CN116870935A - Modified bismuth oxychloride photocatalyst and preparation method thereof - Google Patents
Modified bismuth oxychloride photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 96
- GLQBXSIPUULYOG-UHFFFAOYSA-M bismuth oxychloride Chemical class Cl[Bi]=O GLQBXSIPUULYOG-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 34
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 34
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 33
- 239000002351 wastewater Substances 0.000 claims abstract description 27
- 150000001621 bismuth Chemical class 0.000 claims abstract description 17
- 150000000921 Gadolinium Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 239000012047 saturated solution Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000001804 chlorine Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 claims description 5
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 229960003405 ciprofloxacin Drugs 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical group [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 6
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 38
- 229940073609 bismuth oxychloride Drugs 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 36
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 29
- 239000012467 final product Substances 0.000 description 24
- 229910052688 Gadolinium Inorganic materials 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J37/08—Heat treatment
-
- 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
- C02F2101/34—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
- C02F2101/30—Organic compounds
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a modified bismuth oxychloride photocatalyst and a preparation method thereof, belonging to the technical field of photocatalytic materials. The photocatalyst is prepared by taking bismuth salt, gadolinium salt and chloride salt as raw materials, polyvinylpyrrolidone as a structural modifier, and ethylene glycol as a soft template agent and a solvent simultaneously through solvothermal reaction; wherein, the mole ratio of gadolinium salt and bismuth salt is 4 (0.3-0.4); the molar ratio of the chlorine salt to the bismuth salt is greater than 1:1; the volume ratio of the chloride saturated solution to the glycol is (8-12) (40-60); the feeding ratio of the polyvinyl pyrrolidone and the ethylene glycol is (0.8-1.2) g (40-60) mL; the photocatalyst is of a micron-sized flower-shaped structure formed by multiple layers of nano sheets, can reflect and refract visible light for multiple times, improves the utilization efficiency of the visible light, has high specific surface area and multiple active sites, and can efficiently photo-catalytically degrade organic pollutants in wastewater under the visible light.
Description
Technical Field
The invention relates to a modified bismuth oxychloride photocatalyst and a preparation method thereof, belonging to the technical field of photocatalytic materials.
Background
The photocatalysis technology has high catalytic activity, good stability, low price and environmental protection, and plays an important role in the novel environmental pollution water treatment technology. Bismuth oxychloride has been widely used because of its low toxicity, easily modified band gap, high economic benefit and strong catalytic activity, but bismuth oxychloride has low utilization rate of visible light and easy recombination of photo-generated electrons and holes, and the above disadvantages limit the practical application of bismuth oxychloride in the field of photocatalysis. The bismuth oxychloride photocatalyst has poor utilization condition of visible light, has absorption wavelength in a narrow region near ultraviolet light (lambda < 375 nm), and has low sunlight utilization rate (less than 5%). Therefore, how to improve the catalytic performance of the bismuth oxychloride photocatalyst and to use the catalyst to photo-catalytically degrade industrial wastewater is a problem to be solved in the field.
The bismuth oxychloride photocatalyst can be subjected to surface modification in order to reduce the band gap (eg=3.5 eV) of the bismuth oxychloride photocatalyst, slow the recombination rate of electron-hole pairs and improve the interfacial charge transfer efficiency. Patent application CN107597150a reports a preparation method of a rare earth element doped modified hollow microsphere bismuth oxyiodide photocatalyst, but the rare earth element doped modified hollow microsphere bismuth oxyiodide photocatalyst has limited specific surface area, so that the loading content of active components is limited, and the utilization rate of light of a catalyst formed by a single rare earth element and bismuth oxyiodide is limited, so that the catalyst can only degrade organic pollutant rhodamine B which is easy to degrade under the photocatalytic action, but cannot realize the photocatalytic degradation of organic pollutants which are difficult to degrade, such as isothiazolinone and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide a modified bismuth oxychloride photocatalyst which has a layered structure, can reflect and refract visible light for multiple times, improves the utilization efficiency of the visible light, and has high specific surface area and a large number of active sites;
the second purpose of the invention is to provide a preparation method of the modified bismuth oxychloride photocatalyst, which has the advantages of simple synthesis steps, mild reaction conditions and convenience for mass production.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A modified bismuth oxychloride photocatalyst is prepared from bismuth salt, gadolinium salt and chloride salt as raw materials, polyvinylpyrrolidone as a structural modifier, and ethylene glycol as a soft template agent and a solvent through solvothermal reaction; the photocatalyst is a micron-sized flower-like structure formed by a plurality of layers of nano sheets;
wherein the molar ratio of gadolinium salt to bismuth salt is 4 (0.3-0.4);
the molar ratio of the chlorine salt to the bismuth salt is greater than 1:1;
the volume ratio of the chloride saturated solution to the glycol is (8-12) (40-60);
the feeding ratio of the polyvinylpyrrolidone to the glycol is (0.8-1.2) g (40-60) mL.
Preferably, the bismuth salt is bismuth nitrate or bismuth nitrate pentahydrate; the chloride salt is sodium chloride; the gadolinium salt is gadolinium nitrate or gadolinium nitrate hexahydrate.
Preferably, the modified bismuth oxychloride photocatalyst can degrade organic pollutants in wastewater under the irradiation of a visible light source; the organic pollutant is antibiotics, organic dye or bactericide;
the mass concentration of the organic pollutants in the wastewater is less than or equal to 100 mg.L -1 The addition amount of the modified bismuth oxychloride photocatalyst is 0.8g.L -1 ～4g·L -1 Waste water;
further preferred, the organic contaminant is tetracycline, ciprofloxacin, rhodamine B, or isothiazolinone.
The invention discloses a preparation method of a modified bismuth oxychloride photocatalyst, which comprises the following steps:
(1) Dropwise adding the chloride saturated solution into bismuth salt, and continuously and uniformly stirring to obtain a solution A; then adding gadolinium salt into the solution A, and stirring and mixing uniformly to obtain a solution B;
(2) Dropwise adding ethylene glycol into the solution B obtained in the step (1), and uniformly stirring and mixing to obtain a solution C;
(3) Adding polyvinylpyrrolidone into the solution C obtained in the step (2), and uniformly stirring and mixing to obtain a solution D;
(4) Transferring the solution D obtained in the step (3) into a reaction kettle for solvothermal reaction, wherein the reaction time is 5.5-6.5 h, the reaction temperature is 155-165 ℃, separating the solid, washing and drying to obtain the modified bismuth oxychloride photocatalyst.
Preferably, in the step (3), the stirring speed is 150-200 rpm, and the stirring time is 30-40 min.
Preferably, in step (4), the solids are separated by centrifugation; and the drying condition is that the vacuum drying is carried out for 6 to 8 hours at the temperature of 75 to 85 ℃.
Advantageous effects
(1) The invention provides a modified bismuth oxychloride photocatalyst, which is a polyvinylpyrrolidone modified gadolinium doped bismuth oxychloride composite photocatalyst, wherein the catalyst has stable property, and gadolinium doping can form an active trapping center so as to play a role of trapping a trap, separate electrons from holes, inhibit the recombination of electron pairs and hole pairs, prolong the service life of carriers and further promote the photocatalytic activity of the carriers to be obtainedEnhancement, reducing the electron-hole pair recombination rate; gd (Gd) 3+ D-orbitals of bismuth oxychloride internal Bi 3+ The f tracks of the bismuth oxychloride are overlapped, so that the conduction band of the bismuth oxychloride is widened to move downwards, the forbidden bandwidth of the bismuth oxychloride is narrowed, and the light response range is enlarged; the metal doping captures photo-generated electrons and holes and inhibits electron-hole recombination, so that the photocatalytic activity is improved; in addition, the addition of polyvinylpyrrolidone enables the synthesized modified bismuth oxychloride photocatalyst material to have a multi-layer flower-shaped nanosphere morphology, the photocatalyst has a layered structure, can reflect and refract visible light for multiple times, improves the utilization efficiency of the visible light, has a high specific surface area and a large number of active sites, and further improves the capturing and activating capacity of active substances.
(2) The invention provides a modified bismuth oxychloride photocatalyst, which can realize the efficient treatment of organic pollutants in wastewater under the irradiation of visible light; the photocatalyst is used for degrading organic pollutants in wastewater, and has the advantages of mild reaction conditions, simple operation, high degradation efficiency and short time consumption; the BIT concentration is less than or equal to 100 mg.L -1 According to 0.8 g.L in isothiazolinone waste water -1 ～4g·L -1 After the photocatalyst is put into the reactor and treated for 180min, the BIT removal rate can reach more than 80%, and the catalyst has good photocatalytic performance.
(3) The invention provides a preparation method of a modified bismuth oxychloride photocatalyst, which comprises the steps of carrying out solvothermal reaction on an excessive chloride salt saturated solution, bismuth salt, gadolinium salt and polyvinylpyrrolidone to obtain the modified bismuth oxychloride photocatalyst in one step; gadolinium salt is used as a rare earth metal doped source, polyvinylpyrrolidone is used as a structure modifier, ethylene glycol is used as a solvent and a soft template agent, and the stable multilayer flower-shaped nanosphere morphology modified bismuth oxychloride photocatalyst is prepared by strictly controlling the dosage of each substance and the solvothermal reaction condition; the method has the advantages of simple steps, mild reaction conditions and convenience for mass production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the end product of example 1;
FIG. 2 is an energy dispersive X-ray spectrometer element profile (EDX mapping) of the end product described in example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the final product of example 1 and the photocatalysts of comparative examples 1 to 4;
FIG. 4 is a graph showing the ultraviolet-visible spectra of the final product of example 1 and the photocatalysts of comparative examples 1 to 4;
FIG. 5 is a graph of the Kubelka-Munk curves of the end product of example 1 and the photocatalysts of comparative examples 1-4;
FIG. 6 is a photoluminescence spectrum (PL) spectrum of the final product of example 1 and the photocatalysts of comparative examples 1 to 4.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a gadolinium doped bismuth oxychloride photocatalyst prepared in comparative example 2;
FIG. 8 is a Scanning Electron Microscope (SEM) image of a bismuth oxychloride photocatalyst prepared in comparative example 3 using ethylene glycol as a solvent;
fig. 9 is a Scanning Electron Microscope (SEM) image of the bismuth oxychloride photocatalyst prepared in comparative example 4 using water as a solvent.
Detailed Description
In order to explain the technical scheme and effect of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and the specific embodiments.
(1) The photocatalyst was tested for X-ray diffraction pattern (XRD) and analyzed for crystalline phase and grain size using the japanese instrument, uitima IV. Scanning at a speed of 4 DEG/min, wherein the scanning range is 10-80 deg.
(2) And (3) calculating a forbidden band width: and (5) measuring the ultraviolet-visible light absorption spectrum of the photocatalyst, and calculating to obtain the forbidden bandwidth. The test instrument is a general Beijing-Puxi instrument TU-1901, during testing, firstly, barium sulfate is taken to fill the sample stage for baseline correction, then barium sulfate is taken to fill the sample stage, 10mg of the photocatalyst is weighed and placed on the surface of the sample stage, and the test is carried out after grinding.
(3) Fluorescence spectrum test: the test instrument was a FL-7000 fluorescence spectrometer.
(4) EDS test: EDS was tested using OXFORD INSTRUMENTS X-act and SEM was tested using Germany, zeiss, SUPRA 55 SAPPHIRE.
In the following comparative examples and examples, benzisothiazolinone (BIT) degradation test procedures are as follows:
(1) Weighing 40mg of Benzisothiazolinone (BIT), adding 100mL of deionized water, stirring for dissolution, and placing into a 1L volumetric flask for constant volume after dissolution to obtain BIT concentration of 40mg.L -1 Is a target contaminant solution;
(2) Weighing 50mL of the target pollutant solution, placing the target pollutant solution in a beaker, weighing 0.06g of sample respectively, and adding the sample into the beaker; placing the beaker in a photocatalysis box, and after the beaker reaches adsorption equilibrium after being subjected to dark adsorption for 30 minutes, turning on a light source (500W xenon lamp) to perform photocatalysis reaction;
(3) And (3) degrading for 3 hours, and turning off the light source after the degradation is finished to finish the degradation. Taking out the degradation product, measuring the degradation product by using an ultraviolet-visible photometer, and calculating the degradation efficiency and degradation effect.
The Benzisothiazolinone (BIT) degradation rate is calculated as eta= (C) 0 -C)/C 0 X 100%, wherein eta is degradation rate, C 0 The initial concentration of benzisothiazolinone in the reactor is shown as C, and the concentration of benzisothiazolinone is shown as the concentration of benzisothiazolinone at different times in the photocatalytic reaction.
Example 1
A preparation method of a modified bismuth oxychloride photocatalyst comprises the following steps:
(1) 10mL of saturated sodium chloride solution is added dropwise to 1.940g (4 mmol) of bismuth nitrate pentahydrate, and stirring is continued to be uniform, so as to obtain solution A; then adding 0.158g (0.35 mmol) of gadolinium nitrate hexahydrate into the solution A, and stirring and mixing uniformly to obtain a solution B;
wherein the molar ratio of gadolinium salt to bismuth salt is 4:0.35;
(2) Dropwise adding 50mL of ethylene glycol into the solution B obtained in the step (1), and uniformly stirring and mixing to obtain a solution C;
the volume ratio of the saturated sodium chloride solution to the ethylene glycol is 10:50;
(3) Adding 1.0g of polyvinylpyrrolidone into the solution C obtained in the step (2), uniformly stirring and mixing, wherein the stirring speed is 150rpm, and the stirring time is 40min to obtain a solution D;
the feeding ratio of the polyvinylpyrrolidone to the ethylene glycol is 1.0g to 50mL;
(4) Transferring the solution D obtained in the step (3) into a reaction kettle for solvothermal reaction for 6 hours at a reaction temperature of 160 ℃, centrifugally separating solids, washing the solids with deionized water, and vacuum drying the solids in a vacuum drying oven at 80 ℃ for 8 hours to obtain final product powder.
Example 2
Example 2 the addition of saturated sodium chloride solution in step (1) was replaced by "8mL" from "10mL" based on example 1 only, the feed ratio of polyvinylpyrrolidone and ethylene glycol being 1.0g:50mL;
in the step (3), the stirring rotation speed is 150rpm, the stirring time is 40min, and the stirring rotation speed is 200rpm, and the stirring time is 30 min;
in the step (4), the reaction time is 6 hours, the reaction temperature is 160 ℃, the reaction temperature is 165 ℃ instead of the reaction temperature, and the reaction time is 5.5 hours; other conditions are unchanged, and the final product powder is obtained;
the volume ratio of the saturated sodium chloride solution to the ethylene glycol is 8:50.
Example 3
Example 3 based on example 1 only, the addition of saturated sodium chloride solution in step (1) was replaced by "12mL" from "10mL", the volume ratio of saturated sodium chloride solution to ethylene glycol being 12:50;
in the step (4), ' the reaction time is 6 hours, the reaction temperature is 160 ℃, the reaction temperature is 155 ℃, the reaction time is 6.5 hours, ' the vacuum drying at 80 ℃ is 8 hours, the vacuum drying at 75 ℃ is 6 hours ', and other conditions are unchanged, so that the final product powder is obtained; other conditions were unchanged to obtain the final product powder.
Example 4
Example 4 based on example 1 only, "0.158g (0.35 mmol) of nitric acid hexahydrate" in step (1) was replaced with "0.141g (0.31 mmol)", all other conditions being unchanged, to give the final product powder;
wherein the molar ratio of gadolinium salt to bismuth salt is 4:0.31.
Example 5
Example 5 based on example 1 only, "0.158g (0.35 mmol) of nitric acid hexahydrate" in step (1) was replaced with "0.174g (0.39 mmol)", all other conditions being unchanged, to give the final product powder;
wherein the molar ratio of gadolinium salt to bismuth salt is 4:0.39.
Example 6
Example 6 based on example 1 only, the "1.0g" polyvinylpyrrolidone in step (3) was replaced by "0.8g", all other conditions being unchanged, to give the final product powder;
the feeding ratio of the polyvinylpyrrolidone to the ethylene glycol is 0.8 g/50 mL.
Example 7
Example 7 based on example 1 only, the "1.0g" polyvinylpyrrolidone in step (3) was replaced by "1.2g", all other conditions being unchanged, to give the final product powder;
the feeding ratio of the polyvinylpyrrolidone to the ethylene glycol is 1.2 g/50 mL.
Example 8
Example 8 based on example 1 only, the "50mL ethylene glycol" in step (2) was replaced with "40mL ethylene glycol", all other conditions being unchanged, to give the final product powder;
the volume ratio of the saturated sodium chloride solution to the ethylene glycol is 10:40;
the feeding ratio of the polyvinylpyrrolidone to the ethylene glycol is 1.0 g/40 mL.
Example 9
Example 9 based on example 1 only, the "50mL ethylene glycol" in step (2) was replaced with "60mL ethylene glycol", all other conditions being unchanged, to give the final product powder;
the volume ratio of the saturated sodium chloride solution to the ethylene glycol is 10:60;
the feeding ratio of the polyvinylpyrrolidone to the ethylene glycol is 1.0 g/60 mL.
Comparative example 1
Comparative example 1 only based on example 1, gadolinium nitrate hexahydrate added in step (1) was removed, and other conditions were unchanged, to obtain a polyvinylpyrrolidone-modified bismuth oxychloride photocatalyst.
Comparative example 2
Comparative example 2 only based on example 1, except that the polyvinylpyrrolidone added in step (3) was removed, the other conditions were unchanged, to obtain a gadolinium doped bismuth oxychloride photocatalyst.
Comparative example 3
Comparative example 3 only gadolinium nitrate hexahydrate added in step (1) was removed, and polyvinylpyrrolidone added in step (3) was removed, and other conditions were not changed, to obtain a bismuth oxychloride photocatalyst using ethylene glycol as a solvent.
Comparative example 4
Comparative example 4 the substitution of "ethylene glycol" in step (2) with "deionized water" was performed under otherwise unchanged conditions only on the basis of comparative example 3, to obtain a bismuth oxychloride photocatalyst with deionized water as a solvent.
The final product prepared in the example 1 is subjected to scanning electron microscope characterization, and the result is shown in figure 1, wherein the final product presents a micron-sized flower-like structure consisting of a plurality of layers of nano sheets, and the diameter of the final product is 4.4-7.2 mu m; the scanning electron microscope characterization structures of the final products prepared in examples 2-9 are similar to those of example 1, and all the final products show a micron-sized flower-like structure composed of multiple layers of nano sheets; the structure has large specific surface area and higher number of active sites, and meanwhile, the concave-convex lamellar structure can reflect and refract visible light for multiple times, so that the utilization efficiency of the visible light is improved.
The scanning electron microscope characterization result of the gadolinium doped bismuth oxychloride photocatalyst prepared in the comparative example 2 is shown in fig. 7, and it can be seen that under the condition that polyvinylpyrrolidone as a structure modifier is not added, bismuth oxychloride and bismuth oxychloride generated by a solvothermal method are both in a nano-sheet structure and cannot be assembled into a micron-sized flower-like structure;
comparative example 3 the scanning electron microscope characterization result of the bismuth oxychloride photocatalyst prepared by using ethylene glycol as the solvent is shown in fig. 8, and it can be seen that the bismuth oxychloride photocatalyst can not be assembled into a micron-sized flower-like structure under the condition that only ethylene glycol is used as the soft template agent to carry out solvothermal reaction with the solvent and no structure modifier polyvinylpyrrolidone is added; comparative example 4 the scanning electron microscope characterization result of bismuth oxychloride photocatalyst prepared by solvothermal method using deionized water as solvent is shown in fig. 8, the bismuth oxychloride is in nano-sheet structure, and can not be assembled into micron-sized flower-like structure; according to the scanning electron microscope characterization results of the bismuth oxychloride photocatalysts prepared in comparative examples 3 and 4, it can be seen that the bismuth oxychloride photocatalysts prepared in example 4 by taking deionized water as a solvent only have smooth regular octagon nano-sheet structures, and the diameter of the nano-sheet is 1.7-3.2 μm; the bismuth oxychloride nanosheets prepared in example 3 by using ethylene glycol as a solvent have a certain degree of aggregation and assembly, which indicates that the ethylene glycol only serves as a solvent for solvothermal and also plays a role of a soft template agent.
EDS-mapping scanning is carried out on the final product prepared in the embodiment 1, and the result is shown in a figure 2, wherein Gd, bi, cl, O elements can be detected on the surface of the final product, and the distribution is uniform, which indicates that rare earth gadolinium is successfully doped in bismuth oxychloride; polyvinylpyrrolidone was not directly detected in the EDS-mapping scan due to the lower doping level. EDS-mapping scan results for examples 2-9 are similar to example 1. The final product prepared in example 1 was characterized by X-ray photoelectron spectroscopy (XPS), and an N-characteristic spectrum was detected in the XPS spectrogram, demonstrating that nitrogen doping was achieved and that polyvinylpyrrolidone was successfully doped into the final product. The XPS holomograms of examples 2-9 were similar to example 1.
In summary, the final products prepared in examples 1 to 9 are the modified bismuth oxychloride photocatalyst of the present invention.
As shown in the graph of the result of X-ray diffraction (XRD) analysis of the final product prepared in example 1 and the photocatalysts of comparative examples 1 to 4, as can be seen from the graph, the diffraction peaks of the final product prepared in example 1 and the photocatalysts of comparative examples 1 to 4 are in good agreement with the standard tetragonal phase BiOCl (JCCPDSNo. 06-0249) and no other impurity phase is detected, indicating that the synthesized material contains bismuth oxychloride and has higher purity; meanwhile, compared with the photocatalysts of comparative examples 2 to 4 without polyvinylpyrrolidone modification, the heights of diffraction peaks of the final product of example 1 and the photocatalysts of comparative example 1 with polyvinylpyrrolidone modification are reduced to different degrees, and the half-peak width is widened, so that the crystal structure of the material is greatly changed and moved from nano scale to micro scale; the reason is that the polyvinylpyrrolidone contains five-membered ring side groups, and has a certain steric hindrance so as to regulate and control the growth of bismuth oxychloride crystals, and the ethylene glycol not only serves as a system solvent but also plays a role of a soft template. In addition, the intensity of diffraction peak corresponding to the (001) crystal face and the (002) crystal face is obviously reduced, and the intensity of diffraction peak corresponding to the (110) crystal face is obviously improved. Thus, the crystal exposure crystal face changes greatly, the (001) and (002) crystal face exposure decreases, and the (110) crystal face exposure increases, which is helpful for electron hole separation and active free radical generation. The XRD characterization of the end products of examples 2-9 is similar to that of example 1.
The photocatalysts prepared in the example 1 and the comparative examples 1 to 4 are subjected to ultraviolet-visible diffuse reflection spectroscopy (UV-vis-DRS) analysis, the ultraviolet-visible spectrum diagrams of the final product in the example 1 and the photocatalysts in the comparative examples 1 to 4 are shown in fig. 4, and diffraction peaks of the photocatalysts prepared in the example 1 and the comparative examples 1 to 3 are remarkably improved in absorption in the visible light range compared with the photocatalysts prepared in the comparative example 4; the Kubelka-Munk curves of the end product described in example 1 and the photocatalysts described in comparative examples 1-4 are shown in fig. 5, and it can be seen that the photocatalyst (bandgap 2.23 eV) prepared in comparative example 4 has a relatively low bandgap compared with the photocatalyst (bandgap 2.93 eV) prepared in example 1, which indicates that polyvinylpyrrolidone modification and doping of rare earth gadolinium successfully change the bandgap structure of bismuth oxychloride, and improves the visible light response region of the photocatalyst, which is conducive to separation of electron-hole pairs and generation of active species of the material under visible light conditions. The results of the ultraviolet-visible diffuse reflectance spectroscopic analysis of examples 2 to 9 were similar to that of example 1.
Photoluminescence spectra (PL) analysis was performed on the photocatalysts prepared in example 1 and comparative examples 1 to 4, and the results are shown in fig. 6: as can be seen from the graph, the PL signal of the polyvinylpyrrolidone modified and rare earth gadolinium doped bismuth oxychloride photocatalyst prepared in example 1 is obviously reduced compared with that of the bismuth oxychloride prepared in comparative example 4, which indicates that the recombination rate of the photon-generated carriers is effectively reduced.
The photocatalysts described in examples 1 to 9 and comparative examples 1 to 4 were tested for the photocatalytic degradation efficiency of Benzisothiazolinone (BIT), and the results are shown in table 1:
TABLE 1 removal Rate of the photocatalyst described in examples 1-9 and comparative examples 1-4 for Benzisothiazolinone (BIT)
From Table 1, the catalyst of the invention obviously improves the removal rate of organic pollution of photocatalytic degradation through the synergistic effect of PVP, glycol, gadolinium and bismuth oxychloride.
The effect of the amount of the photocatalyst and the photocatalytic treatment time of the present invention on the removal effect of wastewater from organic pollutants was tested on the basis of the photocatalyst described in example 1, and the specific detection steps were as follows:
(1) 10 parts of the mixture have the concentration of 40 mg.L -1 Adding different amounts of the photocatalyst described in example 1 into the wastewater solution containing Benzisothiazolinone (BIT) respectively to obtain mixed solutions;
the dosage of the photocatalyst is 0.4 g.L in turn -1 Waste water, 0.8 g.L -1 Waste water, 1.2 g.L -1 Waste water, 1.6 g.L -1 Waste water, 2.0 g.L -1 Waste water, 2.4 g.L -1 Waste water, 2.8 g.L -1 Waste water, 3.2 g.L -1 Waste water, 3.6 g.L -1 Waste water, 4.0 g.L -1 And (5) waste water.
(2) Placing the mixed solution prepared in the step (1) into a photocatalysis box of a 200W xenon lamp, wherein the wavelength range of the xenon lamp is 390 nm-780 nm, stirring the mixed solution prepared in the step (1) by adopting a magnetic stirring mode to perform photocatalysis oxidation reaction, wherein the stirring rotating speed is 150rpm, the temperature of the photocatalysis oxidation reaction gradually rises due to the irradiation of the xenon lamp, the reaction temperature range is about 25-45 ℃, and when the reaction time is 30min, 60min, 120min and 180min, the mixed solution is taken out and filtered to realize solid-liquid separation, and the filtered solution is taken for detection.
The detection is that a UV-8000 ultraviolet visible spectrophotometer is adopted to measure the ultraviolet absorbance of the filtered solution, and the BIT content is measured at 318 nm. The removal rate of BIT in reverse osmosis concentrated water under different dosage and treatment time of the photocatalyst prepared in the example 1 is reacted by ultraviolet absorbance, and the test results are shown in Table 2:
the removal rate of BIT by the photocatalyst in different dosage and treatment time
As is clear from Table 2, in the photocatalytic oxidative degradation process of the bismuth oxychloride photocatalyst modified by polyvinylpyrrolidone and doped by rare earth gadolinium prepared in example 1, the addition amount of the photocatalyst is 0.4 g.L in the photocatalytic oxidative degradation process of the BIT in reverse osmosis concentrated water -1 When the wastewater is degraded for 180min by photocatalysis, the BIT removal rate can only reach 33.5 percent; the addition amount of the photocatalyst is 2.0 g.L -1 When the wastewater is used, the degradation efficiency of BIT is highest, the photo-catalytic degradation is carried out for 180min, and the BIT removal rate is as high as 93.3%; continuously increasing the addition amount of the photocatalyst, gradually reducing the degradation efficiency of BIT, and when the addition amount of the photocatalyst is 4.0g.L -1 When the wastewater is degraded for 180min by photocatalysis, the BIT removal rate is 84.9 percent, and the addition amount of the photocatalyst is 1.6g.L -1 When the wastewater is treated, the BIT removal rate is similar after photocatalytic degradation for 180 min; therefore, the catalytic effect and the economic cost of the photocatalyst are comprehensively considered, and the addition amount of the photocatalyst is 0.8g.L -1 ～4g·L -1 Waste water; and in the addition amount rangeIn this case, the removal rate of BIT by the catalyst increases with the photocatalytic treatment time.
As shown by the test results of the comparative examples and the examples, the modified bismuth oxychloride photocatalyst has a lower forbidden bandwidth, can utilize visible light to a greater extent, has a lower photo-generated electron-hole pair recombination rate, and thus has stronger photocatalytic activity; the modified bismuth oxychloride photocatalyst can realize the efficient treatment of organic pollutants in industrial wastewater under the irradiation of visible light, and has the advantages of mild condition, simple operation, high treatment efficiency and short time consumption in the reaction process; in addition, the preparation process of the modified bismuth oxychloride photocatalyst is simple, raw materials are easy to obtain, and the cost is low.
The above examples merely illustrate embodiments of the present invention and are not to be construed as limiting the scope of the invention, it being understood that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention.
Claims (6)
1. A modified bismuth oxychloride photocatalyst is characterized in that: the modified photocatalyst is prepared by taking bismuth salt, gadolinium salt and chloride salt as raw materials, polyvinylpyrrolidone as a structural modifier, and ethylene glycol as a soft template agent and a solvent simultaneously through solvothermal reaction; the photocatalyst is a micron-sized flower-like structure formed by a plurality of layers of nano sheets;
wherein the molar ratio of gadolinium salt to bismuth salt is 4 (0.3-0.4);
the molar ratio of the chlorine salt to the bismuth salt is greater than 1:1;
the volume ratio of the chloride saturated solution to the glycol is (8-12) (40-60);
the feeding ratio of the polyvinylpyrrolidone to the glycol is (0.8-1.2) g (40-60) mL.
2. The modified bismuth oxychloride photocatalyst as set forth in claim 1, wherein: the bismuth salt is bismuth nitrate or bismuth nitrate pentahydrate; the chloride salt is sodium chloride; the gadolinium salt is gadolinium nitrate or gadolinium nitrate hexahydrate.
3. A modified bismuth oxychloride photocatalyst as claimed in claim 1 or 2, wherein: the modified bismuth oxychloride photocatalyst can degrade organic pollutants in wastewater under the irradiation of a visible light source; the organic pollutant is antibiotics, organic dye or bactericide;
the mass concentration of the organic pollutants in the wastewater is less than or equal to 100 mg.L -1 The addition amount of the modified bismuth oxychloride photocatalyst is 0.8g.L -1 ～4g·L -1 And (5) waste water.
4. A modified bismuth oxychloride photocatalyst as claimed in claim 3, wherein: the organic pollutant is tetracycline, ciprofloxacin, rhodamine B or isothiazolinone.
5. A method for preparing the modified bismuth oxychloride photocatalyst according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
(1) Dropwise adding the chloride saturated solution into bismuth salt, and continuously and uniformly stirring to obtain a solution A; then adding gadolinium salt into the solution A, and stirring and mixing uniformly to obtain a solution B;
(2) Adding ethylene glycol into the solution B dropwise, and stirring and mixing uniformly to obtain a solution C;
(3) Adding polyvinylpyrrolidone into the solution C, and stirring and mixing uniformly to obtain a solution D;
(4) Transferring the solution D into a reaction kettle for solvothermal reaction, wherein the reaction time is 5.5-6.5 h, the reaction temperature is 155-165 ℃, separating the solid, washing and drying to obtain the modified bismuth oxychloride photocatalyst.
6. The method for preparing the modified bismuth oxychloride photocatalyst according to claim 5, which is characterized in that: in the step (3), the stirring speed is 150 rpm-200 rpm, and the stirring time is 30 min-40 min; in the step (4), the mode of separating the solids is centrifugal separation; and the drying condition is that the vacuum drying is carried out for 6 to 8 hours at the temperature of 75 to 85 ℃.
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