Classifications

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  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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  • C04B41/87—Ceramics
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
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  • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
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  • B01J35/638—Pore volume more than 1.0 ml/g
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  • B01J35/643—Pore diameter less than 2 nm
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  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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  • B01J35/653—500-1000 nm
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/657—Pore diameter larger than 1000 nm
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  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
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  • B01J37/0201—Impregnation
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/082—Decomposition and pyrolysis
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• • C—CHEMISTRY; METALLURGY
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  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
  • C01B3/042—Decomposition of water
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
  • C04B38/0058—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity open porosity
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0067—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the density of the end product
• • C—CHEMISTRY; METALLURGY
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/007—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores
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  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
• • C—CHEMISTRY; METALLURGY
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  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
  • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
  • C04B41/5041—Titanium oxide or titanates
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  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

• the field of the invention is that of materials with a hierarchical structure. More particularly, the present invention relates to a porous monolith containing TiO 2 and its method of preparation.
• A. Araya et al. (US4888309) and A. Imhof et al. (Nature, vol 389, 30 October 1997, pp. 948-952) describe the implementation of sol-gel processes from alkoxides dissolved in an alcohol and hydrolysed by addition of a small amount of water, being recalled that most alkoxides are very reactive with water and do not give stable emulsions.
• This document also describes the preparation of monodisperse macroporous materials of titanium oxide, zirconia or silica with pore diameters between 50 nm and several microns, from a monodisperse oil emulsion in formamide.
• BP Binks (Advance Mater., 2002, 14, No. 24, p.1824-1827, December 17) discloses the preparation of porous silica from an emulsion stabilized by silica particles only, in the absence of surfactant .
• J. S. Beck et al. describe the preparation of mesoporous solids constituted by a silicate or an aluminosilicate.
• a patent application WO 2015/1 10772 describes the use of a material based on N-TiO 2 in the form of a porous monolith as a photocatalyst for the degradation of pollutants in air or in water under radiation in the visible spectrum or for the cracking of water in H 2 under radiation in the visible spectrum.
• Another patent application FR 2975309 describes a mode of preparation of porous monolith containing TiO 2 and its use as a photocatalyst for the degradation of pollutants in air or in water under irradiation.
• the monoliths claimed have apparent densities of the order of 1 g / mL.
• porous monolithic material containing at least 20% by weight of TiO 2 and having an apparent density of less than 0.19 g / ml.
• the combination of a high TiO 2 content and a low bulk density makes it possible to have monoliths with exposed TiO 2 surfaces increased compared to the prior art.
• the invention describes a porous monolith containing from 20% to 70% by weight of TiO 2 relative to the total weight of the monolith, from 30% to 80% by weight of a refractory oxide selected from silica, alumina or silica-alumina with respect to the total weight of the monolith, and having an apparent density of less than 0.19 g / ml.
• the apparent density is calculated by making the ratio between the mass of the porous monolith and its geometric volume.
• said porous monolith has a mesoporous volume of 0.01 to 1 ml / g for a pore diameter between 0.2 and 50 nm, preferably between 0.05 and 0.5 ml / g.
• said porous monolith has a macroporous volume of type I, ie whose pore diameter is greater than 50 nm and less than or equal to 1000 nm, between 0.1 and 3 ml / g, preferably between 0, 2 and 2.5 ml / g.
• said porous monolith has a macroporous volume of type II, ie whose pore diameter is greater than 1 ⁇ and less than or equal to 10 ⁇ , of between 0.1 and 8 ml / g, preferably between 0 and 5 and 8 ml / g.
• said photocatalyst in the form of a porous monolith has a mesoporosity and / or a macroporosity of type I and / or a macroporosity of type II as described above.
• said porous monolith also has a macroporous volume of less than 0.5 mL / g for a pore diameter greater than 10 ⁇ .
• the macroporous and mesoporous volumes are measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
• said photocatalyst in the form of a porous monolith has a specific surface area (measured according to the ASTM D 3663-78 standard established from the Brunauer method, Emmett, Teller, the BET method, as defined in S.Brunauer, PHEmmett , E.Teller, J. Am. Chem Soc., 1938, 60 (2), pp 309-319.) Between 150 and 700 m 2 / g, preferably between 200 and 600 m 2 / g.
• the TiO 2 is in its anatase and rutile forms, the anatase: rutile ratio being preferably between 95: 5 and 50:50.
• the invention also relates to a process for preparing said porous monolith, in which the Ti precursor is introduced at a step different from that of the silicon oxide and / or aluminum precursor.
• the method comprises the following steps:
• step a) mixing a solution containing a surfactant with an aqueous acidic solution to obtain an acidic aqueous solution comprising a surfactant; b) adding at least one precursor of silicon and / or aluminum to the solution obtained in step a); c) adding to the solution obtained in step b) at least one liquid organic compound, immiscible with the solution obtained in step b) to form an emulsion; d) the emulsion obtained in step c) is allowed to mature in the wet state to obtain a gel; e) washing the gel obtained in step d) with an organic solution; f) drying and calcining the gel obtained in step e) to obtain a porous monolith; g) impregnating a solution comprising at least one soluble precursor of titanium in the porosity of the porous monolith obtained in step f); h) optionally, the porous monolith obtained in step g) is allowed to mature in the wet state; i) drying and calcining the
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• micropores means pores whose diameter is less than 2 nm; mesopores pores whose diameter is greater than 2 nm and less than or equal to 50 nm and macropores pores whose diameter is greater than 50 nm, and more particularly macropores type I pores whose diameter is greater than 50 nm and less or equal to 1000 nm (1 ⁇ ), and type II macropores pores whose diameter is greater than 1 ⁇ and less than or equal to 10 ⁇ .
• the porous monolith comprises between 20% and 70% by weight of TiO 2 relative to the total weight of the monolith, preferably between 20% and 60% by weight of TiO 2 .
• the porous monolith according to the invention also comprises between 30% and 80% by weight of a refractory oxide chosen from silica, alumina or silica-alumina with respect to the total weight of the monolith, preferably between 40% and 80% by weight. % in weight.
• the porous monolith according to the invention has a bulk density of less than 0.19 g / ml, preferably less than 0.16 g / ml.
• the apparent density is calculated by making the ratio between the mass of the porous monolith and its geometric volume.
• said porous monolith may contain at least one element M chosen from an element of groups IA, MA, VI 11 B, IB and NIA of the periodic table of elements in the metallic or oxidized state, alone or as a mixture.
• the total content of element (s) M is between 0.001 and 20% by weight relative to the total weight of the porous monolith.
• the porous monolith can be doped with one or more elements chosen from metal elements, such as for example elements V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La, Ce , Ta, Ti, non-metallic elements, such as for example C, N, S, F, P, or by a mixture of metallic and non-metallic elements.
• metal elements such as for example elements V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La, Ce , Ta, Ti
• non-metallic elements such as for example C, N, S, F, P, or by a mixture of metallic and non-metallic elements.
• the content of doping element is between 0.001 and 5% by weight relative to the total weight of the porous monolith.
• said porous monolith has a mesoporous volume of 0.01 to 1 ml / g, preferably between 0.05 and 0.5 ml / g, for a pore diameter of between 0.2 and 50 nm.
• said porous monolith has a macroporous volume of type I, ie whose pore diameter is greater than 50 nm and less than or equal to 1000 nm (1 ⁇ ), of between 0.1 and 3 ml / g, of preferably between 0.2 and 2.5 mL / g, According to one variant, said porous monolith has a macroporous volume of type II, ie whose pore diameter is greater than 1 ⁇ and less than or equal to 10 ⁇ , of between 0.1 and 8 ml / g, preferably between 0 and 5 and 8 ml g.
• said porous monolith has a mesoporosity and / or a macroporosity of type I and / or a macroporosity of type II.
• said porous monolith also has a macroporous volume of less than 0.5 mL / g for a pore diameter greater than 10 ⁇ .
• said porous monolith has a BET surface area of between 150 and 700 m 2 / g.
• the invention also describes the method of preparation of said porous monolith, such that the precursor of Ti is introduced at a step different from that of the precursor of silicon oxide and / or aluminum:
• step a) mixing a solution containing a surfactant with an aqueous acidic solution to obtain an acidic aqueous solution comprising a surfactant; b) adding at least one precursor of silicon and / or aluminum to the solution obtained in step a); c) adding to the solution obtained in step b) at least one liquid organic compound, immiscible with the solution obtained in step b) to form an emulsion; d) the emulsion obtained in step c) is allowed to mature in the wet state to obtain a gel; e) washing the gel obtained in step d) with an organic solution; f) drying and calcining the gel obtained in step e) to obtain a porous monolith; g) impregnating a solution comprising at least one soluble precursor of titanium in the porosity of the porous monolith obtained in step f); h) optionally, the porous monolith obtained in step g) is allowed to mature in the wet state; i) drying and calcining the
• Step a) preparation of an acidic aqueous solution comprising a surfactant
• a solution containing a surfactant is mixed with an acidic aqueous solution to obtain an acidic aqueous solution comprising a surfactant. This step is preferably carried out at room temperature.
• the surfactant may be anionic, cationic, amphoteric or nonionic.
• the surfactant is a cationic surfactant.
• the surfactant is cetyl trimethylammonium bromide, or myristyltrimethylammonium bromide.
• the acidic aqueous solution is preferably selected from aqueous solutions of inorganic acids such as nitric, sulfuric, phosphoric, hydrochloric or hydrobromic acid or of organic acids such as carboxylic or sulphonic acids, alone or as a mixture.
• the acidic aqueous solution is chosen from an aqueous solution of hydrochloric acid or nitric acid.
• the pH of the solution obtained in step a) is preferably less than 4.
• Step b) (addition of at least one precursor of silicon and / or aluminum)
• step b) of the process according to the invention at least one precursor of silicon and / or aluminum is added to the solution obtained in step a).
• One or more precursors of aluminum and / or of alcoholate type silicon are preferably chosen.
• one or more precursors of aluminum and / or silicon are chosen from aluminum isopropoxide, aluminum t-butylate, tetraethylorthosilicate or tetramethylorthosilicate.
• the weight ratio "precursors / surfactant" is between 0.1 and 10, preferably between 0.2 and 5.
• Step c) formation of an emulsion
• step c) of the process according to the invention at least one liquid organic compound immiscible with the solution obtained in step b) is added to the solution obtained in step b) to form an emulsion.
• This step is preferably carried out at room temperature.
• the liquid organic compound is a hydrocarbon or a mixture of hydrocarbons having 5 to 15 carbon atoms, for example, dodecane may be mentioned.
• the weight ratio "organic liquid compound / solution obtained in step b)" is between 0.2 and 5, preferably between 0.3 and 3.
• Step d) formation of a gel
• step d) of the process according to the invention the emulsion obtained in step c) is allowed to mature in the wet state in order to obtain a gel.
• the maturation is carried out at a temperature between 5 and 80 ° C, preferably between 20 and 70 ° C.
• the maturation is carried out for 1 to 30 days, preferably for 1 to 15 days.
• step d) of the process according to the invention the gel obtained in step d) is washed with an organic solution. This step is preferably carried out at room temperature.
• the organic solution is acetone, ethanol, methanol, isopropanol, tetrahydrofuran, ethyl acetate or methyl acetate, alone or as a mixture.
• the washing step is repeated at least twice.
• step f) of the process according to the invention the gel obtained in step e) is dried and calcined under air to obtain a porous monolith.
• the drying is carried out at a temperature between 5 and 80 ° C, preferably between 20 and 75 ° C.
• the drying is carried out for 1 to 30 days, preferably for 1 to 15 days.
• the drying is generally carried out under air, preferably comprising between 0 and 80 grams of water per kilogram of air, an oxygen content of between 5% and 25% by volume and a carbon dioxide content of between 0% and 10% volume.
• air is a combustion air of a hydrocarbon, preferably methane, or in heated air.
• the calcination is carried out in air at a temperature between 300 and 1000 ° C, preferably between 350 and 900 ° C.
• the calcination is carried out for 1 to 72 hours, preferably between 2 and 48 hours.
• the calcination is carried out in two stages: a first temperature stage of between 120 and 250 ° C. for 1 to 10 hours, then a second temperature stage of between 300 and 950 ° C. for 2 to 24 hours. hours.
• the calcination step is carried out under combustion air, preferably a methane combustion air comprising between 40 and 80 grams of water per kg of combustion air, an oxygen content of between 5% and 15%. % volume and a C0 2 content between 4% and 10% volume.
• combustion air preferably a methane combustion air comprising between 40 and 80 grams of water per kg of combustion air, an oxygen content of between 5% and 15%. % volume and a C0 2 content between 4% and 10% volume.
• a solution comprising at least one soluble precursor of titanium is impregnated into the porosity of the porous monolith obtained in step f).
• the titanium precursor is chosen from a titanium alkoxide, very preferably the titanium precursor is chosen from titanium isopropoxide or tetraethylorthotitanate, alone or as a mixture.
• titanium alkoxide precursor at least one other inorganic titanium precursor of ionic type or in the form of a colloidal sol.
• Step h (optional step of maturation)
• step h) of the process according to the invention the porous monolith obtained in step g) is allowed to mature in the wet state.
• a maturation step is then carried out at a temperature between 5 and 80 ° C, preferably 20 to 75 ° C, and for 0.5 to 30 days, preferably for 1 to 15 days.
• step h) of the process according to the invention the porous monolith obtained in step g) or h) is dried and calcined under air to obtain a porous monolith containing TiO 2 .
• the drying is carried out at a temperature between 5 and 80 ° C, preferably between 20 and 75 ° C.
• the drying is carried out for 1 to 30 days, preferably for 1 to 15 days.
• the drying is generally carried out under combustion air of a hydrocarbon, preferably methane, or in heated air comprising between 0 and 80 grams of water per kilogram of combustion air, an oxygen content of between 5% and 25% volume and a carbon dioxide content between 0% and 10% volume.
• a hydrocarbon preferably methane
• heated air comprising between 0 and 80 grams of water per kilogram of combustion air, an oxygen content of between 5% and 25% volume and a carbon dioxide content between 0% and 10% volume.
• the calcination is carried out under air at a temperature between 300 and 1000 ° C.
• the calcination is carried out for 1 to 72 hours, preferably for 2 to 48 hours.
• an air calcination step is carried out with a first temperature stage of between 80 and 150 ° C. for 1 to 10 hours, then a second temperature stage greater than 150 ° C. and less than or equal to 250 ° C. for a period of 1 to 10 hours. 1 to 10 hours, and finally a third temperature stage between 300 and 700 ° C for 0.5 to 24 hours.
• the calcination step is carried out under combustion air, preferably a methane combustion air comprising between 40 and 80 grams of water per kg of combustion air, an oxygen content of between 5% and 15%. % volume and a C0 2 content between 4% and 10% volume.
• the TiO 2 may be doped with one or more elements chosen from metal ions, such as, for example, elements V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La , Ce, Ta, Ti, non-metallic elements, such as for example C, N, S, F, P, or by a mixture of metallic and non-metallic elements, at any stage of said process and by any method known to those skilled in the art.
• metal ions such as, for example, elements V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La , Ce, Ta, Ti
• non-metallic elements such as for example C, N, S, F, P, or by a mixture of metallic and non-metallic elements, at any stage of said process and by any method known to those skilled in the art.
• an element precursor M selected from an element of groups IA, MA, VIIIB, IB and NIA of the periodic table of elements in the metallic or oxidized state is added to steps a), b) and / or g), possibly after step i).
• the precursor can be solubilized in solution, in the form of a solid powder or in the form of a colloidal sol.
• step i) When it is desired to obtain the element M totally or partially in its metallic form, it will be possible, following step i), to carry out a reduction step under a flow of hydrogen at a temperature of between 100 and 600. ° C, during 0.5 to 24h.
• the porous monolith containing TiO 2 according to the invention can advantageously be used in photocatalysis for the production of dihydrogen by dissociation of water.
• Example 1 Solid A (not in accordance with the invention) Monolith TiO 2
• the mixture is then poured into a petri dish of 5.5 cm internal diameter, which is installed in a saturator (the water vapor content is adjusted by saturator, according to the vapor pressure laws) for 7 days to gelation at room temperature.
• the gel obtained is then washed with isopropanol (Aldrich TM, purity> 99.5%) twice in succession and then dried at room temperature for 2 days.
• the gel is finally calcined in air in muffle furnace at 180 ° C for 2h, then at 350 ° C for 6h.
• the solid A is then obtained in the form of a porous monolith based on TiO 2 .
• the solid A has a mesoporous volume of 0.16 ml / g, a macroporous volume of type I of 0.19 ml / g and a macroporous volume of type II of 2.3 ml / g.
• Solid A has a specific surface area of 94 m 2 / g.
• the porous monolith A has a bulk density of 0.23 g / ml.
• Example 2 Solid B (not in accordance with the invention) monolith TiO 2
• the emulsion is then poured into a petri dish of 5.5 cm internal diameter, which is installed in a saturator for 7 days for gelling at room temperature.
• the gel obtained is then washed a first time with anhydrous tetrahydrofuran (Aldrich TM, purity> 99%), then washed twice in succession with a mixture of anhydrous tetrahydrofuran / acetone (VWR TM, ACS grade) at 70/30 by volume.
• Aldrich TM anhydrous tetrahydrofuran
• VWR TM anhydrous tetrahydrofuran / acetone
• the gel is then dried at room temperature for 7 days.
• the gel is finally calcined in air in a muffle furnace at 200 ° C. for 2 hours and then at 450 ° C. for 6 hours.
• the solid B is then obtained in the form of a porous monolith based on TiO 2 .
• Solid B has a mesoporous volume of 0.29 ml / g, a marcoporous volume of type
• Solid B has a specific surface area of 135 m 2 / g.
• the porous monolith B has a bulk density of 1.1 g / ml.
• Example 3 Solid C (in Accordance with the Invention) Monolith TiOp / SiOp
• the emulsion is then poured into a petri dish of 5.5 cm internal diameter, which is installed in a saturator for 7 days for gelling at room temperature.
• the gel obtained is then washed a first time with anhydrous tetrahydrofuran (Aldrich, purity> 99%), then washed twice in succession with a mixture of anhydrous tetrahydrofuran / acetone (VWR TM, ACS grade) at 70/30 by volume.
• the gel is then dried at room temperature for 7 days.
• the gel is finally calcined in air in a muffle furnace at 180 ° C. for 2 hours, then at 650 ° C. for 5 hours.
• a porous SiO 2 -based monolith having a total pore volume of 10.5 ml / g is then obtained.
• a solution containing 34 mL of distilled water, 44.75 mL of isopropanol (Aldrich TM, purity> 99.5%), 10.74 mL of hydrochloric acid (37% by weight, Aldrich TM, purity 97%) and 10.50 mL of titanium isopropoxide (Aldrich TM, 97% purity) is prepared with stirring. Part of this solution corresponding to the total pore volume is impregnated into the porosity of the monolith, then left to mature for 12 hours at room temperature. The monolith is then dried under ambient atmosphere for 24 hours. The step is repeated a second time.
• the monolith is finally calcined in air in muffle furnace at 120 ° C for 2 hours, then at 180 ° C for 2 hours and finally at 400 ° C for 1 hour.
• a porous monolith comprising TiO 2 in an SiO 2 matrix is then obtained.
• Solid C has a mesoporous volume of 0.20 ml / g, a macroporous volume of type I of 1.15 ml / g and a macroporous volume of type II of 5.8 ml / g.
• Solid C has a surface area of 212 m 2 / g.
• the Ti element content measured by ICP-AES is 27.35% by weight, which is equivalent to 52.1% by weight of the semiconductor TiO 2 in the solid C.
• the porous monolith C has a bulk density of 0.14 g / ml.
• Example 4 Implementation of solids for the photocatalytic production of dihydrogen by dissociation of water in the gas phase
• porous monoliths A, B and C are subjected to a photocatalytic production test of dihydrogen by dissociation of water in the gas phase in a continuous steel through-bed reactor equipped with a quartz optical window and a sintered glass frit. face of the optical window on which the solid is deposited.
• the monoliths are placed on the sintered, their diameter being equal to the diameter of the reactor.
• the irradiated surface for all photocatalysts is 8.042477.10 "04 m 2.
• the tests were performed at room temperature under atmospheric pressure.
• the production of dihydrogen gas produced from the photocatalytic reduction of the water entrained in the saturator is monitored by an analysis of the effluent every 4 minutes by gas chromatography
• the UV-Visible irradiation source is supplied by a Xe-Hg lamp (Asahi TM, MAX302 TM)
• the irradiation power is always maintained at 80 W / m 2 for a wavelength range between 315 and 400 nm.
• the activity values show that the solid according to the invention has better performance when it is used in photocatalytic production of dihydrogen by dissociation of water.

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