EP3525929A1 - Dreiteiliger nanokatalysator und verwendung davon zur fotokatalyse - Google Patents

Dreiteiliger nanokatalysator und verwendung davon zur fotokatalyse

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Publication number
EP3525929A1
EP3525929A1 EP17794011.1A EP17794011A EP3525929A1 EP 3525929 A1 EP3525929 A1 EP 3525929A1 EP 17794011 A EP17794011 A EP 17794011A EP 3525929 A1 EP3525929 A1 EP 3525929A1
Authority
EP
European Patent Office
Prior art keywords
nano
catalyst
triptych
oxide
carbo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17794011.1A
Other languages
English (en)
French (fr)
Inventor
Jérémy CURE
Myrtil Kahn
Kévin COCQ
Gérald CASTEROU
Rémi Chauvin
Valérie MARAVAL
Hala ASSI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CURE, JEREMY
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Universite Toulouse III Paul Sabatier
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Universite Toulouse III Paul Sabatier
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Rennes 1, Universite Toulouse III Paul Sabatier filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3525929A1 publication Critical patent/EP3525929A1/de
Pending legal-status Critical Current

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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J23/52—Gold
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
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    • C01B13/0207—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a nano-catalyst nanoscale composition, as well as a method for producing the nano-catalyst.
  • the present invention also relates to the use for the photo-catalysis of the nano-catalyst of the invention, in particular for the photoelectrolysis of water.
  • Zinc oxide (ZnO) is an n-type semiconductor which has advantageous properties for its use as a photo-catalyst such as high transparency, high electron mobility, high thermal conductivity, a large direct bandgap (3.37 eV) and high excitonic binding energy (60 meV). It also satisfactory fennel and chemical stability, especially in an aqueous medium, and a moderate ecological cost.
  • the semiconductors ZnO and T1O2 which both have a large direct bandgap, do not absorb in the visible range of the solar spectrum but only in the UV range. To be usable as an effective photocatalyst, it appears necessary to increase the absorption range of the material so that it covers a wider range of the solar spectrum.
  • the nano-catalysts thus improved have still unsatisfactory yields and a limited life.
  • the production of these nano-catalysts is complex and expensive. Therefore, there is a need for new nano-catalysts simpler to produce, more efficient and more durable, especially for the production of hydrogen by photo-reduction of water.
  • the Applicant has designed and prepared a novel nano-particulate triptych nano-catalyst comprising the combination of a semiconductor, preferably nano-particulate or nano-rod, metal nanoparticles with plasmonic properties and a organic photo-sensitizer.
  • a semiconductor preferably nano-particulate or nano-rod, metal nanoparticles with plasmonic properties and a organic photo-sensitizer.
  • This triptych surprisingly exhibits photoelectrochemical properties suitable for use as a photo-catalyst, especially for photo-reduction of water and the production of hydrogen.
  • the present invention relates to a triptych nano-catalyst comprising:
  • nanoparticulate semiconductor or in the form of nano-rods
  • an organic photosensitizer which is a carbo-mother, preferably a carbo-bene or a carbo-n-butadiene.
  • the nano-particulate or nano-stick semiconductor is a metal oxide, preferably tin oxide, indium oxide, gallium oxide. , tungsten oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, zinc oxide or titanium oxide, more preferably zinc oxide or titanium oxide.
  • the plasmonic metal is gold, silver, copper, aluminum or platinum, preferably gold, silver or copper, more preferably silver.
  • the carbo-mer is a carbo-benzene, preferably 4- [10- (4-aminophenyl) -4,7,13,164-tetraphenylcyclooctadeca-1,2,3,7,8,9,13 , 14,15-nonaen-
  • the plasmonic metal nanoparticles are located on the surface of the nano-particulate semiconductor metal oxide or in the form of nano-rods.
  • the plasmonic metal nanoparticles are located on the surface of the nanoparticulate semiconductor or in the form of nano-rods. According to one embodiment, the nano-particulate semiconductor metal oxide and or the plasmonic metal nanoparticles are coated by the photosensitizer.
  • the nanoparticulate semiconductor or in the form of nano-rods, and or the plasmonic metal nanoparticles are coated by the photosensitizer.
  • the present invention also relates to a method of manufacturing the nano-triptych catalyst comprising the following steps:
  • step (Ib) mixing the composition obtained in step (la) with an organometallic complex of a plasmonic metal; optionally followed by a stirring step (1c); and
  • step (1b) (2) irradiating the composition obtained in step (1b) under electromagnetic radiation, preferably under sunlight.
  • the method for manufacturing the nano-triptych catalyst comprises the following steps:
  • step (Ib) mixing the composition obtained in step (la) with a complex comprising a ion of a plasmonic metal; optionally followed by a stirring step (1c); and
  • the organometallic complex of a plasmonic metal is an amidinate or carboxylate complex of silver, gold, copper, aluminum or platinum, preferably a amidinate complex of money.
  • the organometallic complex comprises the combination of at least one organic ion with at least one ion of a plasmonic metal.
  • the organometallic complex comprises the combination of at least one organic anion with at least one cation of a plasmonic metal.
  • the organometallic complex comprises the combination of at least one organic anion chosen from aminidates or carboxylates; with at least one cation of a plasmonic metal.
  • the organometallic complex is an amidinate or carboxylate of silver, gold, copper, aluminum or platinum, preferably a silver amidinate.
  • the present invention also relates to the use of the nano-triptych catalyst to produce hydrogen.
  • the present invention also relates to a power supply device, preferably a nomad power supply device, comprising the nano-triptych catalyst.
  • Alkyl relates to any linear, branched or cyclic saturated hydrocarbon-based chain of 1 to 12 carbon atoms, preferably of 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl or isopropyl, and butyl, sec-buryl, isoburyl, t-butyl, pentyl and its isomers (eg n-pentyl, iso-penyl), hexyl and its isomers (eg n-hexyl, uo-hexyl).
  • Alkenyl relates to any linear, branched or cyclic hydrocarbon chain comprising at least one double bond, of 2 to 12 carbon atoms, preferably of 2 to 6 carbon atoms, and not containing an aromatic ring; as for example vinyl or allyl.
  • Alkynyl relates to any linear, branched or cyclic hydrocarbon chain comprising at least one triple bond, of 2 to 12 carbon atoms, preferably of 2 to 6 carbon atoms, and not having an aromatic ring; as for example ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 2-pentynyl and its isomers, 2-hexynyl and its isomers.
  • Aryl refers to a polyunsaturated aromatic hydrocarbyl group having a single ring (eg phenyl) or several fused (eg, naphthyl) or single covalently linked (eg biphenylyl) aromatic rings, typically containing 5 to 20 carbon atoms; preferably 6 to 12, wherein at least one ring is aromatic.
  • the aromatic ring may optionally include one to two additional rings (either cycloalkyl, heterocyclyl or heteroaryl) fused thereto.
  • Non-limiting examples of aryl groups include phenyl, biphenylyl, biphenylenyl, S or tetralinyl, naphthalene-1- or -2-yl, 4, 5, 6 or 7-indenyl, 1- 2-, 3-, 4 or 5-acenaphthylenyl, 3-, 4- or 5-acenaphthenyl, 1- or 2-pentalenyl, 4- or 5-indanyl, 5-, 6-, 7- or 8-tetrahydronaphthyl, 1,2,3,4 tetrahydronaphthyl, 1,4-dihydronaphthyl, 1-, 2-, 3-, 4- or 5-pyrenyl.
  • Heteroaryl refers to aromatic rings of S to 12 carbon atoms or ring systems containing from 1 to 2 rings which are fused together or covalently bound, typically containing from 5 to 6 carbon atoms; at least one ring of which is aromatic, in which one or more carbon atoms in one or more of these rings are replaced by oxygen, nitrogen and / or sulfur atoms; the nitrogen and sulfur atoms can optionally be oxidized and the nitrogen atoms can optionally be quaternized.
  • Such rings may be fused to an aryl, cycloalkyl, heteroaryl or heterocyclyl group.
  • heteroaryl groups include furanyl, thiophenyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, oxatriazolyl, thiatriazolyl, pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, oxazinyl, dioxinyl, thiazinyl, triazinyl, imidazo [2,1b] [1,3] thiazolyl, thieno [3,2-b] furanyl, thieno [3,2-b] thiophenyl, thieno [2,3-d] [1,3] thiazolyl, thieno [2,3-d] imidazolyl, tetrazolo [1,5-
  • Carbo-mer refers to a molecule expanded by insertion of one or more C1 units in all bonds of a generic (topologically defined) set of bonds of any parent molecule (total carbo- cycle mother, peripheral carbo-mother, carbon skeleton carbo-mother, etc.); this expansion retains as a first approximation the local symmetry, the inter-atomic connectivity, and the ⁇ resonance of the parent molecule; the prefix "carbo-" is used as a global locus to designate a carbon skeleton carbo-mer independently of substituents, for example: a carbo-benzene; a carbo-n-butadiene.
  • the term “carbo-mother” does not refer to an infinite covalent structure such as graphene, graphyne or graphdiyne.
  • the term “carbo-mother” does not refer to a covalent structure in the form of a sheet
  • “Goroo-benzene” relates to a carbo-mother constructed by insertion of a C2 unit into each ring bond of benzene or a substituted benzene derivative.
  • a carbo-benzene is a molecule of general formula:
  • the alkyl, alkenyl and alkynyl groups can be linear or branched.
  • Carbo-n-batadiene relates to a carbo-mother built by insertion of a C 2 unit in each of the bonds of the carbon skeleton of n-butadiene, independently of its possible substituents.
  • a carbo-n-butadiene is a molecule of formula the general:
  • the alkyl, alkenyl and alkynyl groups can be linear or branched.
  • the carbon-butadiene relates to a carbo-mother constructed by insertion of a C 2 unit in each of the bonds of the carbon skeleton and into two non-geminal CH bonds of n-butadiene, independently of its possible substituents. .
  • Haldrogen refers to the hydrogen molecule (H2), unless otherwise indicated.
  • Sun light or “solar spectrum” concerns all the electromagnetic waves emitted by the Sun, and in particular the solar radiation received on the surface of the Earth. In particular, sunlight includes visible light.
  • Visible light or “visible spectrum” refers to the part of the electromagnetic spectrum visible to a human being, that is to say the set of monochromatic components of visible light.
  • the International Commission on Illumination defines the visible spectrum as including wavelengths in vacuum from 380 nm to 780 nm.
  • Nano-catalyst relates to a nano-particulate catalyst.
  • Nano-triptych catalyst relates to a nano-catalyst comprising three main elements, as described below.
  • Nano-particle relates to an assembly of atoms of which at least one of the dimensions is at the nanoscale, that is to say is less than about 100 nm.
  • Nanoparticle relates to an assembly of atoms whose three dimensions are at the nanoscale, that is to say a particle whose nominal diameter is less than about 100 nm.
  • “Plasmonia” relates to a resonant interaction obtained under certain conditions between electromagnetic radiation, for example visible light, and free electrons at the interface between a metal (“plasmonic metal”) and a dielectric material, for example air. This interaction generates waves of electron density, behaving like waves and called “plasmons” or "surface plasmons".
  • a plasmonic metal is for example silver, gold or copper.
  • Electromagnetic radiation or “light” refers to light in the UV, visible or Ht range, preferably sunlight or visible light.
  • the present invention relates to a triptych nano-catalyst comprising or consisting of:
  • the present invention relates to a triptych nano-catalyst comprising or consisting of:
  • the triptych nano-catalyst does not comprise or consist of a combination of graphene, cadmium sulphide (CdS) and / or platinum (Pt). According to one embodiment, the triptych nano-catalyst does not comprise or consist of a combination of graphyne, cadmium sulphide (CdS) and / or platinum (Pt). According to one embodiment, the triptych nano-catalyst does not comprise or consist of a combination of graphdiyne, cadmium sulphide (CdS) and / or platinum (Pt). According to one embodiment, the triptych nano-catalyst comprises or consists of:
  • nanoparticulate semiconductor or in the form of rods
  • the organic photosensitizer is not in the form of an infinite covalent structure such as a leaflet.
  • the triptych nano-catalyst is chosen from the compounds NI to N19 described in the following table:
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferentially the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. benzene, relative to the molar amount of Zn of ZnO.
  • the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of Zn from ZnO.
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferentially the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. benzene, relative to the molar amount of Ti of T1O2. According to one embodiment, the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of Ti of T1O2.
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferentially the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. benzene, relative to the molar amount of Cu of CuO.
  • the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of Cu of CuO.
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferentially the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. benzene, relative to the molar amount of Fe of Fe2O3.
  • the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of Fe of Fe203.
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferentially the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. benzene, relative to the molar amount of Ni NiO. According to one embodiment, the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of Ni NiO.
  • the triptych nano-catalyst comprises from more than 0% to 10 mol% of carbo-benzene, preferably from 1% to 5%, more preferably the triptych nano-catalyst comprises approximately 2 mol% of carbo-benzene. -benzene, relative to the molar amount of W of WO3.
  • the triptych nano-catalyst comprises 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10 mol% of carbo-benzene relative to the molar amount of W of WO3.
  • the semiconductor is nano-particulate or in the form of a nano-stick.
  • the nanoparticulated semi-conductor is a ⁇ -VI type semiconductor, for example a nano-particle type oxyde-VI semiconductor electron oxide.
  • the nanoparticulate semiconductor metal oxide is tin oxide (SnO2), indium oxide (I11203), gallium oxide (GaaOi), tungsten oxide (WO3), copper oxide (CuO or C1120), nickel oxide (NiO), cobalt oxide (CoO), iron oxide (FeO, Fe2O3, Fe2O4) ), zinc oxide (ZnO) or titanium oxide (TiO2).
  • the semiconductor is titanium oxide (T1O2) or zinc oxide (ZnO).
  • the semiconductor is titanium oxide (T1O2).
  • the semiconductor is zinc oxide (ZnO).
  • the nano-particulate semiconductor is tin oxide (SnO2), indium oxide (I11203), gallium oxide (Ga2O3), oxide tungsten (WO3), copper oxide (CuO or C0O), nickel oxide (NiO), cobalt oxide (CoO), iron oxide (FeO, ⁇ e2O3, Fe3O-i), zinc oxide (ZnO) or titanium oxide (T1O2).
  • the semiconductor is titanium oxide (T1O2) or zinc oxide (ZnO).
  • the semiconductor is titanium oxide (T1O2).
  • the semiconductor is zinc oxide (ZnO).
  • the nano-particulate semiconductor metal oxide is a mixed oxide such as a spinel type metal oxide (X 2t ) (Y 3+ ) 2 (O a- ) 4 where X and Y are two different metals, for example CoFe204, ZnFe2O4 or MnFe2O4; or a perovskite metal oxide (X 2+ ) (Y 44 ) (O 2 ⁇ ) 3 where X and Y are two different metals, for example CaTiO 3 or CaSnO 3.
  • a spinel type metal oxide X 2t ) (Y 3+ ) 2 (O a- ) 4 where X and Y are two different metals, for example CoFe204, ZnFe2O4 or MnFe2O4
  • a perovskite metal oxide X 2+ ) (Y 44 ) (O 2 ⁇ ) 3 where X and Y are two different metals, for example CaTiO 3 or CaSnO 3.
  • the nanoparticulate semiconductor is a mixed oxide such as a spinel type metal oxide (X 2+ ) (Y 3+ ) 2 (0 2- ) 4 where X and Y are two different metals, for example CoFfao-i, ⁇ 2 ⁇ 4 or MnFe20 4 ; or a perovskite metal oxide (X 2+ ) (Y 44 ) (O 2 ⁇ ) 3 where X and Y are two different metals, for example CaTiO3 or CaSnO3.
  • the nano-particulate semiconductor is a sulfide, an equivalent selenide, or an equivalent tellurium, for example ZnS, CuS, CdSe, CdTe, PbS or PbSe.
  • the nano-particulate semiconductor is a ⁇ -V type semiconductor, for example GaAs, GaN, InAs or InP.
  • the nano-particulate semiconductor is a mixed semiconductor of types ⁇ -VI and IH-V, for example ZnO: GaN.
  • the nano-particulate semiconductor is full. According to one embodiment, the nano-particulate semiconductor is partially or completely hollow.
  • the nano-particulate semiconductor is in the form of isotropic or anisotropic nanoparticles. According to one embodiment, the nanoparticulate semiconductor is in the form of monocrystalline or polycrystalline nanoparticles.
  • the nano-particulate semiconductor has an average diameter of more than 0 nm to 100 nm; preferably from 10 nm to 100 nm; from 20 nm to 100 nm; from 30 nm to 100 nm; from 40 nm to 100 nm; from 50 nm to 100 nm; from 60 nm to 100 nm; from 70 nm to 100 nm; from 80 nm to 100 nm or from 90 nm to 100 nm.
  • the nano-particulate semiconductor has a mean diameter of about 23 nm.
  • the nano-particulate semiconductor has a mean diameter of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 , 80, 85, 90, 95 or 100 nm.
  • the nanoparticulate semiconductor has a mean diameter of more than 0 nm to 50 nm; preferably from 10 nm to 50 nm; from 15 nm to 50 nm; from 20 nm to 50 nm; from 25 nm to 50 nm; from 30 nm to 50 nm; from 35 nm to 50 nm; from 40 nm to 50 nm; or from 45 nm to 50 nm.
  • the nanoparticulate semiconductor is zinc oxide (ZnO) in the form of particles with a mean diameter of more than 0 nm to 100 nm.
  • the nanoparticulate semiconductor is zinc oxide (ZnO) in the form of particles with an average diameter of more than 0 nm to 50 nm.
  • the semiconductor is zinc oxide (ZnO) in the form of nano-rods.
  • the nano-particulate semiconductor is titanium oxide (TiO 2) in the form of particles with a mean diameter of 23 nm.
  • the semiconductor is titanium oxide (10 2) in the form of nano-rods.
  • the nanoparticulate semiconductor is titanium oxide (T1O2) in the form of particles of average diameter from more than 0 nm to 50 nm.
  • the nanoparticulate semiconductor is copper oxide (CuO) in the form of particles with a mean diameter of more than 0 nm to 50 nm.
  • the nanoparticulate semiconductor is iron oxide, preferably Fe 2 O 3, in the form of particles with a mean diameter of more than 0 nm to 50 nm.
  • the nanoparticulate semiconductor is nickel oxide (NiO) in the form of particles with an average diameter of more than 0 nm to 50 nm.
  • the nanoparticulate semiconductor is tungsten oxide (WO 3) in the form of particles having a mean diameter of more than 0 nm to 50 nm.
  • the plasmonic metal nanoparticles are nanoparticles of gold (Au), silver (Ag), copper (Cu), aluminum (Al) or platinum (Pt).
  • the plasmonic metal nanoparticles are nanoparticles of gold (Au), silver (Ag) or copper (Cu).
  • the plasmonic metal nanoparticles are aluminum (Al) or platinum (Pt) nanoparticles.
  • the nanoparticles of plasmonic metal are gold nanoparticles (Au).
  • the plasmonic metal nanoparticles are silver nanoparticles (Ag). In another specific embodiment, the plasmonic metal nanoparticles are copper (Cu) nanoparticles. In one embodiment, the plasmonic metal nanoparticles are a mixture of nanoparticles of at least two plasmonic metals. In one embodiment, the plasmonic metal nanoparticles consist of a mixture of nanoparticles of at least two plasmonic metals.
  • the plasmonic metal nanoparticles for example gold nanoparticles (Au), silver (Ag) or copper (Cu), allow and / or facilitate the absorption of electromagnetic radiation by the nano-catalyst triptych in the visible range.
  • the plasmonic metal nanoparticles for example aluminum (Al) or platinum (Pt) nanoparticles, allow and / or facilitate the absorption of electromagnetic radiation by the triptych nano-catalyst in the UV range.
  • the metal nanoparticles Plasmonics constitute a mixture of nanoparticles of at least two plasmonic metals and allow and / or facilitate the absorption of electromagnetic radiation by the nano-triptychic catalyst in the UV and / or visible range, preferably UV and visible.
  • the nanoparticles of plasmonic metal are solid.
  • the plasmonic metal nanoparticles are partially or entirely hollow.
  • the nanoparticles of plasmonic metal are isotropic.
  • the plasmonic metal nanoparticles are anisotropic.
  • the plasmonic metal nanoparticles are monocrystalline or polycrystalline.
  • the organic photosensitizer has intermolecular self-assembly properties, i.e. the photosensitizer comprises or consists of molecules that adopt an arrangement without the need to apply a external source of energy.
  • the organic photosensitizer is an electrical conductor, that is to say it contains mobile electric charge carriers capable of carrying an electric current.
  • the photosensitizer has a high capacity to separate the charges by its moderate aromatic character and its extensive ⁇ conjugation, thus avoiding unwanted recombination of photoinduced charges.
  • the organic photosensitizer absorbs electromagnetic radiation in the UV, visible and / or IR range, for example sunlight or visible light.
  • the photosensitizer absorbs sunlight.
  • the photosensitizer absorbs visible light.
  • the electromagnetic radiation absorbed by the photosensitizer generates photoinduced charges.
  • the photosensitizer is weakly emissive, that is to say that it emits little or no electromagnetic radiation.
  • the photosensitizer has intermolecular self-assembly properties, is an electrical conductor, and absorbs electromagnetic radiation in the visible spectrum.
  • the organic photosensitizer is a carbo-mer, for example a carbo-benzene or a carbo-n-butadiene.
  • the organic photosensitizer is a carbobenzene, preferably a functionalized carbobenzene, more preferably a carbobenzene comprising one or more organic functions, said organic functions comprising at least one heteroatom.
  • the organic photosensitizer is a carbo-benzene substituted with at least one group selected from amino, hydroxyl, carboxyl, and thiol.
  • the photosensitizer is a carbobenzene, for example a compound of formula (I):
  • the photosensitizer is 4,4 '((4,7,13,16-tetraphenylcyclooctadecyl)
  • the photosensitizer is a carbo-n-butadiene, for example 4- ⁇ 12- [4-aminophenyl] -6,9-diphenyl-1,14-bis [tris (propan-2- yl) silyl] tetradeca-3,4,5,9,10,11-hexa-1,7,13-triyn-3-yl ⁇ -aniline.
  • the amount of nano-particulate semiconductor in the nano-triptych catalyst is between 99.9% and 30%; preferably between 99% and 50%; more preferably between 90% and 70% by weight relative to the total mass of the nano-triptych catalyst.
  • the amount of nano-particulate semiconductor in the nano-triptych catalyst is from 99.9% to 30%; preferably from 99.9% to 40%; from 99.9% to 50%; from 99.9% to 60%; from 99.9% to 70%; from 99.9% to 80%; or from 99.9% to 90% by weight relative to the total mass of the nano-triptych catalyst.
  • the amount of nano-particulate semiconductor in the nano-triptych catalyst is about 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82 , 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, by mass relative to the total mass of the nano-triptych catalyst .
  • the amount of nano-particulate semiconductor in the nano-triptych catalyst is from 99.9% to 30%; preferably from 90% to 30%; from 85% to 30%; from 80% to 30%; from 75% to 30%; from 70% to 30%; from 65% to 30%; from 60% to 30%; from 55% to 30%; from 50% to 30%; from 45% to 30%; from 40% to 30%; or from 35% to 30% by weight relative to the total mass of the triptych nano-catalyst.
  • the amount of plasmonic metal nanoparticles in the nano-triptych catalyst is between 0.01% and 10%; preferably between 0.10% and 8%; more preferably between 0.10% and 5% by weight relative to the total mass of the triptych nano-catalyst.
  • the amount of plasmonic metal nanoparticles in the nano-triptych catalyst is from 0.01% to 10%; preferably from 1% to 10%, preferably from 2% to 10%, preferably from 3% to 10%, preferably from 4% to 10%, preferably from 5% to 10%, preferably 6% at 10%, preferably from 7% to 10%, preferably from 8% to 10%, or preferably from 9% to 10% by weight relative to the total mass of the triptych nano-catalyst.
  • the amount of metal nanoparticles plasmonic in the nano-triptyque catalyst is from 0.01% to 1%; preferably 0.01% and 0.09%; 0.01% and 0.08%; 0.01% and 0.07%; 0.01% and 0.06%; 0.01% and 0.05%; 0.01% and 0.04%; 0.01% and 0.03%; or 0.01% and 0.02%, by mass relative to the total mass of the nano-triptych catalyst.
  • the quantity of plasmonic metal nanoparticles in the nano-triptych catalyst is about 1%, 2%, 3%, 4% or 5%, by mass relative to the total mass of the nano-catalyst. triptych.
  • the proportion of plasmonic metal nanoparticles in the nano-triptych catalyst is about 1%, 2%, 3%, 4% or 5%.
  • the amount of organic photosensitizer in the nano-triptych catalyst is between 0.09% and 60%; preferably between 0.90% and 42%; more preferably between 2% and 25% by weight relative to the total mass of the nano-triptych catalyst.
  • the amount of organic photosensitizer in the nano-triptych catalyst is from 0.09% to 60%; preferably from 0.09% to 55%; from 0.09% to 50%; from 0.09% to 45%; from 0.09% to 40%; from 0.09% to 35%; from 0.09% to 30%; from 0.09% to 25%; from 0.09% to 20%; from 0.09% to 15%; from 0.09% to 10%; from 0.09% to 5%; or from 0.09% to 1% by weight relative to the total mass of the nano-triptych catalyst.
  • the amount of organic photosensitizer in the triptych nano-catalyst is about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25%, by weight relative to the total mass of the triptych nano-catalyst.
  • the proportion of organic photosensitizer in the triptych nano-catalyst is about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.
  • the proportion of plasmonic metal atoms in the nano-triptych catalyst is between 0.01% and 30 % ; preferably between 0.1% and 15%; more preferably between 0.5% and 7%, atomic with respect to the number of metal atoms in the nano-particulate semiconductor.
  • the proportion of plasmonic metal atoms in the triptych nano-catalyst is from 0.01% to 30%; preferably from 0.01% to 25%; from 0.01% to 20%; from 0.01% to 15%; from 0.01% to 10%; from 0.01% to 5% or from 0.01% to 1%.
  • the proportion of plasmonic metal atoms in the nano-triptych catalyst is from 0.1% to 30%; preferably from 1% to 30%; from 5% to 30%; from 10% to 30%; from 15% to 30%; from 20% to 30%, or from 25% to 30%. According to one embodiment, the proportion of plasmonic metal atoms in the triptych nano-catalyst is about 1%, 2%, 3%, 4%, 5%, 6% or 7%.
  • the amount of organic photosensitizer in the nano-triptych catalyst is between 0.01% and 30%; preferably between 0.1% and 15%; more preferably between 0.5% and 7%, molar relative to the molar amount of the metal in the nano-particulate semiconductor.
  • the amount of organic photosensitizer in the nano-triptyque catalyst is from 0.01% to 30%; preferably from 0.01% to 25%; from 0.01% to 20%; from 0.01% to 15%; from 0.01% to 10%; from 0.01% to 5% or from 0.01% to 1%, molar to the molar amount of metal in the nano-particulate semiconductor.
  • the amount of organic photosensitizer in the nano-triptyque catalyst is from 0.1% to 30%; preferably from 1% to 30%; from 5% to 30%; from 10% to 30%; from 15% to 30%; from 20% to 30%, or 25% to 30%, molar to the molar amount of metal in the nano-particulate semiconductor.
  • the amount of organic photosensitizer in the nano-triptych catalyst is about 1%; 1.1%; 1.2%; 1.3%; 1.4%; 1.5%; 1.6%; 1.7%; 1.8%; 1.9%; 2%; 3%; 4%; 5%; 6% or 7%, molar to the molar amount of the metal in the nanoparticulate semiconductor.
  • the proportion of organic photosensitizer in the nano-triptych catalyst is about 1%; 1.1%; 1.2%; 1.3%; 1.4%; 1.5%; 1.6%; 1.7%; 1.8%; 1.9%; 2%; 3%; 4%; 5%; 6% or 7%, molar to the molar amount of the metal in the nano-particulate semiconductor.
  • the plasmonic metal nanoparticles are in contact with the nano-particulate semiconductor. In one embodiment, the plasmonic metal nanoparticles are located on the surface of the nano-particulate semiconductor. According to one embodiment, the nano-particulate semiconductor and / or the plasmonic metal nanoparticles are coated with the organic photosensitizer. In one embodiment, the nano-particulate semiconductor is coated with the photosensitizer. In one embodiment, the plasmonic metal nanoparticles are coated by the photosensitizer. In one embodiment, the nano-particulate semiconductor and the plasmonic metal nanoparticles are coated by the photosensitizer.
  • the coating of the nano-particulate semiconductor and / or plasmonic metal nanoparticles by the photosensitizer increases the photoelectrochemical efficiency in the UV spectrum and / or visible, preferably in the visible spectrum, of the nano - triptych catalyst.
  • the coating of the nano-particulate semiconductor and / or plasmonic metal nanoparticles by the photosensitizer reduces or prevents the corrosion of the nano-particulate semiconductor and / or nanoparticles of plasmonic metal, thus increasing the duration of life of the nano-catalyst triptych.
  • the invention also relates to a method of manufacturing a triptych nano-catalyst according to the invention, as described above.
  • the method comprises the following steps:
  • the method comprises the following steps:
  • step (la) mixing the composition obtained in step (la) with a precursor of nanoparticles of plasmonic metal; and (2) irradiating the composition obtained in step (1b) under electromagnetic radiation.
  • the plasmonic metal nanoparticle precursor decomposes by photo-reduction or photo-oxidation to give the plasmonic metal in the form of metal nanoparticles.
  • the decomposition occurs in contact with the nano-particulate semiconductor.
  • the precursor is an organometallic complex of a plasmonic metal.
  • the precursor is a amidate or carboxylate complex of a plasmonic metal, for example silver (Ag), gold (Au) or copper (Cu).
  • the precursor is a salt of nitrate or chloride of a plasmonic metal, for example silver (Ag), gold (Au) or copper (Cu).
  • the precursor is a silver amidinate complex, preferably silver ⁇ , ⁇ '- diisopropylacetamidinate (Ag).
  • the precursor is an amidinate or carboxylate complex with an ion of a plasmonic metal, such as, for example, silver (Ag), gold (Au) or copper (Cu).
  • a plasmonic metal such as, for example, silver (Ag), gold (Au) or copper (Cu).
  • the precursor is a salt of an ion of the plasmonic metal, the ion being preferably the nitrate ion or the chloride ion.
  • the precursor is a silver amidinate complex, preferably silver ⁇ , ⁇ '-diisopropylacetemidinate (Ag).
  • the organic photosensitizer used in the process of the invention is in solution in a solvent, for example an organic solvent. In one embodiment, the solvent is toluene.
  • the plasmonic metal nanoparticle precursor is in solution in a solvent, for example an organic solvent.
  • the solvent is toluene.
  • the mixing step (1) is followed by a stirring step (1-c) at a temperature of between 10 and 50 ° C., preferably at room temperature.
  • the mixing step (1) is followed by a step (1-c) stirring at a temperature of 10 ° C to 50 ° C, preferably 10 ° C to 40 ° C, 10 ° C to 30 ° C, or 10 ° C to 20 ° C vs.
  • the mixing step (1) (or (1b)) is followed by a step (1-c) of stirring at a temperature of about 10 ° C, 11 ° C, 12 ° C, 13, 14, 15, 16, 17, 18, 19 or 20.
  • step (1-c) lasts between 10 minutes and 2 hours, preferably 1 hour. In one embodiment, step (1-c) lasts from 10 min to 120 min, preferably from 10 min to 110 min; from 10 minutes to 100 minutes; from 10 minutes to 90 minutes; from 10 minutes to 80 minutes; from 10 minutes to 70 minutes; from 10 minutes to 60 minutes; from 10 minutes to 50 minutes; from 10 minutes to 40 minutes; from 10 minutes to 30 minutes or 10 minutes to 20 minutes.
  • the irradiation step (2) lasts between 10 min and 48 h, preferably between 10 min and 24 h, more preferably between 30 min and 5 h. According to one embodiment, the irradiation step (2) lasts Ih, 2h, 3h, 4h, or 5h.
  • the irradiation step (2) lasts 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.
  • the irradiation takes place at a temperature between 10 and 50 ° C, preferably at room temperature.
  • the irradiation takes place at a temperature of 10 ° C to 50 ° C, preferably 10 ° C to 40 ° C, 10 ° C to 30 ° C, or 10 ° C to 20 ° C.
  • the irradiation takes place at a temperature of about 10 ° C, 11 ° C, 12 ° C, 13 ° C, 14 ° C, 15 ° C, 16 ° C, 17 ° C, 18 ° C. ° C, 19 ° C or 20 ° C.
  • the irradiation takes place with stirring.
  • the electromagnetic radiation is light in the UV, visible or IR range, preferably sunlight or visible light.
  • the invention also relates to a method for producing hydrogen (H2) using a nano-triptych catalyst according to the invention, as described above.
  • the hydrogen is produced by a photo-reduction reaction of the water activated by the nano-triptych catalyst according to the invention.
  • the triptych nano-catalyst is immersed in water.
  • hydrogen is produced by electrochemical reduction of water.
  • the hydrogen produced is gaseous.
  • oxygen oxygen (oxygen, O2) is produced simultaneously by an electrochemical oxidation reaction of the water.
  • the product oxygen is gaseous.
  • the invention also relates to an energy source comprising a triptych nano-catalyst according to the invention, as described above.
  • the invention also relates to a power supply device, said device comprising a nano-triptych catalyst according to the invention, as described above.
  • the power supply device is a source of energy. According to one embodiment, the power supply device comprises a source of energy.
  • the energy source produces hydrogen using the triptych nano-catalyst according to the invention, as described above.
  • the hydrogen is produced by a photo-reduction reaction of the water activated by the nano-triptych catalyst according to the invention.
  • the energy source comprises means for storing the hydrogen produced.
  • the device produces hydrogen using the nano-triptych catalyst according to the invention, as described above.
  • the device comprises a means for storing the hydrogen produced.
  • the nano-triptych catalyst of the invention is still active after 60 hours of irradiation, preferably after 70 hours of irradiation, more preferably after 80 hours of irradiation. .
  • the triptych nano-catalyst of the invention is still active after 84 hours of irradiation.
  • the energy source produces electricity from hydrogen.
  • the device produces electricity from hydrogen.
  • the energy source is "static”, that is to say that its dimensions and / or its weight that it can not be easily transported by a single person.
  • the energy source is "nomadic”, that is to say that its dimensions and weight allow it to be transported by a single person for at least one day, preferably at least one week, more preferably at least one month.
  • the device is static or nomadic.
  • the power source and / or the device according to the invention allows the user to consume electricity in the absence of connection to the electrical network.
  • the invention also relates to a method for producing electricity comprising the use of the nano-triptych catalyst of the invention as described above.
  • the method of generating electricity comprises at least one step of using the energy source and / or the device of the invention as described above.
  • the method of generating electricity comprises at least one step of producing dihydrogen.
  • the rate of production of dihydrogen in the gas phase is between more than 0 and 100 ⁇ mol.h -1 .g -1 ; preferably from 1.10 -6 to 10 ⁇ mol.h -1 .g -1 ; more preferably 1.10 -4 to 3 ⁇ mol.h -1 .g -1 .
  • the rate of production of dihydrogen in the gas phase is S.lO-3 .mu.m.h -1 .g -1 .
  • the rate of production of dihydrogen gas phase is 12.2.1 ⁇ -3 ⁇ mol.h -1 .g -1 .
  • the rate of production of dihydrogen in the gas phase is 17.2.1 ° -3 ⁇ mol ⁇ h -1 ⁇ g -1 . According to a mode As a result, the rate of production of dihydrogen in the gas phase is 6.10 -3 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen in the gaseous phase is 0.029 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen gas phase is 7.9.10 -3 umoLhr'.g -1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.015 ⁇ mol.h -1 .g -1 .
  • the rate of production of dihydrogen in the gas phase is 0.085 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.41 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.5 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 2.2 ⁇ mol.h -1 .g -1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 2.7 ⁇ mol.h -1 .g -1. According to one embodiment, the rate of production of dihydrogen in the gaseous phase is 1.4 ⁇ mol. .h -1 .g -1 .
  • Figure 1 is a diagram showing the general UV-visible absorption spectrum of the carbo-benzene molecule shown in the diagram.
  • Figure 2 is a photograph showing the en observations of nano-objects formed after irradiation in the UV alone (Example 2a).
  • Figure 3 is a photograph showing the TEM observations of the nano-objects formed after UV irradiation alone at D + 134 (Example 2a).
  • Figure 4 is a photograph showing the TEM observations of nano-objects formed after irradiation in the visible UV + domains (Example 2b-).
  • Figure 5 is a photograph showing the TEM observations of the nano-objects formed after irradiation in the visible UV + domains at D + 134 (Example 2b-).
  • Figure 6 is a photograph showing the TEM observations of nano-objects formed after irradiation in the visible range alone (Example 2c-).
  • Figure 7 is a photograph showing the en observations of nano-objects formed after irradiation in the visible range alone at D + 134 (Example 2c-).
  • Figure 8 is a photograph showing TEM observations of nano-object formation after 3 hours of irradiation in the visible only domain (Example 4).
  • Figure 9 is a photograph showing the RM NMR spectrum with T2 filter of the gas phase after 45 min of irradiation in the visible UV + domains (Example 4).
  • Figure 10 is a photograph showing the HRTEM observation of nano-objects at D + 20 (Example 4).
  • Figure 11 is a photograph showing the EDX analysis in HRTEM of nano-objects at D + 20 (Example 4).
  • Figure 12 is a photograph showing the analysis of the diffraction pattern of an Ag NP deposited on the surface of a ZnO NP from nano-objects at D + 20 (Example 4).
  • FIG. 13 is a graph showing the evolution of the production of dihydrogen in the gaseous phase as a function of the irradiation time, during the photo reduction of the water, the reaction being catalyzed by zinc oxide nano-rods / 1% carbo-benzene / 3% silver; titanium oxide particles P25 Aeroxide / 2% carbobenzene / 1% silver; with particles of titanium dioxide P2S Aeroxide / 2% carbo-benzene / 2% silver; with titanium oxide particles P25 Aeroxide / 1% carbo-benzene / 1% silver; by titanium oxide / 1% carbon-benzene / 1% silver nanoparticles or Degussa P25 / 2% carbo-benzene / 1% silver titanium oxide particles.
  • NP nanoparticle
  • the nano-particle-type semiconductor used consists of commercial ZnO nanoparticles (NP) (nano-powder of size ⁇ 100 nm, Sigma-Aldrich).
  • the plasmonic nanoparticles used consist of silver NPs resulting from the photo-reduction of a silver amidinate complex, silver ⁇ , ⁇ '-diisopropylacetamidinate, obtained according to the method developed by Gordon [Lim, BS; Rahtu, A.; Park, J.-S .; Gordon, R. G., Inorg. Chem., 2003, 42 (24), 7951-7958].
  • the organic photo-sensitizer (PS) used, of the carbo-benzene type, is the compound "4,4" ((4,7,13,16-tetraphenylcyclooctadeca-1,2,3,7,8,9,13, 14,15-nonaOT
  • the TEM images of the complex obtained by steps 1 / to 4 show Ag NPs distributed on the carbon film of the microscopy grid, which indicates that it remains in the reaction medium of the silver amidinate complex. who did not react.
  • observation of the yellow supernatant means that Ag NPs were formed in solution and not on the surface of ZnO.
  • a 0.36 mg / mL silver amidinate solution is prepared from 18 mg solubilized in 50 mL of dry, degassed toluene. This amount corresponds to 5 atomic% of Ag with respect to the Zn atoms of ZnO.
  • step 7 / a- The solution obtained after step 5 / is illuminated under UV for 1 h (Mercure lamp, 100 W).
  • step 7 / b- The solution obtained after step 5 / is placed in the sun (UV + visible domains) for several hours.
  • step 7 The solution obtained after step 5 / is placed in the sun in a UV-filtered clean room (visible range only) for several hours.
  • the TEM images show that, irrespective of the irradiation source (visible range only, Figures 6 and 7, UV domain only, Figures 2 and 3, UV + visible range, Figures 4 and 5), produces an Ag NP deposit on the surface of the ZnO NPs. These Ag NPs have a size of the order of 8 nm ⁇ 1 nm.
  • the TEM images also show that carbo-benzene is organized in the form of an organic layer visible on the surface of Ag NPs and on the surface of ZnO NPs.
  • ZnO in the nano-particle state and under UV irradiation ( ⁇ ⁇ 350 nm) produces electron-hole pairs.
  • the electron and the hole will migrate to the surface of ZnO for use in reduction and oxidation reactions, respectively.
  • a 0.36 mg / mL silver amidinate solution is prepared from 18 mg in 50 mL of dry, degassed toluene. This amount corresponds to 1 atomic% of Ag with respect to the Zn atoms of ZnO.
  • a septum is placed on the small bottle of F-P for subsequent sampling and this bottle is coated in safelight (which allows the filtration of UV rays).
  • the solution is exposed to the brightness of a clean room (UV filtered room). A sample of the solution is taken at regular intervals to perform TEM observations: 30 min, 1 h, 3 h, 20 h. Results
  • Example 2 Contrary to the results of Example 2, it takes between 3 hours and 20 hours of irradiation to fully form the Ag NP. Several reasons can explain this difference: - the manipulation 3 was carried out in winter, at a time of the year when the sunshine time is considerably reduced and the intensity of the solar radiation is weak;
  • a 0.36 mg / mL silver amidinate solution is prepared from 18 mg in 50 mL of dry, degassed toluene. This amount corresponds to 1 atomic% of Ag with respect to the Zn atoms of ZnO.
  • the bottle of F-P is encapsulated in safelight (which allows the filtration of UV rays).
  • the solution is irradiated by a light source in the visible range only (Xenon lamp, 100 W provided with a filter blocking only UV radiation) with magnetic stirring for 3 h.
  • a light source in the visible range only Xenon lamp, 100 W provided with a filter blocking only UV radiation
  • the Applicant has synthesized several triptych nano-catalysts from the protocol described in Example 2, adapting the carbo-benzene and silver amounts, and / or substituting the zinc oxide particles with other metal oxides. .
  • the compositions of these triptych nano-catalysts are presented in the following table.
  • triptych nano-catalysts were characterized before and after their use in catalysis by one or more of the following techniques: transmission electron microscopy (TEM), high resolution transmission (HRTEM), solid phase UVTV, fluorescence spectroscopy of X-ray (FluoX), X-ray photoelectron spectroscopy, IR infrared spectroscopy, Raman spectroscopy, or NMR nuclear magnetic resonance.
  • TEM transmission electron microscopy
  • HRTEM high resolution transmission
  • UVTV solid phase UVTV
  • FluoX fluorescence spectroscopy of X-ray photoelectron spectroscopy
  • IR infrared spectroscopy IR infrared spectroscopy
  • Raman spectroscopy or NMR nuclear magnetic resonance.
  • the triptych nano-catalysts were used in catalysis according to the following protocol.
  • a quartz reactor with a capacity of 135 ml 30 ml of distilled water and 30 mg of nano-catalyst were mixed and stirred at room temperature.
  • the volume of the gaseous phase is 105 ml.
  • the irradiation was carried out with a UV / visible Xenon lamp of a power of 300 Watts equipped with an optical fiber.
  • the monitoring of the catalysis was carried out by sampling the gas phase every 6 hours.
  • nano-catalysts comprising titanium oxide are more active than those comprising zinc oxide;
  • nano-catalysts in the form of nano-rods are more active than those in nanoparticulate form
  • nano-catalysts comprising 2% carbo-benzene
  • the most active triptych nano-catalyst is composed of nano-rods of T1O2 / 1% carbo-benzene / 3% silver.

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