CN110681405A - N, B codoped In responding to visible light2O3/TiO2Precursor, preparation method and application thereof - Google Patents

N, B codoped In responding to visible light2O3/TiO2Precursor, preparation method and application thereof Download PDF

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CN110681405A
CN110681405A CN201910037039.3A CN201910037039A CN110681405A CN 110681405 A CN110681405 A CN 110681405A CN 201910037039 A CN201910037039 A CN 201910037039A CN 110681405 A CN110681405 A CN 110681405A
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tio
precursor
catalyst
codoped
titanate
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CN110681405B (en
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于晗
叶丽
韩伟健
陈凤华
赵彤
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Institute of Chemistry CAS
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—
    • B01J35/615—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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 discloses a visible light responding N, B codoped In2O3/TiO2A precursor, a preparation method and application thereof. Said In2O3/TiO2In the precursor, the N element accounts for 1-3% of the mass of the precursor, the B element accounts for 0.01-0.6% of the mass of the precursor, and the molar ratio of In to Ti is 0.001-0.03. The N, B codoped In of the invention2O3/TiO2The precursor can be dissolved In a common solvent, so that the precursor can be loaded on substrates such as fibers, molecular sieves, silicon wafers, glass sheets and the like through simple impregnation, the loaded substrates are roasted at high temperature In the air, and the precursor is converted into N and B codoped In2O3/TiO2The photocatalyst is loaded on the substrate, which not only solves the problem of recycling the catalyst, but also solves the problem of common TiO2The catalyst has no response to visible light.

Description

N, B codoped In responding to visible light2O3/TiO2Precursor, preparation method and application thereof
Technical Field
The invention belongs to the field of material science, and particularly relates to N, B codoped In with visible light response2O3/TiO2A precursor, a preparation method and application thereof.
Background
Since the twentieth century, with the continuous development and progress of science and technology, the global industry has been unprecedented. However, the development of industry has promoted economic development and facilitated human life, but has also destroyed the environment in which human lives without any incident, and the influence of air pollution and water pollution caused by the development of industry on human life has become more and more obvious. The photocatalytic oxidation technology based on semiconductor catalyst is increasingly receiving attention from scholars at home and abroad as an advanced oxidation technology. Almost all organic matters can be completely oxidized into CO under the action of photocatalysis2And H2O, and the like, and in addition, the photocatalyst can also reduce heavy metal ions in the water. Among the commonly used semiconductor photocatalysts, TiO2The photocatalyst has the advantages of high activity, good stability, no secondary pollution, no harm to human bodies, low price and the like, can mineralize various organic pollutants without selection, and becomes the photocatalyst which is most valued and has wide application prospect.
TiO2The photocatalytic properties of semiconductors have been demonstrated by many studies, butTwo key problems need to be solved in order to move to practical use, namely that ① traditional photocatalytic research is generally carried out in a suspended state photocatalytic reaction system and TiO exists2② TiO powder is easy to agglomerate and difficult to realize continuous separation, recovery and regeneration of catalyst2The photocatalytic oxidation can be carried out only within the limited wavelength range of ultraviolet light, and the proportion of sunlight is low, so that the popularization and the application of the photocatalytic technology are limited. Thus, the catalyst is immobilized and how this is done by modifying the TiO2The property of the photocatalyst makes the photocatalyst react under visible light, and has great practical significance for the application of photocatalytic oxidation technology in air purification and water treatment.
"visible light active TiO2Preparation and characterization of (Zhaodan, Erie., etc.. visible light active TiO2Preparation and characterization of [ J]The academy of Tianjin City construction, 3 months 2010, vol 16, phase 1: 33-36) with TiOSO4The nano Ti-O-N photocatalyst with visible light activity is prepared by taking ammonia water as a raw material through a chemical precipitation method, the performance of the nano Ti-O-N photocatalyst is characterized by adopting detection methods such as SEM, BET, XRD, UV-vis, ESR, XPS and the like, the catalytic activity of the photocatalyst under visible light is researched through a methyl orange solution degradation experiment, the influence of factors such as specific surface area, visible light absorption intensity, crystal structure and the like on the photocatalytic activity of the photocatalyst is discussed, the prepared nano Ti-O-N photocatalyst can strongly absorb the visible light with the wavelength range of 400-600nm after heat treatment, and the visible light absorption intensity is closely related to the heat treatment temperature of powder. The photocatalysis test shows that: the photocatalyst after heat treatment at 400 ℃ has the strongest absorption to visible light, relatively larger specific surface area and more complete developed crystal structure, and therefore, the photocatalyst shows the best photocatalytic activity under the visible light. However, the obtained catalyst exists in a powder form, which is not beneficial to the recycling of the catalyst, and even if the catalyst is recycled, the catalyst is easy to agglomerate when being used for the second time after being recycled, so that the photocatalytic performance is reduced, and the utilization rate of titanium dioxide in unit mass is low.
Mingyang Xing et al (Xing, M., et al, "Formation of New Structures and theoretical Effects in Boron and Nitrogen Codoped TiO)2for Enhancement of Photoclatrial Performance. "Journal of Physical Chemistry C.2011, 115,7858-7865) and a hydrothermal method were used to synthesize N, B-codoped TiO by using urea and boric acid as N source and B source, respectively2A catalyst. The photocatalysis test shows that: n, B codoped TiO2The degradation rate (75% + -1.0%) of the catalyst to methyl orange under the irradiation of visible light far exceeds that of the catalyst with independent doping of B and N and the catalyst without doping (B-TiO)2：43％±0.8％，N-TiO2: 47% +/-0.5% of undoped TiO2: 32% ± 0.2%). However, the obtained catalyst exists in a powder form, which is not beneficial to the recycling of the catalyst, and even if the catalyst is recycled, the catalyst is easy to agglomerate when being used for the second time after being recycled, so that the photocatalytic performance is reduced, and the utilization rate of titanium dioxide in unit mass is low.
In summary, TiO prepared by the prior art2The photocatalyst generally exists in a powder form, the photocatalytic reaction is generally carried out in a suspended state photocatalytic reaction system, and the photocatalyst has the defects of difficult sedimentation, great recovery difficulty and TiO2The powder is easy to agglomerate, and the continuous separation, recovery, regeneration and utilization of the catalyst are difficult to realize; related research on loading of powder is also carried out, but the problems of uneven loading and easy powder falling generally exist; further, ordinary TiO2The catalyst only responds to ultraviolet light, and the ultraviolet light part in the sunlight only accounts for less than 5 percent, so the problems seriously limit TiO2The application of the photocatalyst in practice.
Disclosure of Invention
The invention provides N, B codoped In2O3/TiO2A precursor of the In2O3/TiO2In the precursor, the N element accounts for 1-3% of the mass of the precursor, the B element accounts for 0.01-0.6% of the mass of the precursor, and the molar ratio of In to Ti can be 0.001-0.03.
For example, the N element accounts for 1.5-2.5% and 1.8-2.2% of the mass of the precursor, and for example, the N element accounts for 1.6%, 1.9%, 2.0% and 2.1% of the mass of the precursor.
For example, the B element accounts for 0.1-0.4%, 0.2-0.3% of the mass of the precursor, and for example, the B element accounts for 0.15%, 0.25%, 0.35% of the mass of the precursor.
For example, the molar ratio of In to Ti may be 0.005 to 0.015, 0.01 to 0.012, and as an example, the molar ratio of In to Ti may be 0.006, 0.007, 0.0075, 0.008, 0.011.
According to the precursor of the present invention, the In2O3/TiO2The precursor may be dissolved in an organic solvent, for example, the organic solvent may be one, two or more of ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and toluene or xylene.
The invention also provides the N, B codoped In2O3/TiO2A method for preparing a precursor, said method comprising the steps of: the precursor is prepared from raw materials containing titanate, a pore-foaming agent, indium salt, a boron-containing compound, a nitrogen-containing compound, a chelating agent, water and alcohol.
According to the technical scheme of the invention, the N and B are codoped with In2O3/TiO2The preparation method of the precursor specifically comprises the following steps:
1) mixing titanate, a pore-forming agent and indium salt, and reacting until the solution is clear and transparent;
2) adding a boron-containing compound into the clear and transparent solution obtained in the step 1), and reacting until the solution is clear and transparent;
3) adding a nitrogen-containing compound into the clear and transparent solution obtained in the step 2), and reacting until the solution is clear and transparent;
4) adding a mixed solution of a chelating agent, water and alcohol into the clear and transparent solution obtained In the step 3), refluxing, cooling, decompressing and removing the solvent to obtain the N, B codoped In2O3/TiO2And (3) precursor.
According to the preparation method of the invention, in step 1), the titanate can be one, two or more of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate and tetraisobutyl titanate.
According to the preparation method of the present invention, in step 1), the pore-forming agent may be one or two or more of polyethylene glycol, polypropylene glycol, polymethyl methacrylate, polyvinyl alcohol and polyvinylpyrrolidone. Wherein the mass of the pore-foaming agent can be 0.05-5 times, such as 0.1-3 times of the mass of Ti atoms in the phthalate ester; illustratively, the mass of the pore-foaming agent can be 0.104, 0.17, 1.25 and 2.5 times of the mass of the Ti element in the phthalate ester.
According to the preparation method of the present invention, in the step 1), the indium salt may be one, two or more of indium nitrate, indium chloride and indium sulfate. Wherein the molar ratio of the indium element in the indium salt to the titanium element in the titanate can be (0.001-0.03): 1, for example, (0.002-0.025): 1, (0.002-0.021): 1; illustratively, the molar ratio of the indium element to the titanium element is 0.0042, 0.0126, 0.025, 0.0252, 0.0256.
According to the preparation method of the invention, in the step 1), the reaction temperature can be 90-130 ℃, for example 100-120 ℃; illustratively, the temperature of the reaction may be 100 ℃, 105 ℃, 110 ℃, 120 ℃. The reaction time may be 0.5 to 5 hours, for example 1 to 5 hours.
According to the preparation method of the invention, in the step 2), the boron-containing compound can be one or two of boric acid and ammonium borate. Wherein the molar ratio of the boron-containing compound to the titanate may be (0.02-0.5): 1; for example, (0.04-0.3): 1, (0.05-0.2): 1, (0.1-0.2): 1; illustratively, the molar ratio of the boron-containing compound to the titanate is 0.12:1, 0.16:1, 0.24:1, 0.3: 1. Preferably, the boron-containing compound is added to the clear and transparent solution of step 1) at a temperature of from room temperature to 100 ℃ (e.g., 50 to 100 ℃; illustratively 70 ℃, 90 ℃ or 100 ℃).
According to the preparation method of the invention, in the step 2), the reaction temperature can be 80-130 ℃, for example 90-120 ℃. The reaction time can be 0.5-5 h, such as 1-4 h; illustratively, the reaction time is 1h, 2h, 4 h.
According to the preparation method of the invention, in the step 3), the nitrogen-containing compound can be one, two or more of urea, ethanolamine, acetamide, acetoacetamide, N-dimethylacetamide, glycine and alanine; preferably, it may be one, two or more of urea, acetamide, acetoacetamide and N, N-dimethylacetamide. Wherein the molar ratio of the nitrogen-containing compound to the titanate ester can be (0.05-5): 1; for example, (0.1 to 3) 1, (0.5 to 2.5): 1. (1-2): 1; illustratively, the molar ratio of the nitrogen-containing compound to the titanate is 0.5:1, 0.3:1, 2:1, 2.5: 1. Preferably, the nitrogen-containing compound is added to the clear and transparent solution of step 2) at a temperature of room temperature to 100 ℃ (e.g., 50 to 100 ℃; illustratively, 60 ℃, 80 ℃, 90 ℃ or 95 ℃).
According to the preparation method of the invention, in the step 3), the temperature may be 80-130 ℃, for example 90-120 ℃. The reaction time can be 0.5-5 h, such as 1-4 h; illustratively, the reaction time is 1h, 2h, 4 h.
According to the preparation method of the invention, in the step 4), the chelating agent can be one or two of acetylacetone and ethyl acetoacetate. Wherein the molar ratio of the chelating agent to the titanate can be (0.05-2): 1; for example, (0.1-1): 1, (0.3-0.8): 1; illustratively, the molar ratio of the chelating agent to the titanate is 0.3:1, 0.5:1, 0.6:1, 0.8: 1. Preferably, the chelating agent is added to the clear and transparent solution of step 3) at a temperature of room temperature to 100 ℃ (e.g., 50 to 100 ℃; illustratively, 80 ℃, 85 ℃, 90 ℃ or 100 ℃).
According to the preparation method of the invention, in the step 4), the molar ratio of the water to the alcohol in the mixed liquid of the water and the alcohol can be 1 (1-30), such as 1 (3-20) and 1 (3-10); illustratively, the molar ratio may be 1:2.5, 1:3, 6:19, 1:4, 1: 5. Preferably, the molar ratio of water to phthalate ester in the mixed solution of water and alcohol may be 1 (0.5-2), for example 1 (0.8-1.3); illustratively, the molar ratio may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:1, 1: 1.2. Preferably, the alcohol may be one, two or more of ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Preferably, the temperature at which the mixture of water and alcohol is added may be room temperature to 95 ℃, for example, 50 to 90 ℃.
According to the preparation method of the invention, in the step 4), the refluxing time can be 1-6 h, such as 1-5 h and 2-4 h.
According to the preparation method of the invention, the room temperature is 20-40 ℃, for example 25-35 ℃; as an example, the room temperature may be 25 ℃ and 30 ℃.
Furthermore, the invention also provides N, B codoped In obtained by the preparation method2O3/TiO2And (3) precursor.
Further, the invention also provides the N, B codoped In2O3/TiO2The application of the precursor in preparing the catalyst. For example, the catalyst may be a powder catalyst and a supported catalyst. Preferably, the supported catalyst may be a supported catalyst supported on a substrate such as a coating, a fiber, or the like.
Furthermore, the invention also provides N, B codoped In2O3/TiO2Catalyst, said In2O3/TiO2The catalyst is co-doped with In by the N and B2O3/TiO2And preparing a precursor. Preferably, the In2O3/TiO2The catalyst is co-doped with In by the N and B2O3/TiO2And roasting the precursor at 350-500 ℃ in the air to obtain the catalyst. Preferably, the N, B codoping In2O3/TiO2The catalyst has In2O3/TiO2A heterojunction structure. Preferably, the N, B codoping In2O3/TiO2The specific surface area of the catalyst can be 100-300 m2G, e.g. 200 to 250m2A specific surface area of 213m2(ii) in terms of/g. Preferably, the N, B codoping In2O3/TiO2The catalyst may be in the form of a powder.
Further, the invention also provides a load type N, B codoped In2O3/TiO2Catalyst, said In2O3/TiO2The catalyst comprises N, B codoped In2O3/TiO2A catalyst and a support; for example, the support may be at least one of a fiber, a molecular sieve, a silicon wafer, a glass sheet, and the like. Preferably, the N, B codoping In2O3/TiO2The catalyst has In2O3/TiO2A heterojunction structure. Preferably, the supported N, B codoped In2O3/TiO2N, B codoped In catalyst2O3/TiO2The loading rate of the catalyst is 15-30%, for example 18-25%.
Further, the invention also provides the load type N, B codoped In2O3/TiO2A method for preparing a catalyst, the method comprising the steps of: co-doping the N, B with In2O3/TiO2Dissolving a precursor In an organic solvent, soaking a matrix In the organic solvent, and curing and cracking the matrix loaded with the precursor to obtain the loaded N, B co-doped In2O3/TiO2A catalyst. Wherein the mass content of Ti in the organic solvent can be 1-5%, for example 1-3%. The matrix may be selected from at least one of fibers, molecular sieves, silicon wafers, glass sheets, and the like, for example, from quartz fiber cotton.
The invention has the beneficial effects that:
the applicant creatively finds that the molar ratio of the titanate, the pore-forming agent, the indium salt, the boron-containing compound, the nitrogen-containing compound, the chelating agent and the water is very critical, a soluble precursor cannot be obtained due to improper selection of the molar ratio of the materials, and hydrolysis precipitation can occur in the reaction process; in the molar ratio range of the present invention, In is obtained2O3/TiO2And (3) precursor.
In the prior art, when the heterojunction structure photocatalyst is synthesized, a semiconductor catalyst powder is often required to be synthesized firstly and then modified for the second time, and complicated steps and long reaction time are required, so that the large-scale preparation is not facilitated. The visible light response N, B codoped In2O3/TiO2The preparation process of the precursor is carried out In solution, the steps are simple, the reaction time is short, the obtained precursor is a high-molecular organic compound, the high-molecular organic compound has the processing characteristics of organic high molecules, the precursor can be loaded on a fiber, a sheet or a porous material (such as a molecular sieve) and other matrixes by simple impregnation, then the matrixes loaded with the precursor are solidified and roasted, the precursor is inorganic, and the precursor is converted into N, B codoped In with visible light response2O3/TiO2The photocatalyst is loaded on the substrate, which not only solves the recovery problem of the catalyst, but also solves the problem of common TiO2The catalyst has no response to visible light.
Meanwhile, the invention also discloses In2O3/TiO2The heterojunction structure is introduced into the microstructure of the catalyst, the high molecular chain segment is cracked In the precursor inorganic process, and the obtained N and B codope In is enabled to be codoped In the precursor inorganic process2O3/TiO2The photocatalyst has a heterojunction structure, and the carrier separation capacity of the catalyst is improved, so that the photodegradation efficiency is improved.
In particular, the invention prepares N, B codoped In2O3/TiO2A precursor which is TiO containing indium, boron and nitrogen in a molecular structure2The specific surface area of the catalyst obtained by high-temperature cracking of the precursor is as high as 213m2Per g (specific surface area without added pore of 76 m)2The catalyst has good photocatalytic capability under ultraviolet light (for example, the degradation rate of methyl orange in 10min can reach 100% under the irradiation of a 500W high-pressure mercury lamp), and has good photocatalytic capability under visible light (for example, the degradation rate of methyl orange in 4h can reach 100% under the irradiation of a 500W xenon lamp, and the degradation rate of norfloxacin in 10min can reach 100%).
Drawings
FIG. 1 shows that the quartz fiber obtained In example 2 is loaded with N, B co-doped In2O3/TiO2The efficiency of the catalyst in degrading norfloxacin was plotted for 45 replicates.
FIG. 2 shows the silica fiber obtained in example 2N, B Co-doped In2O3/TiO2Scanning electron micrographs of the catalyst.
FIG. 3 is a scanning electron micrograph of the silica fiber used in example 2.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Instrument information:
scanning electron microscope: SU8020, Hitachi, japan.
Example 1
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetrapropyl titanate, 120g of polyethylene glycol and 7.57g of indium nitrate are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the system is heated and reacted under stirring at 100 ℃ until the system is clear and transparent;
(2) at the temperature of 100 ℃, adding 0.3mol of boric acid into the system, and reacting for 4 hours under heat preservation;
(3) at the temperature of 95 ℃, adding 0.5mol of ethanolamine into the system, heating to 100 ℃, and carrying out heat preservation reaction for 4 hours;
(4) adjusting the temperature to 90 ℃, adding 0.8mol of acetylacetone, then dripping a mixed solution of 0.6mol of water and 1.9mol of n-propanol, refluxing for 1h after dripping, reducing the temperature, and removing the solvent to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 450 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of methyl orange solution (the concentration is 15mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 92%.
Example 2
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetraisopropyl titanate, 6.51g of indium sulfate and 5g of polymethyl methacrylate are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the mixture is heated and reacted at 110 ℃ under stirring until the system is clear and transparent;
(2) at the temperature of 90 ℃, 0.12mol of amine borate is added into the system under stirring, and the reaction is carried out for 3 hours under heat preservation;
(3) at the temperature of 90 ℃, adding 0.3mol of ethanolamine into the system, and reacting for 4 hours under heat preservation;
(4) adjusting the temperature to 90 ℃, adding 0.3mol of ethyl acetoacetate, then dripping a mixed solution of 1.2mol of water and 6mol of isopropanol, refluxing for 3h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 450 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of methyl orange solution (the concentration is 15mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 76.9%.
Dissolving the precursor In isopropanol to prepare a solution with the Ti content of 3%, dipping 0.15g of quartz fiber, and then curing and cracking to prepare the quartz fiber loaded N, B codoped In2O3/TiO2The catalyst has a catalyst loading rate of about 20%. Adding the supported catalystPutting the mixture into 30mL norfloxacin solution (with the concentration of 20mg/L), and illuminating for 10min by a 500W high-pressure mercury lamp, wherein the degradation rate is 100%; 500W xenon lamp (filter plate filtering wavelength<420 nm) light for 10min, the degradation rate is about 100%, as shown in figure 1, the fabric is repeatedly used for 45 times, and the degradation rate is not obviously changed. The scanning electron microscope of the precursor after cracking at 450 ℃ In air is shown In figure 2, and it can be seen from the figure that the loaded N, B codope In is compared with the scanning electron microscope (figure 3) of the unloaded quartz fiber2O3/TiO2The catalyst is uniformly distributed in the quartz fiber.
Example 3
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetrabutyl titanate, 3.79g of indium nitrate and 60g of polypropylene glycol are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the system is heated and reacted under stirring at 100 ℃ until the system is clear and transparent;
(2) adding 0.24mol of boric acid into the system under stirring at 70 ℃, heating to 90 ℃, and carrying out heat preservation reaction for 5 hours;
(3) adding 2mol of acetamide into the system at 60 ℃, heating to 120 ℃, and carrying out heat preservation reaction for 4 hours;
(4) adjusting the temperature to 80 ℃, adding 0.5mol of ethyl acetoacetate, then dripping a mixed solution of 1mol of water and 2.5mol of n-butanol, refluxing for 2h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 450 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
Adding 30mg of the obtained catalyst into 30mL of methyl orange solution (the concentration is 15mg/L), and irradiating for half an hour by using a 500W high-pressure mercury lamp, wherein the degradation rate is 100%; A500W xenon lamp (a filter plate filters light with the wavelength of less than 420 nm) is illuminated for 4 hours, and the degradation rate is 100 percent.
Example 4
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetraisobutyl titanate, 5.67g of indium chloride and 8g of polyvinylpyrrolidone are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the system is heated and reacted at 120 ℃ under stirring until the system is clear and transparent;
(2) adding 0.16mol of boric acid into the system under stirring at 90 ℃, and reacting for 2 hours under heat preservation;
(3) adding 2mol of acetoacetamide into the system at 90 ℃, and reacting for 1h under heat preservation;
(4) adjusting the temperature to 85 ℃, adding 0.5mol of acetylacetone, then dripping a mixed solution of 0.5mol of water and 2mol of n-propanol, refluxing for 2h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 400 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of methyl orange solution (the concentration is 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 69.3 percent.
Example 5
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetraisopropyl titanate, 1.26g of indium nitrate and 60g of polyethylene glycol are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the system is heated and reacted at 110 ℃ under stirring until the system is clear and transparent;
(2) adding 0.12mol of boric acid into the system under stirring at 70 ℃, heating to 110 ℃, and reacting for 4 hours in a heat preservation way;
(3) adjusting the temperature to 80 ℃, adding 2mol of alanine into the system, heating to 100 ℃, and carrying out heat preservation reaction for 2 hours;
(4) adjusting the temperature to 80 ℃, adding 0.6mol of acetylacetone, dripping a mixed solution of 0.8mol of water and 2.4mol of isobutanol, refluxing for 1h after dripping, reducing the temperature, and removing the solvent to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 450 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of norfloxacin solution (with the concentration of 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is illuminated for 30min, and the degradation rate is 100%.
Example 6
In this example, visible light-responsive N, B codoped In2O3/TiO2The precursor is synthesized by the following steps:
(1) 1mol of tetraisopropyl titanate, 4.34g of indium sulfate and 120g of polyethylene glycol are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the mixture is stirred at 105 ℃ to react until the system is clear and transparent;
(2) adding 0.16mol of boric acid into the system under stirring at room temperature, heating to 100 ℃, and reacting for 4 hours under heat preservation;
(3) adjusting the temperature to 90 ℃, adding 2.5mol of N, N-dimethylacetamide into the system, and reacting for 2 hours under the condition of heat preservation;
(4) adjusting the temperature to 90 ℃, adding 0.6mol of acetylacetone, then dripping a mixed solution of 0.7mol of water and 3.5mol of ethanol, refluxing for 5h after dripping, reducing the temperature, and removing the solvent under reduced pressure to obtain the precursor.
The precursor has better solubility in any one solvent or a mixed solvent of a plurality of solvents of ethanol, normal propyl alcohol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, toluene or xylene.
Roasting the obtained precursor at 350 ℃ In the air to obtain N, B codoped In2O3/TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of methyl orange solution (the concentration is 20mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 66.3 percent.
Comparative example 1
Visible light responsive N, B codoped TiO in this comparative example2The precursor is synthesized by the following steps:
(1) placing 1mol of tetrapropyl titanate and 120g of polyethylene glycol into a drying reaction kettle equipped with a condensing tube and a drying tube, stirring at 120 ℃, and carrying out heat preservation reaction until the system is clear and transparent;
(2) at the temperature of 100 ℃, adding 0.04mol of boric acid into the system, and reacting for 4 hours under heat preservation;
(3) at the temperature of 95 ℃, adding 0.3mol of ethanolamine into the system, heating to 120 ℃, and carrying out heat preservation reaction for 4 hours;
(4) adjusting the temperature to 90 ℃, adding 0.3mol of acetylacetone, then dripping a mixed solution of 0.5mol of water and 0.15mol of n-propanol, refluxing for 1h after dripping, reducing the temperature, and removing the solvent to obtain the precursor.
Roasting the obtained precursor at 450 ℃ in the air to obtain N, B codoped TiO2A catalyst.
30mg of the obtained catalyst is added into 30mL of methyl orange solution (the concentration is 15mg/L), a 500W xenon lamp (a filter plate filters light with the wavelength of 420 nm) is used for illumination for 4 hours, and the degradation rate is 52%.
Comparative example 2
Visible light responsive N, B codoped In this comparative example2O3/TiO2The precursor is synthesized according to the following steps, wherein the amount of indium nitrate and water exceeds the material proportioning range:
(1) 1mol of tetraisopropyl titanate, 12.6g of indium nitrate and 60g of polyethylene glycol are placed in a drying reaction kettle provided with a condensing tube and a drying tube, and the system is heated and reacted at 120 ℃ under stirring until the system is clear and transparent;
(2) adding 0.2mol of boric acid into the system under stirring at the temperature of 80 ℃, heating to 110 ℃, and carrying out heat preservation reaction for 4 hours;
(3) adjusting the temperature to 80 ℃, adding 2mol of acetamide into the system, heating to 120 ℃, and carrying out heat preservation reaction for 4 h;
(4) adjusting the temperature to 90 ℃, adding 0.5mol of acetylacetone, dripping a mixed solution of 1.5mol of water and 2.4mol of isobutanol, generating a white precipitate due to hydrolysis in the dripping process, and failing to prepare the precursor solution.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. N, B codoped In2O3/TiO2A precursor characterized In that In2O3/TiO2In the precursor, the N element accounts for 1-3% of the mass of the precursor, the B element accounts for 0.01-0.6% of the mass of the precursor, and the molar ratio of In to Ti is 0.001-0.03.
2. The N, B co-doped In of claim 12O3/TiO2The precursor is characterized in that the N element accounts for 1.5-2.5% of the mass of the precursor;
preferably, the B element accounts for 0.1-0.4% of the mass of the precursor;
preferably, the molar ratio of In to Ti is 0.005-0.015;
preferably, the In2O3/TiO2The precursor is dissolved in an organic solvent.
3. The N, B-codoped In of claim 1 or 22O3/TiO2The preparation method of the precursor is characterized by comprising the following steps: the precursor is prepared from raw materials containing titanate, a pore-foaming agent, indium salt, a boron-containing compound, a nitrogen-containing compound, a chelating agent, water and alcohol;
preferably, the preparation method specifically comprises the following steps:
1) mixing titanate, a pore-forming agent and indium salt, and reacting until the solution is clear and transparent;
2) adding a boron-containing compound into the clear and transparent solution obtained in the step 1), and reacting until the solution is clear and transparent;
3) adding a nitrogen-containing compound into the clear and transparent solution obtained in the step 2), and reacting until the solution is clear and transparent;
4) adding a mixed solution of a chelating agent, water and alcohol into the clear and transparent solution obtained In the step 3), refluxing, cooling, decompressing and removing the solvent to obtain the N, B codoped In2O3/TiO2And (3) precursor.
4. The method according to claim 3, wherein in step 1), the titanate is one, two or more of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisobutyl titanate;
preferably, the pore-foaming agent is one, two or more of polyethylene glycol, polypropylene glycol, polymethyl methacrylate, polyvinyl alcohol and polyvinylpyrrolidone;
preferably, the mass of the pore-foaming agent is 0.05-5 times of the mass of Ti element in the phthalate ester;
preferably, the indium salt is one, two or more of indium nitrate, indium chloride and indium sulfate;
preferably, the molar ratio of the indium element in the indium salt to the titanium element in the titanate is (0.001-0.03): 1;
preferably, the reaction temperature is 90-130 ℃, and the reaction time is 0.5-5 h.
5. The method according to claim 3 or 4, wherein in the step 2), the boron-containing compound is one or both of boric acid and ammonium borate;
preferably, the molar ratio of the boron-containing compound to the titanate is (0.02-0.5): 1;
preferably, the reaction temperature is 80-130 ℃, and the reaction time is 0.5-5 h.
6. The preparation method according to any one of claims 3 to 5, wherein in the step 3), the nitrogen-containing compound is one, two or more of urea, ethanolamine, acetamide, acetoacetamide, N-dimethylacetamide, glycine and alanine;
preferably, the molar ratio of the nitrogen-containing compound to the titanate is (0.05-5): 1;
preferably, the reaction temperature is 80-130 ℃, and the reaction time is 0.5-5 h.
7. The preparation method according to any one of claims 3 to 6, wherein in the step 4), the chelating agent is one or two of acetylacetone and ethyl acetoacetate;
preferably, the molar ratio of the chelating agent to the titanate is (0.05-2): 1;
preferably, in the mixed liquid of water and alcohol, the molar ratio of the water to the alcohol is 1 (1-30);
preferably, the molar ratio of water to phthalate ester in the mixed liquid of water and alcohol is 1 (0.5-2);
preferably, the reaction temperature is room temperature-95 ℃, and the refluxing time is 1-6 h.
8. The N, B-codoped In of claim 1 or 22O3/TiO2The application of the precursor in preparing the catalyst;
preferably, the catalyst is a powder catalyst or a supported catalyst;
preferably, the supported catalyst is a supported catalyst supported on a substrate such as a coating, a fiber or the like.
N, B codoped In2O3/TiO2A catalyst, characterized In that said In2O3/TiO2The catalyst is co-doped with In from N, B according to claim 1 or 22O3/TiO2Preparing a precursor;
preferably, the N, B codoping In2O3/TiO2The catalyst has In2O3/TiO2A heterojunction structure;
preferably, the N, B codoping In2O3/TiO2The specific surface area of the catalyst is 100-300 m2/g。
10. Supported N, B co-doped In2O3/TiO2A catalyst, characterized In that said In2O3/TiO2The catalyst comprises N, B codoped In as defined In claim 1 or 22O3/TiO2A catalyst and a support;
preferably, the N, B codoping In2O3/TiO2The catalyst has In2O3/TiO2A heterojunction structure;
preferably, the supported N, B codoped In2O3/TiO2N, B codoped In catalyst2O3/TiO2The loading rate of the catalyst is 15-30%.
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