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    • 专利摘要:
    The invention describes a process for photocatalytic reduction of carbon dioxide carried out in the liquid phase and / or in the gas phase under irradiation using a photocatalyst in the form of a porous monolith containing at least one semiconductor, said method being carried out by placing contacting a charge containing the CO2 and at least one sacrificial compound with said photocatalyst, then irradiating the photocatalyst so as to reduce the CO 2 and oxidize the sacrificial compound so as to produce an effluent containing at least in part C1 carbonaceous molecules or more, different from CO2.
    公开号:FR3065650A1
    申请号:FR1753758
    申请日:2017-04-28
    公开日:2018-11-02
    发明作者:Sophie Bernadet；Antoine Fecant；Denis Uzio；Renal Backov；Serge Ravaine
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    Technical field of the invention
    The field of the invention is that of photocatalytic reduction of carbon dioxide (CO 2 ) under irradiation by the use of a photocatalyst.
    State of the art
    Fossil fuels, such as coal, petroleum and natural gas, are the main conventional energy sources in the world due to their availability, stability and high energy density. However, their combustion produces carbon dioxide emissions which are considered to be the main cause of global warming. Thus, there is a growing need to mitigate CO 2 emissions, either by capturing it or by transforming it.
    Although “passive” carbon capture and sequestration (CCS) is generally considered to be an effective process for reducing CO 2 emissions, other strategies can be envisaged, in particular “active” CO 2 conversion strategies into products with economic value, such as fuels and industrial chemicals.
    Such a strategy is based on the reduction of carbon dioxide into valuable products. The reduction of carbon dioxide can be carried out biologically, thermally, electrochemically or even photocatalytically.
    Among these options, photocatalytic CO 2 reduction is gaining increased attention as it can potentially consume alternative forms of energy, for example by harnessing solar energy, which is abundant, inexpensive, and environmentally clean and safe.
    Photocatalytic reduction of carbon dioxide makes it possible to obtain carbon molecules with C1 or more, such as CO, methane, methanol, ethanol, formaldehyde, formic acid or other molecules such as carboxylic acids, aldehydes, ketones or various alcohols. These molecules, such as methanol, ethanol, formic acid or even methane and all C / hydrocarbons can find an energy utility directly. Carbon monoxide CO can also be upgraded energetically as a mixture with hydrogen for the formation of fuels by Fischer-Tropsch synthesis. Molecules of carboxylic acids, aldehydes, ketones or different alcohols can find applications in chemical or petrochemical processes. All these molecules are therefore of great interest from an industrial point of view.
    Methods of photocatalytic reduction of carbon dioxide in the presence of a sacrificial compound are known in the art.
    Halmann et al. (Solar Energy, 31, 4, 429-431, 1983) evaluated the performance of three semiconductors (TiO 2 , SrTiO 3 and CaTiO 3 ) for the photocatalytic reduction of CO 2 in an aqueous medium. They note the production of formaldehyde, formic acid and methanol.
    Anpo et al. (J. Phys. Chem. B, 101, p. 2632-2636, 1997) studied the photocatalytic reduction of CO 2 with water vapor on TiO 2- based photocatalysts anchored in micropores of zeolites. These exhibited very high selectivity for methanol gas.
    TiO 2- based photocatalysts on which platinum nanoparticles are deposited are known to convert a mixture of CO 2 and H 2 O in the gas phase into methane (QH. Zhang et al., Catal. Today, 148, p . 335-340, 2009).
    TiO 2- based photocatalysts loaded with gold nanoparticles are also known from the literature for the photocatalytic reduction of CO 2 in the gas phase (SC Roy et al., ACS Nano, 4, 3, p. 1259-1278, 2010) and in the aqueous phase (W. Hou et al., ACS Catal., 1, p. 929-936, 2011).
    It is also known that the photocatalytic reduction of CO 2 to methanol, formic acid and formaldehyde in aqueous solution can be carried out using various semiconductors such as ZnO, CdS, GaP, SiC or WO 3 (T. Inoue et al ., Nature, 277, p. 637-638, 1979).
    Liou et al. (Energy Environ. Sci., 4, p. 1487-1494, 2011) used lnTaO 4 photocatalysts doped with NiO to reduce CO 2 to CH 3 OH.
    Sato et al. (JACS, 133, p. 15240-15243, 2011) studied a hybrid system combining a p-type semiconductor InP and a polymer complexed with ruthenium in order to effect a selective reduction of CO 2 .
    Finally, a review and a book chapter from the open literature offer a comprehensive review of the photocatalysts used in photocatalytic reduction of carbon dioxide: M. Tahir, N. S. Amin, Energy Conv. Manag., 76, p. 194-214, 2013 on the one hand, and Photocatalysis, Topics in current chemistry 303C.A. Bignozzi Editor, Springer, p. 151,184,2011 on the other hand.
    The object of the invention is to provide a new, sustainable and more efficient way of producing recoverable carbon molecules by photocatalytic conversion of carbon dioxide using electromagnetic energy, using a photocatalyst in the form of monoliths. porous containing at least one semiconductor. The implementation of this type of photocatalysts for the photocatalytic reduction of CO 2 makes it possible to achieve improved performances compared to the known implementations for this reaction. Indeed, it is known from JM Herrmann, Topics in Catalysis Vol. 34, p. 1-4, 2005 that the photocatalytic activity per unit of irradiated area increases with the mass of photocatalyst and then reaches a plateau. Surprisingly, the use of photocatalyst in the form of a porous monolith containing at least one semiconductor for the photocatalytic reduction of carbon dioxide makes it possible to increase the activity per unit of irradiated surface by increasing the mass of photocatalyst, which doesn is not the case for other formatting (powder for example).
    Patent application WO2015 / 11072 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 cracking water into H 2 under radiation in the visible spectrum. The document FR 2975309 describes a method of preparing a porous monolith containing TiO 2 and its use as a photocatalyst for the degradation of pollutants in air or in water under irradiation.
    It is also known to M. Tahir and NS Amin (Appl. Catal. A: General 467 (2013) 483496 and Chem. Eng. J., 230 (2013) 314-327) to use a monolith of the "nest d" type. 'bee' containing millimeter-sized channels coated with a semiconductor compound for photocatalytic reduction of CO 2 . However, this type of object has a high density per unit of volume (of the order of 0.8 to 0.9 g / ml) which does not allow large specific surfaces to be obtained.
    However, no document discloses the use of a photocatalyst in the form of a porous monolith containing at least one semiconductor in a process for the photocatalytic reduction of carbon dioxide.
    Objects of the invention
    The present invention relates to a photocatalytic reduction process of carbon dioxide carried out in the liquid phase and / or in the gas phase under irradiation using a photocatalyst in the form of porous monolith containing at least one semiconductor. Said method more particularly comprises the following steps:
    a) a charge containing carbon dioxide and at least one sacrificial compound is brought into contact with a photocatalyst which is in the form of a porous monolith comprising an apparent density less than or equal to 0.25 g / ml;
    b) the photocatalyst is irradiated with at least one irradiation source producing at least one wavelength less than the forbidden bandwidth of said photocatalyst so as to reduce carbon dioxide and to oxidize the sacrificial compound in the presence of said photocatalyst activated by said irradiation source, so as to produce an effluent containing at least in part carbon molecules in C1 or more, different from CO 2 .
    The apparent density is calculated by making the ratio between the mass of catalyst and its geometric volume.
    According to a variant, and when the process is carried out in the gas phase, the sacrificial compound is a gaseous compound chosen from water, ammonia, hydrogen, methane and an alcohol.
    According to a variant, and when the process is carried out in the liquid phase, the sacrificial compound is a compound soluble in the liquid phase chosen from water, ammonia, an alcohol, an aldehyde or an amine.
    Alternatively, a diluent fluid is present in steps a) and / or b).
    Alternatively, the radiation source is an artificial or natural source of radiation.
    According to a variant, said photocatalyst in the form of a porous monolith has a mesoporous volume, the pore diameter of which is greater than 0.2 nm and less than or equal to 50 nm, between 0.01 and 1 ml / g, preferably between 0.05 and 0.5 mL / g.
    According to a variant, said photocatalyst in the form of a porous monolith has a macroporous volume of type I, ie a macroporous volume whose pore diameter is greater than 50 nm and less than or equal to 1000 nm (1 μm), between 0.1 at 3 mL / g, preferably between 0.2 and 2.5 mL / g.
    According to a variant, said photocatalyst in the form of a porous monolith has a macroporous volume of type II, ie a macroporous volume whose pore diameter is greater than 1 μm and less than or equal to 10 μm, between 0.1 to 8 ml / g for a diameter, preferably between 0.5 and 8 mL / g.
    According to a preferred variant, 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.
    According to a variant, said photocatalyst in the form of a porous monolith also has a macroporous volume, the pore diameter of which is greater than 10 μm, less than 0.5 ml / g.
    According to a preferred variant, said photocatalyst in the form of a porous monolith has an apparent density of between 0.05 and 0.5 g / ml.
    The macroporous and mesoporous volumes are measured by mercury intrusion porosimetry according to standard ASTM D4284-83 at a maximum pressure of 4000 bar, using a surface tension of 484 dyne / cm and a contact angle of 140 °.
    According to a variant, said photocatalyst in the form of a porous monolith has a specific surface (measured according to standard ASTM D 3663-78 established from the Brunauer, Emmett, Teller method, ie the BET method, as defined in S. Brunauer, PHEmmett , E. Teller, J. Am. Chem. Soc., 1938, 60 (2), pp 309-319.) Between 10 and 1000 m 2 / g, preferably between 50 and 600 m 2 / g.
    According to a variant, said photocatalyst in the form of a porous monolith comprises at least one semiconductor diluted within at least one inorganic phase which does not absorb photons of energy greater than 4 eV. Preferably, the inorganic phase contains silica or alumina.
    According to a preferred embodiment, the photocatalyst in the form of a monolith consists of the semiconductor.
    According to a preferred variant, when said photocatalyst in the form of a porous monolith comprises at least one semiconductor dispersed within at least one inorganic phase which does not absorb photons of energy greater than 4 eV, the semiconductor content is between 5 and 70% by weight relative to the total weight of the photocatalyst.
    According to a variant, said photocatalyst can contain at least one element M chosen from an element from groups VIIIB, IB and IIIA of the periodic classification of elements in the metallic state. Preferably, the content of element (s) M in the metallic state is between 0.001 and 20% by weight relative to the total weight of the photocatalyst.
    Preferably, the semiconductor of said photocatalyst is chosen from TiO 2 , ZnO, Cu 2 O, CuO, Ce 2 O 3 , CeO 2 , Inn 2 O 3 , SiC, ZnS, and ln 2 S 3 , alone or as a mixture.
    Detailed description of the invention
    Definitions
    In the following, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, CRC press editor, editor-in-chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new lUPAC classification.
    By sacrificial compound is meant an oxidizable compound. The sacrificial compound can be in gaseous or liquid form.
    The term “carbon molecules in C1 or more” means molecules resulting from the reduction of CO 2 containing one or more carbon atoms, with the exception of CO 2 . Such molecules are for example CO, methane, methanol, ethanol, formaldehyde, formic acid or other molecules such as hydrocarbons, carboxylic acids, aldehydes, ketones or different alcohols.
    In the present description, micropores are understood to mean, according to the lUPAC convention, pores whose diameter is less than 2 nm; mesopores pores with a diameter greater than 2 nm and less than or equal to 50 nm and macropores pores with a diameter greater than 50 nm, and more particularly type I macropores pores with a diameter greater than 50 nm and less or equal to 1000 nm (1 μm), and type II macropores the pores whose diameter is greater than 1 μm and less than or equal to 10 μm.
    Description
    The subject of the present invention is a process for photocatalytic reduction of carbon dioxide carried out in the liquid phase and / or in the gas phase under irradiation using a photocatalyst in the form of a porous monolith containing at least one semiconductor, which process comprises the following steps:
    a) a charge containing carbon dioxide and at least one sacrificial compound is brought into contact with a photocatalyst which is in the form of a porous monolith comprising an apparent density of less than or equal to 0.25 g / ml;
    b) the photocatalyst is irradiated with at least one irradiation source producing at least one wavelength less than the forbidden bandwidth of said photocatalyst so as to reduce carbon dioxide and to oxidize the sacrificial compound in the presence of said photocatalyst activated by said irradiation source, so as to produce an effluent containing at least in part carbon molecules in C1 or more, different from CO 2 .
    According to step a) of the process according to the invention, a charge containing said carbon dioxide and at least one sacrificial compound is brought into contact with said photocatalyst.
    The process according to the invention can be carried out in the liquid phase and / or in the gas phase.
    The charge treated according to the process is in gaseous, liquid or gaseous and liquid two-phase form.
    When the charge is in gaseous form, CO 2 is present in its gaseous form in the presence of all gaseous sacrificial compounds alone or in mixture. The gaseous sacrificial compounds are oxidizable compounds such as water (H 2 O), hydrogen (H 2 ), methane (CH 4 ) or even alcohols. Preferably, the gaseous sacrificial compounds are water or hydrogen. When the charge is in gaseous form, the CO 2 and the sacrificial compound can be diluted by a gaseous diluting fluid such as N 2 or Ar.
    When the charge is in liquid form, it can be in the form of an ionic, organic or aqueous liquid. The filler in liquid form is preferably aqueous. In an aqueous medium, the CO 2 is then dissolved in the form of aqueous carbonic acid (H 2 CO 3 ), hydrogen carbonate or carbonate. The sacrificial compounds are liquid or solid oxidizable compounds soluble in the liquid charge, such as water (Η 2 Ο), alcohols, aldehydes, amines. Preferably, the sacrificial compound is water. When the liquid charge is an aqueous solution, the pH is generally between 1 and 9, preferably between 2 and 7. Optionally, and in order to modulate the pH of the aqueous liquid charge, a basic or acidic agent can be added to the charge. When a basic agent is introduced, it is preferably selected from alkali or alkaline earth hydroxides, organic bases such as amines or ammonia. When an acid agent is introduced, it is preferably selected from inorganic acids such as nitric, sulfuric, phosphoric, hydrochloric, hydrobromic acid or organic acids such as carboxylic or sulfonic acids.
    Optionally, when the liquid charge is aqueous, it can contain in any quantity any solvated ion, such as for example K + , Li + , Na + , Ca 2+ , Mg 2+ , SO4 2 ', Cl, F, NO3 2 '.
    When the process is carried out in the liquid phase or in the gas phase, a diluting fluid, respectively liquid or gaseous, may be present in the reaction medium. The presence of a diluting fluid is not required for the implementation of the invention, however it may be useful to add to the charge to ensure the dispersion of the charge in the medium, the dispersion of the photocatalyst, a control adsorption of reagents / products on the surface of the photocatalyst, control of the absorption of photons by the photocatalyst, dilution of the products to limit their recombination and other parasitic reactions of the same order. The presence of a diluent fluid also makes it possible to control the temperature of the reaction medium which can thus compensate for the possible exo / endothermicity of the photocatalyst reaction. The nature of the diluent fluid is chosen so that its influence is neutral on the reaction medium or that its possible reaction does not harm the achievement of the desired reduction of carbon dioxide. As an example, nitrogen can be chosen as the gaseous diluent.
    Contacting the charge containing carbon dioxide and the photocatalyst can be done by any means known to those skilled in the art. Preferably, the carbon dioxide charge and the photocatalyst are brought into contact in a traversed fixed bed or in a fixed licking bed.
    When the implementation is in a traversed fixed bed, said photocatalyst is preferably fixed within the reactor, and the charge containing the carbon dioxide to be converted in gaseous and / or liquid form is sent through the photocatalytic bed.
    When the implementation is in a fixed licking bed, the photocatalyst is preferably fixed within the reactor and the charge containing the carbon dioxide to be converted in gaseous and / or liquid form is sent to the photocatalytic bed.
    When the implementation is in a fixed bed or in a licking bed, the implementation can be done continuously.
    The photocatalyst in the form of a porous monolith comprises at least one semiconductor.
    The use of this type of monolith photocatalyst in a photocatalytic reduction reaction of CO 2 makes it possible, surprisingly, to obtain improved photocatalytic performances compared to photocatalysts known in the state of the art which are not in the form of monolith porous.
    The semiconductor (s) constituting said photocatalyst are independently chosen from inorganic, organic or organic-inorganic semiconductors. The forbidden bandwidth of inorganic, organic or organic inorganic semiconductors is generally between 0.1 and 4.0 eV.
    According to a first variant, an inorganic semiconductor can be chosen from one or more elements of group IVA, such as silicon, germanium, silicon carbide or silicon-germanium. They can also be composed of elements of groups II IA and VA, such as GaP, GaN, InP and InGaAs, or elements of groups IIB and VIA, such as CdS, ZnO and ZnS, or elements of groups IB and VIIA, such as CuCI and AgBr, or elements of groups IVA and VIA, such as PbS, PbO, SnS and PbSnTe, or elements of groups VA and VIA, such as Bi 2 Te 3 and Bi 2 O 3 , or elements of groups IIB and VA, such as Cd 3 P 2 , Zn 3 P 2 and Zn 3 As 2 , or elements of groups IB and VIA, such as CuO, Cu 2 O and Ag 2 S, or elements of groups VIIIB and VIA, such as CoO, PdO, Fe 2 O 3 and NiO, or elements of groups VIB and VIA, such as MoS 2 and WO 3 , or elements of groups VB and VIA , such as V 2 O 5 and Nb 2 O 5 , or elements of groups IVB and VIA, such as TiO 2 and HfS 2 , or elements of groups IIIA and VIA, such as ln 2 O 3 and ln 2 S 3 , or elements of the VIA groups and lanthanides, such as Ce 2 O 3 , Pr 2 O 3 , Sm 2 S 3 , Tb 2 S 3 and La 2 S 3 , or elements of the VIA groups and actinides, such as UO 2 and UO 3 .
    Preferably, a semiconductor is chosen from TiO 2 , ZnO, Cu 2 O, CuO, Ce 2 O 3 , CeO 2 , ln 2 O 3 , SiC, ZnS, and l 'ln 2 S 3 , alone or in mixture The semiconductor can optionally be doped with one or more elements chosen from metallic 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.
    According to another variant, a semiconductor is chosen from organic semiconductors. Said organic semiconductors can be tetracene, anthracene, polythiophene, polystyrenesulfonate, phosphyrenes and fullerenes.
    According to another variant, a semiconductor is chosen from organic-inorganic semiconductors. Among the organic-inorganic semiconductors, mention may be made of crystallized solids of the MOF type (for Metal Organic Frameworks according to English terminology). MOFs are made up of inorganic subunits (transition metals, lanthanides ...) and connected together by organic ligands (carboxylates, phosphonates, imidazolates ...), thus defining crystallized, sometimes porous, hybrid networks.
    According to another variant, a semiconductor can be sensitized on the surface with all organic molecules capable of absorbing photons.
    According to a variant, said photocatalyst in the form of a porous monolith consists of the semiconductor in the form of a monolith.
    According to a variant, said photocatalyst in the form of a porous monolith comprises at least one semiconductor dispersed within at least one inorganic phase which does not absorb photons with energy greater than 4 eV. Preferably, the inorganic dilution phase contains silica or alumina.
    According to a preferred variant, when said photocatalyst in the form of a porous monolith comprises at least one semiconductor diluted within at least one inorganic phase which does not absorb photons of energy greater than 4 eV, the semiconductor content is between 5 and 70% by weight relative to the total weight of the photocatalyst.
    According to a variant, said photocatalyst can contain at least one element M chosen from an element from groups VIIIB, IB and IIIA of the periodic classification of elements in the metallic state. The term “element in the metallic state” means an element being at the oxidation state zero (and therefore in the form of metal). Preferably, the content of element (s) M in the metallic state is between 0.001 and 20% by weight relative to the total weight of the photocatalyst.
    According to a variant, said photocatalyst in the form of a porous monolith has a mesoporous volume, the pore diameter of which is greater than 0.2 nm and less than or equal to 50 nm, between 0.01 and 1 ml_ / g, preferably between 0.05 and 0.5 mL / g.
    According to a variant, said photocatalyst in the form of a porous monolith has a macroporous volume of type I, ie a macroporous volume whose pore diameter is greater than 50 nm and less than or equal to 1000 nm (1 μm), between 0.1 at 3 mL / g, preferably between 0.2 and 2.5 mL / g.
    According to a variant, said photocatalyst in the form of a porous monolith has a macroporous volume of type II, ie a macroporous volume whose pore diameter is greater than 1 μm and less than or equal to 10 μm, between 0.1 to 8 ml / g for a diameter, preferably between 0.5 and 8 mL / g.
    According to a preferred variant, 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.
    According to a variant, said photocatalyst in the form of a porous monolith also has a macroporous volume, the pore diameter of which is greater than 10 μm, less than 0.5 ml / g.
    According to a preferred variant, said photocatalyst in the form of a porous monolith has an apparent density of between 0.05 and 0.5 g / ml. The apparent density is calculated by making the ratio between the mass of catalyst and its geometric volume.
    According to a variant, said photocatalyst in the form of a porous monolith has a BET surface of between 10 and 1000 m 2 / g, preferably between 50 and 600 m 2 / g.
    The process for preparing the photocatalyst can be any preparation process known to a person skilled in the art and suitable for the desired photocatalyst.
    According to a variant, the process for preparing the photocatalyst comprises the following steps:
    1) mixing a solution containing a surfactant with an acid solution;
    2) adding to the solution obtained in step 1) at least one soluble inorganic support precursor not absorbing photons of energy greater than 4 eV or an inorganic semiconductor precursor absorbing photons of energy between 0 , 1 and 4 eV;
    3) optionally, at least one liquid organic compound, immiscible with the solution obtained in step 2) is added to the solution obtained in step 2) to form an emulsion;
    4) the solution obtained in step 2) or the emulsion obtained in step 3) is left to mature in the wet state to obtain a gel;
    5) washing the gel obtained in step 4) with an organic solution;
    6) the gel obtained in step 5) is dried and calcined to obtain a porous monolith;
    7) a solution comprising at least one soluble semiconductor precursor is impregnated into the porosity of the porous monolith obtained in step 6) when in step 2) at least one precursor is added to the solution obtained in step 1) soluble inorganic support not absorbing photons of energy greater than 4 eV, or optionally impregnating a solution comprising at least one soluble semiconductor precursor in the porosity of the porous monolith obtained in step 6) when in step 2) adding to the solution obtained in step 1) at least one inorganic semiconductor precursor absorbing photons of energy between 0.1 and 4 eV, said precursor being identical to or different from said molecular precursor introduced in step 2);
    8) optionally, the product obtained in step 7) is dried and calcined to obtain a porous monolith.
    The steps are described in detail below.
    Step 1 )
    In step 1) of the process for preparing the photocatalyst, a solution containing a surfactant is mixed with an acidic aqueous solution to obtain an acidic aqueous solution comprising a surfactant.
    The surfactant can be anionic, cationic, amphoteric or nonionic, preferably the surfactant is a poly (ethylene glycol), cetyl trimethylammonium bromide, or myristyltrimethylammonium bromide. The acid agent is preferably selected from inorganic acids such as nitric, sulfuric, phosphoric, hydrochloric, hydrobromic acid or organic acids such as carboxylic or sulfonic acids, alone or as a mixture. The pH of the mixture is preferably less than 4.
    2nd step)
    At step 2) of the process for preparing the photocatalyst, at least one soluble precursor of inorganic support does not absorb photons of energy greater than 4 eV or an inorganic semiconductor precursor absorbing photons of energy included between 0.1 and 4 eV
    When the molecular precursor is an inorganic support precursor that does not absorb photons of energy greater than 4 eV, an alcoholate precursor is preferably chosen from aluminum isopropylate, aluminum tert-butylate, tetraethylorthosilicate or tetramethylorthosilicate, alone or as a mixture.
    When the molecular precursor is an inorganic semiconductor precursor absorbing photons of energy between 0.1 and 4 eV, an alcoholate precursor is preferably chosen from titanium isopropylate or tetreethylorthotitanate, alone or as a mixture.
    Optionally, it is possible to add to the alcoholate precursor of support and / or inorganic semiconductor, another inorganic semiconductor precursor of ionic type or colloidal sol.
    Preferably, the ratio of precursor / surfactant mass is between 0.1 and 10.
    Step 3) [optional
    In step 3), at least one liquid organic compound, immiscible with the solution obtained in step 2) is added to the solution obtained in step 2) to form an emulsion.
    Preferably, the liquid organic compound is a hydrocarbon, or a mixture of hydrocarbons, having 5 to 15 carbon atoms. Preferably, the liquid organic compound / solution mass ratio obtained in step 2) is between 0.2 and 5.
    Step 4)
    In step 4), the solution obtained in step 2) or the emulsion obtained in step 3) is left to mature in the wet state to obtain a gel;
    Preferably, the maturation is carried out at a temperature between 5 and 80 ° C. Preferably, the maturation is carried out for 1 to 30 days.
    Step 5)
    In step 5), the gel obtained in step 4) is washed with an organic solution.
    Preferably, the organic solution is acetone, ethanol, methanol, isopropanol, tetrahydrofuran, ethyl acetate, methyl acetate, alone or as a mixture. Preferably, the washing step is repeated several times.
    Step 6)
    In step 6), the gel obtained in step 5) is dried and calcined to obtain a porous monolith.
    Preferably, the drying is carried out at a temperature between 5 and 80 ° C. Preferably, the drying is carried out for 1 to 30 days. Optionally, absorbent paper can be used to speed up the drying of the materials.
    Preferably, the calcination takes place in two stages: a first temperature plateau between 120 and 250 ° C for 1 to 10 hours, then a second temperature plateau between 300 and 950 ° C for 2 to 24 hours.
    Step 7)
    During step 7), a solution is impregnated comprising at least one soluble semiconductor precursor in the porosity of the porous monolith obtained in step 6) when in step 2) is added to the solution obtained in step 1) at least one soluble precursor of inorganic support that does not absorb photons of energy greater than 4 eV, or an optionally impregnated solution comprising at least one soluble semiconductor precursor in the porosity of the porous monolith obtained in step 6 ) when in step 2) adding to the solution obtained in step 1) at least one inorganic semiconductor precursor absorbing photons of energy between 0.1 and 4 eV, said precursor being identical to or different from said precursor molecular introduced in step 2).
    Preferably, a maturation step is carried out in a humid atmosphere after the impregnation.
    Preferably, a drying step is then carried out at a temperature between 5 and 80 ° C and for 0.5 to 30 days.
    Preferably, a calcination step is then carried out in air with a first temperature plateau between 80 and 150 ° C losing 1 to 10 hours, then a second temperature plateau between 150 and 250 ° C for 1 to 10 hours, and finally a third temperature plateau between 300 and 950 ° C for 0.5 to 24 hours.
    Step 8) [optional step
    In step 8), the product obtained in step 7) is dried and calcined to obtain a porous monolith.
    The precursor may be in the solubilized state in solution or in the form of a colloidal sol.
    Preferably, a drying step is then carried out at a temperature between 5 and 120 ° C and for 0.5 to 2 days.
    Preferably, a calcination step is then carried out in air with a first temperature plateau between 120 and 250 ° C for 0.5 to 10 hours, then a second temperature plateau between 300 and 950 ° C for 0, 5 to 24 hours.
    Preferably, a reduction step is then carried out under a stream of hydrogen at a temperature between 100 and 600 ° C., for 0.5 to 24 hours.
    Step b) of the process according to the invention
    According to step b) of the method according to the invention, the photocatalyst is irradiated with at least one irradiation source producing at least one wavelength less than the prohibited bandwidth of said photocatalyst so as to reduce the carbon dioxide and oxidizing the sacrificial compound in the presence of said photocatalyst activated by said irradiation source, so as to produce an effluent containing at least partly carbon molecules in C1 or more, different from CO 2 .
    Photocatalysis is based on the principle of activation of a semiconductor or a set of semiconductors such as the photocatalyst used in the method according to the invention, using the energy provided by the irradiation. . Photocatalysis can be defined as the absorption of a photon, whose energy is greater than or equal to the prohibited bandwidth or bandgap according to the English terminology between the valence band and the conduction band, which induces the formation of an electron-hole pair in the semiconductor. There is therefore the excitation of an electron at the level of the conduction band and the formation of a hole on the valence band. This electron-hole pair will allow the formation of free radicals which will either react with compounds present in the medium or then recombine according to various mechanisms. Each semiconductor has a difference in energy between its conduction band and its own valence band, or bandgap.
    A photocatalyst composed of one or more semiconductors can be activated by the absorption of at least one photon. Absorbable photons are those whose energy is greater than the bandgap bandgap of semiconductors. In other words, the photocatalysts can be activated by at least one photon with a wavelength corresponding to the energy associated with the forbidden bandwidths of the semiconductors constituting the photocatalyst or with a lower wavelength. The maximum wavelength absorbable by a semiconductor is calculated using the following equation:
    Q _hxc onax t-, E g
    With At max the maximum wavelength absorbable by a semiconductor (in m), h the Planck constant (4.13433559.10 15 eV.s), c the speed of light in a vacuum (299 792 458 ms 1 ) and Eg the band gap or bandgap of the semiconductor (in eV).
    Any irradiation source emitting at least one wavelength suitable for activating said photocatalyst, that is to say absorbable by the photocatalyst, can be used according to the invention. One can for example use natural solar irradiation or an artificial irradiation source such as laser, Hg, incandescent lamp, fluorescent tube, plasma or light-emitting diode (LED, or LED in English for Light-Emitting Diode). Preferably, the source of irradiation is solar irradiation.
    The irradiation source produces radiation of which at least part of the wavelengths is less than the maximum absorbable wavelength (λ max ) by the semiconductor (s) constituting the photocatalyst according to the invention. When the irradiation source is solar irradiation, it generally emits in the ultraviolet, visible and infrared spectrum, that is to say it emits a wavelength range from 280 nm to 2500 nm approximately ( according to ASTM G173-03). Preferably, the source emits at least in a wavelength range greater than 280 nm, very preferably from 315 nm to 800 nm, which includes the UV spectrum and / or the visible spectrum.
    The irradiation source provides a stream of photons which irradiates the reaction medium containing the photocatalyst. The interface between the reaction medium and the light source varies according to the applications and the nature of the light source.
    In a preferred mode when it comes to solar irradiation, the irradiation source is located outside the reactor and the interface between the two can be an optical window made of pyrex, quartz, organic glass or any other interface allowing the photons absorbable by the photocatalyst according to the invention to diffuse from the external medium within the reactor.
    The realization of the photocatalytic reduction of carbon dioxide is conditioned by the supply of photons adapted to the photocatalytic system for the envisaged reaction and therefore is not limited to a specific pressure or temperature range apart from those allowing ensure the stability of the product (s). The temperature range used for the photocatalytic reduction of the charge containing carbon dioxide is generally from -10 ° C to + 200 ° C, preferably from 0 to 150 ° C, and very preferably from 0 and 100 ° vs. The pressure range used for the photocatalytic reduction of the charge containing carbon dioxide is generally from 0.01 MPa to 70 MPa (0.1 to 700 bar), preferably from 0.1 MPa to 2 MPa (1 to 20 bar).
    The effluent obtained after the photocatalytic reduction reaction of carbon dioxide contains on the one hand at least one molecule in C1 or more, different from the carbon dioxide resulting from the reaction and on the other hand the unreacted charge, as well as the possible diluting fluid, but also products of parallel reactions such as for example dihydrogen resulting from the photocatalytic reduction of H 2 O when this compound is used as a sacrificial compound.
    The following examples illustrate the invention without limiting its scope.
    EXAMPLES
    Example 1: Photocatalyst A (not in accordance with the invention) TiO 2 to sew
    Photocatalyst A is a commercial TiO 2- based semiconductor in powder form (Aeroxide® P25, Aldrich ™, purity> 99.5%). The particle size of the photocatalyst is 21 nm and its specific surface is 52 m 2 / g.
    Example 2: Photocatalyst B (not in accordance with the invention) CeO 2
    Photocatalyst B is a semiconductor based on CeO 2 commercial in powder form (Aldrich ™ purity 99.95%). The particle size of the photocatalyst is less than 50 nm and its specific surface is 30 m 2 / g.
    Example 3: Photocatalyst C (according to the invention) Monolith TiO 2 g of polyethylene glycol (Aldrich ™, M w = 20000) is added in 2 ml of distilled water and then mixed with 1 ml of a hydrochloric acid solution ( 37% by mass, Aldrich ™, purity 97%). 1.1 g of titanium isopropylate (Aldrich ™, purity 97%) is added to the mixture and the whole is stirred until a mixture of monophasic appearance is obtained.
    The mixture is then poured into a Petri dish with an internal diameter of 5.5 cm, which is installed in a saturator for 7 days for gelation.
    The gel obtained is then washed with isopropanol (Aldrich ™, purity> 99.5%) 2 times in succession, then dried at room temperature for 2 days. The gel is finally calcined in air in a muffle oven at 180 ° C for 2 hours, then at 350 ° C for 6 hours.
    Photocatalyst C is then obtained in the form of a porous monolith based on TiO 2 .
    Photocatalyst C has a mesoporous volume of 0.16 mL / g, a type I marcoporous volume of 0.19 mL / g and a macroporous type II volume of 2.3 mL / g. Photocatalyst C has a specific surface of 64 m 2 / g.
    Photocatalyst C has an apparent density of 0.23 g / mL.
    Example 4: Photocatalyst D (according to the invention) TiO / SiO monolith
    1.12 g of myristyltrimethylammonium bromide (Aldrich ™, purity> 99%) is added to 2 ml of distilled water and then mixed with 1 ml of a hydrochloric acid solution (37% by mass, Aldrich ™, purity 97 %). 0.18 g of titanium isopropylate (Aldrich ™, purity 97%) and 1.02 g of tetraethylorthosilicate (Aldrich ™, purity> 99%) are added to the mixture and the whole is stirred until a mixture of 'monophasic appearance.
    7g of dodecane (Aldrich ™, purity> 99%) are slowly introduced into the mixture with stirring until an emulsion is formed.
    The emulsion is then poured into a Petri dish with an internal diameter of 5.5 cm, which is installed in a saturator for 7 days for gelation.
    The gel obtained is then washed a first time with anhydrous tetrahydrofuran (Aldrich ™, purity> 99%), then with an anhydrous tetrahydrofuran / acetone mixture (VWR ™, ACS grade) at 70/30 by volume 2 times in succession.
    The gel is then dried at room temperature for 7 days. The gel is finally calcined in air in a muffle oven at 180 ° C for 2 hours, then at 800 ° C for 5 hours.
    Photocatalyst D is then obtained in the form of a porous monolith comprising TiO 2 in an SiO 2 matrix.
    Photocatalyst D has a mesoporous volume of 0.11 mL / g, a type I marcoporous volume of 0.74 mL / g and a macroporous type II volume of 6.4 mL / g. Photocatalyst D has a specific surface of 82 m 2 / g. The content of Ti element measured by ICP-AES is 9.18% by weight, which makes an equivalent of 15.3% by weight of the semiconductor TiO 2 in the photocatalyst D.
    Photocatalyst D has an apparent density of 0.11 g / mL.
    Example 5: Photocatalyst E (according to the invention) TiO 2 / SiO 2 monolith
    1.12 g of myristyltrimethylammonium bromide (Aldrich ™, purity> 99%) is added to 2 ml of distilled water and then mixed with 1 ml of a hydrochloric acid solution (37% by mass, Aldrich ™, purity 97 %). 1.02 g of tetraethylorthosilicate (Aldrich ™, purity> 99%) is added to the mixture and the whole is agitated until obtaining a mixture of monophasic appearance.
    g of dodecane (Aldrich ™, purity> 99%) are slowly introduced into the mixture with stirring until an emulsion is formed.
    The emulsion is then poured into a Petri dish with an internal diameter of 5.5 cm, which is installed in a saturator for 7 days for gelation.
    The gel obtained is then washed a first time with anhydrous tetrahydrofuran (Aldrich ™, purity> 99%), then with an anhydrous tetrahydrofuran / acetone mixture (VWR ™, ACS grade) at 70/30 by volume 2 times in succession.
    The gel is then dried at room temperature for 7 days. The gel is finally calcined in air in a muffle oven at 180 ° C for 2 hours, then at 650 ° C for 5 hours. A porous monolith based on SiO 2 is then obtained.
    A solution containing 34 ml of distilled water, 44.75 ml of isopropanol (Aldrich ™, purity> 99.5%), 10.74 ml of hydrochloric acid (37% by mass, Aldrich ™, purity 97%) and 10.50 ml of titanium isopropylate (Aldrich ™, purity 97%) is prepared with stirring. Part of this solution corresponding to the pore volume is impregnated in the porosity of the monolith, then left to mature for 12 hours. The monolith is then dried under an ambient atmosphere for 24 hours. The step is repeated a second time. The monolith is finally calcined in air in a muffle oven at 120 ° C for 2 hours, then at 180 ° C for 2 hours and finally at 400 ° C for 1 hour. A porous monolith is then obtained comprising TiO 2 in an SiO 2 matrix.
    Photocatalyst E 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. Photocatalyst E has a specific surface of 212 m 2 / g. The content of Ti element measured by ICP-AES is 27.35% by weight, which makes an equivalent of 52.1% by weight of TiO 2 in photocatalyst E.
    Photocatalyst E has an apparent density of 0.14 g / mL.
    Example 6: Photocatalyst F (according to the invention) CeO 2 / SiO 2
    1.12 g of myristyltrimethylammonium bromide (Aldrich ™, purity> 99%) is added to 2 ml of distilled water and then mixed with 1 ml of a hydrochloric acid solution (37% by mass, Aldrich ™, purity 97 %). 1.02 g of tetraethylorthosilicate (Aldrich ™, purity> 99%) is added to the mixture and the whole is stirred until a mixture of monophasic appearance is obtained.
    g of dodecane (Aldrich ™, purity> 99%) are slowly introduced into the mixture with stirring until an emulsion is formed.
    The emulsion is then poured into a Petri dish with an internal diameter of 5.5 cm, which is installed in a saturator for 7 days for gelation.
    The gel obtained is then washed a first time with anhydrous tetrahydrofuran (Aldrich ™, purity> 99%), then with an anhydrous tetrahydrofuran / acetone mixture (VWR ™, ACS grade) at 70/30 by volume 2 times in succession.
    The gel is then dried at room temperature for 7 days. The gel is finally calcined in air in a muffle oven at 180 ° C for 2 hours, then at 650 ° C for 5 hours. A porous monolith based on SiO 2 is then obtained.
    5.3 g of cerium nitrate hexahydrate (Aldrich ™, purity 99%) are dissolved in 95 ml of distilled water with stirring. Part of this solution corresponding to the pore volume is impregnated in the porosity of the monolith, then left to mature for 12 hours. The monolith is then dried under an ambient atmosphere for 24 hours. The monolith is finally calcined in air in a muffle oven at 120 ° C for 2i, then at 180 ° C for 2h and finally at 450 ° C for 1h. A poignant monolith is then obtained comprising CeO 2 in an SiO 2 matrix.
    Photocatalyst F has a mesoporous volume of 0.30 mL / g, a type I marcoporous volume of 1.34 mL / g and a macroporous type II volume of 6.7 mL / g. Photocatalyst F has a specific surface of 257 m 2 / g. The content of Ce element measured by ICP-AES is 13.03% by weight, which makes an equivalent of 16.0% by weight of CeO 2 in photocatalyst F.
    Photocatalyst F has an apparent density of 0.14 g / mL.
    EXAMPLE 7 Use of Photocatalysts in Photocatalytic Reduction of CO 2 in the Gas Phase
    Photocatalysts A, B, C, D, E and F are subjected to a photocatalytic reduction test of CO 2 in the gas phase in a continuous steel through-bed reactor equipped with a quartz optical window and a sintered glass face of the optical window on which the photocatalytic solid is deposited.
    For photocatalysts A and B a sufficient quantity of powder is deposited on the frit so as to cover the whole of the irradiated surface of the reactor. For photocatalysts C, D, E and F, the monoliths are just placed on the frit, their diameter being equal to the diameter of the reactor. The irradiated area for all photocatalysts is 8.042477.10 04 m 2 . The tests are carried out at ambient temperature under atmospheric pressure. A CO 2 flow of 0.3 ml / min passes through a water saturator before being distributed in the reactor. The production of dihydrogen gas produced from the undesirable photocatalytic reduction of the water entrained in the saturator and of CH 4 resulting from the reduction of carbon dioxide is followed, by an analysis of the effluent every 6 minutes by micro chromatography in gas phase. The UV-Visible irradiation source is provided by an Xe-Hg lamp (Asahi ™, MAX302 ™). The irradiation power is always maintained at 80 W / m 2 for a wavelength range between 315 and 400 nm. The duration of the test is 20 hours.
    The photocatalytic activities are expressed in pmol of dihydrogen and methane produced per hour and per m 2 irradiated. These are average activities over the entire duration of the tests. The results are reported in Table 1 (below)
    Table 1: Performance of photocatalysts relative to their average activity for the production of dihydrogen or methane from a CO mixture and H O in gas phase
    Photocatalyst Average activity ch 4 (pmol / h / m 2 ) Average activity H 2 (pmol / h / m 2 ) A (non-compliant) TiO 2 1 21 B (non-compliant) CeO 2 3 7 C (compliant) TiO 2 monolith 56 10 D (compliant) TiO 2 / SiO 2 monolith 17 8 E (compliant) TiO 2 / SiO 2 monolith 93 13 F (compliant) CeO 2 / SiO 2 monolith 78 6
    The activity values show that the use of the solids according to the invention systematically exhibits the best photocatalytic performances and particularly better selectivities towards the photocatalytic reduction of CO 2 .
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. A process for the photocatalytic reduction of carbon dioxide carried out in the liquid phase and / or in the gas phase under irradiation using a photocatalyst in the form of a porous monolith containing at least one semiconductor, which process comprises the following steps:
    a) a charge containing carbon dioxide and at least one sacrificial compound is brought into contact with a photocatalyst which is in the form of a porous monolith comprising an apparent density of less than or equal to 0.25 g / ml;
    b) the photocatalyst is irradiated by at least one irradiation source producing at least one wavelength less than the prohibited bandwidth of said photocatalyst, said step b) being carried out at a temperature between 10 ° C and 200 ° C , and at a pressure between 0.0 MPa and 70 MPa.
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein when said method is carried out in the gas phase, the sacrificial compound is a gaseous compound selected from water, ammonia, hydrogen, methane and an alcohol.
    [3" id="c-fr-0003]
    3. The method of claim 1, wherein when the process is carried out in the liquid phase, the sacrificial compound is a liquid or soluble solid compound selected from water, ammonia, an alcohol, an aldehyde or an amine.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, wherein the irradiation source is a source of artificial or natural irradiation.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein photocatalyst in the form of porous monolith has a mesoporous volume, the pore diameter of which is greater than 0.2 nm and less than or equal to 50 nm, between 0 , 01 to 1 mL / g.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 4, wherein the photocatalyst in the form of porous monolith has a macroporous volume of type I, whose pore diameter is greater than 50 nm and less than or equal to 1000 nm, included between 0.1 and 3 mL / g.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 4, in which the photocatalyst in the form of porous monolith has a macroporous volume of type II, the pore diameter of which is greater than 1 μm and less than or equal to 10 μm, included between 0.1 to 8 mL / g.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 5 to 7, wherein the photocatalyst in the form of porous monolith comprises a mesoporosity and / or a macroporosity of type I and / or a macroporosity of type II.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, in which the photocatalyst in the form of a porous monolith comprises a macroporous volume, the pore diameter of which is greater than 10 μm, less than 0.5 ml / g.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, wherein the photocatalyst in the form of porous monolith comprises an apparent density less than 0.19 g / ml_.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 1 to 10, wherein the photocatalyst in the form of porous monolith has a specific surface of between 10 and 1000 m 2 / g.
    [12" id="c-fr-0012]
    12. Method according to any one of claims 1 to 11, in which the photocatalyst in the form of a porous monolith comprises at least one semiconductor and at least one inorganic phase containing silica or alumina which does not absorb the photons d energy greater than 4 eV.
    [13" id="c-fr-0013]
    13. Method according to any one of claims 1 to 12, wherein the semiconductor content is between 5 and 70% by weight relative to the total weight of the photocatalyst.
    [14" id="c-fr-0014]
    14. Method according to any one of claims 1 to 11, wherein the photocatalyst in the form of porous monolith consists of said semiconductor in the form of monolith.
    [15" id="c-fr-0015]
    15. Method according to any one of claims 1 to 14, wherein the semiconductor is chosen from TiO 2 , ZnO, Cu 2 O, CuO, Ce 2 O 3 , CeO 2 , ln 2 O 3 , SiC, ZnS, and ln 2 S 3 , alone or as a mixture.
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    同族专利:
    公开号 | 公开日
    US20210106977A1|2021-04-15|
    WO2018197435A1|2018-11-01|
    EP3615211B1|2021-08-18|
    FR3065650B1|2019-06-28|
    ES2894600T3|2022-02-15|
    EP3615211A1|2020-03-04|
    JP2020517666A|2020-06-18|
    CN110536750A|2019-12-03|
    AU2018258985A1|2019-10-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR3026965A1|2014-10-14|2016-04-15|Ifp Energies Now|METHOD FOR PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE USING COMPOSITE PHOTOCATALYST.|
    FR2975309A1|2011-05-19|2012-11-23|Centre Nat Rech Scient|Self supported macrocellular monolith, useful e.g. as photocatalyst for decontaminating gaseous pollutants, comprises material comprising titanium oxide matrix comprising titanium dioxide in anatase form or in rutile form|
    DE102013214518A1|2013-07-25|2015-01-29|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Heat exchanger and method for its production and use|FR3065651B1|2017-04-28|2020-05-29|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A MULTIMODAL POROSITY MONOLITE|
    CN110078579B|2019-04-29|2022-01-11|淮北师范大学|By using CO2Method for preparing renewable hydrocarbon compound by reduction bifunctional photocatalytic coupling reaction|
    FR3095598B1|2019-05-02|2021-12-17|Ifp Energies Now|PHOTOCATALYTICAL REDUCTION PROCESS OF CARBON DIOXIDE IN THE PRESENCE OF AN EXTERNAL ELECTRIC FIELD|
    法律状态:
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    2018-11-02| PLSC| Publication of the preliminary search report|Effective date: 20181102 |
    2019-04-25| PLFP| Fee payment|Year of fee payment: 3 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1753758|2017-04-28|
    FR1753758A|FR3065650B1|2017-04-28|2017-04-28|METHOD FOR PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE USING PHOTOCATALYST IN THE FORM OF POROUS MONOLITH|FR1753758A| FR3065650B1|2017-04-28|2017-04-28|METHOD FOR PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE USING PHOTOCATALYST IN THE FORM OF POROUS MONOLITH|
    CN201880028083.1A| CN110536750A|2017-04-28|2018-04-23|Use the photocatalysis carbon dioxide reduction method of the photochemical catalyst of porous monolith form|
    AU2018258985A| AU2018258985A1|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction method using a photocatalyst in the form of a porous monolith|
    JP2019557560A| JP2020517666A|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction method using a photocatalyst in the form of a porous monolith|
    ES18724475T| ES2894600T3|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction procedure using a photocatalyst in the form of a porous monolith|
    PCT/EP2018/060380| WO2018197435A1|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction method using a photocatalyst in the form of a porous monolith|
    EP18724475.1A| EP3615211B1|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction method using a photocatalyst in the form of a porous monolith|
    US16/608,568| US20210106977A1|2017-04-28|2018-04-23|Photocatalytic carbon dioxide reduction method using a photocatalyst in the form of a porous monolith|
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