JPH0574910B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a photoelectrochemical cell used in optical sensors that detect specific light, photovoltaic cells that convert light into electrical energy, and the like. Structure of conventional examples and their problems Materials that convert light into electrical energy are classified into inorganic and organic materials. Silicon is a typical example of an inorganic material, and although it is said to be energy efficient, the product It is said that the cost is high. Many examples of dyes are known as organic substances, but in most cases it is necessary to use a cell in which the anode active material and the cathode active material are separated by a diaphragm. Also,
The disadvantages of cell reliability include that electrode corrosion is common and energy conversion efficiency is low. OBJECTS OF THE INVENTION The present invention is intended to eliminate the above-mentioned drawbacks of the prior art, and its purpose is to provide a photoelectrochemical cell with a simple cell structure, good photoresponsiveness, and high reliability. Structure of the Invention The present invention achieves the above object, and consists of two substrates, at least one of which is transparent, with semiconductor electrodes arranged to face each other, and a photoelectric energy conversion material that is generally used as a photoelectric energy conversion material between the substrates. formula

[Chemical formula] (In the formula, Q represents a benzene ring having at least one of a substituent and a condensed ring, or a benzene ring having neither of these. _{R 1} and R ₂ are the same or different lower alkyl groups, hydroxy Alkyl group, alkoxyalkyl group, R ₃ is hydrogen or alkyl group, alkoxy group, halogen nitrile group,
Represents an aromatic group, a phenoxy group. Z represents an O or S atom. Y represents an alkylene group having 2 to 4 carbon atoms with or without an alkyl substituent necessary to form a cyclic structure together with -N-C-Z-. A represents a condensation reaction residue of an aromatic aldehyde, a heterocyclic aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound. ) A photoelectrochemical cell characterized by enclosing a solution containing a styryl-like compound represented by: DESCRIPTION OF EMBODIMENTS Examples of the present invention will be described below with reference to the drawings. The basic structure of the photoelectrochemical cell of the present invention is shown in FIG. In the figure, 1 is a glass substrate, 2 and 3 are electrodes, 4 is a sealing material, and 5 is a sealing material, and it is sufficient that at least one of the substrates 1 is transparent. As the material for the electrodes 2 and 3, semiconductor electrodes such as In ₂ O ₃ , SnO ₂ , TiO ₂ or a composite thereof are used. As the sealing material 4 and the sealing material 5, epoxy resin, low melting point glass, solder, etc. are used. 6 is a solution containing a substance that performs a photoelectrochemical reaction. The dye contained in this solution is a type of styryl-like compound, and is represented by the following general formula.

embedded image In the formula, Q represents a benzene ring having at least one of a substituent and a condensed ring, or a benzene ring having neither of these. R ₁ and R ₂ are the same or different lower alkyl groups, hydroxyalkyl groups, or alkoxyalkyl groups, and R ₃ represents hydrogen, an alkyl group, an alkoxy group, a halogen nitrile group, an aromatic group, or a phenoxy group. Z is O
Or represents an S atom. Y represents an alkylene group having 2 to 4 carbon atoms with or without an alkyl substituent necessary to form a cyclic structure together with -N-C-Z-. A represents a condensation reaction residue of an aromatic aldehyde, a heterocyclic aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound. Examples of aromatic aldehydes include benzaldehyde, p-acetaminobezoaldehyde,
p-bromobenzaldehyde, m-bromobenzaldehyde, O-bromobenzaldehyde, p-
Dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde, p-dibutylaminobenzaldehyde, O-chlorobenzaldehyde,
p-chlorobenzaldehyde, p-anisaldehyde, O-anisaldehyde, p-tolualdehyde, m-tolualdehyde, O-tolualdehyde,
O-ethoxybenzaldehyde, p-ethoxybenzaldehyde, p-fluorobenzaldehyde, O-fluorobenzaldehyde, p-hytrobenzaldehyde, m-nitrobenzaldehyde, O-nitrobenzaldehyde, p-cyanobenzaldehyde, O- cyanobenzaldehyde,
2.4-dichlorobenzaldehyde, 2.6-dichlorobenzaldehyde, 3.4-dichlorobenzaldehyde, 3.5-dichlorobenzaldehyde, 2.4-dimethoxybenzaldehyde, 2.5-dimethoxybenzaldehyde, 3.4-dimethoxybenzaldehyde, 3.5-dimethoxybenzaldehyde,
2.4-dimethylbenzaldehyde, 2.5-dimethylbenzaldehyde, 3.4-dimethylbenzaldehyde, 3.5-dimethylbenzaldehyde, veratraldehyde (3.4-dimethoxybenzaldehyde), 4-isopropylbenzaldehyde, O-
(2-chloroethyl)benzaldehyde, 2.4.6-
Trimethylbenzaldehyde, 2.4.6-Trimethylbenzaldehyde (mesicaldehyde), 2.4.6
-triethoxybenzaldehyde, 3.4-dimethyl-p-anisaldehyde, 2.5-dimethyl-p
-anisaldehyde, 2-chloro-5-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 2-chloro-3-nitrobenzaldehyde, 6-chloro-2-nitrobenzaldehydevanillane, O-vanillin, Isovanillin, 5
-bromovanillin, 2-chloro-4-dimethylaminobenzaldehyde, 2-chloro-6-fluorobenzaldehyde, 5-bromoveratraaldehyde, 6-bromoveratraaldehyde, 5-bromo-2-methoxybenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, p-dimethylaminocinnamaldehyde, p-diethylcinnamaldehyde, p-nitrocinnamaldehyde, O-nitrocinnamaldehyde, 2-chlorocinnamaldehyde, 9-anthraaldehyde,
Examples include O-chloro-9-anthraaldehyde, 9-phenanthrenecarboxaldehyde, and fluorenecarboxaldehyde. Further, aromatic nitroso compounds include, for example, p-dimethylaminonitrosobenzene, p-diethylaminonitrosobenzene, p-methylnitrosobenzene (p-nitroso-toluene), p-nitronitrosobenzene, O-nitronitrosobenzene, 3-nitrosobenzene, Examples include nitroso-2-nitrotoluene. In addition, examples of the heterocyclic aldehydes include furfural, 5-methylfurfural, 5-bromofurfural, 4-isopropylfurfural, 2-thioquenecarboxaldehyde, 5-methylthioquenecarboxaldehyde, 3-methoxybenzothioquene- 2-carboxaldehyde, 2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, 4-pyridinecarboxaldehyde, 1-ethylindole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde, 1 -Methyl-2-phenylindole-3-carboxaldehyde, N-methylcarbazole-2-carboxaldehyde, N-ethyl-7-bromocarbazole-2-carboxaldehyde, N-(n-octyl)-7 -Nitrocarbazole-2-carboxaldehyde, dibenzofuran-2-carboxaldehyde, pyrrole-2-aldehyde, N-methylpyrrole-2-aldehyde, N-phenylpyrrole-2-aldehyde, 3
-Methylpyrrole-2-aldehyde, 2-ethylpyrrole-5-aldehyde, benzothiazole-
2-Aldehyde, 6-methylbenzothiazole-
2-aldehyde, 6-chlorobenzothiazole-
2-aldehyde, 5-chlorobenzothiazole-
2-aldehyde, 6-methoxybenzothiazole-2-aldehyde, 5,6-dichlorobenzothiazole-2-aldehyde, benzoselenazole-2
-Aldehyde, 6-methoxybenzozelenazole-2-aldehyde, 2,4-dimethylpyrrole-
2-Aldehyde, 4,6-dichloropyrimidine-5
-carboxaldehyde, 2-formyl-4,6-dimethylpyrimidine, quinoline-2-aldehyde,
Acridine-10-aldehyde, 2.4-diphenyl-5.6.7-hexahydrobenzobilane-8-carboxaldehyde, 2.4-diphenyl-6-methyl-5.6.7-bentahydrobenzobilane-8-
Carboxaldehyde, etc. In addition, examples of the heterocyclic troso compound include 3-nitrosoindole, 2-methyl-3-nitrosoindole (3-nitrosomethylketol),
3-nitroso-2-phenylindole, etc. Supporting electrolytes include alkyl ammonium salts such as ClO ₄ ^- , BF ₄ ^- PF ₆ ^- , and halogen ions;
Metal salts such as Li and Na are used. As organic solvents, photoelectrochemical and stable ones, such as
Acetonitrile, r-butyrolactone, propylene carbonate, dimethylformamide, acetic acid esters, etc. are used. Styryl-like compounds exhibit a state of discoloration to color development due to oxidation, that is, release of electrons. Most pigments in a decolored state absorb light in the ultraviolet region, and in a colored state, they absorb light in the visible region. The magnitude of the photovoltaic force is proportional to the amount of light corresponding to the wavelength of light absorption by this dye. Therefore, when using visible light, the energy conversion efficiency is better if the dye is used in a colored state. This example will be explained in more detail. 3.3 is one of the pigments of styryl-like compounds.
-dimethyl-2-(p-dimethylaminocinnamylidene vinylindoly/[2.1-b]oxazoline and using tetrabutylammonium verchlorate as the supporting electrolyte, respectively.
It was dissolved in propylene carbonate at a concentration of 0.1M/, 0.5M/. This solution was injected into a cell as shown in FIG. 1, and the photoresponsiveness was examined. Figure 2 shows the response of photovoltaic current with and without light irradiation. The rise of the photovoltaic current when the light irradiation is turned on is faster than the fall when the light irradiation is turned off. Further, when the dye of Example 1 is allowed to develop a color, it becomes a blue color with an absorption peak around 610 mm. When the photovoltaic current was measured using a cell containing the solution in such a state, a value of 2 to 3 μA/cm ² was obtained by irradiation with visible light. Effects of the Invention In summary, the present invention provides two substrates, at least one of which is transparent and has semiconductor power, arranged facing each other,
During this period, as a photoelectric energy conversion material, the general formula

[Chemical formula] (In the formula, Q represents a benzene ring having at least one of a substituent and a condensed ring, or a benzene ring having neither of these. _{R 1} and R ₂ are the same or different lower alkyl groups, hydroxy Alkyl group, alkoxyalkyl group, R ₃ is hydrogen or alkyl group, alkoxy group, halogen nitrile group,
Represents an aromatic group, a phenoxy group. Z represents an O or S atom. Y represents an alkylene group having 2 to 4 carbon atoms with or without an alkyl substituent necessary to form a cyclic structure together with -N-C-Z-. A represents a condensation reaction residue of an aromatic aldehyde, a heterocyclic aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound. ) A photoelectrochemical cell is provided, characterized in that it is sealed with a solution containing a styryl-like compound shown in
It has good photoresponsiveness and excellent reliability, and can be applied to optical sensors and photovoltaic cells.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the basic structure of the photoelectrochemical cell of the present invention, and FIG. 2 is a diagram showing an example of the photoresponsiveness of the cell. 1... Glass substrate, 2, 3... Electrode, 4... Sealing material, 5... Sealing material, 6... Solution containing photoelectrochemical reactant.

Claims (1)

[Scope of Claims] 1 Semiconductor electrodes are arranged on two substrates, at least one of which is transparent, so as to face each other, and a photoelectric energy conversion material of the general formula Q represents a benzene ring having at least one of a substituent and a condensed ring, or a benzene ring having neither of these. R ₁ and R ₂ are the same or different lower alkyl group, hydroxyalkyl group, or alkoxyalkyl group. , R ₃ is hydrogen or an alkyl group, an alkoxy group, a halogen nitrile group,
Represents an aromatic group, a phenoxy group. Z represents an O or S atom. Y represents an alkylene group having 2 to 4 carbon atoms with or without an alkyl substituent necessary to form a cyclic structure together with -N-C-Z-. A represents a condensation reaction residue of an aromatic aldehyde, a heterocyclic aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound. ) A photoelectrochemical cell characterized by enclosing a solution containing a styryl-like compound represented by: 2. The photoelectrochemical cell according to claim 1, wherein the solution is a styryl-like compound dissolved in a non-aqueous organic solvent and further provided with a supporting electrolyte.