CN111036246A - Composite photocatalytic material and preparation method and application thereof - Google Patents

Composite photocatalytic material and preparation method and application thereof Download PDF

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CN111036246A
CN111036246A CN201911422453.2A CN201911422453A CN111036246A CN 111036246 A CN111036246 A CN 111036246A CN 201911422453 A CN201911422453 A CN 201911422453A CN 111036246 A CN111036246 A CN 111036246A
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titanium dioxide
copper
photocatalytic material
hydroxyapatite
silver
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葛成艳
孙敬方
邹伟欣
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Yancheng Institute of Technology
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/16Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention relates to a composite photocatalytic material, which comprises sheet hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.

Description

Composite photocatalytic material and preparation method and application thereof
Technical Field
The invention relates to a composite photocatalytic material, in particular to a composite photocatalytic material which is formed by coating nano titanium dioxide on the surface of hydroxyapatite and simultaneously depositing silver and copper on the surface of the nano titanium dioxide, and belongs to the technical field of photocatalytic materials.
Background
With the rapid development of economy, the pollution of atmosphere, soil and water has become more serious, and in order to solve the above environmental problems, researchers have focused on the environmental-friendly photocatalytic technical field, and the photocatalytic material refers to a semiconductor catalyst material required for photochemical reaction under the action of light, and can be used as a photocatalytic material in the world, including various oxide sulfide semiconductors such as Titanium Dioxide, zinc oxide, tin oxide, zirconium Dioxide, cadmium sulfide, etc., wherein Titanium Dioxide (Titanium Dioxide) is a most red nano photocatalytic material in the world due to its strong oxidizing ability, stable chemical properties and no toxicity.
TiO2The crystal form, the grain size, the grain diameter, the surface state and other factors have great influence on the photocatalytic performance. The nano-particle with large surface area has good catalytic activity and selectivity due to the surface effect and the volume effect. Nano TiO 22The conduction band energy level and the valence band energy level of the quantum size effect become discrete energy levels due to the quantum size effect, the energy gap is widened, the conduction band potential becomes more negative, and the valence band potential becomes more positive, which means that the quantum size effect has stronger oxidation and reduction capabilities; and because the particle size of the nano particles is small, a photon-generated carrier is easier to migrate to the surface from the inside of the particles than coarse particles, the recombination probability of electrons and holes is obviously reduced, and the photocatalysis performance is also improved.
However, titanium dioxide has a wide band gap (anatase is 3.2eV), so that titanium dioxide only responds to ultraviolet light, the spectrum utilization range is narrow, and in addition, the electron hole is easy to rapidly recombine, so that the carrier efficiency is low, and the problems of low photon efficiency, low catalytic efficiency to be improved, difficult immobilization and difficult recovery of the catalyst and the like exist when the titanium dioxide is applied to the field of photocatalysis, so that the application of titanium dioxide in practice is limited.
In order to solve the problems of titanium dioxide, researchers modify titanium dioxide by different methods, such as ion doping, semiconductor compounding, noble metal loading, morphology crystal face regulation and the like, and mainly aim at widening the light absorption range, improving the quantum efficiency and promoting the occurrence of surface reaction. Through the deposition of the noble metal, photo-generated electrons can be effectively captured, so that the catalytic activity of the semiconductor is improved, and the deposition of the noble metal on the surface of the semiconductor usually has two functions: firstly, the method is beneficial to the effective separation of photo-generated electron-hole pairs; and secondly, the photocatalytic activity is improved by reducing the overpotential of the reduction reaction, but the noble metal is rare and expensive, so that the further practical application of the noble metal is hindered.
Hydroxyapatite has strong adsorption effect on organic pollutants, is non-toxic and harmless, and in recent years, the research on hydroxyapatite/titanium dioxide composite materials is continuously carried out, Taoda and the like wrap hydroxyapatite on the surface of titanium dioxide, so that the functions of titanium dioxide such as sterilization, deodorization and the like are improved. Then, the titanium dioxide/hydroxyapatite hollow composite microspheres are synthesized, and the titanium dioxide/hydroxyapatite composite microspheres show different adsorption properties and ultraviolet light catalysis properties. However, the above methods all require a subsequent heat treatment to obtain titanium dioxide in a crystalline state, which is disadvantageous for obtaining a nanocomposite.
Disclosure of Invention
The invention provides a composite photocatalytic material and a preparation method and application thereof, aiming at the defects of nano titanium dioxide as a photocatalytic material.
The technical scheme for solving the technical problems is as follows:
the composite photocatalytic material comprises flake hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.
Further, the molar ratio of the titanium dioxide to the hydroxyapatite is 1: (0.5 to 5), preferably 1: (2-3).
Further, the molar ratio of the copper to the silver is (3-5): 1.
Further, the molar ratio of the total amount of copper and silver to titanium dioxide is 1: (2-4).
The preparation method of the composite photocatalytic material comprises the following steps:
1) uniformly stirring and mixing the nano titanium dioxide, a solvent and a dispersant to obtain a suspension A; dissolving copper salt, silver salt and glucose in water to prepare a mixed salt solution B for later use;
2) respectively preparing a calcium salt solution and a solution of a phosphorus-containing substance, mixing the calcium salt solution and the solution of the phosphorus-containing substance, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, uniformly mixing, carrying out hydrothermal reaction at 130-160 ℃ for 3-8 h, cooling, standing, and carrying out centrifugal separation and drying to obtain titanium dioxide-coated flaky hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding sodium hydroxide, potassium hydroxide or ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum to obtain the titanium dioxide.
Further, in the step 1), the solvent is absolute ethyl alcohol, the dispersing agent is sodium dodecyl sulfate or polyvinylpyrrolidone, and preferably, the adding amount of the dispersing agent is 0.5-3% of the mass of the nano titanium dioxide.
Further, in the step 1), the copper salt is copper nitrate, copper sulfate or copper chloride, and the silver salt is silver nitrate.
Further, the calcium salt is calcium nitrate tetrahydrate or calcium chloride, and the phosphorus-containing substance is ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
Further, the molar ratio of glucose to copper salt is 1: 1.
Further, the particle size of the nano titanium dioxide is 10-30 nm.
The principle of the composite photocatalytic material is as follows:
1) the hydroxyapatite is taken as a carrier, and the nano titanium dioxide is uniformly loaded on the surface of the hydroxyapatite in the hydrothermal synthesis process of the hydroxyapatite, so that the problem that the nano titanium dioxide is easy to agglomerate can be solved, the strong adsorption effect of the hydroxyapatite can be utilized, and then the titanium dioxide is subjected to photocatalytic degradation to form an adsorption-decomposition dynamic mechanism, the defect of weak adsorption capacity of the titanium dioxide is overcome to a certain extent, the synergistic action capacity of nano hydroxyapatite adsorption and titanium dioxide photocatalysis is fully exerted, a better photocatalytic effect is obtained, the photocatalytic efficiency and the service life of the titanium dioxide are favorably improved, and the application range of the titanium dioxide is expanded;
2) copper and silver are uniformly deposited on the surface of the nano titanium dioxide, the introduction of copper promotes the transfer of electrons, the efficient separation of photon-generated carriers is realized, and the surface ion resonance effect (SPR) of nano copper particles enables the composite photocatalytic material to show high photocatalytic performance under the irradiation of visible light, the adsorption and photocatalytic degradation efficiency of the composite photocatalytic material is obviously superior to that of monomer titanium dioxide, the Ag electron-withdrawing capability is strong, and electrons generated by light excitation are enabled to be separated from TiO2Transfer to Ag and stay the photo-excited holes in TiO2Therefore, the aim of inhibiting the recombination of electrons and holes is fulfilled, and the photocatalytic efficiency of the catalyst is improved;
3) the use amount of noble metal silver is greatly reduced by reasonably controlling the proportion of copper and silver, the noble metal silver is replaced by the cheap metal copper with high natural abundance, glucose is used as a reducing agent of copper, any toxic reducing agent is not introduced, the preparation process is simple and easy to operate, and the copper-silver alloy is green and environment-friendly, meets the requirement of actual production and has larger application potential.
The photocatalytic composite material and the preparation method thereof provided by the invention have the beneficial effects that:
1) the synergistic cooperation of hydroxyapatite, titanium dioxide, copper and silver is fully utilized, and the photocatalytic efficiency and the service life of the composite material are superior to those of the existing material;
2) because the metal copper is used for replacing most of metal silver, the production cost is low, any toxic reducing agent is not introduced, the preparation process is simple and easy to operate, the environment is protected, and the application potential is larger.
Drawings
FIG. 1 is a TEM image of the composite photocatalytic material obtained in example 1 (the scale in the image is 200 nm).
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain suspension A, wherein the use amount of the polyvinylpyrrolidone is 1% of the mass of the titanium dioxide; dissolving copper nitrate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:3, and the molar ratio of the copper nitrate to the silver nitrate to the glucose is 5:1:5 for later use;
2) respectively preparing a calcium nitrate tetrahydrate aqueous solution and a monoammonium phosphate aqueous solution, mixing the calcium nitrate aqueous solution and the monoammonium phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:2, after being uniformly mixed, carrying out hydrothermal reaction for 5 hours at 145 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet hydroxyapatite;
4) and (3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding a sodium hydroxide solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding until the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
The TEM of the composite photocatalytic material obtained in example 1 is shown in fig. 1, and as can be seen from fig. 1, the titanium dioxide with nano-sized dots is distributed on the surface of the flake-shaped hydroxyapatite, and no obvious agglomeration phenomenon occurs.
Example 2:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain a suspension A, wherein the dosage of the polyvinylpyrrolidone is 0.5% of the mass of the titanium dioxide; dissolving copper sulfate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:2, and the molar ratio of the copper sulfate, the silver nitrate and the glucose is 3:1:3 for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:5, after uniformly mixing, carrying out hydrothermal reaction for 8 hours at 130 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet-shaped hydroxyapatite;
4) and (3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding a potassium hydroxide solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding until the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
Example 3:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, a solvent of absolute ethyl alcohol and a dispersant of sodium dodecyl sulfate to obtain a suspension A, wherein the amount of the sodium dodecyl sulfate is 3% of the mass of the titanium dioxide; dissolving copper sulfate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:4, and the molar ratio of the copper sulfate, the silver nitrate and the glucose is 3:1:3 for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1: 0.5, after being uniformly mixed, carrying out hydrothermal reaction for 3 h at 160 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding an ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
Comparative example 1:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain suspension A, wherein the dosage of the polyvinylpyrrolidone is 0.5% of the mass of the titanium dioxide for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:2, after being uniformly mixed, carrying out hydrothermal reaction for 8 hours at the temperature of 130 ℃, cooling and standing, and carrying out centrifugal separation and drying to obtain the titanium dioxide coated sheet hydroxyapatite.
Comparative example 2: nano titanium dioxide with the particle size of 10-30 nm;
the photocatalytic composite material prepared in the embodiment is subjected to performance test, and the test process and the method are as follows:
(1) a comparative test is carried out on example 1 and comparative examples 1 and 2 by taking GB/T23762-2009 (purification test method of a photocatalytic material aqueous solution system) as a performance detection method of a photocatalytic material, and the performance effect of the example 1 and the comparative examples 1 and 2 on treating methylene blue waste liquid is shown in Table 1.
Table 1 performance effect of example 1 and comparative example on treatment of methylene blue waste liquid
Figure 399746DEST_PATH_IMAGE002
As can be seen from the data in table 1, the photocatalytic removal rate of the photocatalytic composite material prepared by the method is 99%, the photocatalytic stability is 98%, and thus, compared with the titanium dioxide/hydroxyapatite composite material in comparative example 1, the photocatalytic removal rate of the product in example 1 on methylene blue is improved by 24%; compared with the pure nano titanium dioxide in the comparative example 2, the photocatalytic removal rate of the composite photocatalytic material prepared in the example 1 on methylene blue is improved by 31%.
As can be seen from the data in Table 1, the photocatalytic stability of the product of example 1 is 98%, 85% and 82% compared with that of comparative examples 1 and 2, respectively, and the composite photocatalytic material prepared in example 1 has better stability and longer service life compared with titanium dioxide/hydroxyapatite composite material and pure titanium dioxide.
(2) Adsorption experiment: in the experimental process, ibuprofen and carbamazepine are selected as pollutants for representing PPCPs (the PPCPs are globally called Pharmaceutical and Personal Care Products and are emerging pollutants, the PPCPs comprise various antibiotics, artificially synthesized musk, analgesics, antihypertensive drugs, contraceptive drugs, hypnotics, weight-reducing drugs, hair spray, hair dye, bactericide and the like), the initial concentration of the ibuprofen and the carbamazepine is 5mg/L, the stirring speed is 100rpm, the ultraviolet light intensity is 12W and 365nm, the adding amount of the photocatalytic adsorption material prepared in the examples 1-3 and the comparative examples 1 and 2 is 5g/L, and the reaction time is 45 min. The removal rate of contaminants before and after the reaction was calculated by high performance liquid chromatography, and the results are shown in table 2.
TABLE 2 removal of carbamazepine and ibuprofen by the materials of examples 1-3 and comparative examples
Figure 316887DEST_PATH_IMAGE004
The data in table 2 show that the adsorption removal effects of the composite photocatalytic materials obtained in examples 1 to 3 on carbamazepine and ibuprofen are far better than those of comparative examples 1 and 2, which shows that the synergistic interaction of hydroxyapatite, copper, silver and nano titanium dioxide obtains a good technical effect, the adsorption performance of the composite materials is improved, the photocatalytic efficiency of the composite materials is improved, the overall performance is excellent, and the application potential is huge.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The composite photocatalytic material is characterized by comprising flake hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.
2. The composite photocatalytic material according to claim 1, wherein the molar ratio of titanium dioxide to hydroxyapatite is 1: (0.5-5).
3. The composite photocatalytic material according to claim 1 or 2, wherein the molar ratio of copper to silver is (3-5): 1.
4. The composite photocatalytic material of claim 3, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1: (2-4).
5. The method for preparing the composite photocatalytic material of claim 1, characterized by comprising the following steps:
1) uniformly stirring and mixing the nano titanium dioxide, a solvent and a dispersant to obtain a suspension A; dissolving copper salt, silver salt and glucose in water to prepare a mixed salt solution B for later use;
2) respectively preparing a calcium salt solution and a solution of a phosphorus-containing substance, mixing the calcium salt solution and the solution of the phosphorus-containing substance, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, uniformly mixing, carrying out hydrothermal reaction at 130-160 ℃ for 3-8 h, cooling, standing, and carrying out centrifugal separation and drying to obtain titanium dioxide-coated flaky hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding sodium hydroxide, potassium hydroxide or ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum to obtain the titanium dioxide.
6. The method for preparing the composite photocatalytic material as recited in claim 5, wherein in step 1), the solvent is absolute ethanol, and the dispersant is sodium dodecyl sulfate or polyvinylpyrrolidone.
7. The method for preparing the composite photocatalytic material according to claim 5, wherein in the step 1), the copper salt is copper nitrate, copper sulfate or copper chloride, and the silver salt is silver nitrate.
8. The method for preparing the composite photocatalytic material according to claim 5, wherein in step 2), the calcium salt is calcium nitrate tetrahydrate or calcium chloride, and the phosphorus-containing substance is ammonium dihydrogen phosphate or ammonium hydrogen phosphate.
9. The method for preparing the composite photocatalytic material according to any one of claims 5 to 8, wherein the addition amount of the dispersing agent is 0.5 to 3% by mass of the nano titanium dioxide, the molar ratio of the glucose to the copper salt is 1:1, and the particle size of the nano titanium dioxide is 10 to 30 nm.
10. The use of the composite photocatalytic material of claim 1 in the field of photocatalytic degradation of PPCPs.
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CN113814003A (en) * 2021-09-29 2021-12-21 广东森格安环保新材料科技有限公司 Air purifying agent made of nano materials
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戴策: ""双金属复合光催化剂的制备及降解废水协同制氢的研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 *

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CN112058263A (en) * 2020-08-27 2020-12-11 中山大学 Preparation method of hydrothermal carbon/copper photocatalyst and application of hydrothermal carbon/copper photocatalyst in degradation of ibuprofen drugs
CN112058263B (en) * 2020-08-27 2022-09-09 中山大学 Preparation method of hydrothermal carbon/copper photocatalyst and application of hydrothermal carbon/copper photocatalyst in degradation of ibuprofen drugs
CN113814003A (en) * 2021-09-29 2021-12-21 广东森格安环保新材料科技有限公司 Air purifying agent made of nano materials
CN115553302A (en) * 2022-01-14 2023-01-03 华升科技集团有限公司 Sterilizing composition containing nano-scale titanium dioxide and preparation method thereof
CN114832821A (en) * 2022-04-25 2022-08-02 山东大学 Preparation method of in-situ photo-assisted copper deposition photocatalyst and atomic layer deposition device

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