CN111097541A - Dye-sensitized black titanium dioxide and preparation method and application thereof - Google Patents
Dye-sensitized black titanium dioxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN111097541A CN111097541A CN201811250774.4A CN201811250774A CN111097541A CN 111097541 A CN111097541 A CN 111097541A CN 201811250774 A CN201811250774 A CN 201811250774A CN 111097541 A CN111097541 A CN 111097541A
- Authority
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- China
- Prior art keywords
- titanium dioxide
- black titanium
- dye
- sensitized
- bis
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 433
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 203
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 80
- 230000001699 photocatalysis Effects 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- -1 bis (isothiocyanato) (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) (4,4 '-dinonyl-2, 2' -bipyridyl) ruthenium Chemical compound 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
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- 229920001155 polypropylene Polymers 0.000 claims description 15
- 239000003504 photosensitizing agent Substances 0.000 claims description 14
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- 231100000719 pollutant Toxicity 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 claims description 11
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 claims description 8
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- 239000004952 Polyamide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- CRAXKQYYMORDPI-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium Chemical compound [Ru].OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 CRAXKQYYMORDPI-UHFFFAOYSA-N 0.000 claims description 3
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- 229960001483 eosin Drugs 0.000 claims 1
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- LULNJFDMQSRXHK-UHFFFAOYSA-L 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine ruthenium(2+) dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 LULNJFDMQSRXHK-UHFFFAOYSA-L 0.000 description 2
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J35/39—
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- B01J35/56—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to dye-sensitized black titanium dioxide and a preparation method and application thereof.
Description
Technical Field
The invention relates to a dye-sensitized black titanium dioxide with wide spectral response, and preparation and application thereof in photocatalytic degradation of water pollutants and purification of water.
Background
With the development of modern industry, the problems of large-scale use of fossil fuels, large-scale emission of industrial pollutants and increasingly serious environmental pollution are solved. The water body pollution and the air pollution seriously damage the health of people. Water body pollution can cause acute and chronic poisoning, induce cancer, and cause great harm to human social development and human healthy life.
In recent years, semiconductor catalysts are increasingly applied in the field of environmental pollution treatment, and titanium dioxide has the characteristics of chemical stability, abundant natural reserves, no toxicity, low cost, simple treatment, stable optical property and the like, so that a great deal of attention and research of scholars are drawn. As a typical semiconductor, the band gap is only 3.2eV, and the semiconductor can only absorb ultraviolet light with the wavelength of less than 390nm, so that a sample can only be excited by the ultraviolet light, and the ultraviolet light only accounts for 5% of the sunlight, thereby greatly limiting the wide commercial application of the semiconductor.
Black TiO developed in recent years2Due to the introduction of a large number of oxygen vacancies, Ti3+Or a surface amorphous layer, etc., exhibiting excellent light absorption properties and photocatalytic activity have attracted much attention. However, prior art black TiO2And based on black TiO2The doped and composite material can improve the photocatalytic activity to a certain extent, but the utilization of sunlight is still limited, and the absorption of the sunlight only accounts for 15% -40% of the full spectrum. In addition, although the absorption spectrum of the conventional dye-sensitized titanium dioxide (such as squarylium cyanine dye-sensitized titanium dioxide proposed by patent CN 102688782 a) can be expanded to visible light, the photocatalytic performance of the conventional dye-sensitized titanium dioxide is poor, and in an experiment for degrading methylene blue, the conventional dye-sensitized titanium dioxide only degrades 60% in 3 hours.
Disclosure of Invention
The invention aims to provide a dye-sensitized black titanium dioxide with wide spectral response, and preparation and application thereof in photocatalytic degradation of water pollutants and purification of water.
Here, in one aspect, the present invention provides a dye-sensitized black titanium dioxide including a black titanium dioxide and an organic complex having light-absorbing and light-emitting characteristics modified on a surface of the black titanium dioxide. With regard to "light-emitting characteristics," it is common that a dye molecule contains a chromophore, and such chromophore contains a conjugated structure, which absorbs light of certain wavelengths to cause energy level transition when the dye molecule is irradiated with light, and reflects the remaining light, which is the color of the dye seen by the naked eye; the action principle of the titanium dioxide pigment and the black titanium dioxide is as follows: after the dye molecules absorb visible light, electrons generated by excitation are quickly transferred to a conduction band of the black titanium, so that the formation of various free radicals such as hydroxyl free radicals, superoxide free radicals and the like is facilitated, and the degradation of pollutants is facilitated.
In one aspect, "black titanium dioxide" refers to TiO in which the outermost layer of titanium dioxide is partially deprived of oxygen to form a defect state (having oxygen vacancies)2-xDisordered structure, constituting a core-shell structure (TiO) with disorder outer layer and crystalline inner layer2@TiO2-x) For example, it may be a black titanium oxide having a core-shell structure in which an amorphous layer is wrapped with a crystalline layer (TiO2@ TiO) prepared by subjecting white titanium oxide to a surface reduction treatment2-x). The black titanium dioxide can greatly widen the light absorption range (visible light or even infrared light), greatly improve the light conversion efficiency and improve the oxidative degradation capability of pollutants, in other words, a large number of oxygen vacancies and Ti are introduced into the black titanium dioxide with the core-shell structure3+The Ti-OH, Ti-H and other groups or surface amorphous layers on the surface and inside of the sample have better photocatalytic performance, and the color of the sample is changed from white to gray or even black due to the structural change inside the sample or the existence of ion doping, element doping or oxygen vacancy, so that the absorption of the sample on visible light or even near infrared light is greatly promoted, and meanwhile, the band gap of the black titanium sample is reduced to 1.54eV due to the change of the internal structure, so that the sample has better photocatalytic activity; on the other hand, dye molecules have special optical characteristics and are modified on black titanium dioxide (TiO2@ TiO)2-x) On the surface, dye molecules are transited from a ground state to an excited state after being irradiated by sunlight, and in the process, the dye molecules inject electrons into a conduction band of black titanium oxide, so that the transfer and the excitation of the electrons can be rapidly realizedThe separation of the photo-generated electron/hole pair further expands the light absorption range, prolongs the carrier life and improves the effect of degrading pollutants by photocatalysis. The surface modification of the organic complex with the light-emitting characteristic can further improve the visible light response characteristic of the black titanium dioxide, and after the organic complex absorbs visible light, the organic complex excites the generated electrons to be rapidly transferred to a conduction band of the titanium dioxide, so that the transition and the separation of current carriers are realized, and free radicals are generated more rapidly and efficiently. The dye sensitization further widens the visible light absorption range of the black titanium dioxide, even expands the visible light absorption range to a near infrared region, greatly improves the light conversion efficiency and the photocatalytic performance, and the titanium dioxide only absorbs the light in an ultraviolet region: 300-380nm light, black titanium dioxide light absorption range: 300-780 (800); the light absorption range of the dye-sensitized black titanium dioxide is as follows: 300-1200.
Preferably, the mass ratio of the black titanium dioxide to the organic complex is (5-20): (1-4).
The black titanium dioxide may comprise an undoped type and/or a doped type, i.e. the black titanium dioxide may be undoped black titanium dioxide and/or doped black titanium dioxide. The doping element of the doped black titanium dioxide can be at least one of N, S, P, B, Fe, Co, Ni, Mn and Mo, and is preferably at least one of Fe, Co, N and B.
The organic complex can be at least one of EY, ARS, N719 and N3. The organic complex has excellent photoresponse characteristics, is excited after illumination, quickly transfers electrons to a conduction band of black titanium dioxide, widens the absorption spectrum, better inhibits the recombination of electrons and holes, prolongs the service life of photo-generated electron holes and improves the photocatalytic performance.
In another aspect, the present invention provides a method for producing any one of the dye-sensitized black titanium dioxide described above, comprising: preparing black titanium dioxide; and mixing the black titanium dioxide with a dye photosensitizer and a solvent, and modifying dye molecules on the surface of the black titanium dioxide by using a hydrothermal method to obtain the dye-sensitized black titanium dioxide.
According to the invention, byMixing the black titanium dioxide with a dye photosensitizer and a solvent, and preparing the dye-sensitized black titanium dioxide by a hydrothermal method. The dye-sensitized black titanium dioxide prepared by the method can widen the light absorption range and further ensure that TiO is coated with the dye-sensitized black titanium dioxide2The absorption spectrum extends into the visible region; on the other hand, the transfer of electrons and the separation of photogenerated electron/hole pairs can be rapidly realized, and the recombination of the photogenerated electron-hole pairs is inhibited. Due to the light absorption property of dye molecules, electrons generated by energy level transition after light absorption are rapidly transferred to a conduction band of the black titanium, namely, the transmission of the electrons is accelerated; in addition, the effect of the dye molecules may contribute to a narrowing of the band gap. In addition, the method has low production cost and good photocatalytic effect, and can realize large-scale production.
The dye photosensitizer may be at least one of bis-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxy) ruthenium (i.e., N719 dye), sodium 1, 2-dihydroxyanthraquinone-3-sulfonate (i.e., alizarin + S; ARS), tetrabromorescin (i.e., dye eosin; EY), bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) ruthenium (i.e., N3 dye), bis (isothiocyanato) (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) (4,4 '-dinonyl-2, 2' -bipyridyl) ruthenium (i.e., Z907 dye). The advantages of using dye molecules as above: 1. the dye molecules selected have strong light absorption and luminescence characteristics; 2. the preparation method is simple and the cost is low; 3. dye molecules are bonded on the surface of the black titanium dioxide through covalent bonds to form a very stable complex; 4. relatively speaking, the stability and the cyclicity are better.
The mass ratio of the black titanium dioxide, the dye photosensitizer and the solvent can be (5-20): (1-4): (30-120).
The solvent may be at least one of water, ethanol, Dimethylformamide (DMF), N-methylpyrrolidone (NMP).
The reaction temperature of the hydrothermal method can be 100-220 ℃, preferably 120-180 ℃, and the time can be 1-8 hours.
The preparation method of the black titanium dioxide can be prepared by a contact type reduction method or a dual-temperature-zone aluminum/magnesium reduction method.
By contact reductionPreparing the black titanium dioxide may include: heating the reducing agent (Mg, Al, CaH) under a certain vacuum degree (5-30Pa)2，NaBH4At least one of the above-mentioned components) and the precursor (white titanium dioxide or white titanium dioxide and doping source) to a specified temperature (400-.
The preparation of black titanium dioxide by a dual temperature zone aluminum/magnesium reduction process may include: placing a precursor (white titanium dioxide or white titanium dioxide and a doping source) and a high-activity metal in a closed system with negative pressure at a certain distance, respectively heating the precursor and the high-activity metal (aluminum and magnesium) to different temperatures for heat treatment for a specified time, so that the oxygen partial pressure in the closed system is lower than the equilibrium oxygen partial pressure of the precursor, and the precursor titanium dioxide can be reduced to black titanium dioxide; wherein, the high-activity metal is heated to a first temperature (the temperature of a high-temperature region: 700-.
In another aspect, the present invention further provides a photocatalytic material, including a mesh substrate and any one of the dye-sensitized black titanium dioxide described above supported on the mesh substrate.
The mesh substrate can be a high-molecular fabric, an inorganic porous material, a metal mesh or carbon fiber cloth.
The polymer fabric can be selected from polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride and polyamide net. The inorganic porous material can be selected from one of alumina, silicon oxide and silicon carbide ceramics.
The preparation method of the photocatalytic material may include: mixing any one of the dye-sensitized black titanium dioxide with a solvent for dispersion and a binder to obtain a dispersion liquid; the dispersion was coated on a mesh substrate.
The solvent for dispersion can be one or a mixture of several of absolute ethyl alcohol, acrylic acid, NMP and deionized water.
The binder can be one or a mixture of more of water-soluble phenolic resin, phenolic resin/polyacrylamide, polyacrylic acid/potassium persulfate (ammonium persulfate), CMC and the like. The adhesive may be a curing agent (i.e., the curing agent may be used as the adhesive), and the curing agent may be, for example, a polyamide resin, an alkyd resin, a water-soluble epoxy resin, or the like.
The proportion of the dye-sensitized black titanium dioxide to the dispersing solvent and the binder can be (3-8): (100-400): (1-4). The coating method may be a dipping method, a spraying method, or the like.
In another aspect, the invention further provides an application of any one of the dye-sensitized black titanium dioxide in photocatalytic degradation of water pollutants and purification of water body, especially in degradation of organic pollutants. The technology has simple implementation process, and the prepared photocatalysis net has very high photocatalysis activity, can effectively reduce pollutants in water and promote TP, TN, COD and NH in black and odorous water3The indexes such as-N and the like are greatly reduced. And the production cost is low, the photocatalysis effect is good, and large-scale production can be realized.
In still another aspect, the present invention also provides a method for producing any one of the dye-sensitized black titanium dioxide described above, comprising: preparing black titanium dioxide; and modifying dye molecules on the surface of the black titanium dioxide by using a sol-gel method (a hydrothermal method can also be used) to obtain the dye-sensitized black titanium dioxide.
The invention has the beneficial effects that:
according to the invention, the light absorption range can be widened, and TiO can be further enabled2The absorption spectrum is expanded to a visible light region, and meanwhile, the transfer of electrons and the separation of photo-generated electron/hole pairs can be rapidly realized, and the recombination of the photo-generated electron-hole pairs is inhibited.
Drawings
FIG. 1 shows a transmission electron micrograph of the nano-black titanium dioxide in example 1;
FIG. 2 is an electron micrograph of the dye-sensitized black titanium dioxide in example 1;
FIG. 3 shows a comparison of the absorption spectra of white titanium dioxide P25, black titanium dioxide and the dye-sensitized black titanium dioxide of example 1 (the photoresponse range of the sample after the reduction treatment is greatly broadened in the figure);
fig. 4 shows a schematic representation of the photocatalytic network prepared in example 1.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the description of the figures and the following embodiments are only illustrative of the present invention and are not limiting.
The invention relates to a dye-sensitized black titanium dioxide with wide spectral response, and preparation and application thereof in photocatalytic degradation of water pollutants and purification of water. The prepared black titanium dioxide is mixed with a dye photosensitizer and a solvent, and the dye-sensitized black titanium dioxide is prepared by a hydrothermal method or a sol-gel method. The invention utilizes the luminescence characteristic of dye molecules to modify the surface of black titanium dioxide (TiO2@ TiO2-x) with a core-shell structure, can obviously improve the visible light absorption performance of the material, and after the dye molecules absorb light, electrons generated by excitation are rapidly transferred to a conduction band of the black titanium oxide to generate H2O2Effectively degrading organic pollutant pollutants, and obviously improving the photocatalytic performance of the material. In a test of degrading methyl orange, the system only needs 3-6min to degrade about 97% of methyl orange. In an experiment for degrading urban black and odorous water, the system also shows excellent performance, and after one month of illumination, various indexes (TN, TP and NH) of the water body3N, COD) is greatly reduced from the original inferior five types and reaches the five types of water standards specified by the state. The technology has low cost and good product recycling performance, and can be widely applied to the fields of pollutant degradation, water body purification, ecological restoration, air purification and the like.
Hereinafter, the dye-sensitized black titanium oxide according to the present invention, and the preparation method and application thereof are exemplified.
(dye-sensitized type Black titanium dioxide)
The dye-sensitized black titanium dioxide according to an embodiment of the present invention includes black titanium dioxide and an organic complex having a light-emitting property, which is modified on a surface of the black titanium dioxide.
The black titanium dioxide may comprise an undoped type and/or a doped type, i.e. the black titanium dioxide may be undoped black titanium dioxide and/or doped black titanium dioxide. The doping element of the doped black titanium dioxide can be at least one of N, S, P, B, Fe, Co, Ni, Mn and Mo, and is preferably at least one of Fe, Co, N and B. The doping amount of the element may be, for example, 0.5 to 7 at%. In the doped black titanium dioxide, the metal elements have the advantages of doping: the lowest energy level of the titanium dioxide conduction band is determined by the d-orbit of the Ti element, and the Ti element in the titanium dioxide crystal lattice is partially isomorphously substituted by using other 3d transition metal elements, so that the d-orbit with the next lower energy level can be introduced, and the conduction band energy level of the titanium dioxide material is changed, so that the absorption of the titanium dioxide material on visible light is enhanced, the recombination of photo-generated charges is reduced, the transmission is accelerated, the surface defects are increased, the surface adsorption is enhanced, the particle size is reduced, and the photocatalysis effect is obviously improved; the doping of the nonmetal elements can not only change the electronic structure of the sample and the chemical state of the elements, but also obviously change the appearance, the structure, the crystal phase and the surface properties of the sample.
The black titanium dioxide can be nanoparticles, and the particle size of the black titanium dioxide can be 15-25 nm. Under the particle size, the material shows better surface effect, volume effect, quantum size effect, macroscopic quantum tunneling effect and the like, and is beneficial to separation of photo-generated electrons and holes.
The black titanium dioxide preferably has a core-shell structure, i.e. in the form of titanium dioxide (TiO)2) TiO in defect state (containing oxygen vacancies) as nuclei2-x(TiO2-x0 < x < 1) is a shell which can be expressed as TiO2@TiO2-x. The particle size of the titanium dioxide core can be 20-25 nm. The thickness of the titanium suboxide shell can be 1-5 nm.
The organic complex may be at least one of EY, ARS, N719 and N3. The organic complex has excellent photoresponse characteristics, is excited after illumination, quickly transfers electrons to a conduction band of black titanium dioxide, widens the absorption spectrum, better inhibits the recombination of electrons and holes, prolongs the service life of photo-generated electron holes and improves the photocatalytic performance. The following formula (1) represents N719:
the mass ratio of the black titanium dioxide to the organic complex can be (5-20): (1-4), preferably (15-20): (1-3). The mass ratio of the black titanium dioxide to the organic complex is (5-20): (1-4), the catalyst has wide spectrum absorption on sunlight, stable combination of black titanium dioxide and an organic complex, and good photocatalytic performance.
The organic complex is modified on the surface of the black titanium dioxide in a covalent bond mode. In one aspect, black titanium dioxide (TiO2@ TiO)2-x) The light absorption range (visible light or even infrared light) is greatly widened, the light conversion efficiency is greatly improved, and the oxidative degradation capability of pollutants is improved; on the other hand, dye molecules have special optical characteristics and are modified on black titanium dioxide (TiO2@ TiO)2-x) On the surface, dye molecules are transited from a ground state to an excited state after being irradiated by sunlight, and in the process, the dye molecules inject electrons into a conduction band of black titanium oxide, so that the transfer of electrons and the separation of photo-generated electron/hole pairs can be quickly realized, the light absorption range is further expanded, the service life of carriers is prolonged, and the effect of degrading pollutants by photocatalysis is improved.
(preparation of dye-sensitized Black titanium dioxide)
First, black titanium dioxide was prepared. The black titanium dioxide can be prepared by a contact reduction method or a dual-temperature-zone aluminum/magnesium reduction method.
The preparation of black titanium dioxide by adopting a contact reduction method comprises the following steps: under the vacuum condition, the mixture of the reducing agent and the precursor (white titanium dioxide or white titanium dioxide and the doping source) is heated to a specified temperature and kept for a specified time. The reducing agent can be calcium hydride, sodium borohydride, hydrazine hydrate, metal magnesium, metal zinc, metal aluminum powder and the like. The reaction vacuum degree can be controlled below 100Pa (preferably 5-30Pa), the reaction temperature is 200-600 DEG, and the reaction temperature isThe reaction time can be 1-5 h. The doping source may be thiourea, NH4OH、NH4Cl, phosphoric acid, H2S、Fe2O3Nickel nitrate, copper sulfate, tungsten oxide, cerium oxide, niobium oxide, and the like. The doping element can also be doped by a gas phase method during the heat treatment.
The preparation of black titanium dioxide by a dual temperature zone aluminum/magnesium reduction process may include: placing a precursor (white titanium dioxide or white titanium dioxide and a doping source) and a high-activity metal in a closed system with negative pressure at a certain distance, respectively heating the precursor and the high-activity metal to different temperatures for heat treatment for a specified time, so that the oxygen partial pressure in the closed system is lower than the equilibrium oxygen partial pressure of the precursor, and the precursor titanium dioxide can be reduced into black titanium dioxide; wherein the high-activity metal is heated to a first temperature (high temperature zone temperature), the precursor is heated to a second temperature (low temperature zone temperature) lower than the first temperature, and the heated high-activity metal reacts with the medium oxygen of the closed system to reduce the oxygen partial pressure of the closed system so that the oxygen partial pressure of the closed system is lower than the equilibrium oxygen partial pressure of the precursor. The temperature of the high temperature zone can be controlled at 700-900 ℃, and the temperature of the low temperature zone can be controlled at 400-600 ℃. The reaction time can be 1-6 h. The doping source may be thiourea, NH4OH、NH4Cl, phosphoric acid, H2S、Fe2O3Nickel nitrate, copper sulfate, tungsten oxide, cerium oxide, niobium oxide, and the like. The doping element can also be doped by a gas phase method during the heat treatment. The apparatus may use a dual temperature zone tube furnace. The gas pressure in the reaction furnace can be set to 5 to 30 Pa.
Next, black titanium dioxide is mixed with a dye photosensitizing agent, a first solvent to obtain a mixture. The order of mixing is not particularly limited, and the black titanium dioxide dispersion liquid may be added to the dye photosensitizer dispersion liquid, or the black titanium dioxide and the dye photosensitizer may be dispersed in the first solvent. The dye photosensitizer may be at least one of bis-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxy) ruthenium (i.e., N719 dye), sodium 1, 2-dihydroxyanthraquinone-3-sulfonate (i.e., alizarin + S; ARS), tetrabromorescin (i.e., dye eosin; EY), bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) ruthenium (i.e., N3 dye), bis (isothiocyanato) (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) (4,4 '-dinonyl-2, 2' -bipyridyl) ruthenium (i.e., Z907 dye).
The first solvent may be at least one of water, ethanol, dimethylformamide, and N-methylpyrrolidone. The mass ratio of the black titanium dioxide to the dye photosensitizer can be (5-20): (1-4). The mass ratio of the black titanium dioxide to the first solvent can be (5-20): (100-400).
Then, the mixture is reacted at a certain temperature for a certain period of time. Modifying dye molecules on the surface of the black titanium dioxide by a hydrothermal method. The hydrothermal temperature can be 100-220 ℃, preferably 120-180 ℃, and the hydrothermal time can be 1-8 h. When the hydrothermal temperature is 100-220 ℃, the groups in the dye molecules are more likely to react with the black titanium dioxide to form bonds. The product may be further dried.
Thus, the organic complex with the luminescent characteristic is modified on the nano black titanium dioxide (TiO)2@TiO2-x) Or element-doped black titanium dioxide (TiO)2@TiO2-x) Constructing dye-sensitized black titanium dioxide on the surface. The method can remarkably improve the visible light response characteristic of black titanium dioxide, and the organic complex excites generated electrons to be quickly transferred to a conduction band of the titanium dioxide after absorbing visible light, so that H is generated2O2And degrading organic pollutants. The oxygen content of the water body is improved, and the material can be used in the fields of water body purification, ecological restoration, air purification and the like.
Here, an example of the preparation of the dye-sensitized black titanium oxide by the hydrothermal method is given, but the dye-sensitized black titanium oxide can also be prepared by the sol-gel method. Specifically, the preparation of the dye-sensitized black titanium dioxide by the sol-gel method may include: preparing black titanium dioxide; and uniformly dispersing the black titanium dioxide in a certain amount of alcohol in a certain amount of solvent, then adding a certain amount of dye molecules into the dispersion system, carrying out ultrasonic treatment for a period of time, stirring for a period of time, and evaporating the solvent to obtain the dye-sensitized black titanium dioxide. The mass ratio of the black titanium dioxide to the dye photosensitizer can be (5-20): (1-4). The mass ratio of the black titanium dioxide to the solvent can be (5-20): (100-400). The ultrasonic power is 100w, the time is 0.5-2h, and the temperature of the evidence-developing solvent is 90 ℃.
(photocatalytic Material based on dye-sensitized Black titanium dioxide)
The photocatalytic material comprises a mesh substrate and any one of the dye-sensitized black titanium dioxide supported on the mesh substrate.
The mesh substrate can be a high-molecular fabric, an inorganic porous material, a metal mesh or carbon fiber cloth. The high polymer fabric can adopt polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyamide net and the like. The inorganic porous material can adopt alumina, silicon oxide, silicon carbide ceramics and the like. The mass ratio of the dye-sensitized black titanium dioxide to the mesh substrate can be (1-3): (10-25).
(preparation of photocatalytic Material)
First, any of the dye-sensitized black titanium dioxides described above is mixed with a second solvent (i.e., a dispersing solvent) and a binder to obtain a dispersion liquid. The order of mixing is not particularly limited, and the binder may be added to the dye-sensitized black titanium dioxide dispersion liquid, or the dye-sensitized black titanium dioxide and the binder may be dispersed in the second solvent. The second solvent can be one or a mixture of several of absolute ethyl alcohol, acrylic acid, NMP and deionized water. The dye-sensitized black titanium dioxide can be ground and crushed to a certain size, such as 10-50nm, before mixing, so that the powder can be more fully and uniformly dispersed in a solvent and can better contact with dye molecules for reaction.
The binder can be one or a mixture of more of water-soluble phenolic resin, phenolic resin/polyacrylamide, polyacrylic acid/potassium persulfate (ammonium persulfate), CMC and the like. The binder may be a curing agent such as polyamide resin, alkyd resin, or water-soluble epoxy resin. The mass ratio of the dye-sensitized black titanium dioxide to the dispersing solvent to the binder can be (0.5-3): (10-20): (0.25 to 1). Stirring may be carried out for 0.5-2h after mixing. In addition, under the condition of not influencing the characteristics of the photocatalytic material, the emulsifier can also be properly added, for example, a proper amount of span-80, tween-80, P123 and the like can be added, so that the full and uniform mixing of the dye-sensitized black titanium dioxide and the binder can be better promoted.
Then, the dispersion is coated on a mesh substrate to construct a photocatalytic network. The coating method may be a dipping method, a spraying method, or the like. In one example, dip coating may include: mixing dye-sensitized black titanium dioxide, a dispersing solvent and a binder according to the ratio of (0.5-3): (10-20): (0.25-1), stirring for 30-60min to fully and uniformly mix all the components, then dipping the substrate material (preferably a high polymer substrate) in the solution, and drying at 90-120 ℃ to obtain the photocatalytic network. The photocatalytic network is a full-spectrum absorption photocatalytic network, and can rapidly degrade pollutants under the irradiation of sunlight to achieve the effect of purifying water quality.
The black titanium dioxide (doped black titanium dioxide) with the core-shell structure has good photocatalytic performance, the dye molecules have special photoresponse characteristics, the black titanium dioxide surface is modified by a certain means, electrons are rapidly transferred from the dye molecules to the black titanium dioxide conduction band after illumination, transition and separation of carriers are realized, and free radicals are generated more rapidly and efficiently. The dye sensitization further widens the visible light absorption range of the black titanium dioxide, even extends to the near infrared region. The light conversion efficiency and the photocatalytic performance are greatly improved. Any one of the dye-sensitized black titanium dioxide can be used for photocatalytic degradation of water pollutants and purification of water body, especially degradation of organic pollutants. The technology has simple implementation process, and the prepared photocatalysis net has very high photocatalysis activity, can effectively reduce pollutants in water and promote TP, TN, COD and NH in black and odorous water3The indexes such as-N and the like are greatly reduced. And the production cost is low, the photocatalysis effect is good, and large-scale production can be realized.
The invention has the advantages that:
according to the invention, after light absorption, dye molecules are excited to rapidly transfer electrons to the conduction band of black titanium dioxide, so that rapid transfer of photo-generated electrons is realized, the light absorption capacity of the material is greatly expanded, the electron-hole recombination can be better inhibited, the service life of the photo-generated electron holes is prolonged, and the photocatalysis performance is improved. The photochemical reaction is used for degrading pollutants in water, so that decomposition of toxic and harmful substances in water can be realized, odor of water can be eliminated, the dissolved oxygen amount of the water is obviously improved, and the photochemical reaction can be widely applied to the fields of water purification, ecological restoration, air purification and the like. According to the dye-sensitized black titanium dioxide, the absorption of sunlight can reach 80-90%, and more than 90% of the dye-sensitized black titanium dioxide can be degraded in 6 minutes in experiments for degrading methyl orange and methylene blue.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly, black titanium dioxide is prepared by a contact Mg reduction method, which comprises the following steps: the metallic magnesium and the P25 are fully mixed (dry mixed) according to the proportion of 10:1, then the mixture is put into a vacuum furnace (5-30Pa), reacts for 2 hours at 500 ℃, and is cooled to room temperature, and then the metallic magnesium and the oxide thereof are washed away by sulfuric acid, thus obtaining the black titanium dioxide sample. Dispersing 10g of black titanium dioxide prepared by a contact Mg reduction method in a certain amount of water, dissolving 2g N719 (namely di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridine-4, 4' -dicarboxyl) ruthenium (purchased from Shanghai Baishun Biotech Co., Ltd.) in a certain amount of ethanol, adding the mixture into the system, placing the mixed solution in a reaction kettle, reacting at 120 ℃ for 6h, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of water-soluble polyamide and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net.
Example 2
Firstly, dispersing 10g of black titanium dioxide prepared by the contact Mg reduction method in a certain amount of water, dissolving N719, namely di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxyl) ruthenium in a certain amount of ethanol according to the proportion of 3:1, adding the mixture into the system, placing the mixed solution in a reaction kettle, reacting for 6 hours at 120 ℃, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. The net degrades about 92% in 9min and degrades 90% in 8min in a methyl orange degradation experiment.
Example 3
Firstly, dispersing 10g of black titanium dioxide prepared by the contact Mg reduction method in a certain amount of water, dissolving N719, namely di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxyl) ruthenium in a certain amount of ethanol according to the proportion of 1:1, adding the mixture into the system, placing the mixed solution in a reaction kettle, reacting for 6 hours at 120 ℃, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. The net degrades by about 94% in 15min and 92% in 10min in a methyl orange degradation experiment.
Example 4
First, by contact CaH2The black titanium dioxide is prepared by a reduction method, which comprises the following steps: CaH2Mixing with P25 at ratio of 5:1 thoroughly (dry mixing), placing the mixture in vacuum furnace (5-30Pa), reacting at 500 deg.C for 2 hr, cooling to room temperature, washing with hydrochloric acid to remove unreacted CaH2And byproducts, namely a black titanium dioxide sample can be obtained. Will contact CaH2Dispersing 10g of black titanium dioxide prepared by a reduction method in a certain amount of water, and adding alizarin according to a ratio of 5:1+ S (ARS) (Beijing Orchidaceae Biotechnology development Co., Ltd.) dissolved in a certain amount of ethanol, adding the above system, placing the mixed solution in a reaction kettle, reacting at 140 ℃ for 6h, and cooling to dry to obtain the powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of water-soluble phenolic resin is added at the same time, and the sample is loaded on a polypropylene net through an impregnation method to construct a full-spectrum absorption photocatalysis net. In an experiment for degrading methyl orange, the degradation rate of the net is about 93% in 9min, and in an experiment for degrading methylene blue, the degradation rate is 94% in 8 min.
Example 5
Firstly, the above-mentioned contact CaH is put into contact with210g of black titanium dioxide prepared by a reduction method is dispersed in a certain amount of water, alizarin + S (ARS) is dissolved in a certain amount of ethanol according to the proportion of 3:1 and then added into the system, the mixed solution is placed into a reaction kettle, the reaction is carried out for 6h at the temperature of 140 ℃, and the powdery dye-sensitized black titanium dioxide is obtained after cold drying. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of water-soluble phenolic resin is added at the same time, and the sample is loaded on a polypropylene net through an impregnation method to construct a full-spectrum absorption photocatalysis net. The net degrades about 92% in 12min and degrades 94% in 8min in a methyl orange degradation experiment.
Example 6
Firstly, the above-mentioned contact CaH is put into contact with210g of black titanium dioxide prepared by a reduction method is dispersed in a certain amount of water, alizarin + S (ARS) is dissolved in a certain amount of ethanol according to the proportion of 1:1 and then added into the system, the mixed solution is placed into a reaction kettle, the reaction is carried out for 6h at the temperature of 140 ℃, and the powdery dye-sensitized black titanium dioxide is obtained after cold drying. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of water-soluble phenolic resin is added at the same time, and the sample is loaded on a polypropylene net through an impregnation method to construct a full-spectrum absorption photocatalysis net. In an experiment for degrading methyl orange, the degradation rate of the net is about 94% in 15min, and in an experiment for degrading methylene blue, the degradation rate is 95% in 6 min.
Example 7
Firstly, preparing cobalt-doped black titanium dioxide by a dual-temperature-zone aluminum reduction method, which comprises the following steps: soaking 15g P25 in 50ml of cobalt chloride aqueous solution with the concentration of 5mg/ml, heating while stirring (70 ℃) to evaporate water to obtain P25 loaded with cobalt chloride, then placing P25 in a low-temperature area (500 ℃) of a double-temperature-area tube furnace, placing metal aluminum powder in a high-temperature area (800 ℃) of the double-temperature-area tube furnace, preserving heat for two hours, and cooling to room temperature to obtain cobalt-doped black titanium dioxide. Dispersing 10g of cobalt-doped black titanium dioxide prepared by a double-temperature-zone aluminum reduction method in a certain amount of water, dissolving N719, namely di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxyl) ruthenium in a certain amount of ethanol according to a ratio of 5:1, adding the above system, placing the mixed solution in a reaction kettle, reacting for 6 hours at 120 ℃, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. In an experiment for degrading methyl orange, the degradation rate of the net is about 93% in 6min, and in an experiment for degrading methylene blue, the degradation rate is 94% in 4 min.
Example 8
Firstly, preparing nickel-doped black titanium dioxide by a dual-temperature-zone aluminum reduction method, which comprises the following steps: soaking 15g P25 in 50ml of nickel nitrate aqueous solution with the concentration of 4mg/ml, heating while stirring (70 ℃) to evaporate water to obtain P25 loaded with nickel nitrate, then placing P25 in a low-temperature area (500 ℃) of a double-temperature-area tube furnace, placing metal aluminum powder in a high-temperature area (800 ℃) of the double-temperature-area tube furnace, preserving heat for two hours, and cooling to room temperature to obtain the nickel-doped black titanium dioxide. Dispersing 10g of nickel-doped black titanium dioxide prepared by a contact aluminum reduction method in a certain amount of water, dissolving N719, namely di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxyl) ruthenium in a certain amount of ethanol according to a ratio of 5:1, adding the above system, placing the mixed solution in a reaction kettle, reacting at 120 ℃ for 6h, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. In an experiment for degrading methyl orange, the net degrades by about 94% in 9min, and degrades by 94% in 6 min.
Example 9
Firstly, preparing Fe-doped black titanium dioxide by a dual-temperature-zone aluminum reduction method, which comprises the following steps: soaking 15g P25 in 50ml of 2mg/ml aqueous solution, slowly adding 2.5ml of 1M sodium hydroxide solution into the aqueous solution under stirring, evaporating water to obtain Fe (OH) -loaded substance3And then placing the P25 in a low-temperature area (500 ℃) of a double-temperature-area tube furnace, placing the metal aluminum powder in a high-temperature area (800 ℃) of the double-temperature-area tube furnace, preserving the heat for two hours, and cooling to room temperature to obtain the doped black titanium dioxide. Dispersing 10g of prepared Fe-doped black titanium dioxide into a certain amount of water, dissolving N3 (purchased from Shanghai Yaji Biotech Co., Ltd.) into a certain amount of ethanol according to a ratio of 5:1, adding the mixture into the system, placing the mixed solution into a reaction kettle, reacting for 6h at 120 ℃, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. The net degrades about 93% in 12min in a methyl orange degradation experiment, and degrades 91% in 10min in a methylene blue degradation experiment.
Example 10
Firstly, preparing black titanium dioxide by a two-temperature-zone aluminum reduction method, which comprises the following steps: placing 15g P25 in the low temperature zone (500 ℃) of a double-temperature zone tube furnace, placing 10g of metal aluminum powder in the high temperature zone (800 ℃) of the double-temperature zone tube furnace, preserving the heat for two hours, and cooling to the room temperature to obtain the cobalt-doped black titanium dioxide. Dispersing 10g of black titanium dioxide prepared by a double-temperature-zone aluminum reduction method in a certain amount of water, dissolving N719 in a certain amount of ethanol according to a ratio of 5:1, adding the mixture into the system, placing the mixed solution in a reaction kettle, reacting at 120 ℃ for 6 hours, and cooling to dry to obtain powdery dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. In an experiment for degrading methyl orange, the degradation rate of the net is about 94% in 15min, and in an experiment for degrading methylene blue, the degradation rate is 91% in 12 min.
FIG. 1 shows a transmission electron micrograph of the nano-black titanium dioxide in example 1. As can be seen from FIG. 1, the black titanium dioxide has a core-shell structure, and an outer layer of vacancies (disordered structure) wraps an inner ordered structure. FIG. 2 is an electron micrograph of the dye-sensitized black titanium dioxide in example 1. As can be seen from fig. 2, the dye-sensitized black titanium oxide has a thicker surface amorphous layer. Fig. 3 shows the comparison of the absorption spectra of P25, black titania and the dye-sensitized black titania prepared in example 1, and it can be seen from the comparison that the black titania after the reduction treatment of P25 has a wider photoresponse range, and the spectrum absorption after the dye-sensitized treatment has been further widened. Fig. 4 shows a schematic representation of the photocatalytic network prepared in example 1. As can be seen from figure 4, the prepared dye-sensitized black titanium dioxide can be uniformly loaded on a polymer net, in an experiment for degrading methyl orange, the net can degrade 94% of methyl orange in 3min, and in an experiment for degrading polluted river water, the indexes of the river water are rapidly reduced after sufficient sunlight irradiation for ten days, the COD is reduced by about 70%, the ammonia nitrogen is reduced by 56%, and the total nitrogen is reduced by 63%.
Example 11
The preparation of the dye-sensitized black titanium dioxide by the sol-gel method may include: preparing black titanium dioxide by using a contact Mg reduction method, then uniformly dispersing 10g of black titanium dioxide in 200ml of NMP, then adding 1g of dye molecules into the dispersion system, carrying out ultrasonic treatment for 30min, and evaporating the solvent (80 ℃) while stirring to obtain the dye-sensitized black titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net.
Comparative example 1
Dispersing 10g P25 in a certain amount of water, dissolving N719 in a certain amount of ethanol according to a ratio of 5:1, adding the mixture into the system, placing the mixed solution into a reaction kettle, reacting at 120 ℃ for 6 hours, and cooling to dry to obtain powdery dye-sensitized titanium dioxide. Then 10g of the sample is taken to be dispersed in 200ml of ethanol solution, 2g of curing agent and 2g of span-80 are added at the same time, the mixture is stirred for 1 hour, and the mixture is loaded on a polypropylene net through an impregnation method to construct a full spectrum absorption photocatalysis net. The net degrades by about 91% in 30min in a methyl orange degradation experiment, and degrades by 90% in 24min in a methylene blue degradation experiment (the test time is 30min, and the performance parameter given by each sample is how long the degradation reaches more than 90% of the initial value).
Claims (12)
1. The dye-sensitized black titanium dioxide is characterized by comprising black titanium dioxide and an organic complex which is modified on the surface of the black titanium dioxide and has a light-emitting characteristic.
2. The dye-sensitized black titanium dioxide according to claim 1, wherein the mass ratio of the black titanium dioxide to the organic complex is (5-20): (1-4).
3. The dye-sensitized black titanium dioxide according to claim 1 or 2, characterized in that said black titanium dioxide comprises an undoped type and/or a doped type.
4. The dye-sensitized black titanium dioxide according to claim 1 or 2, wherein said organic complex is at least one of EY, ARS, N719, N3.
5. A method for producing the dye-sensitized black titanium dioxide according to any one of claims 1 to 4, comprising: preparing black titanium dioxide; and mixing the black titanium dioxide with a dye photosensitizer and a solvent, and modifying dye molecules on the surface of the black titanium dioxide by using a hydrothermal method to obtain the dye-sensitized black titanium dioxide.
6. The method according to claim 5, wherein the dye photosensitizer is at least one of bis-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxyl) ruthenium, sodium 1, 2-dihydroxyanthraquinone-3-sulfonate, tetrabromofluorescein, bis (isothiocyanato) bis (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) ruthenium, and bis (isothiocyanato) (2,2 '-bipyridyl-4, 4' -dicarboxylic acid) (4,4 '-dinonyl-2, 2' -bipyridyl) ruthenium.
7. The preparation method according to claim 5 or 6, wherein the mass ratio of the black titanium dioxide, the dye photosensitizer and the solvent is (5-20): (1-4): (30-120), wherein the solvent is at least one of water, ethanol, dimethylformamide and N-methylpyrrolidone.
8. The method according to any one of claims 5 to 7, wherein the reaction temperature of the hydrothermal method is 100 to 220 ℃ for 1 to 8 hours.
9. A photocatalytic material, characterized by comprising a mesh substrate and the dye-sensitized black titanium dioxide according to any one of claims 1 to 4 supported on the mesh substrate.
10. The photocatalytic material according to claim 9, wherein the mesh substrate is a polymer fabric, an inorganic porous material, a metal mesh or a carbon fiber cloth, preferably, the polymer fabric is selected from one of polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride and polyamide mesh, preferably, the inorganic porous material is selected from one of alumina, silica and silicon carbide ceramic.
11. Use of the dye-sensitized black titanium dioxide according to any one of claims 1 to 4 for photocatalytic degradation of water body pollutants.
12. A method for producing the dye-sensitized black titanium dioxide according to any one of claims 1 to 4, comprising: preparing black titanium dioxide; and modifying dye molecules on the surface of the black titanium dioxide by using a sol-gel method to obtain the dye-sensitized black titanium dioxide.
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