EP3525929A1

EP3525929A1 - Three-part nano-catalyst and use thereof for photocatalysis

Info

Publication number: EP3525929A1
Application number: EP17794011.1A
Authority: EP
Inventors: Jérémy CURE; Myrtil Kahn; Kévin COCQ; Gérald CASTEROU; Rémi Chauvin; Valérie MARAVAL; Hala ASSI
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Universite Toulouse III Paul Sabatier
Current assignee: CURE, JEREMY; Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Universite Toulouse III Paul Sabatier
Priority date: 2016-10-17
Filing date: 2017-10-16
Publication date: 2019-08-21
Also published as: US20190255517A1; WO2018073525A1; US11446649B2; FR3057471B1; FR3057471A1

Abstract

The present invention relates to a nanocatalyst-type nanoscale composition comprising a nanoparticle semiconductor, plasmonic metal nanoparticles and an organic photosensitiser of the carbo-mer type. The present invention also relates to a method for producing the nano-catalyst of the invention. The invention further relates to the use of the nanocatalyst of the invention for photoelectrolysis , in particular, for the photoelectrolysis of water, as well as to a power source comprising said nanocatalyst.

Description

NANO-CATALYST TRIPTYQUE AND ITS USE FOR

PHOTO-CATALYST

FIELD OF THE INVENTION 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.

STATE OF THE ART

The search for new sources of clean energy is a particularly critical problem of our time. The production of hydrogen by the splitting of water by visible light is a promising way that uses water and sunlight, ie an abundant raw material and an unlimited source of energy to the environment. human scale. Therefore, this method is of great economic and environmental interest.

One of the most promising processes is the photo-catalytic conversion of water into hydrogen. This requires the use of a photocatalyst capable of absorbing sunlight and generating the charges for the oxidation-reduction of water thus producing hydrogen. Of the many metal or organometallic photocatalysts that have been developed in recent decades, nano-catalysts have been of particular interest because of their high specific surface area, which gives them better catalytic efficiency.

Semiconducting metal oxides are often included in these nano-catalysts, of which zinc oxide (ZnO) and titanium oxide (TiΟ2) are the most commonly used. 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.

Nevertheless, 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. Various methods have been proposed for improving the photoelectrochemical efficiency of nano-catalysts: for example, the modification of the three-dimensional structure of the semiconductor; coupling with another semiconductor whose direct forbidden band is less important; the association of the semiconductor with a metal with plasmonic properties in the visible range; the inclusion within the crystalline structure of the semiconductor of other metals or non-metals ("doping"), the association with organic or organometallic chromophores acting as photo-sensitizers; the creation of defects in the structure of the semiconductor; development and integration on nanoparticles of mimicking complexes The active center of hydrogenase type enzymes (for example Ni / Fe); or the development of nanoparticles in peptides in a biological medium.

However, the nano-catalysts thus improved have still unsatisfactory yields and a limited life. In addition, 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. The Applicant has found that this triptych surprisingly exhibits photoelectrochemical properties suitable for use as a photo-catalyst, especially for photo-reduction of water and the production of hydrogen. ABSTRACT

The present invention relates to a triptych nano-catalyst comprising:

a nanoparticulate semiconductor or in the form of nano-rods;

nanoparticles of plasmonic metal; and

an organic photosensitizer which is a carbo-mother, preferably a carbo-bene or a carbo-n-butadiene.

According to one embodiment, 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.

According to one embodiment, the plasmonic metal is gold, silver, copper, aluminum or platinum, preferably gold, silver or copper, more preferably silver. According to one embodiment, 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-

5,11,17-triyn-1-yl] aniline or 4,4 '((4,7,13,16-tetraphenylcyclooctadecal) 2,3,7,8,9,13,14,15-nonaen -5,11,17-triyne-l, 10-diyl) bis (ethyne-2,1-diyl) dianiline, more preferably 4,4 '((4,7,13,16-tetraphenylcyclooctadecane) 1,2,3,7,8,9,13,14,15-nonaen-5,11,17-triyne-1,10-diyl) bis (athyne-2,1-diyl)) dianitine.

According to one embodiment, the plasmonic metal nanoparticles are located on the surface of the nano-particulate semiconductor metal oxide or in the form of nano-rods.

According to one embodiment, 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.

According to one embodiment, 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:

(la) mixing a nanoparticulate or nano-stick semiconductor, preferably a semiconductor metal oxide, with an organic photoresist;

(Ib) mixing the composition obtained in step (la) with an organometallic complex of a plasmonic metal; optionally followed by a stirring step (1c); and

(2) irradiating the composition obtained in step (1b) under electromagnetic radiation, preferably under sunlight.

According to one embodiment, the method for manufacturing the nano-triptych catalyst comprises the following steps:

(la) mixing a nanoparticulate or nano-stick semiconductor with an organic photosensitizer;

(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

(2) irradiating the composition obtained in step (1b) under electromagnetic radiation, preferably under sunlight. According to one embodiment, 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.

According to one embodiment, the organometallic complex comprises the combination of at least one organic ion with at least one ion of a plasmonic metal. According to a mode of realization, the organometallic complex comprises the combination of at least one organic anion with at least one cation of a plasmonic metal. According to one embodiment, 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. According to one embodiment, 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.

DEFINITIONS

In the present invention, the terms below are defined as follows:

"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. Non-limiting examples of 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-a] pyridinyl, indolyl, indolizinyl, iso-indolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, isobenzothiophenyl, indazolyl, benzimidazolyl, benzoxazolyl, 1,3,1, 2-benzisoxazolyl, 2,1-benzisoxazolyl, 1,3-benzotbiazolyl,

1,2-benzoisothiazolyl, 2,1-benzoisothiazolyl, benzotriazolyl,

1,2,3-benzoxadiazolyl, 2,1,3-benzoxadiazolyl, 1,2,3-benzotbiadiazolyl, 2,1,3-benzotbiadiazolyl, thienopyridinyl, purinyl, imidazofl, 2-a] pyridinyl, 6-oxo-pyridazin-1 (6H) -yl, 2-oxopyridin-1 (2H) -yl, 6-oxo-pyridazin-1 (6H) -yl, 2-oxopyridin-1 (2H) -yl, 1, 3-benzodioxolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl.

"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 π 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. For the purposes of the present invention, the term "carbo-mother" does not refer to an infinite covalent structure such as graphene, graphyne or graphdiyne. In particular, in the present invention, 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. In the invention, a carbo-benzene is a molecule of general formula:

in which the substituents R ¹ , i = 1-6, are identical or different, generally of at most two types: atomic hydrogen groups (-H) of the heteroatomic functions (linked to the heteroatom Cis macrocycle); or more commonly organic groups: alkyl, alkenyl, alkynyl, aryl, alkylaryl-, alkenylaryl-, alkynylaryl- or heteroaryl-, optionally substituted with at least one alkyl, alkenyl, alkynyl, aryl, heteroaryl, amino (-NH2) group, carbonitrile (-CN), nitro (-NO2), halogen (-F, -Cl, -Br, -I), hydroxyl (-OH), ether (-O-), oxo (= O), thioether (-S -) thioxo (= S) or sulfhydryl (-SH). The alkyl, alkenyl and alkynyl groups can be linear or branched. Preferably, R 1 = 1-6, is an alkynylaryl or phenyl group, optionally substituted by an amino group.

"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. In the invention, a carbo-n-butadiene is a molecule of formula the general:

in which the substituents Ri, i = 1-6, are identical or different, generally of at most two types: atomic hydrogen groups (-H), heteroatomic functions (linked to the linear CM skeleton by a heteroatom), or more commonly organic groups: alkyl, alkenyl, alkynyl, aryl, alkylaryl-, alkenylaryl-, alkynylaryl- or heteroaryl, optionally substituted with at least one alkyl, alkenyl, alkynyl, aryl, heteroaryl, amino (-NH2), carbonitrile (-CN) group; ), nitro (-NO2), halogen (-F, -Cl, -Br, -I), hydroxyl (-OH), ether (-O-), oxo (= O), thioether (-S-), thioxo (= S), silylalkyl (-Si (R ') 3) where the groups R' are atomic hydrogen (-H), alkyl, alkenyl, alkynyl, aryl, alkylaryl-, alkenylaryl-, alkynylaryl- or sulphhydryl groups (- SH). The alkyl, alkenyl and alkynyl groups can be linear or branched. Preferably, Ri, i = 1-6, is an alkynylaryl or phenyl group, optionally substituted with an amino group. According to one embodiment, 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. .

- "About" placed in front of a number, means plus or minus 10% of the nominal value of that number.

- "Hydrogen" refers to the hydrogen molecule (H2), unless otherwise indicated. "Solar 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". In the invention, 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. DETAILED DESCRIPTION

Nano-triptych catalyst

The present invention relates to a triptych nano-catalyst comprising or consisting of:

a semiconductor;

nanoparticles of a plasmonic metal; and

- an organic photo-sensitizer

According to one embodiment, the present invention relates to a triptych nano-catalyst comprising or consisting of:

a nano-particulate semiconductor;

nanoparticles of plasmonic metal; and

- an organic photo-sensitizer

According to one embodiment, 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:

a nanoparticulate semiconductor or in the form of rods;

nanoparticles of plasmonic metal; and

- an organic photo-sensitizer;

provided that the organic photosensitizer is not in the form of an infinite covalent structure such as a leaflet.

According to one embodiment, the triptych nano-catalyst is chosen from the compounds NI to N19 described in the following table:

According to one embodiment, 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. 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 Zn from ZnO. According to one embodiment, 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. According to one embodiment, 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. 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 Cu of CuO.

According to one embodiment, 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. 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 Fe of Fe203.

According to one embodiment, 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.

According to one embodiment, 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. 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 W of WO3. According to one embodiment, the semiconductor is nano-particulate or in the form of a nano-stick. According to one embodiment, the nanoparticulated semi-conductor is a Π-VI type semiconductor, for example a nano-particle type oxyde-VI semiconductor electron oxide.

In one embodiment, 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). In a specific embodiment, the semiconductor is titanium oxide (T1O2) or zinc oxide (ZnO). In a specific embodiment, the semiconductor is titanium oxide (T1O2). In a specific embodiment, the semiconductor is zinc oxide (ZnO).

In one embodiment, 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, Ρe2O3, Fe3O-i), zinc oxide (ZnO) or titanium oxide (T1O2). In a specific embodiment, the semiconductor is titanium oxide (T1O2) or zinc oxide (ZnO). In a specific embodiment, the semiconductor is titanium oxide (T1O2). In a specific embodiment, the semiconductor is zinc oxide (ZnO). In another embodiment, 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. In another embodiment, 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, ΖηΡβ2θ4 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. In another embodiment, the nano-particulate semiconductor is a sulfide, an equivalent selenide, or an equivalent tellurium, for example ZnS, CuS, CdSe, CdTe, PbS or PbSe.

According to another embodiment, the nano-particulate semiconductor is a ΙΠ-V type semiconductor, for example GaAs, GaN, InAs or InP. According to another embodiment, the nano-particulate semiconductor is a mixed semiconductor of types Π-VI and IH-V, for example ZnO: GaN.

According to one embodiment, the nano-particulate semiconductor is full. According to one embodiment, the nano-particulate semiconductor is partially or completely hollow.

According to one embodiment, 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.

According to one embodiment, 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. According to one embodiment, the nano-particulate semiconductor has a mean diameter of about 23 nm. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, the nanoparticulate semiconductor is zinc oxide (ZnO) in the form of particles with a mean diameter of more than 0 nm to 100 nm. According to one embodiment, the nanoparticulate semiconductor is zinc oxide (ZnO) in the form of particles with an average diameter of more than 0 nm to 50 nm. According to one embodiment, the semiconductor is zinc oxide (ZnO) in the form of nano-rods. According to one embodiment, the nano-particulate semiconductor is titanium oxide (TiO 2) in the form of particles with a mean diameter of 23 nm. According to one embodiment, the semiconductor is titanium oxide (10 2) in the form of nano-rods. According to one embodiment, the nanoparticulate semiconductor is titanium oxide (T1O2) in the form of particles of average diameter from more than 0 nm to 50 nm. According to one embodiment, the nanoparticulate semiconductor is copper oxide (CuO) in the form of particles with a mean diameter of more than 0 nm to 50 nm. According to one embodiment, 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. According to one embodiment, the nanoparticulate semiconductor is nickel oxide (NiO) in the form of particles with an average diameter of more than 0 nm to 50 nm. According to one embodiment, 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. According to one embodiment, the plasmonic metal nanoparticles are nanoparticles of gold (Au), silver (Ag), copper (Cu), aluminum (Al) or platinum (Pt). In one embodiment, the plasmonic metal nanoparticles are nanoparticles of gold (Au), silver (Ag) or copper (Cu). In another embodiment, the plasmonic metal nanoparticles are aluminum (Al) or platinum (Pt) nanoparticles. In a specific embodiment, the nanoparticles of plasmonic metal are gold nanoparticles (Au). In another specific embodiment, 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.

Advantageously, 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. Advantageously, 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. Advantageously, 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. According to one embodiment, the nanoparticles of plasmonic metal are solid. According to one embodiment, the plasmonic metal nanoparticles are partially or entirely hollow. According to one embodiment, the nanoparticles of plasmonic metal are isotropic. According to one embodiment, the plasmonic metal nanoparticles are anisotropic. According to one embodiment, the plasmonic metal nanoparticles are monocrystalline or polycrystalline.

According to one embodiment, 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. According to one embodiment, the organic photosensitizer is an electrical conductor, that is to say it contains mobile electric charge carriers capable of carrying an electric current. Advantageously, the photosensitizer has a high capacity to separate the charges by its moderate aromatic character and its extensive π conjugation, thus avoiding unwanted recombination of photoinduced charges.

According to one embodiment, the organic photosensitizer absorbs electromagnetic radiation in the UV, visible and / or IR range, for example sunlight or visible light. In one embodiment, the photosensitizer absorbs sunlight. In one embodiment, the photosensitizer absorbs visible light. In one embodiment, the electromagnetic radiation absorbed by the photosensitizer generates photoinduced charges. In one embodiment, the photosensitizer is weakly emissive, that is to say that it emits little or no electromagnetic radiation. In a specific embodiment, the photosensitizer has intermolecular self-assembly properties, is an electrical conductor, and absorbs electromagnetic radiation in the visible spectrum.

According to one embodiment, the organic photosensitizer is a carbo-mer, for example a carbo-benzene or a carbo-n-butadiene.

According to one embodiment, 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. According to one embodiment, the organic photosensitizer is a carbo-benzene substituted with at least one group selected from amino, hydroxyl, carboxyl, and thiol.

In one embodiment, the photosensitizer is a carbobenzene, for example a compound of formula (I):

wherein n is from 0 to 3, for example 4- [10- (4-aminophenyl) -4,7,13,16-tetramethylcyclooctadeca-1,2,3,7,8,9,13, 14, 1S-nonaen-5,11,17-triyn-1-yl] aniline (n = 0) or 4,4 '((4,7,13,16-tetraphenylcyclooctadeca- 1, 2,3,7, 8,9,13,14,15-nonaen-5,11,17-triyne-1,10-diyl) bis (ethyne-2,1-diyl) -diamondine (n = 1). In a specific embodiment, the photosensitizer is 4,4 '((4,7,13,16-tetraphenylcyclooctadecyl)

(n = 1) In one embodiment, 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.

According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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 . According to one embodiment, 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.

According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, the proportion of plasmonic metal nanoparticles in the nano-triptych catalyst is about 1%, 2%, 3%, 4% or 5%. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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%. According to one embodiment, 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%.

According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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. According to one embodiment, 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.

According to one embodiment, 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.

Advantageously, 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.

Advantageously, 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.

Process for manufacturing the nano-catalyst

The invention also relates to a method of manufacturing a triptych nano-catalyst according to the invention, as described above.

According to one embodiment, the method comprises the following steps:

(1) mixing a nano-particulate semiconductor with an organic photosensitizer and with a precursor of plasmonic metal nanoparticles; and (2) irradiating the composition obtained under electromagnetic radiation.

According to another embodiment, the method comprises the following steps:

(la) mixing a nano-particulate semiconductor with an organic photosensitizer;

(1b) 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.

According to one embodiment, the plasmonic metal nanoparticle precursor decomposes by photo-reduction or photo-oxidation to give the plasmonic metal in the form of metal nanoparticles. In one embodiment, the decomposition occurs in contact with the nano-particulate semiconductor.

According to one embodiment, the precursor is an organometallic complex of a plasmonic metal. In one embodiment, the precursor is a amidate or carboxylate complex of a plasmonic metal, for example silver (Ag), gold (Au) or copper (Cu). In another embodiment, the precursor is a salt of nitrate or chloride of a plasmonic metal, for example silver (Ag), gold (Au) or copper (Cu). In a specific embodiment, the precursor is a silver amidinate complex, preferably silver Ν, Ν '- diisopropylacetamidinate (Ag).

In one embodiment, 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). In another embodiment, the precursor is a salt of an ion of the plasmonic metal, the ion being preferably the nitrate ion or the chloride ion. In one embodiment, the precursor is a silver amidinate complex, preferably silver Ν, Ν'-diisopropylacetemidinate (Ag). According to one embodiment, 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.

According to one embodiment, the plasmonic metal nanoparticle precursor is in solution in a solvent, for example an organic solvent. In one embodiment, the solvent is toluene.

According to one embodiment, the mixing step (1) (or (1b)) is followed by a stirring step (1-c) at a temperature of between 10 and 50 ° C., preferably at room temperature. . According to one embodiment, the mixing step (1) (or (Ib)) 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. According to one embodiment, 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. In one embodiment, 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. According to one embodiment, 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. According to one embodiment, the irradiation step (2) lasts 10 min, 20 min, 30 min, 40 min, 50 min or 60 min. In one embodiment, the irradiation takes place at a temperature between 10 and 50 ° C, preferably at room temperature. According to one embodiment, 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. According to one embodiment, 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. In one embodiment, the irradiation takes place with stirring. In one embodiment, the electromagnetic radiation is light in the UV, visible or IR range, preferably sunlight or visible light.

Hydrogen production method

The invention also relates to a method for producing hydrogen (H2) using a nano-triptych catalyst according to the invention, as described above.

According to one embodiment, the hydrogen is produced by a photo-reduction reaction of the water activated by the nano-triptych catalyst according to the invention. In one embodiment, the triptych nano-catalyst is immersed in water. In one embodiment, hydrogen is produced by electrochemical reduction of water. In one embodiment, the hydrogen produced is gaseous. In one embodiment, oxygen (oxygen, O2) is produced simultaneously by an electrochemical oxidation reaction of the water. In one embodiment, the product oxygen is gaseous.

Source of energy / energy supply device

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.

According to one embodiment, the power supply device is a source of energy. According to one embodiment, the power supply device comprises a source of energy.

According to one embodiment, the energy source produces hydrogen using the triptych nano-catalyst according to the invention, as described above. In one embodiment, the hydrogen is produced by a photo-reduction reaction of the water activated by the nano-triptych catalyst according to the invention. In one embodiment, the energy source comprises means for storing the hydrogen produced. According to one embodiment, the device produces hydrogen using the nano-triptych catalyst according to the invention, as described above. In one embodiment, the device comprises a means for storing the hydrogen produced. According to one embodiment, during the photo-reduction of water, 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. . According to one embodiment, during the photo-reduction of water, the triptych nano-catalyst of the invention is still active after 84 hours of irradiation. According to one embodiment, the energy source produces electricity from hydrogen. According to one embodiment, the device produces electricity from hydrogen.

According to one embodiment, 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. According to another embodiment, 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. According to one embodiment, the device is static or nomadic.

Advantageously, 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.

Method of producing electrical energy

The invention also relates to a method for producing electricity comprising the use of the nano-triptych catalyst of the invention as described above.

According to one embodiment, 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.

According to one embodiment, the method of generating electricity comprises at least one step of producing dihydrogen.

According to one embodiment, the rate of production of dihydrogen in the gas phase is between more than 0 and 100 μmol.h ^-1 .g ^-1 ; preferably from 1.10 ^-6 to 10 μmol.h ^-1 .g ^-1 ; more preferably 1.10 ^-4 to 3 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is S.lO-3 .mu.m.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen gas phase is 12.2.1ο ^-3 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 17.2.1 ° ^-3 μmol · 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 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gaseous phase is 0.029 μmol.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 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.085 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.41 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 0.5 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 2.2 μmol.h ^-1 .g ^-1 . According to one embodiment, the rate of production of dihydrogen in the gas phase is 2.7 μmol.h ^-1 .g ^-1. According to one embodiment, the rate of production of dihydrogen in the gaseous phase is 1.4 μmol. .h ^-1 .g ^-1 .

BRIEF DESCRIPTION OF THE FIGURES

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.

EXAMPLES

The present invention will be better understood on reading the following examples which illustrate the invention in a nonlimiting manner.

Abbreviations

NP: nanoparticle;

FP: Fisher-Porter; BAG: Gloves box;

TEM: Transmission Electron Microscopy;

HRTEM: High Resolution Transmission Electron Microscopy;

PS: photo-sensitizer. Equipment

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 Ν, Ν'-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

1,1-diyl) bis (ethyne-2,1-diyl) dianiline, of formula:

which is obtained by the synthesis method developed by R. Chauvin's team for an analogous compound [Rives, A.; Baglai, I; Malytskyi, V.; Maraval, V.; Saffon-Merceron, N.; Voitenko, Z .; Chauvin, R. Chem. Commun., 2012, 48, 8763-8765]. The UV-visible absorption spectrum of this compound is shown in FIG.

Example 1 Manufacture of a Diptych Nano Catalyst, in the Absence of an Organic Photoresensor

Method

1/60 mg of commercial ZnO are degassed in a small Fisher-Porter (F-P) bottle and then introduced in a glove box (BAG).

2/20 mg of silver amidinate complex in solution in 5 mL of dry toluene and degassed are added. This amount corresponds to 20 atomic% of Ag with respect to the Zn atoms of ZnO.

3 / A white precipitate is observed in the solution, which is subjected to UV radiation (Mercury lamp, 100 W) for 2 h.

4 / A yellow suspension appears after manual stirring. An observation is made inTEM.

In a second test, the manipulation is carried out with a UV exposure time of 30 min and with stirring. A yellow supernatant is also observed in this case.

Results

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. In addition, observation of the yellow supernatant means that Ag NPs were formed in solution and not on the surface of ZnO.

The direct photo-reduction of the silver amidinate complex by UV radiation of the ZnO NPs therefore does not make it possible to grow Ag NPs in the absence of a ligand. An organic molecule ("ligand") acting as a stabilizing agent is needed to stabilize the Ag NPs formed. In Examples 2 to 4, a photo-sensitizer organic (carbo-benzene type) is used, which plays this role of ligand in the process of manufacturing the nano-catalyst.

EXAMPLE 2 Manufacture of a Nano-Catalyst Triptych in the Presence of UV and / or Visible Radiation (5% Ag.5% Carbo-Benzene) Method

1 / 2.15 mg of commercial ZnO are degassed in a small bottle of F-P and then entered in BAG.

2 / 1.0 mL of carbobenzene dissolved in dry toluene and degassed (1.0 mg / mL) are added. This amount of carbo-benzene (1.0 mg) corresponds to 5 mol% of carbo-benzene relative to the molar amount of Zn of ZnO.

3 / The resulting mixture is stirred at room temperature in BAG for 1 h.

4/5 mL of dry, degassed toluene is added.

5 / In parallel, 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.

6/6 ml of this solution are introduced into a Schlenk tube containing the previously prepared solution of ZnO + carbo-benzene NP.

7 / a- The solution obtained after step 5 / is illuminated under UV for 1 h (Mercure lamp, 100 W).

8 / a- TEM analysis is performed just after manipulation (Figure 2) and then at D + 134 (Figure 3).

Repeat steps 1 / to 6 / then:

7 / b- The solution obtained after step 5 / is placed in the sun (UV + visible domains) for several hours.

8 / b- A TEM analysis is performed just after the manipulation (Figure 4) and then at D + 134 (Figure 5). Repeat steps 1 / to 6 / then:

7 / c- The solution obtained after step 5 / is placed in the sun in a UV-filtered clean room (visible range only) for several hours.

8 / c- An analysis ΤΈΜ is performed just after the manipulation (Figure 6) and then at D + 134 (Figure 7).

Results

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.

It is known that ZnO in the nano-particle state and under UV irradiation (λ ~ 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.

This experiment reveals four effects of carbo-benzene used as photo-sensitizer (PS):

(1) formation of a colloidal solution of the ZnO NPs in the solvent used (here degassed dry toluene). Indeed, in the absence of carbo-benzene, the ZnO NPs are in the form of a suspension in the solvent used and not in colloidal form;

(2) stabilization of Ag NPs formed from photo-reduction of silver amidinate complex. In fact, contrary to what has been observed in the absence of carbo-benzene (Example 1), here all the NPs of Ag are in contact with the surface of the NP of ZnO and not isolated;

(3) formation of a protective organic layer on the surface of ZnO NPs and Ag NPs;

(4) generation of electron / hole pairs within the ZnO from visible radiation (whether or not it is associated with UV radiation). Indeed, Manipulations 2a-, 2b- and 2c-, which were carried out under different radiation conditions (UV only, visible only and UV + visible), do not reveal any significant difference in the formation of Ag NP by photo-reduction silver amidinate. Conversely, in the absence of a photo-sensitizer, ZnO NPs directly create electron / hole pairs only under UV radiation.

EXAMPLE 3 Manufacture of a Nano-Catalyst Triptych in the Absence of UV Radiation f 1% Ae. 1% carbo-benzene)

Method

1 / 2.1 mg of commercial ZnO are degassed in a small bottle of F-P and then entered in BAG.

2 / 0.2 mL of carbo-benzene solution dissolved in dry, degassed toluene (1.0 mg / mL) with 1 mL of dry, degassed toluene is added. This amount of cartobenzene (0.2 mg) corresponds to 1 mol% of carbo-benzene relative to the molar amount of Zn of ZnO.

3 / In parallel, 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.

4 / 0.4 ml of this solution is introduced into the small bottle of F-P containing the previously prepared solution of NP ZnO + carbo-benzene, then 1 ml of dry toluene and degassed is added.

5 / 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).

6 / 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

The TEM images of the different samples of the solution show that, as early as 30 min, the Ag NPs are formed by photo-reduction of the silver amidinate complex. Nevertheless, only Ag NPs are also visible on the carbon film of the TEM grid, which means that part of the silver amidinate complex has not reacted.

Observations at 1 and 3 h show identical results.

On the other hand, after 20 hours of irradiation in the Visible region alone, there is no longer any Ag NP alone on the carbon film of the microscopy grid, which means that all the silver amidinate has been photo-reduced. As in Example 2, all of the observed Ag NPs are localized to the surface of the ZnO NPs and the carbo-benzene is organized as an organic layer visible on the surface of the Ag NPs and the surface of the NP of ZnO.

These results show that carbo-benzene acts well as a photo-sensitizer for ZnO at Visible radiation. Since ZnO NPs can not produce electron / hole pairs directly (since the UV domain has been filtered), it is necessarily corbo-benzene that absorbs the Visible radiation (given its profile in UV spectroscopy). Visible, the maximum absorption is at λ _max = 493 nm), which transfers the energy of the irradiation to the NP of ZnO so that the latter produce electron / hole pairs that will participate in the photo-reduction. silver amidinate complex

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;

there was free amidinate ligand in the silver amidinate sample, which can be oxidized or reduced in place of the complex itself; there was no carbo-benzene "impregnation" step around the ZnO NPs, that is to say that stirring for 1 h between the ZnO NPs alone and the carbon dioxide. benzene did not occur, contrary to the method of Example 2.

EXAMPLE 4 Manufacture and Use of a Nano Catalyst Triptych (1% Ag. 1% Carbo-benzene) in the Absence of UV Radiation for the Photocatalytic Production of Hydrogen

Method

1 / 2.15 mg of commercial ZnO are degassed in a small bottle of F-P and introduced into BAG.

2 / 0.20 mL of carbobenzene solution in dry, degassed toluene (1.0 mg / mL) is added with 0.8 mL of dry, degassed toluene. This amount of carbo-benzene (0.20 mg) corresponds to 1 mol% of carbo-benzene relative to the molar amount of Zn of ZnO).

3 / The mixture is stirred at room temperature in the BAG for 15 min.

4 / In parallel, 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.

5 / 0.4 mL of this solution is introduced into the small FP bottle containing the previously prepared solution of NP ZnO + carbo-benzene, and then 3.6 mL of dry, degassed toluene are added (total volume of the solution: 5 mL).

6 / The bottle of F-P is encapsulated in safelight (which allows the filtration of UV rays).

7 / 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.

8 / An observation is made in TEM for the control of the formation of nano-objects and the total photo-reduction of silver ramidinate (Figure 8). 9 / The solution is then concentrated and transferred to a pressure-resistant NMR tube.

10 / The solvent is completely evaporated in the NMR tube, which is placed under an inert atmosphere by 3 empty cycles / argon.

11/200 microliters of degassed distilled water under argon flow are added, the tube is conditioned under argon pressure (100 mbar) and then irradiated by a light source emitting in the UV + visible range (Xenon lamp, 100 W ) for 45 minutes.

12 / The presence of dihydrogen H ₂ is monitored by NMR * H spectroscopy in the gas phase with application of a T2 relaxation filter (FIG. 9).

13 / An observation is made in HRTEM (High Resolution TEM, Figure 10), followed by an EDX analysis at D + 20 (Figure 11) and a representation of the diffraction pattern of an NP of Ag deposited at the surface of a ZnO NP at D + 20 formed nano-objects (Figure 12).

Results The control of the irradiation for the formation of the NP of Ag (FIG. 8) shows that the photo-reduction of the silver amidinate complex takes place after 3 hours of irradiation.

The photo-reduction of the water is followed by ¹ H NMR in the gas phase, with the application of a T2 relaxation filter which makes it possible to cancel the signal of the water in the vapor phase (saturation vapor pressure). Two fine signals are observed after application of this T2 filter: one corresponding to the dihydrogen H ₂ (δ ~ 5 ppm) and the other corresponding to an unidentified protonated gaseous gaseous species (δ ~ 4 ppm) (Figure 9).

The HRTEM observations of the nano-objects at D + 20 show that the Ag NPs are deposited either directly on the ZnO NPs or on the organic carbo-benzene layer (Figure 10). EDX analyzes show the formation of Ag NP on the surface of ZnO (Figure 11). The analyzes of the diffraction pattern of an NP of Ag deposited on the surface of a ZnO NP (FIG. 12) show that the deposited silver nanoparticles are not oxidized in contact with water. This observation makes it possible to envisage an overall photoelectrolysis of water, that is to say the reduction of water (formation of gaseous H2-hydrogen) and the oxidation of water (formation of oxygen O2 gas ) at the same time. The term "global photoelectrolysis of water" is understood here to mean the chemical decomposition of water to lead to the simultaneous formation of hydrogen dihydrogen and O2 oxygen gas.

Example 5 Manufacture and Use of Nano-Catalyst Triptychs in the Absence of UV Radiation for Photocatalytic Hydrogen Production

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.

These 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.

The triptych nano-catalysts were used in catalysis according to the following protocol. In 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 (hydrogen production rate as a function of the irradiation time) was carried out by sampling the gas phase every 6 hours.

The results (FIG. 13) show that the best results are obtained for the TiO ₂ /2% card-benzene / 3% silver triptych nano-catalysts.

Furthermore, the Applicant has also measured the rate of production of dihydrogen gas phase by different catalysts after 84 hours of irradiation. The results are presented in the following table:

The results show that even after 84 hours of irradiation, the nano-catalysts of the invention remain still active. In a general way,

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;

when particulate nanocatalysts are employed, the best results are obtained with nano-catalysts comprising 2% carbo-benzene;

the most active triptych nano-catalyst is composed of nano-rods of T1O2 / 1% carbo-benzene / 3% silver.

Claims

1. A triptych nano-catalyst comprising:

a nanoparticulate semiconductor or in the form of nano-rods;

nanoparticles of plasmonic metal; and

an organic photosensitizer which is a carbo-mer, preferably a benzene-card or a carbo-n-butadiene. Nano-catalyst according to claim 1, wherein the nanoparticulate 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, more preferably zinc oxide or titanium oxide. A nanocatalyst according to claim 1 or claim 2, wherein the plasmonic metal is gold, silver, copper, aluminum or platinum, preferably gold, silver or copper , more preferentially money. 4. Nano-catalyst according to any one of claims 1 to 3, wherein the carbo-mer is a benzene-card, preferably 4- [10- (4-aminophenyl) -4,7,13,16- tetraphenylcyclooctadeca-1,2,3,7,8,9,13,14,15-nona-5,11,17-triyn-1-yl] aniline or 4,4 '((4,7,13,16) -tétraphénylcyclooctadéca-l,

2

3,7,8,9,13,14,15-nonaen-5,11,17-triyne-l, 10-diylbis (ethyne-2,1-dliyl) imide, more preferably 4,

4 '((4,7,13,16-tetraphenylcyclooctadecal, 2,3,7,8,9,13,14,15-ronaen-5,11,17-triyne-1,10-diyl) bis ( ethyne-2,1-diyl)) dianiline.

The nanocatalyst according to any one of claims 1 to 4, wherein the plasmonic metal nanoparticles are located on the surface of the nanoparticulate semiconductor or in the form of nano-rods.

6. Nano-catalyst according to any one of claims 1 to 5, wherein the nanoparticulate semiconductor or in the form of nano-rods, and or nanoparticles of plasmonic metal are coated by the photosensitizer.

A process for producing a triptych nano-catalyst according to any of claims 1 to 6 comprising the steps of:

(la) mixing a nanoparticulate semiconductor or in the form of nano-rods, with an organic photosensitizer;

8. Method according to claim 7, characterized in that the complex comprising an ion of the plasmonic metal is a amidinate or carboxylate of silver, gold, copper, aluminum or platinum, preferably a silver amidinate 9. Use of a triptych nano-catalyst according to any one of claims 1 to 6 for producing hydrogen. 10. A power supply device, preferably a nomad power supply device, comprising a nano-triptych catalyst according to any one of claims 1 to 6.