]

[0322] Table 19 shows the results obtained.

[0340]

[0323] Table 19 summarizes the results obtained (a) at the purge time required to reach 0 ppm, (b) at the maximum acrylic acid concentration detected by the PID and (c) at the equivalent volumes of acrylic acid detected (pL) by the PID in the presence of an adsorbent for injected IpL as well as the deduction of the adsorption capacities.

[0341] [Table 19]

[0342]

[0324] Table 19 summarizes the data inherent in the adsorption measurements carried out in the presence of the different composites (zeolite activated carbon, MIL-100(Fe)) and their average as well as the average percentages of acrylic acid adsorption for each composite.

[0343]

[0325] Capture of furfural

[0344]

[0326] The VOC analyzed here is furfural, cellulose paper and paper membranes formulated (see part 6) from Al-PDA nanoparticles as well as microparticles of activated carbon and MIL- 100(Fe) were tested.

[0345]

[0327] Results - capture tests

[0346]

[0328] Table 20 shows the results obtained.

[0329] Table 20 summarizes the results obtained (a) at the purge time required to reach Oppm, (b) at the maximum furfural concentration detected by the PID and (c) at the equivalent volumes of furfural detected (pL) by the PID in the presence of an adsorbent for I pL injected as well as at the deduction of the adsorption capacities as well as at the deduction of the adsorption capacities.

[0347] [Table 20]

[0348]

[0330] Table 20 summarizes the data inherent in the adsorption measurements carried out in the presence of the different composites (activated carbon, Al-PDA and MIL-100(Fe)) and their average as well as the average percentages of furfural adsorption for each composite.

[0349]

[0331] Part 9: Release tests of paper membranes after capture of VOCs

[0350]

[0332] The objective of this part is to study the release by the different paper membranes after capture of pollutants (the pollutants studied in part 8).

[0351]

[0333] Release of VOCs

[0352]

[0334] After the capture tests, the paper membranes were placed independently in closed bottles (500 cm 3 ) for 24 hours in the presence of a passive diffusion tube (marketed by GASTEC) in order to quantify the quantity of pollutant emitted by the composite.

[0353]

[0335] Results - release tests

[0354]

[0336] Tables 21-24 compile the data obtained.

[0355]

[0337] Table 21 concerns the concentration of formic acid detected in the bottle showing the potential releases by the paper membrane after capture.

[0356] [Table 21]

[0357]

[0338] Table 21 summarizes the formic acid concentrations measured after 24 hours in the bottle in the presence of the paper membrane formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0358]

[0339] Table 22 concerns the acetic acid concentration measured in the bottle showing the potential releases by the paper membrane after capture.

[0359] [Table 22]

[0360]

[0340] Table 22 summarizes the acetic acid concentrations measured after 24 hours in the bottle in the presence of the paper membrane formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0361]

[0341] Table 23 concerns the acrylic acid concentrations measured in the bottle showing the potential releases by the paper membrane after capture. [Table 23]

[0362]

[0342] Table 23 summarizes the acrylic acid concentrations measured after 24 hours in the bottle in the presence of the paper membrane formulated from NaY zeolite, activated carbon or MIL-100(Fe).

[0363]

[0343] Table 24 concerns the furfural concentrations measured in the bottle showing the potential releases by the paper membrane after capture.

[0364] [Table 24]

[0365]

[0344] Table 24 summarizes the furfural concentrations measured after 24 hours in the bottle in the presence of the paper membrane formulated from activated carbon, Al-PDA or MIL-100(Fe).

[0366] References

[0367]

[0345] The following table lists the references cited previously in the text:

[0368] [Table 21]

Claims

Demands

1. A process for preparing a porous membrane comprising the following steps: a- preparing an aqueous mixture comprising a dispersion of fibers from an organic material in water, a nanoscale structuring agent comprising cellulose microfibrils and porous solid particles suspended in water; b- leaving the resulting aqueous mixture comprising the fibers, the nanoscale structuring agent comprising cellulose microfibrils and the porous solid particles under agitation for at least 10 minutes at room temperature; c- vacuum-filtering the mixture and recovering a composite material; and d- pressing the composite material obtained in step c- to form a porous membrane;in which the porous solid particles are selected from at least one of the following particles: a zeolite particle, an activated carbon particle, and a structured metallo-organic compound particle, referred to as MOF, which MOF comprises polydentate chelating ligands; and are taken in a content greater than or equal to 55% relative to the total mass of the porous membrane obtained.

2. A preparation method according to claim 1, wherein the fibers are bio-based fibers, preferably cellulose fibers.

3. A preparation method according to any one of claims 1 or 2, wherein the cellulose microfibrils are 0.5 to 50 µm in length.

4. Porous membrane obtained according to the process according to claims 1 to 3 for the capture of volatile organic compounds qualified as VOCs, comprising: 50 - 85% of a porous solid particle; 15-50% of a cellulosic matrix; the percentages being mass percentages of the mass of the ingredient considered relative to the total mass of the porous membrane; the porous solid particle being selected from at least one of the following particles: a zeolite particle, an activated carbon particle, and a structured metallo-organic compound particle, called MOF, which MOF comprises polydentate chelating ligands.

5. Porous membrane according to claim 4, wherein the porous solid particle is a MOF particle taken in a content of 55 to 80% relative to the total mass of the porous membrane.

6. Porous membrane according to any one of claims 4 or 5, wherein the MOF particle comprises 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. Porous membrane according to any one of claims 4 to 6, wherein the polydentate chelating ligand comprises C24-C24 aromatic compounds having at least one carboxylic acid function, Preferably, the polydentate 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-dihy droxy-3-cy lobutene-1,2-dione.

8. Porous membrane according to any one of claims 4 to 7, wherein the porous solid particle comprises at least one of the elements selected from nanoparticles and microparticles of 50 nm to 80 µm in diameter.

9. Porous membrane according to any one of claims 4 to 8, wherein the MOF is selected from MIL-100(Fe), MIL-127(Fe), Ca-Squarate, Al-PDA, MIP-202(Zr), MIL-91(Ti), UiO-66(Zr)-2CF3, MIL-53(A1)-CF3, CALF-20, and ZIF-8.

10. Porous membrane according to any one of claims 4 to 9, wherein the thickness of the membrane is 150-500 lim.

11. Use of a porous membrane according to any one of claims 4 to 10, to purify ambient air or to purify a storage space containing VOC-sensitive objects.

12. Use of a porous membrane according to any one of claims 4 to 11, for capturing CO2 in Pair ambient or industrial environment, separating gases, storing gases (hydrogen, methane), for proton conductivity in sustainable energy systems, for treating air by water adsorption for dehumidification, fresh water production, air conditioning or heating or decontaminating exhaust gases from an engine containing NOx.

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