WO2006115271A1

WO2006115271A1 - Organic photocatalyst

Info

Publication number: WO2006115271A1
Application number: PCT/JP2006/308748
Authority: WO
Inventors: Keiji Nagai; Toshiyuki Abe
Original assignee: Osaka University; Hirosaki University; Kansai Technology Licensing Organization Co., Ltd.
Priority date: 2005-04-26
Filing date: 2006-04-26
Publication date: 2006-11-02
Also published as: JP5182665B2; JPWO2006115271A1

Abstract

An organic photocatalyst that in a gas phase or a liquid phase containing water, is capable of efficiently decomposing an organic matter or an inorganic matter containing nitrogen, sulfur, phosphorus, etc. under irradiation with light (especially, visible light); a process for producing the same; and use thereof. In particular, there is provided an organic photocatalyst comprising a p-type organic semiconductor and an n-type organic semiconductor, which organic photocatalyst is used to decompose an organic matter or an inorganic matter containing nitrogen, sulfur, phosphorus, etc. under light irradiation. More particularly, there is provided an organic photocatalyst of double-layer structure comprising a base material and, superimposed thereon, a p-type organic semiconductor layer and an n-type organic semiconductor layer.

Description

Specification

Organic photocatalyst

Technical field

The present invention relates to an organic photocatalyst used for decomposing an organic substance or an inorganic substance containing nitrogen, sulfur, phosphorus, etc. under light irradiation, particularly under visible light irradiation, a method for producing the same, and use of the organic photocatalyst About.

Background art

[0002] A photocatalyst is a catalytic material that decomposes harmful substances, etc., using acid / reducing power generated by the input of light energy, and does not use toxic chemicals or fossil fuels. As a result, various chemical substances that are difficult to be decomposed can be safely and easily decomposed only by using the energy of light. Therefore, it is attracting attention as an environmentally friendly environmental cleaning material.

[0003] Currently, photocatalytic materials such as titanium oxide (TiO 2), zinc oxide, and tungsten oxide are available.

2

Photocatalysts composed of organic compounds are known, and among these, titanium oxide is the material that has the most excellent photocatalytic action size and safety, as well as resource and cost, and has been widely studied. There are also commercialized products (see Non-Patent Document 1).

[0004] This titanium oxide titanium exhibits photocatalytic activity by light in the ultraviolet region, but only ultraviolet light corresponding to an energy density of 3% of natural light is used. Therefore, from the viewpoint of solar energy conversion efficiency, a photocatalyst that can effectively use visible light that accounts for about half of the natural light energy density is desired.

[0005] Further, when titanium oxide is used as a pigment of a paint, there is a problem that an organic component of the paint is decomposed by titanium oxide to cause a choking phenomenon.

[0006] By the way, with respect to photocatalysts having organic compound power, there have been few reports so far, and polybaraphthalene and derivatives thereof have only been reported (see Non-Patent Document 2). These are ultraviolet light-responsive materials and have problems such as difficulty in use in a gas phase (wet air) phase or a liquid phase containing water.

Non-Patent Document 1: Illustrated photocatalysts all (supervised by Kazuhito Hashimoto and Akira Fujishima), Industrial Research Committee (2003 )

Non-Patent Document 2: J. Chem. Soc. Faraday Trans., 93, 221 (1997)

Disclosure of the invention

Problems to be solved by the invention

[0007] In view of the above problems of the prior art, the present invention provides an organic substance or an inorganic substance containing nitrogen, sulfur, phosphorus, or the like efficiently under light (particularly visible light) irradiation in a gas phase or a liquid phase containing water. It is an object to provide an organic photocatalyst capable of decomposing water and a method for producing the same. Moreover, an object of this invention is to provide the use of this organic photocatalyst.

Means for solving the problem

[0008] As a result of intensive studies to achieve the above object, the present inventors have found that visible light (wavelength: 400 to 750 nm) is applied to a material composed of a specific p-type organic semiconductor and a specific _n- type organic semiconductor. ), A photocatalytic acid-oxidation reduction reaction occurs via unidirectional photo-induced electr on transfer. Further, the present inventors have found that the material exhibits photocatalytic activity under light irradiation in a gas phase or a liquid phase, and can efficiently decompose an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus. Based on these findings, the present inventor has further developed and completed the present invention.

That is, the present invention provides the following organic photocatalyst, method for producing the same, and use of the organic photocatalyst.

Item 1 An organic photocatalyst comprising a p-type organic semiconductor and an n-type organic semiconductor, which is used for decomposing an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus under light irradiation.

Item [0011] The organic photocatalyst according to Item 1, wherein the organic photocatalyst has a two-layer structure in which a p-type organic semiconductor layer and an n-type organic semiconductor layer are laminated.

Item 3 The organic photocatalyst according to Item 1, wherein the p-type organic semiconductor layer has a thickness of about 20 to 500 nm, and the n-type organic semiconductor layer has a thickness of about 50 to 800 nm.

Item 4 The organic photocatalyst according to Item 1, wherein the organic photocatalyst has a three-layer structure including a co-deposition layer of a p-type organic semiconductor and an n-type organic semiconductor between the p-type organic semiconductor layer and the n-type organic semiconductor layer.

Item 5 A two-layer structure in which a p-type organic semiconductor layer and an n-type organic semiconductor layer are stacked on a substrate. Item 2. The organic photocatalyst according to Item 1.

[0015] Item 6. The organic material according to Item 1, wherein the substrate has a three-layer structure including a co-deposited layer of a p-type organic semiconductor and an n-type organic semiconductor between the p-type organic semiconductor layer and the n-type organic semiconductor layer. photocatalyst.

Item 7 The item in which the material of the p-type organic semiconductor is a macrocyclic ligand compound or a metal complex thereof.

1. The organic photocatalyst according to 1.

[0017] Item 8. The organic photocatalyst according to Item 7, wherein the material of the p-type organic semiconductor is at least one selected from the group force consisting of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative.

Item 9 The organic photocatalyst according to Item 8, wherein the material of the p-type organic semiconductor is a phthalocyanine derivative.

[0019] Item 10. The organic photocatalyst according to Item 1, wherein the n-type organic semiconductor material is a polycyclic aromatic compound.

Item 11: Material strength of n-type organic semiconductor Item 10 is a group force consisting of fullerenes, carbon nanotubes, conductive polymers doped with electron donors, perylene derivatives, and naphthalene derivatives. The organic photocatalyst described in 1.

Item 12 The organic photocatalyst according to Item 11, wherein the n-type organic semiconductor material is at least one selected from the group consisting of fullerenes and perylene derivatives.

[0022] Item 13. A method for producing an organic photocatalyst according to Item 5, wherein an n-type organic semiconductor layer and a p-type organic semiconductor layer are laminated on a substrate to form a two-layer structure. Manufacturing method.

[0023] Item 14. A method for producing an organic photocatalyst according to Item 6, wherein an n-type (or p-type) is formed on a substrate.

) An organic semiconductor layer is formed, on which an n-type organic semiconductor and a p-type organic semiconductor are co-evaporated to form a co-deposited layer, on which a p-type (or n-type) organic semiconductor layer is formed. A manufacturing method characterized by having a layer structure.

Item 15 A method for decomposing an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus in a gas phase or an aqueous phase, wherein the organic photocatalyst according to Item 1 is treated with an organic substance or nitrogen, sulfur or phosphorus under light irradiation. A method of decomposing by contacting with an inorganic substance.

[0025] Item 16. A coating composition comprising the organic photocatalyst according to item 1 and a coating material.

[0026] Item 17. The organic photocatalyst described in item 1 is an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus. A method of treating water by dispersing it in water to be treated containing substances and irradiating it with light.

Item 18 Further, after the treatment, the organic photocatalyst is recovered by filtration and again subjected to water treatment.

The water treatment method according to 7.

[0028] Hereinafter, the present invention will be described in detail.

I. Organic light erosion

The organic photocatalyst of the present invention includes a p-type organic semiconductor and an n-type organic semiconductor. Specifically, it has a structure in which a portion made of a P-type organic semiconductor (balta layer) and a portion made of an n-type organic semiconductor (balta layer) are in contact with each other. The organic photocatalyst of the present invention causes unidirectional photoinduced electron transfer at the interface where the p-type organic semiconductor material and the n-type organic semiconductor material are in contact with each other by light irradiation, which contains organic matter or nitrogen, sulfur or phosphorus. Used for inorganic decomposition. Therefore, this organic photocatalyst is used for decomposing organic substances or inorganic substances containing nitrogen, sulfur or phosphorus under light irradiation in a gas phase or a liquid phase.

_[0029] Ώ organic semiconductor

Examples of the cage organic semiconductor include a macrocyclic ligand compound or a metal complex thereof. A macrocyclic ligand compound means a cyclic compound that contains an atom having an unpaired electron on the ring and can be a metal ligand, and the metal complex is a macrocycle. It means a metal complex that also consists of a ligand and a metal nuclear power. As an atom which has an unpaired electron, a nitrogen atom and an oxygen atom are mentioned, for example, A nitrogen atom is preferable. As a metal atom, each metal element of 1-15 group of a periodic table is mentioned, Preferably it is a 4-14 group metal element. In addition, the metal complex is usually one in which the metal atom and the macrocyclic ligand compound are composed of 1: 1 (molar ratio) to form a planar four-coordinate complex.

[0030] Specific examples of the macrocyclic ligand compound or the metal complex thereof include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, and the like.

[0031] The phthalocyanine derivative means a compound having a basic skeleton of phthalocyanine.

Specifically, for example, the following formula (1A) or (1B):

[0032] [Chemical 1]

(1A) (IB)

[In the formula, M ¹ represents a group force selected from group 4 to group 14 force in the periodic table, and represents a selected metal atom or an atomic group containing the metal atom, and a dotted line represents a coordination bond)

The phthalocyanine derivative represented by these is mentioned.

[0034] Among the metal atoms of groups 4 to 14 of the periodic table represented by M ¹ , group 4 (especially Ti), group 5 (particularly V), group 6 (particularly Mo), group 7 ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (especially Al), and Group 14 (especially Pb). Further, the atomic group containing the metal atom means a group in which another ligand (for example, oxygen or cyan group) is coordinated to the metal (for example, THD).

[0035] Among the above, phthalocyanine represented by the formula (1A), or M ¹ in the formula (1B) is Ti, Co,

Pt, Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Ru are preferred phthalocyanine derivatives, especially from the viewpoint of photocatalytic activity for decomposition of organic substances or inorganic substances containing nitrogen, sulfur or phosphorus (1A) metal-free phthalocyanine, (1B) iron phthalocyanine and cobalt phthalocyanine are preferred. These compounds are either commercially available or can be easily produced by those skilled in the art.

[0036] The naphthalocyanine derivative means a compound having a basic skeleton of naphthalocyanine. Specifically, for example, the following formula (2A) or (2B):

[0037] [Chemical 2]

[In the formula, M ² represents a group force selected from group 4 to group 14 forces in the periodic table, and represents a selected metal atom or an atomic group including the metal atom, and a dotted line represents a coordination bond.]

The naphthalocyanine derivative represented by these is mentioned.

[0039] Preferably one of the Periodic Table 4-14 metals atom represented by M ^2, Group 4 (especially, Ti), Group 5 (in particular, V), Group 6 (in particular, Mo), 7 group ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (especially Al), and Group 14 (especially Pb). Further, the atomic group containing the metal atom means a group in which another ligand (for example, oxygen or cyan group) is coordinated to the metal (for example, THD).

[0040] Among the above, the naphthalocyanine represented by the formula (2A) or the formula (2B)! /, Where M ² is Ti, Co,

Naphthalocyanine derivatives which are Pt, Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Ru are preferred, especially in terms of photocatalytic activity for decomposition of organic substances or inorganic substances containing nitrogen, sulfur or phosphorus To (2A) metal-free naphthalocyanine and (2B) iron naphthalocyanine-cobalt naphthalocyanine. These compounds are either commercially available or can be easily produced by those skilled in the art.

[0041] The porphyrin derivative means a compound having a basic skeleton of porphyrin. Specifically, for example, the following formula (3A) or (3B):

[0042] [Chemical 3]

(3B)

(Wherein R ³ is a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and M ³ is a group force selected from Group 4 to 14 of the periodic table, including a selected metal atom or a metal atom thereof. (Shows atomic group, dotted line shows coordination bond)

The porphyrin derivative represented by these is mentioned.

[0044] Here, the alkyl group represented by R ³ is a linear or branched alkyl group of C.

1 -20

And a kill group, preferably an alkyl group of c. Specifically, methyl, ethi

1-10

, N-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.

[0045] Further, examples of the aryl group represented by R ³ include monocyclic or bicyclic aryl groups, and specific examples include phenyl and naphthyl.

In addition, examples of the heteroaryl group represented by R ³ include pyridyl and pyrajur.

[0047] Of the metal atoms in groups 4 to 14 of the periodic table represented by M ³ , group 4 (especially Ti), group 5 (particularly V), group 6 (particularly Mo), group 7 ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (especially Al), and Group 14 (especially Pb). Further, the atomic group containing the metal atom means a group in which another ligand (for example, oxygen or cyan group) is coordinated to the metal (for example, THD).

[0048] Among the above, a porphyrin of the formula (3A), or M ³ in the formula (3B) Ti, Co, Pt , Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or A porphyrin derivative in which Ru and R are ferrules or hydrogen atoms is preferred, particularly from the viewpoint of photocatalytic activity for the decomposition of organic substances or inorganic substances containing nitrogen, sulfur or phosphorus (3A) metal-free porphyrins or (3B ) Iron Borhuili Nya cobalt porphyrin is preferred. These compounds are either commercially available or can be easily produced by those skilled in the art.

[0049] n-type organic semiconductor

Examples of the n-type organic semiconductor include polycyclic aromatic compounds. The polycyclic aromatic compound may be partially saturated. A polycyclic aromatic compound is a compound having a structure in which at least two aromatic rings are condensed, or a structure in which a plurality of aromatic rings are bonded through unsaturated bonds (double bonds, triple bonds, etc.). It means the compound etc. which have. As the aromatic ring, in addition to a benzene ring, a heteroaromatic ring such as a pyrrole ring, an imidazole ring, a pyridine ring, or a quinoxaline ring is also included (a part of the shift ring may be saturated) .

[0050] The polycyclic aromatic compound may have various substituents as long as the present invention is not adversely affected. Examples of the substituent include an electron withdrawing group, and specific examples include a carbonyl group, a sulfone group, and a sulfoxide group.

[0051] Specific examples of the polycyclic aromatic compound include fullerenes such as C 1, C 2, C 3, C 5 and C 5.

60 70 76 82 84

Carbon nanotubes; Conductive polymers doped with electron donors (such as phenylenediamine, tetraaminoethylene, tris (2,2-biviridine) ruthenium) (polyimide, polyphenylene vinylene, polyparaphenylene, polypyrrole) Etc.); perylene derivatives; naphthalene derivatives and the like. Among them, perylene derivatives, naphthalene derivatives, fullerenes (C etc.

60

And the like are preferably employed, and perylene derivatives and fullerenes (C and the like) are particularly preferred.

60

[0052] The perylene derivative means a compound having a basic skeleton of perylene. In particular

For example, the following formulas (4A) to (4C):

[0053] [Chemical 4]

[In the formula, R ¹ represents an alkyl group or an aryl group]

The perylene derivative represented by these is mentioned.

[0055] The naphthalene derivative means a compound having a basic skeleton of naphthalene. Specifically, for example, the following formula (5A):

[0056] [Chemical 5]

(5A)

[In the formula, R ² represents an alkyl group or an aryl group]

The naphthalene derivative represented by these is mentioned.

Here, the alkyl group represented by the above R ¹ or R ² is a C straight or branched chain.

1-20

And an alkyl group of C is preferable. Specifically, methyl

1-10

, Ethyl, n-propyl, isopropyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-butyl, n-octyl and the like.

[0059] The aryl group represented by R ¹ or R ² is a monocyclic or bicyclic aryl group. Specific examples include phenyl and naphthyl.

[0060] Organic photocatalyst

The organic photocatalyst of the present invention contains the above p-type organic semiconductor and n-type organic semiconductor. The bonding form of the P-type organic semiconductor and the n-type organic semiconductor in the organic photocatalyst is not particularly limited, but from the viewpoint of photocatalytic activity (that is, quantum yield), it is preferable to bond the two so that the contact area between the two increases. . Since the contact area between the n-type organic semiconductor and the n-type organic semiconductor is increased, photo-induced electron transfer is efficiently generated when light is irradiated, and the photocatalytic acid is effectively removed. This is because a reduction reaction occurs.

[0061] Specific examples of the organic photocatalyst of the present invention include a laminated (film) structure in which a p-type organic semiconductor and an n-type organic semiconductor are laminated.

[0062] The laminated structure is preferably, for example, a two-layer structure in which a p-type organic semiconductor and an n-type organic semiconductor are laminated. This may be a film itself having a two-layer structure strength, or may have a two-layer structure of an n-type organic semiconductor and a P-type organic semiconductor on a substrate.

[0063] When the organic photocatalyst has a two-layer structure on a film or a substrate having a two-layer structure, the thickness of each layer is not particularly limited. For example, the n-type organic semiconductor layer has a thickness of 50 to About 800 nm, preferably about 100 to 650 nm, and the thickness of the p-type organic semiconductor layer is about 20 to 500 nm, preferably about 30 to 350 nm. It is preferable because the photocatalytic activity is optimized by adopting a strong thickness.

[0064] The laminated structure is a three-layer structure in which a co-evaporated layer formed by co-evaporating an n-type organic semiconductor and a p-type organic semiconductor is sandwiched between the p-type organic semiconductor layer and the n-type organic semiconductor layer. Also good. Of course, the substrate may have this three-layer structure.

[0065] When the organic photocatalyst has a three-layer structure on a film or a substrate having a three-layer structure, the thickness of each layer is not particularly limited. For example, the n-type organic semiconductor layer has a thickness of 50 to About 800 nm, preferably about 100 to 650 nm, the co-deposition layer is about 5 to 10 nm, and the thickness of the ρ-type organic semiconductor layer is about 20 to 500 nm, preferably about 30 to 350 nm. is there. Adopting a strong thickness is preferable because the photocatalytic activity is optimized.

[0066] In order to increase the activity of the photocatalyst, a transition metal catalyst (for example, Ag, Cu, Ni, Pd, Pt, Ir catalyst, etc.) may be added to the organic photocatalyst of the present invention as necessary. . [0067] The substrate on which the laminated structure is formed is selected from materials and shapes according to the purpose.

[0068] Further, the organic photocatalyst of the present invention is, for example, in the form of a powder (particles, fine particles, etc.) that is easily pulverized and cut into the above-mentioned film having a laminated structural force and easily dispersed in a medium. I'll do it.

[0069] The above-described organic photocatalyst (for example, a substrate (carrier) having a laminated structure (powder), a powdery substance, etc.) can be dispersed in a liquid medium (for example, water) and can be recovered by filtration or the like. Therefore, they can be dispersed in a medium containing an object to be processed such as organic matter (for example, water), subjected to decomposition treatment by light irradiation, and after treatment, only the photocatalyst can be separated by filtration or the like and reused. There is.

[0070] The organic photocatalyst of the present invention decomposes organic substances or inorganic substances containing nitrogen, sulfur, phosphorus, etc., efficiently absorbing natural light and visible light under irradiation of light in the gas phase or liquid phase. Can do. The organic photocatalyst of the present invention can effectively utilize light in the visible region contained in natural light with high catalytic efficiency as an energy source. Furthermore, since the organic photocatalyst of the present invention is an organic compound, it is excellent in processability and moldability and is stable in water.

TT. Organic ^ ¾ testimony

Although the manufacturing method of the organic photocatalyst of this invention is demonstrated below, it is not limited to this.

[0071] As the p-type organic semiconductor, those described above can be used, and typical examples include phthalocyanine derivatives, naphthalocyanine derivatives, and porphyrin derivatives. More preferable examples include compounds represented by the formulas (1A), (1B), (2A), (2B), (3A), (3B). In particular, a metal-free phthalocyanine of the formula (1A), an iron phthalocyanine of the formula (1B), or a cobalt phthalocyanine of the formula (1B) is preferable.

[0072] As the n-type organic semiconductor, those described above can be used, and those having a good pn junction relationship with the p-type organic semiconductor are used. Typical examples of the n-type organic semiconductor include perylene derivatives, naphthalene derivatives, and fullerenes. More preferable examples include compounds represented by the formulas (4A), (4B), (4C), and (5A). In particular, an efficient key Perylene derivatives (3,4,9,10-perylenetetraforce ruboxyl-bisbenzimidazole) or fullerenes (C, etc.) represented by formula (4A) are preferably used from the viewpoint of formation of carriers.

60

[0073] The organic photocatalyst of the present invention includes a transition metal catalyst (for example, Ag, Cu, etc.) as necessary in addition to the n-type organic semiconductor and the p-type organic semiconductor in order to increase the activity of the photocatalyst.

Ni, Pd, Pt, Ir catalyst, etc.) may be added.

[0074] The organic photocatalyst of the present invention has a form in which an n-type organic semiconductor and a p-type organic semiconductor have a pn junction so as to increase the contact area, and can be a manufacturing method capable of forming a strong junction form. There is no particular limitation.

[0075] For example, when the organic photocatalyst is a two-layer structure film in which an n-type organic semiconductor and a p-type organic semiconductor are stacked, the n-type organic semiconductor and the p-type organic semiconductor are stacked on the substrate to form a two-layer structure. And the two-layer structure film can be produced by peeling the substrate force. In this case, the material of the substrate is not particularly limited as long as the formed two-layer structure film can be easily peeled off. For example, a glass substrate is mentioned. The obtained two-layer structure film can be used as it is as a photocatalyst. If necessary, an adhesive layer is provided on the two-layer structure film and adhered to a substrate, or crushed and cut into a powder form. Is also possible.

Alternatively, an n-type (or p-type) organic semiconductor and a p-type (or n-type) organic semiconductor are directly laminated on a specific substrate from the beginning, and an organic photocatalytic layer is provided on the substrate. You can also. In this case, as the material of the substrate, any material that can be laminated with the organic photocatalyst of the present invention is suitable. For example, ceramics (silica, alumina, zirconia, etc.), metal, alloy, wood, activated carbon, pumice, concrete, paper , Fiber, filter paper and the like. In addition, the shape of the substrate may be any depending on the application.

[0077] As a method of laminating an n-type organic semiconductor and a p-type organic semiconductor on a substrate, a known method can be employed, for example, vacuum deposition, sputtering, electrochemical coating (electrodeposition), coating And the like. Among these, for the perylene derivative Z phthalocyanine derivative system, a vacuum deposition method is preferable because a uniform coating film can be obtained.

[0078] When the organic semiconductor has a two-layer structure, the thickness of each layer is not particularly limited, but is preferably set as appropriate within the above-described range. That is, the thickness of the p-type organic semiconductor layer is about 20 to 500 nm. The thickness is preferably about 30 to 350 nm, and the thickness of the n-type organic semiconductor layer is about 50 to 800 nm, preferably about 100 to 650 nm.

[0079] Also, when the organic semiconductor has a three-layer structure, a p-type (or n-type) organic semiconductor layer is formed on the substrate, and a co-deposition layer comprising the p-type organic semiconductor and the n-type organic semiconductor is formed thereon. In addition, an organic photocatalyst having a three-layer structure on a substrate may be formed by forming an n-type (or p-type) organic semiconductor layer thereon. Further, the three-layer structure film can be formed by peeling the three-layer structure film from the substrate. In addition, said lamination | stacking method can be employ | adopted for a lamination | stacking method, and a co-deposition layer can also be formed using a well-known method.

[0080] When the organic semiconductor has a three-layer structure, the film thickness of each layer is not particularly limited, but is preferably set as appropriate within the above-described range. That is, the thickness of the n-type organic semiconductor layer is about 50 to 800 nm, preferably about 100 to 650 nm, the co-deposited layer is about 5 to 10 nm, and the thickness of the p-type organic semiconductor layer is 20 It is about ˜500 nm, preferably about 30 to 350 nm.

[0081] Further, in addition to the laminated structure, a transition metal catalyst (for example, Ni, Pd, Pt, Ag, Ir catalyst, etc.) is further formed on the outer layer by using an electrolytic deposition method, a suspension casting method, or the like. , Preferably Ag or IrO

2 catalyst) may be supported. The transition metal catalyst to be supported need not be completely covered with the outer layer, but may be dispersed and supported. The average particle diameter of the transition metal catalyst may be in the fine particle state of about 5 to 800 nm (preferably about 10 to 100 nm).

in. ^ Mm ^ ^ rm ^

The organic photocatalyst of the present invention can be decomposed by contact with an organic substance contained in the gas phase or aqueous phase or an object to be decomposed such as an inorganic substance containing nitrogen, sulfur or phosphorus under light irradiation.

[0082] The light used in the organic photocatalyst of the present invention can be light having a wide range of wavelengths (wavelength of about 220 to 1200 nm). For example, natural light (sunlight), fluorescent lamp, halogen lamp, high pressure mercury lamp, low pressure mercury lamp, black light, excimer laser, deuterium lamp, xenon lamp, Hg-Zn-Pb lamp, etc. Or two types of light sources with different wavelength ranges can be used. In particular, the organic photocatalyst of the present invention is extremely practical in that natural light (wavelength of 300 to 800 nm), particularly visible light (wavelength of 400 nm or more, particularly about 400 to 750 nm) can be used. In acid titanium used as an inorganic photocatalyst, Considering the necessity of an ultraviolet light source indoors, this is extremely meaningful.

[0083] Further, the organic photocatalyst of the present invention can efficiently decompose organic substances or inorganic substances containing nitrogen, sulfur or phosphorus only by light irradiation. In this respect, the method of decomposing organic matter by irradiating the photocatalyst with light while applying a bias electrochemically (for example, ChemPhysChem 2004, 5, 716-720) is a distinct line. is there. In the electrochemical decomposition method, for example, negative charges (electrons) generated by oxidative decomposition on the surface of the catalyst are removed through the electrode, but in the organic photocatalyst of the present invention, the electrons are accepted by oxygen present in the treatment medium. It is thought that it will be removed. Therefore, the decomposition reaction proceeds more efficiently when oxygen is present in a high concentration in the gas phase or the liquid phase (aqueous phase). For example, in the gas phase, the oxygen concentration is preferably 20% by volume, more preferably 25% by volume or more. Also, in the liquid phase (for example, water), it is preferable to supply air or oxygen-containing gas (such as publishing) or to react while stirring the liquid phase.

[0084] Degradable substances in the gas phase or aqueous phase include malodorous substances, dust, microorganisms, viruses, sick house syndrome causative substances (formaldehyde, etc.), odorous components (cigarette odor, pet odor, etc.), toxic substances (Dioxin, PCB, etc.), agricultural chemicals, ethylene gas, nitrogen compounds (ammonia, NOx, etc.), sulfur compounds (mercapbutane, sulfide, etc.) and phosphorus compounds (organic phosphorus, etc.).

[0085] Further, the organic photocatalyst of the present invention is excellent in processing or moldability because the difference between the p-type organic semiconductor and the n-type organic semiconductor is also composed of an organic substance. The inorganic photocatalyst, titanium oxide, has difficulty in processability and moldability, but the organic photocatalyst of the present invention can solve such problems. Therefore, it is used for a very wide range of applications that exceed the applications of titanium oxide.

[0086] The organic photocatalyst of the present invention can be used as a surface material of various filters for filtering and decomposing an object to be decomposed in the gas phase to the aqueous phase. As a method for fixing the organic photocatalyst of the present invention to a single filter substrate, the above-described methods such as vacuum deposition, sputtering, electrochemical coating (electrodeposition), and coating may be used.

[0087] Further, the organic photocatalyst of the present invention is dispersed in water to be treated containing an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus, subjected to a decomposition treatment by light irradiation, and further filtered after the treatment. Can be separated and recovered and used again for water treatment. [0088] Further, the organic photocatalyst of the present invention can be mixed into a paint to obtain a paint composition having photocatalytic activity. In the coating composition, since the organic photocatalyst has a high affinity for the coating, the catalyst can be dispersed uniformly.

[0089] Since the organic photocatalyst of the present invention is stable against water, the treatment of water containing the decomposition target can be carried out efficiently. For example, the powder is dispersed in water to be treated and irradiated with light to treat the water. After the treatment, the powder is filtered to obtain treated water, and the powder can be easily recovered. The water phase (treated water) includes, for example, industrial circulating water, industrial wastewater, industrial wastewater, clean water, sewage, soil and groundwater, ponds, pools, domestic wastewater, pesticide residue wastewater, bath, water storage Examples include tanks, lakes, and dams. These aqueous phases can be treated efficiently without any particular limitation on pH, hardness, and the like. In particular, the pH is preferably about 7 to L1.

The invention's effect

[0090] The organic photocatalyst comprising the p-type organic semiconductor and the n-type organic semiconductor titanium oxide of the present invention has a high catalytic activity against the decomposition of organic substances and the like by visible light irradiation. In particular, the organic photocatalyst of the present invention is a photocatalyst that can use light energy in the entire visible light range, and is a very effective photocatalyst in particular because it can sufficiently use solar light (natural light).

[0091] Unlike the inorganic photocatalyst, the organic photocatalyst of the present invention is obtained by simply laminating a p-type organic semiconductor and an n-type organic semiconductor, and has a very high practicality because it is extremely easy to mold.

[0092] The organic material is generally easily decomposed by acid, but the organic photocatalyst of the present invention functions stably in the gas phase or liquid phase. Of course, it can be used indoors as well as outdoors. Brief Description of Drawings

FIG. 1 is a schematic diagram of a test cell for a photocatalytic reaction using an organic photocatalyst used in Examples 1 and 2.

FIG. 2 is a schematic diagram of a test cell for a photocatalytic reaction using the organic photocatalyst used in Comparative Example 1.

FIG. 3 is a graph showing the relationship between the reaction time (minutes) and the methylene blue concentration (μΜ) in the photocatalytic reactions of Examples 1 and 2 and Comparative Example 1.

FIG. 4 is a graph showing the relationship between the reaction time (minutes) and the methylene blue concentration (μΜ) in the photocatalytic reactions of Examples 3 and 4 and Comparative Examples 2 to 4. BEST MODE FOR CARRYING OUT THE INVENTION

[0094] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0095] ¾ Example ί (Activity of organic light touch in visible and light illumination)

(1) Organic photocatalyst materials include η-type semiconductors such as 3,4,9,10 perylenetetracarboxyl bisbenzimidazole (hereinafter referred to as “PV”) and p-type semiconductors containing metal-free lid mouth cyanine (hereinafter “ H Pc ”). In the present invention, each sublimation purification

2

What was done was used.

(2) The double layer film used as the organic photocatalytic element was produced by a vacuum deposition method. First, PV on the glass substrate with a thickness of 220 nm, then HPc with a thickness of 70 nm on the PV.

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7 wastes.

(3) Configuration of the experimental apparatus · The method was as follows. First, a test cell as shown in Fig. 1 was fabricated. As a cylindrical test rod, a multifoam made by Marumoto Struth Co., Ltd. (inner diameter: 40 mm, height: 30 mm (code: EFOPY, No: 40300046)) was used. A polypropylene sheet was laid on the glass plate, and the tile was used as the bottom of the cell. In order to seal between the cylindrical test cage and the polypropylene sheet, silicon grease (for high vacuum and chemical resistance) was applied to the contact area. (Reference: Photocatalyst Product Forum, wet decomposition performance test method for photocatalyst products (revised on May 28, 2004))

(4) Methylene blue trihydrate was a special grade reagent stipulated in JIS K 8897, and purified water conforming to the 14th Japanese Pharmacopoeia standard was used. A fresh aqueous methylene blue solution (10 μmol / 1) was prepared and adjusted to pH 10 using sodium hydroxide or potassium hydroxide. The double layer film prepared in (2) above was peeled off from the glass substrate using a methylene blue aqueous solution and allowed to stand on the top of the test tube. The effective area of the organic photocatalyst at this time was about 12.5 cm ² , and the test bowl was filled with 35 ml of methylene blue aqueous solution. The upper part of the cylindrical test cell was closed with a cut-off filter (L-42, manufactured by HOYA, 5 X 5 cm ² ).

(5) The organic photocatalytic reaction was carried out by irradiating visible light (wavelength: 400 to 750 nm) with an intensity of about 60 mW cm- ² for 3 hours using a halogen lamp (manufactured by Nihon PI Corporation) as a light source. At this time, the upper force of the test cell was also irradiated with light. When 180 minutes have passed since the start of the reaction, The visible absorption spectrum of one aqueous solution was measured, and the amount of decomposition was quantified. The visible absorption spectrum was measured using a MultiSpec-1500 manufactured by Shimadzu Corporation. The spectrophotometer measurement cell was made of rosin and had an optical path length of 10 mm, and had a light transmittance in the wavelength range of 600 to 700 nm. More than 80% was used.

(6) As a result of (5) above, a decrease in absorbance was observed as methylene blue decomposed. After 180 minutes, the concentration of the aqueous methylene blue solution decreased by about 0.5 mol / 1, confirming that about 5% decomposition of the initial concentration occurred. The results are shown in Figure 3.

[0096] Example 2 (Evaluation of the activity of organic photoerosion during visible irradiation)

(1) PV as an n-type semiconductor and iron phthalocyanine (hereinafter referred to as “FePc”) as a p-type semiconductor were used as organic photocatalyst materials. In the present invention, those purified by sublimation were used.

(2) The double layer film used as the organic photocatalytic element was produced by a vacuum deposition method. First, scrape PV on the glass substrate with a thickness of 130 nm, then scrape FePc on the PV with a thickness of 70 nm.

(3) Configuration of the experimental apparatus The method was the same as (3) to (5) in Example 1.

(4) As a result of the experiment, a decrease in absorbance was observed as methylene blue decomposed. After 180 minutes, the concentration of the aqueous methylene blue solution decreased by about 1.2 mol / 1, confirming that about 12% of the initial concentration had decomposed.

On the other hand, when an experiment was performed under the same conditions as in Example 1 except that no organic photocatalyst was used, the decomposition of methylene blue was confirmed even under light irradiation.

[0098] From the results of Examples 1 and 2, it was found that the decomposition reaction of methylene blue occurred using an organic photocatalyst that absorbs a wide range of visible light. The results are shown in Figure 3.

[0099] Comparative Example 1 (Evaluation of the activity of titanium oxide photoemission during visible irradiation)

(1) A methylene blue decomposition test was conducted by the method according to Examples 1 and 2 using an acid-titanium photocatalyst.

(2) A photocatalyst standard sample (50SQC, manufactured by Photocatalyst Laboratory Co., Ltd.) was used as an acid-titanium photocatalyst. This is a glass plate coated with a titanium oxide photocatalyst, with a titanium oxide thickness of μm and a glass plate size of 50 mm x 50 mm x (thickness) 1.8 mm. (3) Since titanium dioxide has the property of adsorbing methylene blue on its surface, the surface was saturated and adsorbed with methylene blue. The reagents and water used were the same as in Examples 1 and 2. Using a 20 mol / 1 methylene blue aqueous solution prepared to pHIO, adsorption was performed on the surface of titanium oxide in a test cell as shown in Fig. 2. After adsorption for 12 hours, remove the liquid

When the absorbance was measured, the concentration of the methylene blue aqueous solution was decreased, and therefore, adsorption was carried out using a 20 mol / 1 aqueous solution of methylene blue for another 12 hours. Since the concentration of the methylene blue aqueous solution at this time was 10 μmol / 1 or more, titanium oxide with saturated adsorption of methylene blue on the surface was used for the photocatalytic reaction.

(4) A photocatalytic reaction was performed using a test cell as shown in FIG. As a test rod, Marumoto Struas Multiform (inner diameter 40 mm, height 30 mm (code: EFOPY, No: 403000 46)) was used. The test cell was filled with a fresh aqueous methylene blue solution (10 μmol / U 35 ml) adjusted to pHIO.

(5) The photocatalytic reaction was performed by irradiating with a halogen lamp (manufactured by Nippon P-I Co., Ltd.) for 3 hours at a wavelength of about 60 mWcm " ² (wavelength: 400 to 750 nm). When the reaction was started 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, and 180 minutes after the start of the reaction, the visible absorption of the methylene blue solution was observed. The petrol was measured and the amount of decomposition was quantified, and the visible absorption spectrum measuring apparatus and measuring cell were the same as in Examples 1 and 2.

(6) As a result of the above (5), no progress of decomposition of methylene blue was observed.

[0100] Further, an experiment was conducted under the same conditions as in Example 1 except that no titanium oxide photocatalyst was used. As a result, decomposition of methylene blue was not confirmed even under irradiation with visible light.

[0101] From the results of Examples 1 and 2 and Comparative Example 1, it can be seen that the organic double layer film is a photocatalyst having a wide range of visible light responsiveness. It was confirmed that the photocatalyst was superior to tan. The results are shown in Figure 3.

[0102] Example 3 (Evaluation of activity of organic photoerosion during visible irradiation)

(1) As organic photocatalyst materials, n-type semiconductor 3,4,9,10 perylenetetracarboxyl bisbenzimidazole (PV) and p-type semiconductor metal-free phthalocyanine (HPc) Using. In the present invention, those purified by sublimation were used.

(2) The double layer film used as the organic photocatalytic element was produced by a vacuum deposition method. First, PV on the glass substrate with a thickness of 200 nm, then HPc on the PV with a thickness of 120 nm.

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7 wastes.

(3) Configuration of the experimental apparatus' method was performed as follows. First, a glass cell (1 cm × 1 cm × 5 cm) was filled with a predetermined concentration of methylene blue aqueous solution.

(4) Methylene blue trihydrate was a special grade reagent stipulated in JIS K 8897, and purified water conforming to the 14th Japanese Pharmacopoeia standard was used. A fresh methylene blue aqueous solution (10 μmol / 1) was prepared and adjusted to pHIO using sodium hydroxide. The photocatalyst carrying substrate produced in the above (2) was placed on the side surface of the cell so that the catalyst surface was inside. The area of the organic photocatalyst at this time was about 5 cm ² , and the test tube was filled with 5 ml of methylene blue aqueous solution. The upper part is open and in contact with the atmosphere. The bottom of the cell is stirred with a magnetic stirrer.

(5) The organic photocatalytic reaction was carried out by irradiating visible light (wavelength: 400 to 750 nm) for 3 hours using a halogen lamp (manufactured by Nihon PI Corp., 100 mWcm- ² ) as a light source. At this time, light was applied from the side of the test cell. Irradiation area is lcm ^2. During the reaction, white light of 1 / z Wcm- ² was irradiated from a right angle, and the visible absorption spectrum of the aqueous solution of methylene blue was measured, and the amount of decomposition was quantified. For measurement of the visible absorption spectrum, MPCD-7000 manufactured by Otsuka Electronics was used.

(6) As a result of (5) above, a significant decrease in absorbance was observed as methylene blue decomposed. The results are shown in Fig. 4.

Example 4 (Evaluation of activity of organic photoerosion during visible irradiation)

(1) PV as an n-type semiconductor and FePc as a p-type semiconductor were used as organic photocatalytic materials. In the present invention, those purified by sublimation were used.

(2) The double layer film used as the organic photocatalytic element was produced by a vacuum deposition method. First, PV was laminated on a glass substrate with a thickness of 200 nm, and then FePc was laminated on the PV with a thickness of 50 nm. For FePc, a method of casting from a solution was also employed.

(3) Configuration of the experimental apparatus The method was the same as in (3) to (5) of Example 3. (4) As a result of the experiment, a significant decrease in absorbance was observed as methylene blue decomposed. The results are shown in Fig. 4.

[0104] i: hfei row 2 (no blanking in Γ vision, illumination)

Visible light was irradiated in the same manner as in Example 3 except that no organic photocatalyst was used. As a result of experiments, it was found that the absorbance of methylene blue gradually decreased by light irradiation. The results are shown in Fig. 4. This is thought to be due to the reaction of methylene blue with dissolved oxygen and the like by light irradiation.

[0105] Comparative Example 3 (Blank test without corrosion and without light irradiation)

Example 3 was the same as Example 3 except that no organic photocatalyst was used and no light was irradiated (tested in a dark room). As a result of the experiment, the absorbance of methylene blue did not change at all, and decomposition did not occur. The results are shown in Fig. 4.

[0106] Comparative example 4 (Visible, light irradiation: PV activity review)

(1) Sublimation-purified PV alone was used as the organic photocatalytic material.

(2) As an organic photocatalyst element, PV was deposited on a glass substrate with a thickness of 200 ° C by vacuum deposition.

(3) Configuration of the experimental apparatus The method was the same as in (3) to (5) of Example 3.

(4) As a result of the experiment, the decomposition of methylene blue progressed, but the decrease in absorbance was equivalent to the blank test of Comparative Example 2, and it was found that the photocatalytic reaction hardly progressed with PV alone. The results are shown in Fig. 4.

Claims

The scope of the claims

[I] An organic photocatalyst comprising a p-type organic semiconductor and an n-type organic semiconductor, which is used for decomposing an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus under light irradiation.

[2] The organic photocatalyst according to claim 1, which has a two-layer structure in which a p-type organic semiconductor layer and an n-type organic semiconductor layer are laminated.

[3] The thickness of the p-type organic semiconductor layer is about 20 to 500 nm, and the thickness of the n-type organic semiconductor layer is 50

The organic photocatalyst according to claim 1, which is about -800 nm.

[4] The organic photocatalyst according to claim 1, wherein the organic photocatalyst has a three-layer structure including a co-deposited layer of a p-type organic semiconductor and an n-type organic semiconductor between the p-type organic semiconductor layer and the n-type organic semiconductor layer.

5. The organic photocatalyst according to claim 1, which has a two-layer structure in which a p-type organic semiconductor layer and an n-type organic semiconductor layer are laminated on a substrate.

6. The organic photocatalyst according to claim 1, wherein the organic photocatalyst has a three-layer structure including a co-deposition layer of a p-type organic semiconductor and an n-type organic semiconductor between the p-type organic semiconductor layer and the n-type organic semiconductor layer on the substrate. .

[7] The material of the p-type organic semiconductor is a macrocyclic ligand compound or a metal complex thereof.

1. The organic photocatalyst according to 1.

[8] The organic photocatalyst according to claim 7, wherein the material of the p-type organic semiconductor is at least one selected from the group force consisting of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative.

[9] The organic photocatalyst according to claim 8, wherein the material of the p-type organic semiconductor is a phthalocyanine derivative.

[10] The organic photocatalyst according to claim 1, wherein the material of the n-type organic semiconductor is a polycyclic aromatic compound.

[II] The material of the n-type organic semiconductor is at least one selected from the group consisting of fullerenes, carbon nanotubes, conductive polymers doped with electron donors, perylene derivatives, and naphthalene derivatives. The organic photocatalyst described.

12. The organic photocatalyst according to claim 11, wherein the material of the n-type organic semiconductor is at least one selected from the group consisting of fullerenes and perylene derivatives.

[13] A method for producing an organic photocatalyst according to claim 5, wherein an n-type organic semiconductor is formed on a substrate. A manufacturing method, wherein a layer and a P-type organic semiconductor layer are laminated to form a two-layer structure.

[14] A method for producing an organic photocatalyst according to claim 6, wherein an n-type (or p-type) organic semiconductor layer is formed on a substrate, and the n-type organic semiconductor and the p-type organic semiconductor are coexisted thereon. A manufacturing method comprising forming a co-evaporated layer by vapor deposition and forming a p-type (or n-type) organic semiconductor layer thereon to form a three-layer structure.

[15] A method for decomposing an organic substance or an inorganic substance containing nitrogen, sulfur or phosphorus in a gas phase or an aqueous phase, wherein the organic photocatalyst according to claim 1 is treated with an organic substance or nitrogen, sulfur or phosphorus under light irradiation. A method of decomposing by contacting with an inorganic substance.

[16] A coating composition comprising the organic photocatalyst according to claim 1 and a coating material.

[17] A method for treating water by dispersing the organic photocatalyst according to claim 1 in water to be treated containing an organic substance or an inorganic substance containing nitrogen, sulfur, or phosphorus, and irradiating it with light.

18. The water treatment method according to claim 17, further comprising collecting the organic photocatalyst by filtration after the treatment and subjecting it to water treatment again.