 NANOCOMPOSITES NANOMATERIAU / COLLOIDAL POLYMOLECULAR SYSTEM, AND METHODS OF PREPARATION
专利摘要:
The present invention relates in particular to a laminar nanomaterial nanomaterial / natural polymolecular system in which the nanomaterial is an exfoliated and / or dispersed laminar material, and the polymolecular system has a hydrophilic / lipophilic balance (HLB) ≥ 8. The present invention also relates to to a colloid nanocomposite laminar nanomaterial / natural polymolecular system in a polar solvent, wherein the concentration of exfoliated nanomaterial / dispersed in the polar solvent is ≥ 1 g / L, and wherein the nanomaterial is laminar material exfoliated and / or dispersed , and the natural polymolecular system has a hydrophilic / lipophilic balance ≥ 8. The present invention also relates to a method for preparing a nanocomposite colloid according to the invention, as well as to a method of exfoliation and / or dispersion of a laminar material. The present invention also relates to a nanocomposite or nanocomposite colloid obtainable by a method according to the invention, as well as its use, in particular for the manufacture of inks, conductive coatings such as a conductive paint, catalysts such as metal-free catalysts for the selective dehydrogenation of ethylbenzene or styrene, or energy storage systems; or as an additive in polymers and composites, as a catalyst support, in the manufacture of electrodes, conductive films, in the production of layers for mechanical reinforcement, in tribology, for the formation of conductive networks, for example by self-assembly, or in applications in batteries, supercapacitors, and magnetism applications. 公开号:FR3058418A1 申请号:FR1660935 申请日:2016-11-10 公开日:2018-05-11 发明作者:Izabela Janowska；Lai TRUONG-PHUOC；Housseinou BA；Cuong Pham-Huu 申请人:Centre National de la Recherche Scientifique CNRS；Universite de Strasbourg； IPC主号:
专利说明:
Holder (s): NATIONAL CENTER OF SCIENTIFIC RESEARCH - CNRS - Public establishment, UNIVERSITE DE STRASBOURG Public establishment. Extension request (s) Agent (s): NOVAGRAAF TECHNOLOGIES. NANOMATERIAL NANOCOMPOSITES / COLLOIDAL POLYMOLECULAR SYSTEM, AND METHODS OF PREPARATION. FR 3 058 418 - A1 The present invention relates in particular to nanocomposite laminar nanomaterial / natural polymolecular system in which the nanomaterial is an exfoliated and / or dispersed laminar material, and the polymolecular system has a hydrophilic / lipophilic balance (HLB) 8. The present invention also relates to a colloid of nanocomposite laminar nanomaterial / natural polymolecular system in a polar solvent, in which the concentration of nanomaterial exfoliated / dispersed in the polar solvent is 1 g / L, and in which the nanomaterial is a laminar material exfoliated and / or dispersed, and the natural polymolecular system has a hydrophilic / lipophilic balance 8. The present invention also relates to a process for the preparation of a nanocomposite colloid according to the invention, as well as to a process for exfoliation and / or dispersion of a laminar material. The present invention also relates to a nanocomposite or colloid of nanocomposite capable of being obtained by a process according to the invention, as well as its use, in particular for the manufacture of inks, of conductive coatings such as a conductive paint, catalysts such as metal-free catalysts for the selective dehydrogenation of ethylbenzene or styrene, or energy storage systems; or as an additive in polymers and composites, as a catalyst support, in the manufacture of electrodes, conductive films, in the development of layers for mechanical reinforcement, in tribology, for the formation of conductive networks for example by self-assembly, or in applications in batteries, supercapacitors, and applications in magnetism. NANOMATERIAL NANOCOMPOSITES / COLLOIDAL POLYMOLECULAR SYSTEM, AND METHODS OF PREPARATION DESCRIPTION Technical area The present invention relates in particular to a nanocomposite consisting of a laminar nanomaterial and of a natural polymolecular system in which the nanomaterial is a laminar material (for example graphitic) exfoliated and / or dispersed, and the polymolecular system has a hydrophilic equilibrium / lipophilic (HLB)> 8. The present invention also relates to a colloid of nanocomposite laminar nanomaterial / natural polymolecular system in a polar solvent, in which the concentration of exfoliated / dispersed nanomaterial in the polar solvent is> 1 g / L, and in which the nanomaterial is a material. laminar (eg graphitic) exfoliated and / or dispersed, and the natural polymolecular system has a hydrophilic / lipophilic balance> 8. The present invention also relates to a process for the preparation of a nanocomposite colloid according to the invention, as well as to a process for exfoliation and / or dispersion of a laminar material, for example graphitic. The present invention also relates to a nanocomposite or colloid of nanocomposite capable of being obtained by a process according to the invention, as well as its use, in particular for the manufacture of inks, of conductive coatings such as a conductive paint, catalysts such as metal-free catalysts for the selective dehydrogenation of ethylbenzene or styrene, or energy storage systems; or as an additive in polymers and composites, as a catalyst support, in the manufacture of electrodes and conductive layers, in the manufacture of transparent electrodes and layers facilitating the transport of charges, in the manufacture of conductive films, in the development of layers for mechanical reinforcement, in tribology, for the formation of conductive networks for example by self-assembly, or in applications in batteries, supercapacitors, and applications in magnetism. In the description below, the references in square brackets ([]) refer to the list of references presented after the examples. STATE OF THE ART Graphene is a two-dimensional (monoplane) carbon crystal whose stack constitutes graphite. It has excellent electronic properties and is potentially available in large quantities by exfoliation of graphite. Graphene constitutes a basic construction motif of a large family of nano-graphitic materials, generally of very large specific surface, which combine a certain number of properties such as high electrical and thermal conductivity, good mechanical and chemical resistance, a specific sensitivity and adsorption force, or absorption of light allowing access to numerous applications in high performance composites, (opto) electronics, energy storage and transfer, catalysis or the field biomedical. The structure-property-application relationship is however an important consideration and the specific properties of graphene will depend on how it is geometrically and chemically shaped. Nanocarbons such as tubes, ribbons, dots, and multilayer graphenes rely on the winding, cutting and stacking of graphene sheets. Contrary to certain fields, where large size and high crystallinity graphene sheets (multi-sheet) or carbon nanofibers with high aspect ratio are determining for the formation of continuous paths easily propagating the electrical or mechanical properties, Small sheets with high oxygen content can be beneficial for other applications such as biomedical applications or catalysis. In the latter case, the introduction of defects or heteroatoms having a different electronegativity not only increases the binding capacity towards active metallic nanoparticles but also makes the graphitic materials active themselves. This concerns the field of metal-free catalysis, which for environmental (and economic) reasons, is the subject of increased interest in the scientific and industrial community. The most important examples include the vertically aligned N-doped carbon nanotubes which are very active in the oxygen reduction reaction [1], as well as the nanodiamonds which are very promising as a catalyst for the selective dehydrogenation of ethylene benzene to styrene [2], Given the important prospects of these nanocarbons, the choice of their synthesis is determined not only by the properties linked to their structure, but also by economic and environmental considerations. For application sectors, where a high yield of nanocarbons with flat structures is necessary, top-down methods, including different methods of exfoliation of graphitic materials, are desirable, in particular when obtaining multilayer graphene is not detrimental, even better. This is particularly true for effective methods of exfoliation in liquid medium of multilayer graphene, and which can be implemented on an industrial scale, for application in composites, energy storage and sectors of conductive coatings, where often graphene dispersions of significant concentration are of great interest (inks). Significant work has notably been devoted to the liquid exfoliation of graphite, expanded graphite or (more rarely) graphitic fibers in organic solvents with an appropriate surface tension (~ 40 mN / m), or with electronic properties allowing solvent-graphene interactions by charge transfer. The advantages of methods in an aqueous medium compared to organic solvents are mainly related to environmental and practical aspects, while the use of surfactants is necessary because of the hydrophobic nature of graphite. Typically, the surfactant molecules used generally include porphyrins [3,4], polymers [5, 6, 7], or large conjugated polycyclic aromatic hydrocarbons (PAHs) such as pyrenes [5,8] , which have significant toxicity. On the other hand, strongly oxidizing graphite intercalation products have been used in the case of exfoliation of graphite oxide in water to lead to graphene oxide, in which the conductive network However, C = C conjugate must then be restored, which results in a laborious overall process and vigorous reaction conditions. [9.10] There is therefore a real need for a process which overcomes the aforementioned defects, drawbacks and obstacles of the prior art, in particular a process for exfoliating and / or dispersing laminar materials, for example graphitic materials such as in the aqueous medium. than graphite, with very good yields and at very high concentrations. Description of certain advantageous embodiments of the invention The object of the present invention is precisely to meet this need by providing a method of exfoliation and / or dispersion of a laminar material, for example graphitic, characterized in that it includes exposing a laminar material to a source of shear forces in a polar solvent in the presence of a natural polymolecular system of hydrophilic / lipophilic equilibrium> 8. Said method leads to the formation of a nanocomposite constituted by the material in nanometric form (nanomaterial) and the natural polymolecular system, preferably in the form of a colloid. Preferably, when the nanomaterial is graphene (mono- or multi-sheet), the natural polymolecular system is not gum arabic, guar gum, locust bean gum, carrageenan, xanthan gum, or a combination thereof, particularly when the process is used to form a colloid with a single or multi-layer graphene concentration <0.5 to 1 g / L of nanocomposite . The method according to the invention implements two phenomena depending on the nature of the laminar material: exfoliation and dispersion. These two phenomena are linked but do not necessarily take place together with all the laminar materials capable of being used in the process of the present invention. In general, the method of the invention makes it possible to obtain a colloidal dispersion of exfoliated and / or dispersed nanomaterials, in the form of colloidal nanocomposite with the natural polymolecular system of HLB> 8. Whatever the nature of the laminar material used in the process, a dispersion is obtained, and this with yields and concentrations significantly higher than the known dispersion methods of the prior art. Thus, according to another aspect, the present invention also relates to a process for the preparation of a nanocomposite colloid, comprising the exfoliation and / or dispersion of a laminar material in a polar solvent in the presence of a natural polymolecular system hydrophilic / lipophilic balance> 8 under the action of a source of shear forces. The source of shear forces can be a sonicator, an emulsifier, a homogenizer or a system generating turbulence or vibrations, mechanical agitator. Preferably the source of shear forces is a sonicator, such as an ultrasonic bath or an ultrasonic finger assisted by a mechanical agitator. Advantageously, the sonicator is used at a frequency of 45 to 65 Hz, preferably 50 to 60 Hz. Advantageously, the sonicator is used with an intensity of 30 to 50 W, preferably 35 to 45W, preferably 40W ± 2W. Preferably, for the aforementioned methods, the action of the source of shear forces is coupled to mechanical agitation. Advantageously, the action of the source of shearing forces, optionally coupled to mechanical agitation, is carried out for 5 minutes to 50 hours, preferably for 15 minutes to 5 hours, more preferably for 1 to 3 hours. Depending on the nature of the materials used and the intended applications, the parameters of the method according to the invention, in particular the duration of application of the shear forces, and / or the intensity of these forces can be modified in order to obtain colloids of nanocomposites more and more exfoliated and / or dispersed, even more and more functionalized. For example, the extension of the exfoliation time of the expanded graphite from 2 h to 5 h gives multilayer graphene with smaller side sizes because it is more dispersed, and also having a higher oxygen level. The amounts of laminar material, of natural starting polymolecular system, the ratio between the two and the polar solvent can be adjusted according to the desired final consistency (solution, gel, paste, etc.), and the concentration of nanomaterial exfoliated / dispersed targeted in the final colloid. By way of example, a ratio x: y: z may be used around 10: 1: 10, x representing the amount of starting laminar material in mg, y representing the amount of natural starting polymolecular system in mg, and z representing the volume of polar solvent in ml. This ratio can be particularly advantageous when the natural polymolecular system is one or more proteins, such as hemoglobin, myoglobin or bovine serum albumin, in particular for obtaining colloids in the form of fluid colloids. To obtain colloids in ink form (concentration between - 5 - 30g / L), we can use a ratio x: y: z around 10: 1: 2, xy and z having the same meaning as ci -above. To obtain colloids in foam / gel form, an x: y: z ratio can be used around 40: 4: 1, xy and z having the same meaning as above (concentration between -30-70 g / L). To obtain colloids in paste form (concentration> 70g / L), we can use a ratio x: y: z around 80: 8: 1, x y and z having the same meaning as above. Of course, the above ratios can be modulated depending on the intended application, and the desired colloid consistency. According to a variant, the abovementioned methods may also comprise a step of filtration or centrifugation of the colloid obtained, or any other step allowing the separation of the constituents of the colloid having different morphologies, for example multilayer graphene of size and / or number of various layers. Such a separation of the constituents of the colloid according to the invention can be implemented for example by a non-chemical separation step, such as decantation, centrifugation, a source of vibration, or by combustion. According to a variant, the aforementioned methods can comprise a step of concentrating the colloid obtained. This concentration step can be implemented for example by evaporation of the polar solvent, and in particular makes it possible to reach higher concentrations of nanomaterial exfoliated and / or dispersed in the colloid. The polar solvent can be evaporated without substantial aggregation of the nanocomposite. The polar solvent can be evaporated until the solvent has been completely eliminated, thus resulting in a dry solid nanocomposite, which can be subsequently redispersed in a solvent, preferably a polar solvent such as H2O, a C1 to C8 alcohol of preferably C2 to C4, or a mixture thereof; preferably H2O, / -PrOH, or a mixture thereof; preferably H2O. Thus, the methods according to the present invention may further comprise a step of drying the colloid (evaporation of the polar solvent), and optionally a step of redispersing the solid nanocomposite thus obtained in a solvent, preferably polar. According to a variant, the aforementioned methods can also comprise a step of separation or destruction of the natural polymolecular system of the colloid. Preferably, it can be a separation or chemical destruction step, for example by acid or basic hydrolysis. For example, the natural polymolecular system can be partially or completely eliminated by treatment with aqua regia or nitric acid under reflux. The aforementioned methods can also comprise a step of separation of the solvent. The aforementioned methods may also comprise a calcination step at high temperature, preferably at a temperature T> 200 ° C, under an inert atmosphere or between 60 and 600 ° C under an oxygenated atmosphere (e.g. in the presence of air, or oxygen). By inert atmosphere is meant an environment in which reactions sensitive to air or humidity can be carried out, for example argon, helium or nitrogen. Advantageously, this calcination step can make it possible to perfect the elimination and / or the carbonization of the natural polymolecular system, in particular if a prior separation or destruction step by acid or basic treatment has not made it possible to eliminate the system 100%. natural polymolecular. Advantageously, the exfoliation and / or dispersion under the action of a source of shearing forces can be carried out in the presence of at least one metal salt, at least one source of dopant, at least one pore-forming agent, at least one water-soluble polymer or water-soluble polymer monomer, and / or a pH modifier. For example, the metal salt can be iron nitrate. Advantageously, the dopant can be nitrogen, boron or sulfur (the source of dopant can be eg carbonate ammonium, urea, thiourea. The blowing agent can be eg polystyrene beads Le water-soluble polymer or water-soluble polymer monomer can be, for example, polymethyl methacrylate (PMMA), polyethylene oxide, polyacrylamide, polyvinyl pyrrolidone (PVP), latex, polyvinyl acetate (PVA), polyethylene glycol (PEG). The pH modifier can be an inorganic base such as NaOH, KOH or inorganic acids, such as HCl for example. Preferably, the pH modifier will be used under conditions which do not lead to the hydrolysis or the degradation of the natural polymolecular system and / or of the nanocomposite. Typically, this will involve adjusting the temperature and concentration conditions of the pH modifier to moderate values to avoid hydrolysis or degradation. Natural polymolecular system In general, the above-mentioned natural polymolecular system having a hydrophilic / lipophilic balance (HLB)> 8 can be a natural polymolecular system of plant, animal, mushroom, algae or crustacean origin. Advantageously, the natural polymolecular system having a hydrophilic / lipophilic balance (HLB)> 8 and is chosen from phosphoglycerides, omega-3 fatty acids, plant extracts (preferably aqueous or hydroalcoholic) or biopolymers selected from proteins, polysaccharides or natural gums, preferably from a source of plant, animal, mushroom, algae or crustacean origin. Thus, polynucleotides (RNA, DNA) and monomolecular biomolecules, such as flavin, are excluded from the scope of the present invention. The hydrophilic / lipophilic balance can be determined by calculations based on a concept of Griffin and Davis according to the equation: HBL = Z (of number of hydrophilic groups) - Σ (of number of lipophilic groups) +7, or preferably by a simplified equation: HBL = 0.2 * (molecular weight of the hydrophilic part) / (total molecular weight of the natural polymolecular system). In practice, all polymolecular systems of natural origin which are soluble in water, or which have at least a low solubility in water, generally have an adequate hydrophilic / lipophilic balance within the scope of the invention (ie> 8). This is the case, for example, for polymolecular systems derived from plant extracts, in particular aqueous or hydroalcoholic extracts. Advantageously, the natural polymolecular system can be a protein. For example, it can be hemoglobin, myoglobin or bovine serum albumin. These proteins can be extracted / obtained by any suitable method known in the state of the art. Hydrophobins are excluded from the scope of the invention, insofar as this class of fungal proteins of a hundred amino acids is known for its capacity to form a hydrophobic film on the surfaces where they are formed / self- assemble, especially at the air / water interface. Advantageously, the natural polymolecular system can be a polysaccharide, preferably having hydrocolloid properties. For example, it may be maltodextrin, pectins such as pectin E 440, alginates, or gelatin. Advantageously, the natural polymolecular system can be lecithin, casein, or chitin. Advantageously, the natural polymolecular system can be a natural source of omega-3 fatty acid. For example, it can be a fish liver oil, such as cod liver oil, sardines, salmon, herring, or flaxseed oil, or rapeseed oil. Advantageously, the natural polymolecular system can be any plant extract capable of being obtained by conventional methods in the field. It may, for example, be plant extracts obtained by hydrodistillation (water vapor entrainment), by expression, using volatile organic solvents such as petroleum ether, hexane, ethyl ether, alcohol. ethyl, acetone, carbon dioxide, methylene chloride, benzene, toluene, etc ... or other types of extraction such as cold maceration, hot digestion, boiling decoction, leaching or percolation at cold or under pressure, hot infusion then cold, and alcoholic tincture. These can be crude plant extracts, or refined plant extracts obtained from fractionation of crude extracts (eg, the usual techniques for this include cryoconcentration, distillation under reduced pressure, ultrafiltration, osmosis reverse, etc ...). In general, the whole plant is not extracted, but only certain parts such as roots, rhizomes, wood, bark, leaves, flowers, flower buds, fruits, seeds, fruit juice, or excretions from the plant (gums or exudate ). Advantageously, the natural polymolecular system can be an okra extract (Abelmoschus esculentus) or an extract of ground fruit and leaves of African baobab (Adansonia digitata), preferably an aqueous or hydroalcoholic extract. Advantageously, the dried leaves and pods can be ground and used directly as a natural polymolecular system, without having to resort to prior extraction (the components of the plant are extracted in the polar solvent during the implementation of the process). Advantageously, the natural polymolecular system can be a gum, preferably having hydrocolloid properties. For example, it can be tragacanth, gum karaya, tara gum, gellan gum, konjac gum, or agar-agar. Preferably, the natural polymolecular system can comprise phosphoglycerides, omega-3 fatty acids, plant extracts (preferably aqueous or hydroalcoholic), or biopolymers selected from proteins, polysaccharides or natural gums. Preferably, the natural polymolecular system can be hemoglobin, myoglobin, bovine serum albumin, maltodextrin, agar-agar or an extract (preferably aqueous or hydroalcoholic) of okra or of crushed fruit and African baobab leaves. Advantageously, at least two natural polymolecular systems of hydrophilic / lipophilic balance (HLB) different and> 8, from any two of the natural polymolecular systems described above, can be used. Preferably, it may be two natural polymolecular systems chosen from hemoglobin, myoglobin, bovine serum albumin, maltodextrin, agar-agar or an extract (preferably aqueous or hydroalcoholic) of okra or of ground fruit and African baobab leaves. Laminar material Advantageously, the laminar material used in the above-mentioned processes is chosen from laminar carbonaceous materials, laminar nitrogenous materials, inorganic lamellar materials, pseudo-graphitic carbonaceous materials based on silicon, or laminar minerals. Advantageously, the laminar material can be a laminar carbonaceous material, for example graphitic, such as preferably expanded graphite, bundles of carbon nanofibers, nanodiamonds, or nanocornets. Advantageously, the laminar material can be a laminar nitrogenous material such as carbon nitride or boron nitride. Advantageously, the material can be a pseudo-graphitic carbon material based on silicon, such as silicon carbide. Advantageously, the laminar material can be a lamellar inorganic material from the family of metal chalcogenides such as WS 2 , MoS 2 , WSe2 or GaSe, semi-metals (eg WTa 2 , TcS 2 ), superconductors (p .ex. NbS 2 , TaSe 2 ), or even topological insulators and thermoelectric materials (eg Bi 2 Se 3 , Bi2Te). Advantageously, the laminar material can be a laminar mineral (also called “lamellar mineral”). Lamellar minerals include clay, clay, and all minerals in general that can be cleaved on flat surfaces, including: eg gypsum, muscovite, calcite, galena, halite; - the family of “laminar oxides” in general, eg V 2 Os, MoO 3 , MnO 2 , LaNb 2 C> 7, TiO 2 ; - Lamellar phyllosilicates, such as talc (Mg 3 Si40io (OH) 2 ), micas and montmorillonite. Phyllosilicates consist of a regular stack of elementary sheets of crystal structure, the number of which varies from a few units to a few thousand units. Among the phyllosilicates, the group comprising in particular talc, mica and montmorillonite is characterized by the fact that each elementary sheet is constituted by the association of two layers of tetrahedra located on either side of a layer of octahedra . This group corresponds to 2: 1 phyllosilicates, which include smectites. In view of their structure, 2: 1 phyllosilicates are also qualified as TOT type (tetrahedron- octahedron-tetrahedron). Lamellar phyllosilicates are for example used in the form of fine particles in many industrial sectors, such as: thermoplastics, elastomers, paper, paint, varnishes, textiles, metallurgy, pharmaceuticals, cosmetics, products phytosanitary or fertilizers in which phyllosilicates such as talc are used, by incorporation in a composition, as inert filler (for their chemical stability or for the dilution of active compounds of higher cost) or functional fillers (for example to strengthen the mechanical properties of certain materials). - all the oxides often also called “lamellar” of general formula AxMCL, where A = alkali metal ion, M = transition element and x is between 0.5 and 1 (e.g. NaxMCL, NaxVCL, LiCoCL); - the lamellar Perovskite oxides such as p. ex. M [La2Ti 3 Oio] where M = Co, Cu, Zn; - "double-lamellar hydroxides" (or "LDH") (eg Mg6Al2 (OH) i6); or - lamellar metal halides (eg CdL, MgBr2). Lamellar oxides can advantageously find application in batteries, supercapacitors, and applications in magnetism. Advantageously, the laminar nanomaterial can be an interleaved laminar nanomaterial (eg with cations or anions), such as Na + , Li +, K + , Ca 2+ , CIO4 'or metallic halides MCIx (eg M = Zn, Ni, Cu, Al, Fe where x = 2-4). Advantageously, at least two different laminar materials, from any two of the laminar materials described above, can be used. Polar solvent Advantageously, the polar solvent can be H2O, a C1 to C8 alcohol, preferably C2 to C4 alcohol, or a mixture of these; preferably H2O, / -PrOH, or a mixture thereof; preferably H2O. Definitions To facilitate understanding of the invention, a number of terms and expressions are defined below: The term “natural polymolecular system”, within the meaning of the present invention, refers to a macromolecular system of natural origin (derived from plants, animals, fungi, algae, crustaceans) consisting of compounds or entities of different molecular dimensions and / or similar but not strictly identical molecular structures, such as biopolymers, natural oils, sources of fatty acids, polysaccharides, proteins, etc. The natural polymolecular system in the context of the present invention therefore consists of a set molecules of natural origin which are not strictly identical (not isomolecular) and not strictly linked by covalent bonds, but which exist in the system in the form of a collectivity of molecules generally of the same class responding to a distribution curve and having a precise biological function in living or natural species in general. The term "nanomaterial nanomaterial / natural polymolecular system", within the meaning of the present invention, refers to a composite consisting of a laminar nanomaterial and a natural polymolecular system. The terms “laminar material” or “laminar material” are used interchangeably in the present document and designate, within the meaning of the present invention, a material in which an element or its texture (structure) exists in the form of a blade. Laminar or lamellar materials within the meaning of the invention include graphitic materials, pseudographitic carbonaceous materials, lamellar minerals as defined above, metal chalcogenides with a lamellar structure, of general formula MaXb, in which M represents a metal and X a chalcogen, a and b representing the respective proportions of metal and chalcogen, such as WS2, M0S2, MoSe2, MoTe2, WSe2 or GaSe, GaTe. These materials have a hexagonal and lamellar structure, that is to say consist of crystallographic planes of MX2 semiconductor sheets linked by van der Waals interactions. An MX2 sheet consists of a plane of metal atoms (M) sandwiched by two planes of chalcogen atoms (X). Within the sheets, the atomic bonds between M and X are covalent and therefore solid. On the other hand, the sheets are linked together by weak atomic interactions (van der Waals forces between the planes of chalcogen), thus allowing an easy sliding perpendicular to the sheets, which is at the origin of their capacity of lubrication with the solid state. Laminar materials, within the meaning of the present invention, also include semi-metals (eg WTa2, TCS2), superconductors (eg NbS2, TaSe2), or even topological insulators and thermoelectric materials (p. e.g. Bi2Se 3 , Bi2Te 3 ). The term “graphitic material”, within the meaning of the present invention, designates a crystalline laminar material consisting of a stack of sheets of hexagonal structure, in which the sheets are linked together by weak atomic interactions (van der Waals forces) , thus allowing easy sliding perpendicular to the direction of the stacking of the sheets, like graphite. The term “pseudo-graphitic carbon material”, within the meaning of the present invention, designates a crystalline material characterized by the regular arrangement of tetrahedra of metal (eg silicon) and carbon like graphite and diamond . Silicon carbide is one of these pseudographitic carbonaceous materials. Indeed, the structure of silicon carbide is marked as for graphite and diamond by the regular arrangement of silicon and carbon tetrahedra which can be arranged in a cubic structure of ZnS type: β-SiC, but also in hexagonal or rhombohedral structures: α-SiC which is the usual structure of high temperatures, however the β-SiC structure can be stabilized by small amounts of impurities. There is also a method of synthesizing graphene from SiC by thermal decomposition of SiC (Si sublimates and C graphitizes). The term “nanomaterial”, within the meaning of the present invention, designates a material whose size is a few nanometers in at least one of the dimensions of space. For example, the size of the material in at least one of the dimensions of the space is between 1 and 100 nm, preferably between 1 and 50 nm, preferably between 1 and 20 nm, preferably between 1 and 5 nm. The term “nanocarbon”, within the meaning of the present invention, designates any ordered structure based on carbon of nanometric dimension. By carbon-based structure of nanometric dimension is meant a carbonaceous material whose size is between approximately the thickness of a graphene plane to a few nanometers in at least one of the spatial dimensions. For example, the size of the carbonaceous material in at least one of the dimensions of the space can be between 0.3 and 100 nm, preferably between 0.3 and 50 nm, preferably between 0.3 and 20 nm, preferably between 0.3 and 10 nm, more preferably between 0.3 and 2 nm. Nanocarbons include carbon nanofibers, nanodiamonds, and carbon nanocornets. Other forms of ordered carbon such as hydrogenated or partially hydrogenated forms of the aforementioned nanocarbons such as partially hydrogenated graphene (for example, graphyne, graphane), as well as fullerene materials, carbon nanotubes (simple (SWCNT) , double (DWCNT), few- (FWCNT) and multi-walled (MWCNT)), cups of stacked nanocarbons (“cup-stacked nanocarbons”), carbon nanocones, etc., or any hydrogenated or partially hydrogenated form of these are also encompassed by the term nanocarbon. Nanocarbons include i) nanocarbon compounds having a single definable structure (for example, individual carbon nanofibers, graphene planes exfoliated from graphite, or individual units of carbon nanocornets, or nanodiamonds); or ii) aggregates of nanocarbon structures (for example, raw carbon nanofibers, stacked graphene planes (i.e. graphite or turbostratic carbon), raw nanodiamonds, or raw carbon nanocornets. The term "dispersed", within the meaning of the present invention, refers to a composition in which the material considered is suspended (or dispersed) in a solvent. In other words, the dispersion contains solid particles of material in suspension / dispersion in the solvent. Generally, the term "dispersed nanomaterial" in the context of the present invention covers fully individualized nanomaterials (eg, single-sheet graphene), as well as partially disaggregated nanomaterials such as multi-sheet graphene, or cut carbon nanofibers. When the nanomaterial considered is laminar, for example a graphitic material, it can be exfoliated in addition to being dispersed. In the context of the present invention, the dispersion is further stabilized by the natural polymolecular system used to implement the dispersion / exfoliation process according to the invention. The term "polar solvent", within the meaning of the present invention, refers to any organic or aqueous solvent whose dielectric constant is> 4. In particular, it may be a protic polar solvent. As mentioned above, the process according to the invention leads to the formation of a nanocomposite constituted by the laminar material exfoliated and / or dispersed, the size of which in at least one of the dimensions of the space is between 1 and 100 nm, and the natural polymolecular system, preferably in the form of a colloid. Also, the present invention also relates to a nanomaterial nanomaterial / natural polymolecular system in which the nanomaterial is an exfoliated and / or dispersed laminar material whose size in at least one of the dimensions of the space is between 1 and 100 nm, and the polymolecular system has a hydrophilic / lipophilic balance (HLB)> 8 and is chosen from phosphoglycerides, omega-3 fatty acids, plant extracts (preferably aqueous or hydroalcoholic), or biopolymers selected from proteins, polysaccharides or natural gums. Preferably, when the nanomaterial is graphene (mono- or multi-sheet), the natural polymolecular system is not gum arabic, guar gum, locust bean gum, carrageenan, xanthan gum, or a combination thereof, particularly when the process is used to form a colloid with a single or multi-layer graphene concentration <0.5 to 1 g / L of nanocomposite . Exfoliated and / or dispersed laminar nanomaterial Advantageously, the exfoliated and / or dispersed laminar nanomaterial can be chosen from nanocarbons, nitrogenous nanomaterials, lamellar inorganic nanomaterials, pseudo-graphitic nanomaterials based on silicon, or laminar minerals. Advantageously, it can be: - a nanocarbon, for example graphitic, exfoliated and / or dispersed such as graphene, multi-sheet graphene, carbon nanofibers, nanodiamonds or nanocornets; - a dispersed nitrogen nanomaterial such as carbon nitride or boron nitride; - an inorganic lamellar nanomaterial exfoliated and / or dispersed from the family of metal chalcogenides such as WS2, M0S2, WSe2 or GaSe; semimetals (eg WTa2, TCS2), superconductors (eg NbS2, TaSe2), or topological insulators and thermoelectric materials (eg Bi2Se 3 , Bi2Te); - a pseudo-graphitic nanomaterial dispersed based on silicon such as silicon carbide; or - a dispersed lamellar / laminar mineral such as: • clay, clay, gypsum, muscovite, calcite, galena, halite; • the family of “laminar oxides” in general, eg V2O5, MOO3, MnCA, LaNb2O7, TiO 2 ; • lamellar phyllosilicates, such as talc (Mg3Si40w (OH) 2 ), micas and montmorillonite; • the lamellar oxides of general formula AxMO 2 , where A = alkali metal ion, M = transition element and x is between 0.5 and 1 (such as NaxMO 2 , NaxVO 2 , LiCoO 2 ); • the lamellar Perovskite oxides such as M [La 2 Ti30io] where M = Co, Cu, Zn; • “double-lamellar hydroxides” (or “LDH”) (eg Mg 6 AI 2 (OH) i6); or • lamellar metal halides (eg Cdl 2 , MgBr 2 ). Concerning the nanocomposite according to the invention, the natural polymolecular system constituting it can be as defined above for the exfoliation and / or dispersion method according to the invention, namely a protein such as hemoglobin, myoglobin or l bovine serum albumin; a polysaccharide such as maltodextrin, pectins such as pectin E 440, alginates, or gelatin; lecithin, casein, chitin; a natural source of omega-3 fatty acid such as fish liver oil; a plant extract such as an okra extract or an extract of ground fruit and leaves of African baobab (preferably aqueous or hydroalcoholic extracts); or a gum such as tragacanth, karaya gum, tara gum, gellan gum, konjac gum or agar-agar. According to another aspect, the invention relates to a colloid of nanocomposite nanomaterial / natural polymolecular system in a polar solvent, in which the concentration of nanomaterial exfoliated / dispersed in the polar solvent is> 1 g / L, preferably> 2 g / L, more preferably> 3 g / L, even more preferably> 4 g / L, or even> 5 g / L, and in which the nanomaterial is an exfoliated and / or dispersed laminar material, and the natural polymolecular system has a balance hydrophilic / lipophilic> 8 and is chosen from phosphoglycerides, omega-3 fatty acids, plant extracts (preferably aqueous or hydroalcoholic), or biopolymers selected from proteins, polysaccharides or natural gums. As regards the colloid according to the invention, the nanomaterial and the natural polymolecular system are as defined above for the nanocomposite according to the invention. Preferably, the natural polymolecular system can be hemoglobin, myoglobin, bovine serum albumin, maltodextrin, agaragar or an extract (preferably aqueous or hydroalcoholic) of okra or of ground fruit and leaf leaves. African baobab. As regards the colloid according to the invention, the polar solvent is as defined above for the exfoliation and / or dispersion process, namely Η 2 Ο, a C1 to C8 alcohol, preferably C2 to C4, or a mixture thereof; preferably H2O, / -PrOH, or a mixture thereof; preferably H2O. Advantageously, the colloid according to the invention can be in the form of an emulsion, gel, suspension, paste or solution. We will speak of “solution” in the case of natural polymolecular systems with very high hydrophilic / lipophilic balance (typically> 12) and small exfoliated / dispersed nanomaterials (a few nanometers) and low concentration (<5 g / L) of nanomaterial exfoliated / dispersed in the colloid obtained. According to another aspect, the invention relates to the use of a nanocomposite or colloid of nanocomposite according to the invention, for the manufacture of inks, of conductive coatings such as conductive paints, of catalysts such as catalysts without metal for selective dehydrogenation of ethylbenzene or styrene, or energy storage systems. The nanocomposite or colloid of nanocomposite according to the invention can also be used as an additive in polymers and composites to modify the electrical, mechanical, thermal, barrier properties (for example of oxygen, humidity, gas), in the cement, as catalyst support, in the manufacture of electrodes and conductive layers, in the manufacture of transparent electrodes and layers facilitating the transport of charges in the types of slides: photovoltaic, liquid crystals, light-emitting diode, touch screens and “smart Windows ”in general, in the production of conductive films, in the development of layers for mechanical reinforcement, in tribology (this term covers, among other things, all areas of friction, wear, the study of interfaces and lubrication), for the formation of conductive networks for example by self-assembly or assembly under an electric field / magnetic, in biomedical applications (e.g. prosthesis, sensors, vectors for drugs), or in membranes / filters, or in applications in batteries, supercapacitors, and applications in magnetism. In general, any use where the properties of the exfoliated and / or dispersed nanomaterial may be of interest, can be envisaged in the context of the present invention. By way of example, the exfoliation and / or dispersion method according to the invention, applied to carbon nanofibers of the “fishbone” type makes it possible to obtain carbonaceous structures which have been found to be very effective as as a catalyst, for example in the reaction for the dehydrogenation of ethylbenzene to styrene. Benefits The present invention offers numerous advantages, in particular: - obtaining colloids of nanocomposites, with a very high concentration of exfoliated / dispersed nanomaterial (eg in the form of gels, suspensions or emulsions, these can be applied for example in conductive inks, paints and pastes), or in the form of a solution with great stability, and this without having to resort to a step of concentrating the colloid, for example by evaporation of the polar solvent. In particular, the process according to the invention makes it possible to obtain colloids of nanomaterial nanomaterial / natural polymolecular system in a polar solvent, in leguel the concentration of nanomaterial exfoliated / dispersed in the polar solvent is> 1 g / L, preferably> 2 g / L, more preferably> 3 g / L, even more preferably> 4 g / L, or even> 5 g / L, without subsequent colloid concentration step. Of course, this concentration of nanomaterial exfoliated / dispersed in the colloid can be increased by subjecting the colloid to a concentration step (eg by evaporation of the polar sovant). However, the major advantage of the process compared to other known methods is the possibility of directly obtaining colloids of concentration> 1 g / L, preferably> 2 g / L, more preferably> 3 g / L, even more preferably> 4 g / L, or even> 5 g / L, without having to use a concentration step. - The yields of exfoliated and / or dispersed nanomaterial obtained by the process according to the invention are significantly higher than those that can be expected with other existing methods. On average, yields of 60 to 80%, or even up to 100%, can be obtained according to the process of the invention. - The concentrations (several grams per liter) of exfoliated and / or dispersed nanomaterial obtained by the process according to the invention are also much higher than those obtained with other existing methods. These high concentrations allow in particular the production of graphene (mono- or multilayer) in large quantities with a very low cost. - In addition, the method according to the invention is based on an implementation in an aqueous solvent, or even water, and is, as such, environmentally friendly, economical and attractive from an industrial point of view . Other advantages may still appear to a person skilled in the art on reading the examples below, with reference to the appended figures, given by way of illustration and not limiting. Equivalents The following representative examples are intended to illustrate the invention and are not intended to limit the scope of the invention, nor should they be interpreted as such. Indeed, various variants of the invention and many other embodiments thereof, as well as other advantages than those described in this document, will appear to those skilled in the art from the whole of the content. of this document, including the following examples. The examples which follow contain important additional, illustrative, and teaching information which may be adapted to the practice of this invention in its various embodiments and the equivalents thereof. BRIEF DESCRIPTION OF THE FIGURES Figure 1: Photographs representing A) a suspension of expanded graphite (EG) in water, B) a suspension of expanded graphite (EG) in water in the presence of hemoglobin (HEM) before exfoliation / dispersion according to the process of the invention, C) a FLG-water-HEM colloid (multilayer graphene / water / hemoglobin) according to the invention. Figure 2: SEM micrographs of multilayer graphene nanocomposite / HEM obtained after exfoliation of EG in water in the presence of HEM for 2 h of ultrasonication and 2 days of decantation Α, Β) representing the fraction in the supernatant (FLG-HEM) and C, D) the part decanted with a large part of the hemoglobin residues. Figure 3: MET micrographs of multilayer graphene colloid obtained in the supernatant, after exfoliation of EG in water in the presence of HEM for 2 h and 2 days of decantation. Image B shows the FLG cut. The number of layers in the product can be counted well on images C and D. Figure 4: A) Raman spectra of FLG-HEM nanocomposite showing a high degree of graphitization (peak D, and very low D / G peak ratio) and a number of varied layers (up to 5 layers), B ) UV-Vis spectra of the aqueous solution 0 of HEM, and of the FLG-HEM suspension in water before and after ultrasonication. Figure 5: A) representative curves l (V) obtained by the four-point method on a “paper” of FLG-HEM and FLG-HEM-700 ° C, B and C) SEM micrographs of the paper highlighting its thickness and its surface. Figure 6: Α, Β) SEM and C micrographs, D) MET, graphene micrographs 5 multilayer obtained by exfoliation and dispersion of EG in water in the presence of HEM for 5 hours of ultrasonication and 2 days decantation (supernatant). Figure 7: A) ATG derivatives of EG, FLG-HEM and FLG-HEM-5h showing that the combustion temperature gradually decreases after a prolonged ultrasonic treatment, B) XPS spectra of EG, FLG-HEM and FLG-HEM- 5h. Figure 8: SEM and TEM micrographs of multilayer graphene nanocomposite obtained by exfoliation of EG in water in the presence of ASB (nanocomposite FLGASB) during 2 h of ultrasonication and decantation 2 days of (supernatant). Figure 9: A) Representative curves l (V) obtained by the four-point method on the “papers” of FLG-ASB and FLG-acid (treated by hydrolysis), B and C) SEM micrographs of these "papers" highlighting their thicknesses. Figure 10: ATG derivatives of FLG-acid and FLG-acid-700 ° C showing an increase in the combustion temperature for the sample treated at high temperature with Helium. Figure 11: Photograph of colloid FLG-ASB (with a ratio of 10: 1) in water with a concentration of A) 40 g / L, B) of 0.04 g / L (i.e. diluted 1000 times) Figure 12: Photograph of colloid FLG-ASB (with a ratio of 10: 1) in water: A) 40 g / L, B) 4.0 g / L, C) 0.4 g / L, D) 0.04 g / L with the formation of aggregates, E) 0.04 g / L with a FLG-ASB ratio of 10: 2, or amount of ASB was added in D) and sonicated for 10 min. Figure 13: Optical image of FLG-ASB colloid obtained in the ultrasonic bath. Figure 14: A) Photograph of colloid FLG-ASB with a concentration of 11.3 g / L, B) corresponding SEM micrographer. Figure 15: Optical image of aqueous colloids of (from left to right) boron nitride, carbon nitride, nanodiamonds, silicon carbide, carbon nanofibers obtained after ultrasonication for 2 hours in the presence of ASB. Figure 16: A) SEM micrograph and B) TEM micrograph of starting carbon nanofibers (CNF). Figure 17: MET micrographs of colloid of carbon nanofibers in water 2 5 obtained by ultrasonication in the presence of HEM for 1 hour (colloid of nanocomposite CNF-HEM). Figure 18: A) ATG derivatives of the starting carbon nanofibers (CNF) and of the CNF-HEM nanocomposite obtained according to the process of the invention, B) Desorption at programmed temperature of the starting CNFs and of the CNF-HEM nanocomposite. Figure 19: The results of the catalytic tests (conversion and selectivity in the dehydrogenation reaction of ethylbenzene to styrene, as a function of time under flow) obtained on two catalysts: initial carbon nanofibers (CNF), and the product obtained after exfoliation of CNF in water in the presence of HEM according to the process of the invention (CNF-HEM nanocomposite). Figure 20: Comparison of the catalytic performance of catalyst obtained by the process according to the invention (CNF-HEM nanocomposite) with the starting material (CNF), a commercial catalyst (K-Fe) and a carbon catalyst, the most active known to date in the literature. Figure 21: MET micrographs of the FLG-CNF-HEM composite obtained according to the method of the invention after ultrasound treatment of EG and CNF in water in the presence of HEM (nanocomposite FLG-CNF-HEM). Figure 22: MET micrographs of nanocomposite FLG-maltodextrin according to the invention and photograph of this colloid in water and in isopropanol. Figure 23: (A, B) Images illustrating the flexibility and the electrical conductivity of FLG / tissue obtained by exfoliation of expanded graphite in the presence of maltodextrin according to the invention, for intelligent textile applications. (B, C) Image of the FLG / polyurethane foam composite showing the variation in electrical conductivity as a function of pressure for their use as a sensor. Figure 24: SEM micrographs of: A and B) graphite, the starting material, B and C) the heavy part (bottom) of the colloid after exfoliation of graphite in water + HEM for 5 h, decanted for 24 h. Figure 25: SEM micrographs of the products found in the separated supernatant after the graphite exfoliation process in water in the presence of HEM for 5 h, and 24 h of decantation, A and B) second fraction (heavier), C and D ) first fraction (light). Figure 26: MET micrographs of multilayer graphene obtained after exfoliation of EG by ultrasonic treatment in water in the presence of Agar-agar. Figure 27: Images illustrating (A) Dispersion of C 3 N 4 in the absence and presence of maltodextrin after the ultrasound process and rest for 1 day. (B) Dispersion of C 3 N 4 in the absence and presence of maltodextrin 15 days later. EXAMPLES Abbreviations CNF: carbon nanofibers EG: expanded graphite FLG: multilayer graphene Aa: agar-agar ASB: bovine serum albumin HEM: hemoglobin SEM: scanning electron microscopy TEM: transmission electron microscopy Starting materials Bovine blood hemoglobin and bovine serum albumin were purchased from Sigma-Aldrich. Expanded graphite (EG) was purchased from Carbone Lorraine. The graphite pellets were purchased from the Timcal company. Boron nitride was purchased from Johnson Matthey Company. The nanodiamonds were purchased from Carbodeon Co. Ltd. The silicon carbide was purchased from SICAT SARL. The carbon nanofibers were prepared by chemical vapor deposition by catalytic (“CCVD” or “catalytic Chemical vapor deposition” in English). Catalytic tests The conditions used for the catalytic test, the analysis and the conversion of the products, and the selectivity calculations are the same as those previously reported [11]. Briefly, a dehydrogenation without steam of ethylbenzene to styrene was carried out with 300 mg of catalyst (CNF-HEM, or CNF), at a flow rate of ethylbenzene (2.8% in He) of 30 ml / min at 550 ° C. under atmospheric pressure. The reagents and products were analyzed online by gas chromatography (Perichrom, PR 2100) by flame ionization detection (FID). Characterization Scanning electron microscopy (SEM): the microscopy was carried out on a JEOL 2600F instrument operating at an acceleration voltage of 15 kV and an emission current of 10 mA. Transmission electron microscope (MET) images were taken on JEOL 2100F at an acceleration voltage of 200 kV, equipped with a probe corrector for spherical aberrations, and a resolution of 0.2 nm from point to point . Before the analysis, drops of aqueous suspensions were deposited on a film, a grid covered by a carbon membrane. The measurements in X-ray photoelectron spectroscopy (XPS) were carried out in a U HT installation (basic pressure 1 χ 10 ' 9 mbar) equipped with a hemispherical electronic analyzer WA class VSW (150 mm radius) with a detector multichanneltron. A monochromatic X-ray source (Al Ka anode operating at 240 W) was used as incident radiation. XP spectra were recorded in the fixed transmission mode using pass energies of 90 for exploratory scans and 44 eV for narrow scans. The Shirley method was used for the subtraction of the background, before the adjustment procedure. Raman spectra were recorded using LabRAMARAMIS Horiba Raman spectrometry equipment in the range of 500 - 4000 cm -1 at the laser excitation wavelength of 532 nm. Before the measurements, the samples were deposited on a SiCU / Si substrate by impregnation using a Pasteur pipette and then carefully dried. The UV-Vis spectra of the dispersions were recorded on a spectrophotometer equipped with a Peltier PTP1 effect system (PerkinElmer Lambda 35) at room temperature. Layer resistance The layer resistance measurements (Rs) were carried out on thin paper by the four point method (“FPP”), inducing a different current (I); from 1 pA to 1 mA using two external probes and measuring the voltage difference (V) between two internal probes, with a Keithley 220 programmable current source coupled to a Hewlett-Packard 34401A multimeter. In the calculation of Rs values from Ohm's law, a geometric factor of the samples was considered [12], General protocol for exfoliation and / or dispersion of laminar materials x mg of laminar starting material and y mg of natural polymolecular system of HLB> 8 are added to z ml of distilled water with the ratio x: y: z varied. The ultrasound treatment may or may not be assisted by mechanical agitation and the duration is between 5 min and 50 h. The ultrasonic power and the mixing volume can be varied. The colloids obtained contain exfoliated / dispersed nanomaterials in the form of nanocomposites with the molecules of the natural polymolecular system. In order to obtain stable dispersions and / or exfoliated / dispersed nanomaterials, the dispersions are left to stand (1 h - a few days) in order to decant the heavy parts and / or are centrifuged. The supernatants thus obtained are stable for high durations (days-months). The concentrations and yields of exfoliated and / or dispersed nanomaterial are calculated from the quantity of the heavy parts decanted. The colloid obtained is thus separated from the heavy parts, which are dried and weighed. The yields and the concentrations are calculated on the basis of the mass of exfoliated and / or dispersed nanomaterials remaining stable in the colloid. Example 1 - Nanocomposite FLG-HEM 300 mg of expanded graphite (EG) and 30 mg of hemoglobin (HEM) are added to 300 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical stirring for 2 hours (fig. 1). The mixture obtained is left to decant for 2 days. The 250 ml of supernatant containing the exfoliated multi-layer graphene (in the form of FLGHEM nanocomposite) and a remaining part of the hemoglobin are then separated from the bottom. The exfoliation yield calculated as a function of the mass of multilayer graphene obtained in the supernatant relative to the initial mass of expanded graphite is 60%. The SEM images of multilayer graphene obtained in the supernatant are presented in FIG. 2 A, B. The SEM images of the decanted part (bottom) containing the major part of the residues of hemoglobin and graphite with a lower degree of exfoliation (sheets with higher number of layers) are represented in fig . 2 C, D. The number of layers is varied and low (<10) in the multilayer graphene obtained (fig. 3) and these observations are confirmed by Raman spectroscopy performed on several FLGs (the 2D peak) (fig. 4 A). The full spectrum also highlights the high quality of FLG obtained, with a very low defect rate (the peak D and the ratio of peak D and G is very small). The dispersion obtained is filtered in the form of blotting paper and dried at 130 ° C., and the electrical resistance of the material obtained is measured by the four-point method. The electrical conductivity is then calculated on the basis of the resistance obtained (adjusted by the geometric factor) and the average thickness of the “paper” of 50 μm determined by SEM imaging. The paper is also subjected to a high temperature treatment of 700 ° C. under He and its electrical conductivity has been measured. The conductivity of the starting material is of the order of 10 2 S / m and increases to 10 4 S / m after the treatment at 700 ° C. Fig. 5 shows curves l (V) and the associated SEM images. Example 2 - Nanocomposite FLG-HEM-5h 300 mg of expanded graphite (EG) and 30 mg of hemoglobin (HEM) are added to 300 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical stirring for 5 hours (fig. .1). The mixture obtained is left to decant for 2 days. The 250 ml of supernatant containing the multilayer graphene (in the form of nanocomposite FLG-HEM) and a remaining part of the hemoglobin are then separated from the bottom. The SEM, MET, XPS and ATG analysis confirms that the multilayer graphene obtained in the supernatant shows smaller sheet sizes (more cut) and contains more structural defects with a higher oxygen level fig. 6 and fig. 7. The ATG analysis shows that the combustion temperature gradually decreases after prolonged ultrasonication treatment (fig.7A). XPS analysis confirms that the oxygen level for EG, FLGHEM and FLG-HEM-5h gradually increases, the O / C ratio calculated by the respective O1s / C1s ratio is 0.024, 0.039 and 0.090, and width at mid -peak height C1s also increases successively with prolonged ultrasonic treatment: 1.18, 1.21, 1.25. Example 3- Nanocomposite FLG-ASB 300 mg of expanded graphite (EG) and 30 mg of bovine serum albumin (BSA) are added to 300 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 h. The mixture obtained is left to decant for 2 days. The 250 ml of supernatant containing the multilayer graphene (in the form of nanocomposite FLG-ASB) and a remaining part of the albumin are then separated from the bottom. The exfoliation yield calculated as a function of the mass of multilayer graphene obtained in the supernatant relative to the initial mass of expanded graphite is 70%, and the SEM and TEM images of multilayer graphene obtained in the supernatant are shown in FIG. . 8. a) The dispersion obtained is filtered in the form of blotting paper and dried at 130 ° C. and the electrical resistance of the material obtained is measured by the four-point method. The electrical conductivity is then calculated on the basis of the resistance obtained (adjusted by the geometric factor) and the average thickness of "paper" of 30 μm determined by SEM imaging. The material conductivity is of the order of 10 2 S / m. Figs. 9 A and B show the curve l (V) and the associated SEM image. It should be noted that the filtration of the FLG-ASB nanocomposite gives a structure in the form of a sponge. This is due to the presence of ASB which has detergent properties (fig. 9B). The FLG-ASB “paper” was subjected to a treatment at high temperature (700 ° C. under He) for 2 h and its conductivity went from 10 2 S / me to 10 4 S / m. b) The dispersion obtained is dried and the product is subjected to the hydrolysis treatment in aqua regia under reflux for 2 hours. the product is then filtered and washed to neutral pH and dried at 130 ° C for 2 h, and then redispersed in isopropanol and filtered to form a "paper". The “paper” obtained is dried for 20 h at 50 ° C. and its electrical resistance is measured by the four-point method. The electrical conductivity calculated for a thickness of 0.4 pm is of the order of 10 5 S / m. Figs. 9A and C show the curve l (V) and the associated SEM image. The increase in conductivity after treatment at high temperature is linked to desorption of oxygenated groups and other possible impurities. The FLG-acid “paper” is also treated at high temperature (700 ° C, 2h). The ATG derivatives of the FLG-acid and FLG-acid-700 ° C samples show a higher combustion temperature for the sample treated at high temperature (fig. 10). The XPS analysis agrees with this data and shows a decreasing O to C ratio from 0.035 to 0.025. Example 4- Nanocomposite Ink FLG-ASB 2.5 g of expanded graphite (EG) and 250 mg of bovine serum albumin (BSA) are added to 500 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 h. The dispersion is left to stand for 24 h and the resulting colloid (supernatant) has a multilayer / monolayer graphene concentration of 6.3 g / L and can be used as ink, conductive paint. The exfoliation yield calculated as a function of the mass of multilayer / monolayer graphene obtained in the supernatant relative to the initial mass of expanded graphite is 63%. EXAMPLE 5 Foam and Pulp of Nanocomposite FLG-ASB 12.8 g of expanded graphite (EG) and 1.28 g of bovine serum albumin (ASB) are added to 320 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the type Branson Digital Sonifier 450, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 hours. Fig. 11. A shows the resulting colloid with a foam appearance linked to the detergent function of ASB. Fig. 11 B shows this colloid diluted a thousand times. The dispersion remains very stable (fig. 12A: 40 g / L, B) 4 g / L, C) 0.4 g / L). At dissolution a thousand times (0.04g / L) we can observe the formation of light aggregates (fig. 12D) which can be re-dispersed by short sonication (10min) by adding a very small amount of ASB. In the colloid FLG-ASB of multilene / monolayer graphene concentration of 40 g / L, 4.5 g of EG and 0.45 g of ASB were added. The resulting mixture is then subjected to sonication assisted by stirring for 1 h. The final colloid has a multilayer / monolayer graphene concentration of 54 g / L. After 24 hours, the stable final colloid (supernatant) is recovered and has a multilayer / monolayer graphene concentration of 46 g / L for an exfoliation yield of 85%. Additional drying for 24 hours gives a paste with a concentration of multilayer / monolayer graphene of 80 g / L. Example 6-Nanocomposite FLG-ASB g of expanded graphite (EG) and 1 g of bovine serum albumin (ASB) are added to 800 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasound treatment using a Bransonic type ultrasonic bath, with a frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical stirring for 15 h. A quantity of water is added from time to time to fill the evaporated water. The colloid (FLG-ASB) of very high concentration of multilayer / monolayer graphene is obtained (fig. 13). Example 7- FLG-ASB Nanocomposite 7.5 g of glitter graphite and 0.75g of bovine serum albumin (BSA) are added to 250 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 3 h. The resulting colloid is left to stand for 24 h. Then, the decanted part and the stable part (supernatant) of 200 ml are separated. The yield of this exfoliation calculated on the basis of the stable part is 30% for a multilayer / monolayer graphene concentration of 11.3 g / L (fig. 14). Example 8 - HEM Nanocomposites 2g of different laminar / lamellar materials (chosen from boron nitride, carbon nitride, nanodiamonds, silicon carbide, carbon nanofibers) and 0.2 g of ASB are added to 250 ml of distilled water in a 600 ml beaker. Each mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 hours. The colloids obtained are left to stand for 24 hours and photographs of these samples have been collected (fig. 15). Example 9 CNP-HEM Nanocomposite 300 mg of carbon nanofibers (CNF) (fig. 16) and 30 mg of HEM are added to 300 ml of distilled water in a 1000 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 h. The dispersion obtained contains exfoliated and dispersed (cut) nanofibers and remains stable for months, resulting in an estimated yield of 100%. The suspension is then filtered and dried for 24 hours at room temperature, then 2 hours at 130 ° C. The product obtained is presented in the MET images (fig. 17). The analyzes of XPS and ATG show that the product obtained has a higher degree of graphitization (FIG. 18A) than the starting CNFs. The results collected with ATG and XPS show that the combustion temperature increases and highlights a decrease in the oxygen level, after the ultrasound treatment. The O / C ratio is 0.083 and 0.022 for CNF and CNF-HEM respectively. Analysis of the desorption at programmed temperature shows that the type of grouping in the two samples changes (fig. 18B). The specific surface of this material measured by the BET method is 135 m 2 / g against 154 m 2 / g for the starting carbon nanofibers. CNF-HEM nanocomposite has also been used as a catalyst in the dehydrogenation reaction of ethylbenzene to styrene. The catalytic tests carried out as a function of time under flow show that the CNFHEM nanocomposite is very efficient with a conversion of 32% and selectivity of 99%, compared to the starting catalyst based on starting nanofibers which has a conversion of 10% and the 93% selectivity (fig. 19). The catalytic tests were carried out with 300 mg of catalysts and an ethylbenzene concentration by volume of (2.8%) with a flow of 30 ml / min of He at 550 ° C under atmospheric pressure. The reagents and products were analyzed online by gas chromatography. The dehydrogenation activity of ethylbenzene to styrene of the CNF-HEM catalyst was also compared to commercial iron-based catalysts, so that nanodiamond which is currently the most active metal-free catalyst known in the literature (fig. 20) . Example 10 CNP-FLG-HEM Nanocomposite 150 mg of CNF, 150 mg of EG and 30 mg of HEM are added to 300 ml of distilled water in a 600 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 hours. The dispersion obtained contains a nanofiber nanocomposite / multilayer graphene / hemoglobin (fig. 21). EXAMPLE 11 Nanocomposite FLG-Maltodextrin 300 mg of EG and 30 mg of maltodextrin are added to 300 ml of distilled water in a 600 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 2 hours. a) the mixture obtained is centrifuged at a speed of 5500 rpm. The supernatant containing the FLG-Maltodextrin nanocomposite (FIG. 22 - TEM micrographs) is then separated from the bottom, filtered and dried at 80 ° C. under vacuum for 2 h. The product obtained is redispersed in isopropanol (fig. 22). b) the mixture obtained is left to stand for 1 day. The supernatant fraction is then separated and used to deposit a conductive layer on insulating materials. An illustration of this type of material deposited very homogeneously on a “zetex” fabric (smart or reinforced textiles) and a three-dimensional polyurethane foam (sensors) is presented in fig. 23. Example 12 - Nanocomposite FLG-HEM-5h 300 mg of graphite and 30 mg of HEM are added to 300 ml of distilled water in a 600 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 5 h. The mixture obtained is left to decant for 1 day. The supernatant (separated into two fractions) containing the nanocomposite FLG-HEM is separated from the bottom (FIG. 24 B, C-bottom). The first part of 70 ml which is a top fraction of the supernatant (fig. 25 C, D) and the second part of the 70 ml is the next fraction lying below the first fraction (fig. 25 A, B). The second fraction contains a nanocomposite with thicker multilayer graphene (with a higher number of layers). This example shows that by simple decantation based on Arrhenius law it is possible to separate the multilayer graphene with a different degree of exfoliation (number of layers) and a lateral size. The yield calculated for the fraction is 23%. EXAMPLE 13 Nanocomposite FLG-Aa 600 mg of EG and 60 mg of agar-agar (Aa) are added to 300 ml of distilled water in a 600 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 1 hour. The mixture obtained is left to decant for 2 days. The 250 ml of supernatant containing the nanocomposite FLG-Aa is separated from the bottom. TEM images of multilayer graphene obtained in the supernatant (in the form of nanocomposite) are presented in FIG. 26. Example 14 Nanocomposite C3N4-Maltodextrin 300 mg of carbon nitride (C3N4) and 30 mg maltodextrin are added to 300 ml of distilled water in a 600 ml beaker. The mixture is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical agitation for 1 hour. The resulting mixture is transferred to 50 ml pill organizers. Fig. 27 shows the stability of this colloid obtained after 1 and 15 days of rest, compared with a suspension of C3N4 obtained by ultrasonication in the absence of maltodextrin. Example 15 - FLG-Gombo Nanocomposite 10 g okra are boiled in 300 ml of water for 15 min. The solid residue is pressed in order to extract the maximum of natural polymolecular system and separated from the liquid phase. In the water containing the natural polymolecular system are added 300 mg of expanded graphite and everything is subjected to an ultrasonic treatment using an ultrasonic finger of the Branson Digital Sonifier 450 type, 0 frequency of ~ 50/60 Hz with an intensity of 10% of 400W, and assisted by mechanical stirring for 2h. The resulting colloid is left to stand for 24 h. Then, the decanted part and the stable part (supernatant) of 200 ml are separated. List of References [1] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai., Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction, Science 2009, 323, 760-764. [2] Jian Zhang, Dang Sheng Su, Raoul Blume, Robert Schlogl, Rui Wang, Xiangguang Yang, Andreja Gajovic. Surface Chemistry and Catalytic Reactivity of a Nanodiamond in the Steam-Free Dehydrogenation of Ethylbenzene. Angew. Chem. Int. Ed. 2010, 49, 8640-8644. [3] Jianxin Geng, Byung-Seon Kong, Seung Bo Yang, Hee-Tae Jung. Preparation of graphene relying on porphyrin exfoliation of graphite. Chem. Commun., 2010, 46, 5091-5093. [4] Jenny Malig, Adam W. I. Stephenson, Pawel Wagner, Gordon G. Wallace, David L. Officer and Dirk M. Guldi. Direct exfoliation of graphite with a porphyrin creating functionalizable nanographene hybrids; Chem. Commun., 2012,48, 87458747. [5] Fei Liu, Jong Young Choi, Tae Seok Seo, DNA mediated water-dispersible graphene fabrication and gold nanoparticle-graphene hybrid. Chem. Common. 2010, 46, 2844-2846. [6] L. Guardia, M.J. Fernândez-Merino, J.l. Paredes, P. Solis-Fernândez, S. Villar-Rodil, A. Martinez-Alonso, J.M.D. Tascôn. High-throughput production of pristine graphenein an agueous dispersion assisted by non-ionic surfactants. Carbon 2011, 49, 1653-1662. [7] Athanasios B. Bourlinos, Vasilios Georgakilas, Radek Zboril, Théodore A. Steriotis, Athanasios K. Stubos, Christos Trapalis. Agueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes. Solid State Communications 149, 2009, 2172-2166. [8] H. Yang, Y. Hernandez, A. Schlierf, A. Felten, A. Eckmann, S. Johal, P. Louette, J.-J. Pireaux, X. Feng, K. Mullen, V. Palermo, C. Casiraghi. A simple method for graphene production based on exfoliation of graphite in water using 15 pyrenesulfonic acid sodium knows. Carbon 2013, 53, 357-365. [9] D.R. Dreyer, A. D. Todd, C.W. Bielawski, Harnessing the chemistry of graphene oxide, Chem. Soc. Rev. 2014, 43, 5288-5301. [10] R. Rozada, J. I. Paredes, S. Villar-Rodil, A. Martinez-Alonso, J. M. D. Tascôn. Towards full repair of defects in reduced graphene oxide films by two-step graphitization, Nano Research 2013, 6 (3), 216-233. [11] “A few-layer graphene-graphene oxide composite containing nanodiamonds as metal-free catalysts“ T. T. Thanh, H. Ba, T.-P. Lai, J.-M. Nhut, O. Ersen, D. Bégin, I. Janowska, D. L. Nguyen, P. Granger, C. Pham-Huu. J. Mater. Chem. At 2014, 2, 11349-11357. [12] F. Smith. Measurement of sheet resistivities with four-point probe. Bell Syst. Tech. Newspaper. 1958, 711-718.
权利要求:
Claims (20) [1" id="c-fr-0001] 1. Nanomaterial nanomaterial / natural polymolecular system in which the nanomaterial is an exfoliated and / or dispersed laminar material whose size in at least one of the dimensions of the space is between 1 and 100 nm, and the polymolecular system has a hydrophilic equilibrium / lipophilic (HLB)> 8 and is chosen from phosphoglycerides, omega-3 fatty acids, plant extracts (preferably aqueous or hydroalcoholic), or biopolymers selected from proteins, polysaccharides or natural gums; provided that when the nanomaterial is graphene (mono- or multi-sheet), the natural polymolecular system is not a hydrophobin, lysozyme, gum arabic, guar gum, locust bean gum ("locust bean gum "In English), a carrageenan, a xanthan gum, or a combination of these. [2" id="c-fr-0002] 2. Nanocomposite according to claim 1, in which the exfoliated and / or dispersed laminar nanomaterial is: - a nanocarbon, for example graphitic, exfoliated and / or dispersed such as graphene, multi-sheet graphene, carbon nanofibers, nanodiamonds, or nanocornets; - a dispersed nitrogen nanomaterial such as carbon nitride or boron nitride; - an inorganic lamellar nanomaterial exfoliated and / or dispersed from the family of metal chalcogenides such as WS2, MO2, WSe2 or GaSe; semi-metals (eg WTa2, TCS2), superconductors (eg NbS2, TaSe2), or topological insulators and thermoelectric materials (eg Bi2Se 3 , Bi2Te); or - a pseudo-graphitic nanomaterial dispersed based on silicon such as silicon carbide; or - a dispersed laminar mineral, such as: • clay, clay, gypsum, muscovite, calcite, galena, halite; • laminar oxides, such as V2O5, MoO 3 , MnO2, LaNb2O7, TiO2; • lamellar phyllosilicates, such as talc (Mg [3" id="c-fr-0003] 3Si40io (OH) 2 ), micas and montmorillonite; • the lamellar oxides of general formula AxMO 2 , where A = alkali metal ion, M = transition element and x is between 0.5 and 5 1 (NaxMO 2 , NaxVO 2 , LiCoO 2 ), • lamellar Perovskite oxides such as M [La 2 TÎ30io] where M = Co, Cu, Zn, • double-lamellar hydroxides such as Mg6AI 2 (OH) i6 ), • lamellar metal halides such as Cdl 2 , MgBr 2 . 3. Nanocomposite according to claim 1 or 2, in which the natural polymolecular system is: - a protein chosen from hemoglobin, myoglobin or bovine serum albumin; - A polysaccharide chosen from maltodextrin, pectins such as pectin 15 E 440, alginates, or gelatin; - lecithin, casein, or chitin; - a natural source of omega-3 fatty acid chosen from fish liver oil, such as cod liver oil, sardines, salmon, herring, or linseed oil, or rapeseed; 2 0 - an okra extract or an extract of ground fruit and African baobab leaves; - a gum chosen from tragacanth, karaya gum, tara gum, gellan gum, konjac gum, or agar-agar. [4" id="c-fr-0004] 4. Nanomaterial nanocomposite colloid / natural polymolecular system in a polar solvent, in which the concentration of exfoliated / dispersed nanomaterial in the polar solvent is> 1 g / L, and in which the nanomaterial is an exfoliated laminar material and / or dispersed whose size in at least one of the dimensions of the space is between 1 and 100 nm, and the natural polymolecular system has a hydrophilic / lipophilic balance> 8 and is chosen from phosphoglycerides, omega-3 fatty acids, plant extracts, or biopolymers selected from proteins, polysaccharides or natural gums. [5" id="c-fr-0005] 5. Colloid according to claim 4, in which the nanomaterial is as defined in claim 2, and the natural polymolecular system is as defined in 5 claim 3, preferably the natural polymolecular system is hemoglobin, myoglobin, bovine serum albumin, maltodextrin, agaragar or an extract of okra or ground fruit and leaves of African baobab. [6" id="c-fr-0006] 6. Colloid according to claim 4 or 5, wherein the polar solvent is H 2 O, a C1 to C8 alcohol preferably C2 to C4, or a mixture thereof; of Preferably H 2 O, / -PrOH, or a mixture thereof; preferably H 2 O. [7" id="c-fr-0007] 7. Colloid according to any one of claims 4 to 6, which is in the form of emulsion, gel, suspension or solution. [8" id="c-fr-0008] 8. Method for preparing a nanocomposite colloid according to any one of claims 4 to 7, comprising exfoliation and / or dispersion of a material 15 laminar in a polar solvent in the presence of a natural polymolecular system of hydrophilic / lipophilic equilibrium> 8 under the action of a source of shearing forces, preferably coupled to mechanical agitation, for 5 minutes to 50 hours, preferably for 15 minutes to 5 hours, more preferably for 1 to 3 hours. 2 0 [9" id="c-fr-0009] 9. A method of exfoliation and / or dispersion of a laminar material, characterized in that it comprises exposing a laminar material to a source of shear forces, preferably coupled to mechanical agitation, for 5 minutes at 50 hours, preferably for 15 minutes to 5 hours, more preferably for 1 to 3 hours, in a polar solvent in the presence of a system 2 5 natural polymolecular hydrophilic / lipophilic balance> 8. [10" id="c-fr-0010] 10. Method according to claim 8 or 9, in which: a) the laminar material is - a laminar carbonaceous material such as graphite, preferably expanded, bundles of carbon nanofibers, nanodiamonds, or nanocornets; - a laminar nitrogenous material such as carbon nitride or boron nitride; a pseudo-graphitic carbonaceous material based on silicon, such as silicon carbide: - a lamellar inorganic material from the family of metal chalcogenides such as WS 2 , MoS 2 , WSe 2 or GaSe; semi-metals (eg WTa 2 , TcS 2 ), superconductors (eg NbS 2 , TaSe 2 ), or topological insulators and thermoelectric materials (eg Bi 2 Se3, Bi 2 Te ); or - a laminar mineral, such as: • clay, clay, gypsum, muscovite, calcite, galena, halite; • laminar oxides, such as V 2 Os, ΜοΟβ, MnO 2 , LaNb 2 C> 7, TiO 2 ; • lamellar phyllosilicates, such as talc (Mg3Si40io (OH) 2 ), micas and montmorillonite; • the lamellar oxides of general formula AxMO 2 , where A = alkali metal ion, M = transition element and x is between 0.5 and 1 (NaxMO 2 , NaxVO 2 , LiCoO 2 ), • the lamellar Perovskite oxides such as M [La 2 Ti30w] where M = Co, Cu, Zn, • double-lamellar hydroxides such as Mg6AI 2 (OH) i6), • lamellar metal halides such as Cdl 2 , MgBr 2 . b) the natural polymolecular system is as defined in claim 3, preferably hemoglobin, myoglobin, bovine serum albumin, maltodextrin, agar-agar or an extract of okra or of ground fruit and of baobab leaves. c) the polar solvent is as defined in claim 6. [11" id="c-fr-0011] 11. The method of claim 8 or 9, wherein the source of shear forces is a sonicator, an emulsifier, a homogenizer or a system generating turbulence or vibrations, mechanical stirrer, preferably the source of shear forces is a sonicator , such as an ultrasonic bath or an ultrasonic finger, assisted by a mechanical stirrer. [12" id="c-fr-0012] 12. Method according to any one of claims 8 to 11, in which at least two different polymolecular natural hydrophilic / lipophilic balance (HLB) systems are used. [13" id="c-fr-0013] 13. Method according to any one of claims 8 to 12, in which at least two different laminar materials are used. [14" id="c-fr-0014] 14. Method according to any one of claims 8 to 13, further comprising a step of filtration or centrifugation of the colloid obtained, or other step allowing the separation of the components of the colloid having different morphologies, for example multilayer graphene in size and / or many different layers. [15" id="c-fr-0015] 15. Method according to any one of claims 8 to 14, in which the exfoliation and / or dispersion under the action of a source of shear forces is carried out in the presence of: - at least one metal salt, such as iron nitrate; - at least one source of dopant, such as nitrogen, boron or sulfur; - at least one pore-forming agent, such as polystyrene beads; - at least one water-soluble polymer, or at least one water-soluble polymer monomer such as PMMA, polyethylene oxide, polyacrylamide, PVP, latex, PVA, PEG; - a pH modifier, such as NaOH, KOH or inorganic acids, under conditions which do not lead to hydrolysis or degradation of the natural polymolecular system and / or of the nanocomposite. [16" id="c-fr-0016] 16. Method according to any one of claims 8 to 15, further comprising a non-chemical separation step, such as decantation, centrifugation, a source of vibration or by combustion. [17" id="c-fr-0017] 17. Method according to any one of claims 8 to 16, further comprising a step of concentrating the colloid obtained, drying the nanocomposite, and optionally redispersing the nanocomposite in a polar solvent. [18" id="c-fr-0018] 18. Method according to any one of claims 8 to 17, further comprising a calcination step at a temperature T> 200 ° C under an inert atmosphere or between 60 and 600 ° C under an oxygenated atmosphere (air, oxygen). [19" id="c-fr-0019] 19. Method according to any one of claims 8 to 17, further comprising a step of separation or destruction of the natural polymolecular system of the colloid, for example by acid or basic hydrolysis, and separation of the solvent. 10 20. Nanocomposite or colloid of nanocomposite capable of being obtained by a process according to any one of claims 8 to 18. 21. Use of a nanocomposite or colloid of nanocomposite according to any one of claims 1 to 7, 17, 18, 19 and 20: - for the manufacture of inks, 15 - for the manufacture of conductive films, of conductive coatings such as a conductive paint or in the manufacture of electrodes, - for the formation of conductive networks, for example by self-assembly, - for the manufacture of energy storage systems, or in applications in batteries, supercapacitors, and in magnetism, [20" id="c-fr-0020] As catalysts such as metal-free catalysts for the selective dehydrogenation of ethylbenzene or styrene, or as a catalyst support, or - as an additive in polymers, in composite materials, in the development of layers for mechanical reinforcement, in tribology.
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同族专利:
公开号 | 公开日 EP3538607A1|2019-09-18| US20190382561A1|2019-12-19| WO2018087484A1|2018-05-17| FR3058418B1|2020-07-10|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US20060155018A1|2003-01-08|2006-07-13|Heinz-Dieter Metzemacher|Master batches based on pre-exfoliated nanoclays and the use of the same| CA2483049A1|2003-09-29|2005-03-29|Le Groupe Lysac Inc.|Polysaccharide phyllosilicate absorbent or superabsorbent nanocomposite materials| FR2958650A1|2010-04-13|2011-10-14|Univ Limoges|PROCESS FOR PRODUCING NANOCOMPOSITE FILM AND USES AS EDIBLE FILM|CN109449410A|2018-10-30|2019-03-08|陕西科技大学|A kind of preparation method of nitrogen, sulphur codope tungsten disulfide anode material of lithium-ion battery| CN109137030A|2018-06-29|2019-01-04|洛阳师范学院|A kind of preparation method of two selenizings niobium pentoxide film| CN108927195A|2018-07-06|2018-12-04|常州大学|A kind of vanadium oxide catalyst and preparation method thereof for oxidative dehydrogenation of propane| CN109772419B|2019-03-11|2021-12-28|辽宁石油化工大学|Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space| CN111013552B|2019-12-24|2020-12-29|中南大学|Clay-based composite material for storing ozone| CN113555646A|2021-08-10|2021-10-26|大连理工大学|Preparation method of coagulant type lithium-sulfur battery positive electrode side interlayer material|
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