WO2012124482A1 - Pigment à base de complexe métallique, composition de pigment à base de complexe métallique, élément de conversion photoélectrique, et cellule photoélectrochimique - Google Patents

Pigment à base de complexe métallique, composition de pigment à base de complexe métallique, élément de conversion photoélectrique, et cellule photoélectrochimique Download PDF

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WO2012124482A1
WO2012124482A1 PCT/JP2012/055141 JP2012055141W WO2012124482A1 WO 2012124482 A1 WO2012124482 A1 WO 2012124482A1 JP 2012055141 W JP2012055141 W JP 2012055141W WO 2012124482 A1 WO2012124482 A1 WO 2012124482A1
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group
general formula
metal complex
dye
ring
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PCT/JP2012/055141
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English (en)
Japanese (ja)
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征夫 谷
達也 薄
小林　克
木村　桂三
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a metal complex dye, a metal complex dye composition, a photoelectric conversion element, and a photoelectrochemical cell that have high conversion efficiency and excellent durability.
  • the photoelectric conversion element is used in various optical sensors, copying machines, photoelectrochemical cells (for example, solar cells) and the like.
  • Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
  • a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected greatly as it uses inexhaustible clean energy.
  • silicon solar cells have been researched and developed for a long time. It is spreading due to the policy considerations of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.
  • Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye by applying this technique.
  • a photoelectric conversion element using an inexpensive organic dye as a sensitizer has been reported.
  • Patent Document 2 reports a metal complex dye having a specific structure, a photoelectric conversion element and a photovoltaic cell using the same.
  • the photoelectric conversion element is required to have excellent durability with little decrease in conversion efficiency even during long-term use. In terms of durability, the photoelectric conversion elements described in Patent Documents 1 and 2 are not sufficient.
  • An object of the present invention is to provide a metal complex dye, a metal complex dye composition, a photoelectric conversion element, and a photoelectrochemical cell that have high conversion efficiency and excellent durability.
  • a metal complex dye having a specific structure having a cyano group as an essential ligand as a ligand is excellent in durability, photoelectric conversion element and photoelectricity excellent in durability It has been found that a chemical battery can be provided.
  • the present invention has been made based on this finding.
  • a metal complex dye represented by the following general formula (1) M 1 (LL 1) m1 ( LL 2) m2 (CN) m3 (X1) m4 ⁇ CI 1 ⁇ (1)
  • M 1 represents a metal atom
  • LL 1 is a bidentate ligand represented by the following general formula (2)
  • LL 2 is a bidentate ligand represented by the following general formula (3)
  • m1 and m2 both represent 1.
  • m3 is 1 or 2.
  • m4 is 0 or 1.
  • X1 represents a ligand and is at least one selected from an isothiocyanate group, an isocyanate group, an isoselenocyanate group, water, a halogen atom, and a dimethylformamide group.
  • CI 1 represents a counter ion when a counter ion is required to neutralize the charge.
  • R ⁇ 1 > and R ⁇ 2 > represents an alkyl group, an amino group, and a heterocyclic group each independently.
  • L 1 and L 2 independently represent at least one divalent linking group selected from the group consisting of a single bond, an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group.
  • n1 represents 0 or 1.
  • R 3 and R 4 independently represent a substituent, and b1 and b2 each represent an integer of 0 to 3. When b1 is 1 or more, R 3 may be linked to L 1 to form a ring, and when b2 is 1 or more, R 4 may be linked to L 2 to form a ring.
  • R 3 When b1 is 2 or more, R 3 may be the same or different. When b2 is 2 or more, R 4 may be the same or different. When both b1 and b2 are 1 or more, R 3 and R 4 may be linked to form a ring. ]
  • a 1 and A 2 represents an acidic group or a salt thereof independently.
  • L 3 and L 4 independently represent at least one divalent linking group selected from the group consisting of a single bond, an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group.
  • n2 and n3 independently represent an integer of 0 to 3, and at least one is 1 or more.
  • R 5 and R 6 independently represent a substituent.
  • b3 and b4 independently represent an integer of 0 to 3. When b3 is 1 or more, R 5 may be linked to L 3 to form a ring, and when b4 is 1 or more, R 6 may be linked to L 4 to form a ring.
  • R 5 When b3 is 2 or more, R 5 may be the same or different, but they are not connected to each other to form a ring.
  • R 6 When both b3 and b4 are 1 or more, R 5 and R 6 may be linked to form a ring.
  • M 1 in the general formula (1) is Ru.
  • ⁇ 3> The metal complex dye according to ⁇ 1> or ⁇ 2>, wherein the metal complex dye is represented by the following general formula (4) or general formula (5).
  • R 71 to R 73 and R 81 to R 83 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, or an amino group. Represents a group. However, at least one of R 71 to R 73 and R 81 to R 83 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, or an amino group.
  • R 91 to R 93 and R 101 to R 103 are independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group or amino group. Represents. However, at least one of R 91 to R 93 and R 101 to R 103 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, or an amino group.
  • X independently represents S, O, Se, NR 110 , R 110 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and A 3 to A 6 are It represents an acidic group or a salt thereof.
  • R 111 to R 114 independently represent an alkyl group, an alkynyl group, or an alkoxy group.
  • a 7 to A 10 represent a carboxyl group, a phospho group, or a salt thereof.
  • a metal complex dye composition comprising the metal complex dye according to any one of ⁇ 1> to ⁇ 4> and a metal complex dye represented by the following general formula (8).
  • M 2 has the same meaning as M 1 in the general formula (1).
  • LL 3 has the same meaning as LL 1 in the general formula (1).
  • LL 4 is synonymous with LL 2 in the general formula (1).
  • X2 is synonymous with X1 in the general formula (1).
  • CI 2 represents a counter ion when a counter ion is required to neutralize the charge.
  • CI 2 is synonymous with CI 1 in the general formula (1).
  • m21 and m22 are both 1.
  • m23 is 1 or 2.
  • M 2 is the same as M 1
  • LL 3 is the same structure as LL 1
  • LL 4 is the same structure as LL 2
  • CI 2 is the same as CI 1.
  • ⁇ 5> The metal complex dye composition according to ⁇ 5>.
  • ⁇ 7> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 6>, wherein the metal complex is used as a sensitizing dye.
  • ⁇ 8> A photoelectrochemical cell comprising the photoelectric conversion element according to ⁇ 7>.
  • a metal complex dye a metal complex dye composition, a photoelectric conversion element, and a photoelectrochemical cell having high conversion efficiency and excellent durability can be provided.
  • the present inventors have found that a metal complex dye having a specific structure having a cyano group as an essential ligand as a ligand has been used as a ligand for conventional metal complex dyes.
  • the electron donating property is low, the HOMO is low, and the reduction (electron delivery) from the electrolyte can be smoothly performed. Therefore, it is possible to provide a photoelectric conversion element and a photoelectrochemical cell with high conversion efficiency, and the electron donating property is low. Therefore, it discovered that it was excellent in durability.
  • the present invention has been made based on this finding.
  • the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1.
  • the conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5.
  • the photoreceptor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter also simply referred to as a dye) 21. At least a part of the sensitizing dye 21 is adsorbed on the semiconductor fine particles 22 (the sensitizing dye 21 is in an adsorption equilibrium state and may be partially present in the charge transfer layer 3).
  • the charge transfer body layer 3 functions as, for example, a hole transport layer that transports holes.
  • the conductive support 1 on which the photoreceptor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.
  • the light receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer 2 (semiconductor film) of semiconductor fine particles 22 adsorbed by a sensitizing dye 21 coated on the conductive support 1.
  • a photosensitive layer 2 semiconductor film
  • the excited dye has high energy electrons. Therefore, the electrons are transferred from the sensitizing dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion.
  • the molecule of the sensitizing dye 21 is an oxidant.
  • the electrons on the electrode return to the oxidant while working in the external circuit 6, thereby acting as the photoelectrochemical cell 100.
  • the light receiving electrode 5 functions as a negative electrode of the battery.
  • the photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 to which a dye described later is adsorbed. This dye may be partially dissociated in the electrolyte.
  • the photoreceptor layer 2 is designed according to the purpose and has a multilayer structure.
  • the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.
  • the porous semiconductor layer is sensitized with at least one dye 21 represented by the general formula (1).
  • M 1 represents a metal atom.
  • Metal atom M 1 represents a metal atom.
  • M 1 is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn or Zn. Particularly preferred is Ru, Os, Fe or Cu, and most preferred is Ru.
  • the metal complex dye represented by the general formula (1) has a cyano group as an essential ligand.
  • M3 which is the number of cyano groups is 1 or 2. From the viewpoint of light resistance, m3 is preferably 2. On the other hand, m3 is preferably 1 from the viewpoint of a long wave. Since the cyano group has a low electron donating property, it has a low HOMO and can be smoothly reduced (electron delivery) from the electrolytic solution.
  • a cyano group as a ligand, light resistance in a solution when excited by light irradiation and light resistance when adsorbed on a semiconductor fine particle layer due to improved stability of one-electron oxidation state Can be improved.
  • the metal complex dye since the cyano group has high stability with respect to the nucleophilic species in the electrolytic solution and is not easily oxidized, the metal complex dye has excellent light resistance. Therefore, combined with other structures in the metal complex dye represented by the general formula (1) described later, an effect of imparting excellent durability to the metal complex dye can be achieved.
  • the ligand LL 1 is a bidentate ligand represented by the general formula (2).
  • M1 representing the number of ligands LL 1 is 1.
  • R 1 and R 2 in the general formula (2) each independently represent an alkyl group, an amino group, or a heterocyclic group. These functional groups may be further substituted with a substituent W described later.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, octyl, nonyl, 1-ethylhexyl, benzyl, 2-ethoxyethyl, 1- Carboxymethyl etc.).
  • the amino group is preferably an amino group having 4 to 20 carbon atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N, N-dihexylamino group, N-ethylamino, anilino, etc. More preferred is an amino group having 4 to 16 carbon atoms, and particularly preferred is an amino group having 6 to 16 carbon atoms.
  • the heterocyclic group is preferably a heterocyclic group having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, and 3-indolyl.
  • the electron donating group is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group or a hydroxyl group, and an alkyl group, an alkoxy group, an amino group or a hydroxyl group. Is more preferable, and an alkyl group is particularly preferable.
  • L 1 and L 2 each independently represent at least one divalent linking group selected from the group consisting of a single bond, an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group as described above.
  • the heteroarylene group is a divalent aromatic heterocyclic group.
  • L 1 and L 2 are each independently preferably at least one selected from the group consisting of an ethenylene group, an ethynylene group, an arylene group and a heteroarylene group, more preferably a group consisting of an ethenylene group and a heteroarylene group.
  • Is at least one selected from These groups are conjugated with R 1 or R 2 together with the pyridine ring, and by being conjugated, an effect of improving ⁇ by conjugated system extension can be exhibited.
  • the substituent is preferably an alkyl group, and more preferably methyl.
  • L 1 and L 2 are each independently preferably a conjugated chain having 2 to 8 carbon atoms, more preferably ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene, particularly ethenylene or butadienylene.
  • ethenylene is most preferred.
  • L 1 and L 2 may be the same or different, but are preferably the same.
  • each double bond may be a trans isomer, a cis isomer, or a mixture thereof.
  • n1 represents 0 or 1
  • n1 is preferably 1.
  • R 3 and R 4 each independently represent a substituent.
  • the substituent is preferably a hydrophobic group.
  • the substituent is preferably an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1- Carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms such as vinyl, allyl, oleyl etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms such as ethynyl, butadiynyl, etc.) , Phenylethynyl, etc.), a cycloalkyl group (preferably a cycloalkyl group having 3-20 carbon atoms, such as cyclopropyl
  • Aryl groups such as phenyl, 1-naphthyl, 4 Methoxyphenyl, 2-chlorophenyl, 3-methylphenyl and the like), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2 -Thiazolyl, 2-oxazolyl, etc.).
  • R 3 and R 4 as hydrophobic groups and having an acidic group in LL 2 as described later, LL 2 is oriented to the semiconductor fine particle side, and R 3 and R 4 are opposite to the semiconductor fine particle layer.
  • b1 and b2 each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
  • R 3 may be linked to L 1 to form a ring
  • R 4 may be linked to L 2 to form a ring.
  • b1 is 2 or more
  • R 3 may be the same or different
  • R 3 may form a ring
  • b2 is 2 or more
  • R 4 may be the same or different, and R 4 may form a ring.
  • both b1 and b2 are 1 or more, R 3 and R 4 may be linked to form a ring.
  • the ring to be formed include a benzene ring, a pyridine ring, a thiophene ring, a pyrrole ring, a cyclohexane ring, a cyclopentane ring and the like.
  • Ligand LL 2 In the general formula (1), the ligand LL 2 represents a bidentate ligand. M2 representing the number of ligands LL 2 is 1.
  • Ligand LL 2 is a bidentate ligand represented by the general formula (3).
  • a 1 and A 2 independently represent an acidic group or a salt thereof.
  • a 1 and A 2 include a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CONCH 3 OH, etc.), phosphoryl group (For example, —OP (O) (OH) 2 or the like) or a phosphonyl group (for example, —P (O) (OH) 2 or the like) or a salt thereof.
  • a 1 and A 2 are preferably an acidic group such as a carboxyl group, a phosphoryl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a salt thereof. It is.
  • L 3 and L 4 each independently represent at least one divalent linking group selected from the group consisting of a single bond, an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group.
  • L 3 and L 4 are each independently preferably a single bond or at least one selected from the group consisting of an ethenylene group and a heteroarylene group, and more preferably a single bond.
  • L 3 and L 4 may be the same as L 1 and L 2 in LL 1 .
  • n2 and n3 each independently represents an integer of 0 to 3, at least one of which is 1 or more, preferably n2 and n3 are both 1.
  • R 5 and R 6 each independently represent a substituent.
  • substituent W examples include the substituent W described later.
  • b3 and b4 independently represent an integer of 0 to 3. When b3 is 1 or more, R 5 may be linked to L 3 to form a ring, and when b4 is 1 or more, R 6 may be linked to L 4 to form a ring. When b4 is 2 or more, R 6 may be the same or different, but they are not connected to each other to form a ring. When b4 is 2 or more, R 6 may be the same or different, but they are not connected to each other to form a ring. When both b3 and b4 are 1 or more, R 5 and R 6 may be linked to form a ring.
  • the ligand LL 2 is preferably represented by the following general formula (9-1) or (9-2).
  • R 201 to R 204 are depicted as substituted on one ring for the sake of illustration, but even on that ring, Alternatively, it may be substituted with a different ring from that shown.
  • R 201 and R 203 each independently represents an acidic group.
  • R 201 and R 203 are, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CONCH 3 OH, etc.), phosphoryl group ( For example, —OP (O) (OH) 2 etc.) or a phosphonyl group (eg —P (O) (OH) 2 etc.) or a salt thereof is represented.
  • R 201 and R 203 are preferably a carboxyl group, a phosphoryl group, a phosphonyl group or the like, or a salt thereof, more preferably a carboxyl group, a phosphonyl group, or a salt thereof, and more preferably a carboxyl group or a salt thereof.
  • R 202 and R 204 each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group.
  • R 201 to R 204 may be bonded to any position on the ring.
  • E1 to e4 each independently represents an integer of 1 to 3, preferably an integer of 1 to 3, and more preferably 2.
  • R 201 to R 204 may be the same or different from each other, but do not form a ring with each other.
  • Ligand X1 represents a monodentate ligand.
  • M4 representing the number of ligands X1 is 0 or 1.
  • the ligand X1 is at least one selected from an isothiocyanate group, an isocyanate group, an isoselenocyanate group, water, a halogen atom, and a dimethylformamide group.
  • X1 is preferably an isothiocyanate group, an isocyanate group, an isoselenocyanate group, or a halogen atom, more preferably an isothiocyanate group or a halogen atom, and particularly preferably an isothiocyanate group.
  • Counter ion CI 1 CI 1 in the general formula (1) represents a counter ion when a counter ion is necessary to neutralize the charge.
  • a dye is a cation or an anion, or has a net ionic charge, depends on the metal, ligand and substituent in the dye.
  • the dye of the general formula (1) may be dissociated and have a negative charge because the substituent has a dissociable group.
  • the charge of the whole dye of the general formula (1) is electrically neutralized by the counter ion CI 1 .
  • the counter ion CI 1 is a positive counter ion
  • the counter ion CI 1 is an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion, etc.), an alkali metal ion, or a proton.
  • the counter ion CI 1 may be an inorganic anion or an organic anion.
  • halogen anions eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.
  • substituted aryl sulfonate ions eg, p-toluene sulfonate ions, p-chlorobenzene sulfonate ions, etc.
  • aryl disulfones Acid ions for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.
  • alkyl sulfate ions for example, methyl sulfate ion
  • sulfate ions thiocyanate ions
  • an ionic polymer or another dye having a charge opposite to that of the dye may be used, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.
  • the dye having the structure represented by the general formula (1) has at least one suitable bonding group (interlocking group) for the surface of the semiconductor fine particles. It is more preferable that the bonding group has 1 to 6 bonding groups, more preferably 1 to 4 bonding groups, and particularly preferably 1 or 2 bonding groups.
  • the bonding group examples include a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (for example, —CONHOH), a phosphoryl group (for example, —OP (O) (OH) 2 ), and a phosphonyl group (for example, — It is preferable to have an acidic group (substituent having a dissociative proton) such as P (O) (OH) 2 in the dye.
  • the metal complex dye is preferably represented by the general formula (4) or the general formula (5).
  • X independently represents S, O, Se, NR 110 , R 110 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and A 3 to A 6 are It represents an acidic group or a salt thereof.
  • the metal complex dye having the structure represented by the following general formula (4) or general formula (5) has a high electron donating property to the Ru atom because the complex 5-membered ring having a high electron donating property and bipyridine are conjugated. This can reinforce the defect of the CN ligand having a low electron donating property as compared with the isothiocyanato group, suppress the decrease in the HOMO level of the dye, and have the effect of suppressing the shortening.
  • the metal complex dye is preferably represented by the general formula (6) or the general formula (7).
  • the metal complex dye having the structure of the general formula (4) or the general formula (5) has a longer wave length due to the high electron donating property of thiophene, stability to the nucleophilic species of thiophene, and the proximity of water by having a hydrophobic group. Can be achieved, and the effect of suppressing the desorption of the pigment can be exhibited.
  • metal complex dye composition containing the metal complex dye of the said general formula (I) and the metal complex dye represented by the said General formula (8) it is preferable to set it as the metal complex dye composition containing the metal complex dye of the said general formula (I) and the metal complex dye represented by the said General formula (8).
  • These metal complex dyes of the general formula (I) and the metal complex dye composition containing the metal complex dye represented by the general formula (8) may cause performance degradation when adsorbed on the oxide semiconductor. The effect which suppresses an inconvenient meeting can be show
  • M 2 is the same as M 1
  • LL 3 is the same structure as LL 1
  • LL 4 is the same structure as LL 2
  • CI 2 is the same as CI 1
  • the content of the dye represented by the general formula (1) is not particularly limited, but is preferably 0.001 to 1 mmol, and preferably 0.1 to 0.5 mmol, with respect to 1 g of semiconductor fine particles. It is more preferable that By setting it to the above lower limit or more, a sensitizing effect in a semiconductor can be sufficiently obtained, and by setting it to the above upper limit or less, reduction of the sensitizing effect due to desorption of a dye can be suppressed.
  • the amount (S) of the dye represented by the general formula (1) is not particularly limited in relation to the amount (R) of the metal complex dye represented by the general formula (8), but the addition amount is adjusted. It is preferable to do. Specifically, in terms of molar ratio, R / S is preferably 200 to 30, more preferably 150 to 30, and particularly preferably 100 to 30. In the present invention, two or more dyes represented by the general formula (1) may be used.
  • the dyes represented by the general formulas (1) and (8) have a maximum absorption wavelength in the solution in the range of 500 to 700 nm, and more preferably in the range of 500 to 650 nm.
  • the dye represented by the general formula (1) can be prepared with reference to JP-A-2001-291534. These dyes, as shown in the following scheme, using the M 11 CN as CN source, as well as introducing a CN group of Ru atoms, using M 10 X1, prepared by introducing X1 to Ru be able to.
  • the order of introducing M 11 CN and M 10 X1 is not particularly limited, and they may be simultaneously added to the reaction solution. Have the same meaning as M 10 and M 11, as the M 10 and M 11, inorganic or organic ammonium ion, and alkali metal ions and the like.
  • the dye of the general formula (8) can be prepared in the same manner.
  • the present invention is not limited thereto.
  • dye in the following specific example contains the ligand which has a proton dissociable group, this ligand may dissociate as needed and may release a proton, and may form a counter salt.
  • the ligand which has a proton dissociable group
  • this ligand may dissociate as needed and may release a proton, and may form a counter salt.
  • any of them may be used, or a mixture may be used.
  • alkyl groups preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl).
  • a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl
  • a bicycloalkyl group preferably having 5 to 30 carbon atoms.
  • a substituted or unsubstituted bicycloalkyl group that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo Including [2,2,2] octane-3-yl) and tricyclo structures with more ring structures It is intended to.
  • An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described above also represents an alkyl group having such a concept.
  • -Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group.
  • alkenyl groups preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl
  • cycloalkenyl groups preferably substituted or unsubstituted 3 to 30 carbon atoms or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl)
  • Bicycloalkenyl group a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond.
  • bicyclo [2,2,1] hept-2-en-1-yl bicyclo [2,2 2] is intended to encompass oct-2-en-4-yl).
  • An alkynyl group preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group
  • An aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, 4-methoxyphenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl
  • a heterocyclic group preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a carbon number of 3
  • a 5- or 6-membered aromatic heterocyclic group of ⁇ 30 for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl
  • a silyl group preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethyls
  • a hydroxyl group An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy, 2-ethylhexyloxy), An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 4-hexylphenoxy, 2 -Tetradecanoylaminophenoxy), A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethyl
  • Amino groups preferably amino groups, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted anilino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino N-methyl-anilino, diphenylamino
  • Acylamino group preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), Aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atom
  • alkyl or arylsulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl
  • a sulfamoyl group preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsul
  • Aryloxycarbonyl group preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl
  • An alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl
  • a carbamoyl group preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl
  • iodine and iodide for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.
  • alkyl viologens for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
  • examples thereof include combinations of divalent and trivalent iron complexes (for example, red blood salt and yellow blood salt).
  • a combination of iodine and iodide is preferred.
  • the cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • the compound represented by the general formula (1) is not an iodine salt, republished WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol.65, No.11, p.923 (1997) It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.
  • the electrolyte composition used for the photoelectric conversion element 10 of the present invention preferably contains iodine together with a heterocyclic quaternary salt compound.
  • the iodine content is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 5% by mass, based on the entire electrolyte composition.
  • the electrolyte composition used for the photoelectric conversion element 10 of the present invention may contain a solvent.
  • the content of the solvent in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the entire composition.
  • solvents those having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both are preferable because they can exhibit excellent ion conductivity.
  • solvents include carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol , Propylene glycol, glycer
  • an electrochemically inert salt that is in a liquid state at room temperature and has a melting point lower than room temperature may be used.
  • an electrochemically inert salt that is in a liquid state at room temperature and has a melting point lower than room temperature
  • 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, etc. nitrogen-containing heterocyclic quaternary salt compounds such as imidazolium salts and pyridinium salts, or tetraalkylammonium salts Is mentioned.
  • the electrolyte composition used in the photoelectric conversion element of the present invention may be added with a polymer or an oil gelling agent, or may be gelled (solidified) by a technique such as polymerization of polyfunctional monomers or polymer crosslinking reaction. .
  • the polyfunctional monomers are preferably compounds having two or more ethylenically unsaturated groups, such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.
  • divinylbenzene ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.
  • the gel electrolyte may be formed by polymerization of a mixture containing a monofunctional monomer in addition to the above polyfunctional monomers.
  • Monofunctional monomers include acrylic acid or ⁇ -alkyl acrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.) or their esters or amides or vinyl esters (vinyl acetate, etc.), maleic acid or fumaric acid or their derivatives.
  • Esters (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (Styrene, p-chlorostyrene, t-butylstyrene, ⁇ -methylstyrene, sodium styrenesulfonate, etc.), N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N- Methylacetamide, Vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methacryl sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (such as methyl vinyl ether), ethylene,
  • the blending amount of the polyfunctional monomer is preferably 0.5 to 70% by mass and more preferably 1.0 to 50% by mass with respect to the whole monomer.
  • the above-mentioned monomers are the same as those described in Takayuki Otsu and Masaaki Kinoshita “Experimental Methods for Polymer Synthesis” (Chemistry Dojin) and Takayuki Otsu “Lecture Polymerization Reaction Theory 1 Radical Polymerization (I)” (Chemical Doujinshi). Polymerization can be performed by radical polymerization which is a polymer synthesis method.
  • the monomer for gel electrolyte used in the present invention can be radically polymerized by heating, light or electron beam, or electrochemically, and is particularly preferably radically polymerized by heating.
  • preferably used polymerization initiators are 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropyl). Pionate), azo initiators such as dimethyl 2,2′-azobisisobutyrate, peroxide initiators such as lauryl peroxide, benzoyl peroxide, and t-butyl peroctoate.
  • a preferable addition amount of the polymerization initiator is 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.
  • the weight composition range of the monomer in the gel electrolyte is preferably 0.5 to 70% by mass. More preferably, the content is 1.0 to 50% by mass.
  • a polymer having a crosslinkable reactive group and a crosslinking agent is added to the composition.
  • Preferred reactive groups are nitrogen-containing heterocycles such as pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, and the preferred crosslinking agent is a functional group capable of nucleophilic attack by the nitrogen atom.
  • the electrolyte composition of the present invention metal iodides (LiI, NaI, KI, CsI , CaI 2 , etc.), a metal bromide (LiBr, NaBr, KBr, CsBr , CaBr 2 , etc.), quaternary ammonium bromine salt (tetraalkylammonium Ammonium bromide, pyridinium bromide, etc.), metal complexes (ferrocyanate-ferricyanate, ferrocene-ferricinium ion, etc.), sulfur compounds (sodium polysulfide, alkylthiol-alkyl disulfides, etc.), viologen dye, hydroquinone-quinone Etc. may be added. These may be used as a mixture.
  • a charge transport layer containing a hole conductor material may be used.
  • the hole conductor material 9,9'-spirobifluorene derivatives and the like can be used.
  • an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated.
  • a hole transport material that functions as a p-type semiconductor can be used as the hole transport layer.
  • an inorganic or organic hole transport material can be used as a preferred hole transport layer.
  • the inorganic hole transport material include CuI, CuO, and NiO.
  • the organic hole transport material include high molecular weight materials and low molecular weight materials, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane.
  • organic polysilanes are preferable because, unlike conventional carbon-based polymers, ⁇ electrons delocalized along the main chain Si contribute to photoconduction and have high hole mobility (Phys. Rev. B, 35, 2818 (1987)).
  • the conductive layer is not particularly limited as long as it has good conductivity, and examples thereof include inorganic conductive materials, organic conductive materials, conductive polymers, and intermolecular charge transfer complexes. Among them, an intermolecular charge transfer complex formed from a donor material and an acceptor material is preferable. Among these, what was formed from the organic donor and the organic acceptor can be used preferably.
  • the thickness of this conductive layer is not particularly limited, but is preferably such that the porous layer can be completely filled.
  • the above donor material is preferably rich in electrons in the molecular structure.
  • organic donor materials include those having an amine group, hydroxyl group, ether group, selenium or sulfur atom in the ⁇ -electron system of the molecule, specifically, phenylamine-based, triphenylmethane-based, carbazole-based , Phenol-based materials, and tetrathiafulvalene-based materials.
  • the acceptor material those lacking electrons in the molecular structure are preferable.
  • organic acceptor materials include fullerenes, those having a substituent such as a nitro group, a cyano group, a carboxyl group or a halogen group in the ⁇ -electron system of the molecule, specifically, PCBM, benzoquinone, naphthoquinone, etc. Quinone, fluoroenone, chloranil, bromanyl, tetracyanoquinodimethane, tetracyanoethylene and the like.
  • (C) Conductive Support As shown in FIG. 1, in the photoelectric conversion element of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 on a conductive support 1. Is formed. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.
  • the conductive support 1 glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal.
  • the conductive support 1 is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or polymer material coated with a conductive metal oxide can be used as the conductive support 1, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the support of glass or polymer material. When a transparent conductive support is used, light is preferably incident from the support side.
  • polymer materials examples include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy.
  • a surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in JP-A-2002-260746 is improved.
  • a metal support can also be preferably used.
  • examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.
  • the conductive support 1 has a function of blocking ultraviolet light.
  • a method in which a fluorescent material capable of changing ultraviolet light into visible light is present in the transparent support or on the surface of the transparent support, or a method using an ultraviolet absorber is also included.
  • JP-A-11-250944 may be further provided on the conductive support 1.
  • Preferred conductive films include metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.) ).
  • the thickness of the conductive film is preferably from 0.01 to 30 ⁇ m, more preferably from 0.03 to 25 ⁇ m, particularly preferably from 0.05 to 20 ⁇ m.
  • the conductive support 1 preferably has a lower surface resistance.
  • the range of the surface resistance is preferably 50 ⁇ / cm 2 or less, more preferably 10 ⁇ / cm 2 or less. This lower limit is not particularly limited, but is usually about 0.1 ⁇ / cm 2 .
  • a collecting electrode may be disposed.
  • One or both of a gas barrier film and an ion diffusion preventing film may be disposed between the conductive support 1 and the transparent conductive film.
  • a resin film or an inorganic film can be used as the gas barrier layer.
  • a transparent electrode and a porous semiconductor electrode photocatalyst containing layer may be provided.
  • the transparent conductive film may have a laminated structure, and as a preferable method, for example, FTO can be laminated on ITO.
  • the photoelectric conversion element 10 of the present invention has a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on a porous semiconductor fine particle 22 on a conductive support 1. Is formed.
  • the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution.
  • the semiconductor fine particles 22 are preferably metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles.
  • metal chalcogenides for example, oxides, sulfides, selenides, etc.
  • perovskite fine particles Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like.
  • Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
  • n-type semiconductors there are an n-type in which carriers involved in conduction are electrons and a p-type in which carriers are holes.
  • n-type is preferable in terms of conversion efficiency.
  • intrinsic semiconductors for example, intrinsic semiconductors
  • the electron carrier concentration is reduced by structural defects derived from impurities.
  • high n-type semiconductors there are high n-type semiconductors.
  • the n-type inorganic semiconductor preferably used in the present invention is TiO 2 , TiSrO 3 , ZnO, Nb 2 O 3 , SnO 2 , WO 3 , Si, CdS, CdSe, V 2 O 5 , ZnS, ZnSe, SnSe, KTaO. 3 , FeS 2 , PbS, InP, GaAs, CuInS 2 , CuInSe 2 and the like.
  • the most preferred n-type semiconductors are TiO 2 , ZnO, SnO 2 , WO 3 , and Nb 2 O 3 .
  • a semiconductor material in which a plurality of these semiconductors are combined is also preferably used.
  • the gel-sol method described in Sakuo Sakuo's “Science of Sol-Gel Method”, Agne Jofusha (1998), etc. is preferable. Also preferred is a method of producing an oxide by high-temperature hydrolysis of chloride developed by Degussa in an oxyhydrogen salt.
  • the semiconductor fine particles 22 are titanium oxide
  • the sol-gel method, the gel-sol method, and the high-temperature hydrolysis method in oxyhydrogen salt of chloride are all preferable. It is also possible to use the sulfuric acid method and the chlorine method described in Gihodo Publishing (1997).
  • the sol-gel method the method described in Journal of American Ceramic Society, Vol. 80, No. 12, 3157-3171 (1997), or the chemistry of Burnside et al. The method described in Materials, Vol. 10, No. 9, pages 2419-2425 is also preferable.
  • a method for producing semiconductor fine particles for example, as a method for producing titania nanoparticles, preferably, a method by flame hydrolysis of titanium tetrachloride, a combustion method of titanium tetrachloride, hydrolysis of a stable chalcogenide complex, orthotitanic acid Hydrolysis of the soluble part, formation of fine semiconductor particles from soluble and insoluble parts, dissolution and removal of soluble part, hydrothermal synthesis of peroxide aqueous solution, or production of core / shell structured titanium oxide fine particles by sol-gel method A method is mentioned.
  • crystal structure of titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable.
  • ⁇ Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles.
  • ⁇ Titania may be doped with a nonmetallic element or the like.
  • an additive may be used on the surface to improve the necking or to prevent reverse electron transfer.
  • preferred additives include ITO, SnO particles, whiskers, fibrous graphite / carbon nanotubes, zinc oxide necking binders, fibrous materials such as cellulose, metals, organic silicon, dodecylbenzenesulfonic acid, silane compounds, etc. Examples thereof include a mobile binding molecule and a potential gradient dendrimer.
  • titania may be acid-base or redox treated before dye adsorption. Etching, oxidation treatment, hydrogen peroxide treatment, dehydrogenation treatment, UV-ozone, oxygen plasma, or the like may be used.
  • (E) Semiconductor fine particle dispersion In the present invention, a semiconductor fine particle dispersion in which the solid content other than the semiconductor fine particles is 10% by mass or less of the entire semiconductor fine particle dispersion is applied to the conductive support 1, A porous semiconductor fine particle coating layer can be obtained by heating to a high temperature.
  • a method of preparing a semiconductor fine particle dispersion is a method of depositing fine particles in a solvent and using them as they are when synthesizing a semiconductor. Ultrafine particles are irradiated with ultrasonic waves. Or a method of mechanically pulverizing and grinding using a mill or a mortar.
  • the dispersion solvent one or more of water and various organic solvents can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
  • a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used in a small amount as a dispersion aid.
  • these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support.
  • the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
  • the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.
  • the viscosity of the dispersion is preferably 10 to 300 N ⁇ s / m 2 at 25 ° C. More preferably, it is 50 to 200 N ⁇ s / m 2 at 25 ° C.
  • a roller method, a dip method, or the like can be used as an application method.
  • an air knife method, a blade method, etc. can be used as a metering method.
  • the application method and the metering method can be made the same part.
  • the wire bar method disclosed in Japanese Patent Publication No. 58-4589, the slide hopper method described in US Pat. No. 2,681,294, etc., the extrusion The method and the curtain method are preferable. It is also preferable to apply by a spin method or a spray method using a general-purpose machine.
  • the wet printing method intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness. Further, since the semiconductor fine particle dispersion of the present invention has a high viscosity and has a viscous property, it may have a strong cohesive force and may not be well adapted to the support during coating. In such a case, by performing cleaning and hydrophilization of the surface by UV ozone treatment, the binding force between the applied semiconductor fine particle dispersion and the surface of the conductive support 1 is increased, and it becomes easy to apply the semiconductor fine particle dispersion. .
  • the preferred thickness of the entire semiconductor fine particle layer is 0.1 ⁇ m to 100 ⁇ m.
  • the thickness of the semiconductor fine particle layer is further preferably 1 ⁇ m to 30 ⁇ m, and more preferably 2 ⁇ m to 25 ⁇ m.
  • the amount of the semiconductor fine particles supported per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g.
  • the applied semiconductor fine particle layer is subjected to heat treatment in order to enhance the electronic contact between the semiconductor fine particles and to improve the adhesion to the support and to dry the applied semiconductor fine particle dispersion. .
  • heat treatment By this heat treatment, a porous semiconductor fine particle layer can be formed.
  • light energy can be used in addition to heat treatment.
  • the surface may be activated by applying light absorbed by the semiconductor fine particles 22 such as ultraviolet light, or only the surface of the semiconductor fine particles 22 is activated by laser light or the like.
  • the impurities adsorbed on the particle surfaces are decomposed by the activation of the particle surfaces, and can be brought into a preferable state for the above purpose.
  • the heating is preferably performed at 100 ° C. or higher and 250 ° C. or lower or preferably 100 ° C. or higher and 150 ° C.
  • the semiconductor fine particle dispersion may be applied to the conductive support 1 and subjected to other treatments other than heating and light irradiation. Examples of preferred methods include energization and chemical treatment.
  • the pressure may be applied after application, and examples of the method of applying pressure include Japanese Patent Publication No. 2003-500857.
  • Examples of light irradiation include JP-A No. 2001-357896.
  • Examples of plasma, microwave, and energization include JP-A-2002-353453.
  • Examples of the chemical treatment include JP-A-2001-357896.
  • the semiconductor fine particles 22 described in Japanese Patent No. 2664194 can be used in addition to the method of applying the semiconductor fine particle dispersion on the conductive support 1. It is possible to use a method such as a method in which the precursor is applied on the conductive support 1 and hydrolyzed with moisture in the air to obtain a semiconductor fine particle film.
  • Examples of the precursor include (NH 4 ) 2 TiF 6 , titanium peroxide, metal alkoxide / metal complex / metal organic acid salt, and the like.
  • a method of forming a semiconductor film by applying a slurry in which a metal organic oxide (such as an alkoxide) coexists, and heat treatment, light treatment, etc., a slurry in which an inorganic precursor coexists, titania dispersed in the pH of the slurry The method which specified the property of particle
  • a binder may be added to these slurries in a small amount, and examples of the binder include cellulose, fluoropolymer, crosslinked rubber, polybutyl titanate, carboxymethyl cellulose and the like.
  • Examples of the technology relating to the formation of the semiconductor fine particles 22 or the precursor layer thereof include a method of hydrophilizing by a physical method such as corona discharge, plasma, and UV, a chemical treatment with alkali, polyethylenedioxythiophene and polystyrenesulfonic acid, polyaniline, etc. Forming an intermediate film for bonding.
  • dry method examples include vapor deposition, sputtering, and aerosol deposition method. Further, electrophoresis or electrodeposition may be used.
  • a method of once forming a coating film on a heat-resistant substrate and then transferring it to a film such as plastic may be used.
  • a method of transferring via EVA described in JP-A No. 2002-184475, a semiconductor layer / conductive layer on a sacrificial substrate containing an inorganic salt that can be removed with ultraviolet rays and an aqueous solvent described in JP-A No. 2003-98977 And a method of removing the sacrificial substrate after transfer to an organic substrate.
  • the semiconductor fine particles 22 preferably have a large surface area so that a large amount of the sensitizing dye 21 can be adsorbed.
  • the surface area thereof is preferably 10 times or more, more preferably 100 times or more the projected area.
  • it is about 5000 times.
  • JP 2001-93591 A and the like can be mentioned.
  • the thickness of the semiconductor fine particle layer increases, so that the amount of the sensitizing dye 21 that can be carried per unit area increases, so that the light absorption efficiency increases.
  • the loss due to charge recombination increases because the diffusion distance of the generated electrons increases.
  • the preferred thickness of the semiconductor fine particle layer varies depending on the use of the device, but is typically 0.1 ⁇ m to 100 ⁇ m.
  • the thickness is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m.
  • the semiconductor fine particles may be heated at a temperature of 100 ° C. to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support.
  • the film forming temperature is preferably 400 ° C to 600 ° C.
  • the film forming method may be any one of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrodeposition method), preferably (1) a wet method, or ( 2) A dry method, more preferably (1) a wet method.
  • the coating amount of the semiconductor fine particles 22 per 1 m 2 of the support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.
  • the sensitizing dye 21 In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution composed of the solution and the dye according to the present invention for a long time.
  • the solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to the present invention.
  • ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol and the like can be used. Among these, ethanol and toluene can be preferably used.
  • the dye solution for dye adsorption comprising the solution and the dye of the present invention may be heated to 50 ° C. to 100 ° C. as necessary.
  • Adsorption of the sensitizing dye 21 may be performed before or after the application of the semiconductor fine particles 22.
  • the semiconductor fine particles 22 and the sensitizing dye 21 may be applied and adsorbed simultaneously. Unadsorbed sensitizing dye 21 is removed by washing.
  • the sensitizing dye 21 to be adsorbed may be one kind of the dye A1 described above, or may be mixed with another dye.
  • the dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible.
  • the total amount of the sensitizing dye 21 is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support. In this case, it is preferable that the usage-amount of the sensitizing dye 21 concerning this invention shall be 5 mol% or more.
  • the adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably 0.001 mmol to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.
  • a sensitizing effect in a semiconductor can be sufficiently obtained.
  • the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.
  • a colorless compound may be co-adsorbed for the purpose of reducing the interaction between the dyes such as association.
  • hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid and pivaloyl acid).
  • the surface of the semiconductor fine particles 22 may be treated with amines.
  • Preferred amines include 4-tert-butylpyridine, polyvinylpyridine and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
  • the counter electrode 4 functions as a positive electrode of the photoelectrochemical cell.
  • the counter electrode 4 is generally synonymous with the conductive support 1 described above, but a support for the counter electrode is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity.
  • the material of the counter electrode 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.
  • the structure of the counter electrode 4 is preferably a structure having a high current collecting effect.
  • Preferred examples include JP-A-10-505192.
  • the light receiving electrode 5 may be a composite electrode such as titanium oxide and tin oxide (TiO 2 / SnO 2 ).
  • a mixed electrode of titania include Japanese Patent Application Laid-Open No. 2000-1113913.
  • Examples of mixed electrodes other than titania include Japanese Patent Application Laid-Open Nos. 2001-185243 and 2003-282164.
  • the photoelectric conversion element may have a structure in which a first electrode layer, a first photoelectric conversion layer, a conductive layer, a second photoelectric conversion layer, and a second electrode layer are sequentially stacked.
  • the dyes used for the first photoelectric conversion layer and the second photoelectric conversion layer may be the same or different, and if they are different, it is preferable that the absorption spectra are different.
  • the light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light.
  • Examples of preferred tandem type configurations include those described in JP-A Nos. 2000-90989 and 2002-90989.
  • a light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided.
  • Preferable examples include those described in JP-A-2002-93476.
  • a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent reverse current due to direct contact between the electrolyte and the electrode.
  • Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.
  • a spacer or a separator In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator.
  • a preferable example is JP-A-2001-283941.
  • Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.
  • D-16 (Preparation of metal complex dye) ⁇ Preparation of Exemplified Dye D-16> Among the metal complex dyes of the general formula (1) shown in the specific examples, D-16 was prepared by the following method with reference to the method described in JP-A No. 2001-291534.
  • D-17 was prepared in the same manner as in the preparation of D-16, except that ammonium thiocyanate was not used and 35 equivalents of potassium cyanide was used per Ru atom.
  • d-2-1 25 g of d-2-1 was dissolved in 500 mL of tetrahydrofuran and cooled with ice, and 1.05 equivalent of n-butyllithium (1.6 mol / L hexane solution) was added dropwise. Thereafter, 1.5 equivalent of dimethylformamide was added dropwise and stirred at room temperature for 1 hour. Saturated aqueous ammonium chloride solution was added dropwise, followed by liquid separation / extraction, concentration, and purification by distillation under reduced pressure to obtain 25.6 g of compound d-2-2. Thereafter, D-15 was obtained in the same manner except that d-1-2 used in preparing D-16 was changed to d-2-2. Furthermore, D-14 was obtained by making the system strongly acidic using 0.2N nitric acid.
  • the stability test was performed on additives such as nucleophilic species present in the dye electrolyte by determining the residual ratio of the dye using the same HPLC.
  • the remaining rate of each dye was 99-100% as A, 98-99% as B, 95-98% as C, 95% or less as D, and A, B and C as light fastness pass.
  • the resulting mixture was uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion.
  • This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a semiconductor fine particle electrode.
  • a dispersion containing 40:60 (mass ratio) of silica particles and rutile-type titanium oxide is prepared, and this dispersion is applied to the light receiving electrode and heated at 500 ° C. to form an insulating porous material. Formed body.
  • a carbon electrode was formed as a counter electrode.
  • the above insulating property is added to an ethanol solution (concentration of each dye is shown in Table 1) containing both the sensitizing dye represented by the general formula (1) and the sensitizing dye represented by the general formula (2).
  • the glass substrate on which the porous body was formed was immersed for 12 hours.
  • the glass dyed with the sensitizing dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and naturally dried.
  • the thickness of the photosensitive layer thus obtained was 10 ⁇ m, and the coating amount of semiconductor fine particles was 20 g / m 2 .
  • the semiconductor fine particle electrode produced by the above method was immersed in each dye solution in the dark at 40 ° C. for 3 hours.
  • the semiconductor fine particle electrode after dye adsorption was desorbed with a 10% TBAOH methanol solution, and the initial adsorption amount of each dye was quantified by HPLC.
  • an adsorption light resistance test was performed on the semiconductor fine particle electrode after dye adsorption prepared in the same manner.
  • a light source for the adsorption light resistance test a Xe lamp light source was used, and a sharp cut filter (Kenko L-42) was used.
  • the residual rate of each dye after irradiation for 420 hours was determined by quantifying by HPLC.
  • the residual rate of each dye after 420 hours is 96% to 100% or less A, 93% to less than 96% B, 90% to less than 93% C, 87% to less than 90% D. Less than 87%.
  • a and B were regarded as passing light resistance.
  • the metal complex dye composition was calculated using the molecular weight of the metal complex dye having the higher content, and a 0.1 mM solution was prepared.
  • the semiconductor fine particle electrode produced in the above “4. Light resistance test in which the semiconductor fine particle electrode was immersed in the dye solution” was immersed in each dye solution at 40 ° C. for 3 hours in the dark.
  • the semiconductor fine particle electrode was disposed opposite to the platinum sputtered FTO substrate through a 50 ⁇ m thick thermoplastic polyolefin resin sheet, and the resin sheet portion was melted by heat to fix the bipolar plate.
  • the electrolyte solution was injected from the injection port of the electrolyte solution previously opened in the platinum sputter
  • the peripheral part and the electrolyte solution injection port were finally sealed with an epoxy-based sealing resin, and a silver paste was applied to the current collecting terminal part to obtain a photoelectric conversion element.
  • As the electrolytic solution a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / L) and iodine (0.1 mol / L) was used.
  • Table 1 shows the relative value of the conversion efficiency after 500 hours based on the initial value of the conversion efficiency of the photoelectrochemical cell thus determined. A relative value of 0.90 or more was considered acceptable.
  • Initial value conversion efficiency measured by the current voltage device Initial value conversion efficiency measured by the current voltage device: ⁇ (%), Short circuit current density: Jsc (mA / cm 2 ), Open voltage: Voc (V ) was used to calculate the fill factor from the following equation.
  • FF ⁇ / (Jsc ⁇ Voc)
  • a dye absorbs light and is excited, and then electrons are injected into the oxide semiconductor very quickly in the femtosecond order.
  • the reduction of dyes from redox systems (for example iodine) is very slow on the order of picoseconds. It is this dye cation reduction step that is the slowest and rate-determining step in the electron transfer cycle of the battery.
  • the HOMO potential of the dye In order for the dye cation reduction process to proceed smoothly, the HOMO potential of the dye must be sufficiently lower than the redox potential. As an evaluation item reflecting this influence, the fill factor of the photoelectric conversion element was evaluated.
  • the following metal complex dye was used.
  • the fill factor value is It was low and inferior in light resistance, stability, and adsorption light resistance in the dye solution.
  • the metal complex dye of the present invention was used, all of the characteristics were at acceptable levels and showed excellent characteristics.

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Abstract

La présente invention concerne un pigment à base de complexe métallique présentant une durabilité supérieure et un rendement de conversion élevé ; une composition de pigment à base de complexe métallique ; un élément de conversion photoélectrique ; et une cellule photoélectrochimique. Le pigment à base de complexe métallique selon la présente invention est caractérisé en ce qu'il est représenté par la formule générale (1) indiquée ci-dessous : M1(LL1)m1(LL2)m2(CN)m3(X1)m4·CI1 …(1) [M1 représente un atome de métal ; LL1 représente un ligand bidenté représenté par la formule générale (2) ; LL2 représente un ligand bidenté représenté par la formule générale (3) ; m1 et m2 valent tous les deux 1 ; m3 vaut 1 ou 2 ; m4 vaut 0 ou 1 ; X1 représente un ligand spécifique ; et CI1 représente un contre-ion au cas où un contre-ion est nécessaire pour neutraliser une charge électrique.]
PCT/JP2012/055141 2011-03-11 2012-02-29 Pigment à base de complexe métallique, composition de pigment à base de complexe métallique, élément de conversion photoélectrique, et cellule photoélectrochimique WO2012124482A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106801231A (zh) * 2017-02-07 2017-06-06 辽宁大学 分子水平铱催化剂修饰的wo3复合光阳极及其应用

Families Citing this family (1)

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CN103403099B (zh) * 2011-03-11 2015-10-21 富士胶片株式会社 金属错合物色素组成物、光电转换元件及光电化学电池

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Publication number Priority date Publication date Assignee Title
JP2001291534A (ja) * 2000-01-31 2001-10-19 Fuji Photo Film Co Ltd 光電変換素子および光電池ならびに金属錯体色素
JP2007063266A (ja) * 2005-08-03 2007-03-15 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池
JP2007112987A (ja) * 2005-09-22 2007-05-10 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池
WO2007091525A1 (fr) * 2006-02-08 2007-08-16 Shimane Prefectural Government Colorant photosensibilisateur
JP2009520861A (ja) * 2005-12-23 2009-05-28 コミツサリア タ レネルジー アトミーク 増感錯体、その製造方法、それを備えた無機／有機ハイブリッド型半導性材料、及び、該材料を備えた太陽電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103403099B (zh) * 2011-03-11 2015-10-21 富士胶片株式会社 金属错合物色素组成物、光电转换元件及光电化学电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001291534A (ja) * 2000-01-31 2001-10-19 Fuji Photo Film Co Ltd 光電変換素子および光電池ならびに金属錯体色素
JP2007063266A (ja) * 2005-08-03 2007-03-15 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池
JP2007112987A (ja) * 2005-09-22 2007-05-10 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池
JP2009520861A (ja) * 2005-12-23 2009-05-28 コミツサリア タ レネルジー アトミーク 増感錯体、その製造方法、それを備えた無機／有機ハイブリッド型半導性材料、及び、該材料を備えた太陽電池
WO2007091525A1 (fr) * 2006-02-08 2007-08-16 Shimane Prefectural Government Colorant photosensibilisateur

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106801231A (zh) * 2017-02-07 2017-06-06 辽宁大学 分子水平铱催化剂修饰的wo3复合光阳极及其应用
CN106801231B (zh) * 2017-02-07 2019-01-01 辽宁大学 分子水平铱催化剂修饰的wo3复合光阳极及其应用

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