CN112808287B - Magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof - Google Patents
Magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 122
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 122
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 122
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000011258 core-shell material Substances 0.000 title claims abstract description 48
- GACUIHAEKGVEIC-UHFFFAOYSA-L [Bi+2]=O.C([O-])([O-])=O Chemical compound [Bi+2]=O.C([O-])([O-])=O GACUIHAEKGVEIC-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 76
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 47
- 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 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
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- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GQLMQWWBIJYOFC-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O Chemical compound [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O GQLMQWWBIJYOFC-UHFFFAOYSA-M 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 230000031700 light absorption Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
- 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 description 10
- 229940043267 rhodamine b Drugs 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 7
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- CCEKXLJXSBYSEB-UHFFFAOYSA-N ethane-1,2-diol;hydrobromide Chemical compound Br.OCCO CCEKXLJXSBYSEB-UHFFFAOYSA-N 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
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- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000007796 conventional method Methods 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
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052610 inosilicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and a preparation method thereof. CTAB-EG solution prepared by dissolving cetyl trimethyl ammonium bromide CTAB in glycol EG is used as a template agent and a reducing agent, bismuth nitrate-ferric nitrate solution is used as a raw material, and magnetic core-shell Fe is sequentially added after the pH value is regulated 3 O 4 @SiO 2 The microsphere and the purified sepiolite are fully mixed and then subjected to hydrothermal reaction to generate the core-shell bismuth oxide carbonate/sepiolite composite photocatalyst with controllable morphology. EG or CTAB is oxidized and decomposed under hydrothermal conditions to generate carbonate, the effective control of the product structure and morphology is realized through the surface activity of CTAB, the template effect and the interfacial effect of sepiolite, the recombination rate of energy band gap and photo-generated carriers is reduced, the visible light absorption utilization rate and the adsorption performance on organic matters are improved, and the excellent magnetic separation performance is endowed to the catalyst, so that the photocatalytic activity, separation recovery and recycling performance of the catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation of organic pollutants, and particularly relates to a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and a preparation method thereof.
Background
The discharge of organic matters such as organic dyes and antibiotics into the environment causes serious pollution to the ecological environment, constitutes an increasingly serious threat to human health, and has become a serious global environmental problem. For these pollution, various treatments have been developed, such as adsorption, ion exchange, reverse osmosis, biodegradation, chemical oxidation, advanced oxidation, photocatalytic degradation, etc. The photocatalytic degradation method utilizes light energy to excite a catalyst to generate a photo-generated carrier to degrade pollutants, can be realized by artificial illumination or natural illumination, is convenient and cheap, has high degradation degree, mild conditions and simple operation, and is the organic pollution treatment method with the most popularization and application value and application prospect. The effect of photocatalytic degradation depends mainly on the performance of the photocatalyst. Traditional photocatalysts, such as titanium dioxide and zinc oxide, can only show photocatalytic activity under irradiation of ultraviolet rays (lambda less than or equal to 387.5 nm) due to high energy band gaps (both above 3.2 eV). The ultraviolet content of the solar radiation is only about 5% of the total solar radiation, and the effective utilization rate of the natural light serving as a light source to the solar energy is too low. Therefore, there is a need to develop new visible light driven photocatalysts. Among the visible light catalysts developed, bismuth oxide carbonate (Bi 2 O 2 CO 3 ) Is a typical Aurivillius oxide belonging to the tetragonal system and having a unique structure of [ Bi ] 2 O 2 ] 2+ And CO 3 2- Layered structure composed of alternate layers, the internal electric field generated by polarization is beneficial to the separation of photoelectrons and holes, therefore Bi 2 O 2 CO 3 Has higher photocatalysis performance. But Bi is 2 O 2 CO 3 The defects of higher energy band gap (3.2-3.5 eV), low absorption rate to visible light, high photo-generated electron/hole pair recombination rate and the like still exist, the catalytic degradation effect is limited, the photocatalyst after treatment is difficult to separate and recycle, and the recycling performance is poor, so that the structure and the performance of the photocatalyst are required to be further improved and improved to realize popularization and application.
The photocatalyst with excellent performance must have proper energy band gap, high light absorptivity and quantum efficiency, low recombination rate of photo-generated carriers, excellent structural morphology, good pollutant adsorption performance, high photocatalytic degradation efficiency, low cost and good separation, recovery and recycling performance. The photocatalysis is required to have optimized composition, larger specific surface area, stable structure and morphology which are beneficial to light absorption, and performance which is beneficial to separation and recovery after degradation. The conventional methods for improving the performance of the photocatalyst mainly comprise regulation and control of the structure and morphology of the photocatalyst, doping, heterojunction formation and recombination formation with other components, and the like. Sepiolite (Sepiolite) is a magnesium-containing porous inosilicate mineral, has unique nano-structure pore diameter, larger pore volume and specific surface area, strong adsorption capacity, light weight and good chemical stability, and particularly, a large number of acid-base centers exist in the Sepiolite, so that other materials can form and grow on the Sepiolite. The material can be used as a template or a support for generating other photocatalysts, and can provide active sites for generating the photocatalysts to influence the structure and the morphology of the photocatalysts, so that the purpose of regulating and controlling the structure and the morphology of the material is achieved. The method for improving the separation and recovery performance of the photocatalyst after treatment mainly comprises the following steps: (1) The granularity of the photocatalyst is increased so as to improve the performance of precipitation separation or filtration separation; (2) Endowing the photocatalyst with magnetism, and carrying out magnetic separation by an external magnetic field, thereby being convenient for realizing the continuity and automatic control of the photocatalytic degradation process.
Disclosure of Invention
In view of Bi 2 O 2 CO 3 The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a magnetic core-shell bismuth oxide carbonate/sepioliteComposite photocatalyst (Fe) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite) in the form of magnetic core-shell type ferroferric oxide @ silica (Fe 3 O 4 @SiO 2 ) The microsphere is taken as a core, and a layer of bismuth oxide carbonate is coated on the surface to form a bismuth oxide carbonate/sepiolite composite material (Bi 2 O 2 CO 3 Sepiolite) to form a core-shell composite photocatalyst, denoted Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite wherein the magnetic core Fe 3 O 4 @SiO 2 The grain diameter of the microsphere is 350-500 nm, and the magnetic core Fe 3 O 4 @SiO 2 、Bi 2 O 2 CO 3 The mass ratio of the composite material to Sepiolite is 0.62-1.10:1:0.16-0.78. The composite photocatalyst has a core-shell spherical structure with regular morphology, good visible light response performance and magnetic separation performance, and solves the problem of Bi 2 O 2 CO 3 The visible light catalytic activity is not high, the separation and recovery are difficult, and the recycling performance is poor.
Another object of the present invention is to provide a magnetic core-shell Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Preparation method of Sepiolite composite photocatalyst, and the method is characterized in that Fe 3 O 4 @SiO 2 And in situ Bi formation in the presence of sepiolite 2 O 2 CO 3 Can be used for Bi 2 O 2 CO 3 Effectively controls the structure and the morphology of the alloy and ensures that Bi 2 O 2 CO 3 The sepiolite compound is uniformly and firmly coated on Fe 3 O 4 @SiO 2 Forming a core-shell structure on the microsphere surface; the method specifically comprises the following steps:
(1) Adding cetyl trimethyl ammonium bromide into ethylene glycol, and stirring ultrasonically for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking the solution as solution A;
(2) Bismuth nitrate pentahydrate and ferric nitrate nonahydrate are added into deionized water at the same time according to the mol ratio of 1:0.9-1.0, and are stirred for 20-40 min by ultrasonic stirring to be dissolved and prepared into the productBismuth nitrate-ferric nitrate mixed solution, denoted as solution B, wherein Bi 3+ The concentration is 0.02 to 0.033mol/L, fe 3+ The concentration is 0.018-0.033 mol/L;
(3) Slowly dripping the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH to 9.5-10.5, and continuously ultrasonically stirring at room temperature for 3-4 h to obtain a mixture C;
(4) In the mixture C obtained in the step (3), according to Fe 3 O 4 @SiO 2 The mass ratio of the microsphere to the bismuth nitrate pentahydrate is 0.32-0.57:1, and Fe is added 3 O 4 @SiO 2 Microsphere, ultrasonic stirring for 40-80 min; then adding purified sepiolite according to the mass ratio of the sepiolite to the bismuth nitrate pentahydrate of 0.082-0.41:1, and then carrying out ultrasonic stirring for 40-80 min to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst, namely Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite。
Further, in the step (3), a strong alkali solution with the pH of 8-12 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
Further, in the step (4), the Fe 3 O 4 @SiO 2 The particle size of the microsphere is 350-500 nm.
Further, in the step (4), the purified sepiolite is treated by the following method: grinding sepiolite, sieving with 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85deg.C under reflux for 0.5-1 hr, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide (CTAB) solution with the solid-to-liquid ratio (g/mL) of 1:40-60, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000-mesh sieve, and taking a screen bottom for later use.
Further, in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene lining high-pressure reaction kettle.
Further, the ultrasonic stirring is ultrasonic auxiliary mechanical stirring, and the ultrasonic power is 200-250W.
Further, the reagents used, cetyl trimethylammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol and hydrochloric acid, were all analytically pure.
The invention relates to a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst. Firstly, cetyl trimethyl ammonium bromide is dissolved in glycol to prepare a template agent-reducing agent solution, then bismuth nitrate-ferric nitrate mixed solution is dripped into the template agent-reducing agent solution, and a strong alkali solution is used for regulating the pH value of the mixed solution to obtain a mixture; then Fe is added 3 O 4 @SiO 2 The microspheres and the treated purified sepiolite are respectively added into the mixture, and after being fully mixed, the mixture is transferred into an autoclave with a polytetrafluoroethylene lining for hydrothermal reaction to generate Fe 3 O 4 @SiO 2 Is nuclear, bi 2 O 2 CO 3 Magnetic core-shell Fe with Sepiolite composite material as coating layer 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite composite photocatalyst. Oxidative decomposition of ethylene glycol or cetyltrimethylammonium bromide under hydrothermal conditions to produce carbonate by bismuth nitrate and ferric nitrate, and with Bi 3+ Bismuth oxide carbonate is generated under alkaline conditions; the generated Bi is caused to be under the comprehensive actions of the surface activity and the template action of hexadecyl trimethyl ammonium bromide and the stronger interfacial effect of sepiolite 2 O 2 CO 3 Bi is formed by using sepiolite as a support 2 O 2 CO 3 Sepiolite and is firmly and uniformly coated on Fe 3 O 4 @SiO 2 Microsphere surface, bi is solved 2 O 2 CO 3 Is formed by the process of (a) and (b) of coating layer Bi 2 O 2 CO 3 Effective regulation and control of structure and morphology of Sepiolite and Bi coating layer 2 O 2 CO 3 Sepiolite and magnetic core Fe 3 O 4 @SiO 2 To overcome the fusion problem of other magnetic cores such as Fe 3 O 4 And gamma-Fe 2 O 3 Not stable enough under acidic environment and Fe 3 O 4 The method has the advantages that heterojunction is formed between the core and the outer photocatalyst easily, so that recombination of electron hole pairs is accelerated, the photocatalysis efficiency is reduced, the recombination rate of energy band gap and photogenerated carriers is reduced, the visible light absorption utilization rate and the adsorption performance on organic matters are improved, the photocatalysis degradation performance on organic pollution is obviously improved, and excellent magnetic separation performance is provided for the photocatalyst.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The bismuth nitrate and ferric nitrate are oxidized and decomposed under hydrothermal condition to obtain carbonate radical, the amount of the carbonate radical is controlled by the oxidation and decomposition reaction speed, so that Bi can be effectively regulated and controlled by the reaction condition 2 O 2 CO 3 Is a generation speed of (2); the surface active action or template action of hexadecyl trimethyl ammonium bromide and glycol or the interfacial action of sepiolite are adopted to realize the coating layer Bi 2 O 2 CO 3 Effective regulation and control of structure and morphology of Sepiolite.
(2) Fe prepared by the invention 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The composite photocatalyst of Sepiolite is of a core-shell structure, and a coating layer Bi 2 O 2 CO 3 Sepiolite is in Fe 3 O 4 @SiO 2 On-line generation of magnetic microsphere in the presence of magnetic core shell SiO 2 The surface has rich active oxygen-containing groups such as-OH, -O-and the like, which is beneficial to Bi 2 O 2 CO 3 The Sepiolite is loaded and grown on the surface of the core-shell material, so that the cladding layer and the shell layer have better fusion property, and the prepared core-shell material has better stability.
(3) Fe prepared by the invention 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The surface layer of the Sepiolite composite photocatalyst is of a porous structure, and the specific surface area is higher than BFe generated in the absence of Sepiolite 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The size of the film is obviously increased,by sepiolite and magnetic core Fe 3 O 4 @SiO 2 The surface rich oxygen-containing groups and the interface function promote the coating layer Bi 2 O 2 CO 3 The formation of the Sepiolite structure increases the adsorption of organic contaminants and the absorption of light.
(4) BFe prepared by the invention 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite composite photocatalyst, sepiolite promotes and regulates Bi supported on Sepiolite by special pore canal structure 2 O 2 CO 3 The formation of the structure and the morphology of the polymer reduces the recombination rate of energy band gaps and photon-generated carriers and improves the photocatalytic degradation performance on organic pollutants; and BFe prepared 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The Sepiolite composite photocatalyst has excellent magnetic separation performance and recycling performance, and is beneficial to continuous operation and automatic control of the photocatalytic degradation process of organic pollutants.
(4) The product of the invention has excellent visible light catalytic degradation performance and mineralization capability on organic pollutants, has excellent catalytic decoloration performance on organic dye wastewater, is safe and nontoxic, and is suitable for treating various organic pollution wastewater.
(5) The preparation method has the advantages of simple preparation process, easy control of the process, less three-waste emission, lower manufacturing cost, and easy realization of industrial production due to the fact that the required equipment is conventional equipment, and has wide application prospect.
Drawings
FIG. 1 is a synthetic route diagram of a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
FIG. 2 shows a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst (m (Bi) 2 O 2 CO 3 ) XRD pattern of: (Sepilolite) =1:0.4).
FIG. 3 shows a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst (m (Bi) 2 O 2 CO 3 ) SEM image of: (Sepilolite) =1:0.4).
FIG. 4 is a schematic illustration of magnetic core-shell bismuth subcarbonate/sepioliteComposite photocatalyst (m (Bi) 2 O 2 CO 3 ) Photocatalytic degradation efficiency profile for: (Sepilolite) =1:0.4).
FIG. 5 shows a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst (m (Bi) 2 O 2 CO 3 ) Cyclic usage effect graph of: (Sepilolite) =1:0.4)
Note that: m (Bi) 2 O 2 CO 3 ) The mass ratio of bismuth oxide carbonate to sepiolite is shown in the specification of m.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples, but the invention is not limited thereto.
Example 1
(1) Adding 5.83g of cetyltrimethylammonium bromide into 128mL of ethylene glycol, and stirring ultrasonically for 20min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.125 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.62g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 320mL of deionized water at the same time, and stirring for 20min by ultrasonic to dissolve the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi 3+ The concentration is 0.020mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15min, then adjusting the pH to 10.5 by using 10mol/L KOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) 1.79g of Fe with the granularity of about 500nm is taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 80min by ultrasonic waves; then adding 0.47g of purified sepiolite, and stirring for 80min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3 hours at the temperature of 250 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ to constant weight to obtain 3.83g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 2
(1) Adding 5.83g of cetyltrimethylammonium bromide into 107mL of ethylene glycol, and stirring ultrasonically for 25min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.57g of ferric nitrate nonahydrate with the content of 98.5 percent, simultaneously adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 256mL of deionized water, and stirring ultrasonically for 25min to dissolve Bi 3+ The concentration is 0.025mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.024 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 20min, then adjusting the pH to 10.0 by using 10mol/L KOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) 1.57g of Fe with a particle size of about 500nm was taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 70min by ultrasonic waves; then adding 0.26g of purified sepiolite, and stirring for 70min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 4 hours at 230 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 4 times respectively, and drying at 115 ℃ to constant weight to obtain 3.37g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 3
(1) Adding 5.83g of cetyltrimethylammonium bromide into 80mL of ethylene glycol, and stirring for 30min by ultrasonic to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.20 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.49g of ferric nitrate nonahydrate with the content of 98.5 percent, adding into 213mL of deionized water at the same time, and stirring ultrasonically for 25min to dissolve Bi 3+ The concentration is 0.030mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.029 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 20min, then adjusting the pH to 9.8 by using 8mol/L KOH solution, and continuously ultrasonically stirring at room temperature for 3h to obtain a mixture C;
(4) 1.41g of Fe with the granularity of about 450nm is taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 60min by ultrasonic waves; then adding 0.63g of purified sepiolite, and stirring for 65min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 5 hours at 210 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 5 times respectively, and drying at 120 ℃ to constant weight to obtain 3.59g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Samples were taken and assayed on a D8 advanced X-powder diffractometer (40 kV,40mA, bruce AXS, germany) and scanned at 10℃to 80℃using the MDI Jade 5.0 analyte phase, the results of which are shown in FIG. 2. As can be seen from FIG. 2, diffraction peaks at 2 theta of 30.2 DEG, 35.5 DEG, 43.1 DEG, 53.2 DEG, 57.1 DEG and 62.8 DEG, etc. and Fe 3 O 4 The standard diffraction peaks of (JCPDS No. 19-0629) (220), (311), (400), (422), (511) and (440) correspond to each other, and the samples are proved to contain Fe 3 O 4 . The diffraction peak at 25 deg. is typical of amorphous silica, indicating Fe 3 O 4 The microspheres were successfully coated with a layer of amorphous silica. Sample Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite XRD pattern except for Fe 3 O 4 And SiO 2 Diffraction peaks 23.9 °, 30.3 °, 32.7 ° and 48.9 ° apart from those corresponding to the standard peak, and Bi 2 O 2 CO 3 Standard peaks (JCPDS No. 41-1488) are consistent, indicating Bi 2 O 2 CO 3 Has been formed and covered with Fe 3 O 4 @SiO 2 And (3) upper part. The new diffraction peak at 26.6 corresponds to the (080) crystal plane of sepiolite, indicating that sepiolite is contained therein. The above results all show that the sample Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite is composed of Fe 3 O 4 、SiO 2 、Bi 2 O 2 CO 3 And sepiolite.
Fe prepared in the absence of sepiolite was measured using a S-4800 type field emission scanning electron microscope (FESEM, hitachi Co., japan) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 And the morphology of the sample of this example, the results are shown in FIG. 3. FIG. 3 (a) shows Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Is spherical particles coated by a plurality of dense fine spherical particles with fluff; FIG. 3 (b) shows that Fe is formed in the presence of sepiolite 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The composite Sepiolite photocatalyst is formed by coating the outer surface of the sphere with coarser irregularly-shaped particles to form a porous coating layer. This means that the presence of sepiolite alters the coating Bi 2 O 2 CO 3 Is beneficial to improving the photoelectrochemical property (improving the light absorption performance, reducing the energy band gap and the recombination rate of photo-generated electrons and holes) and the adsorption capability to pollutants of the photocatalyst.
Determination of Fe with specific surface area-pore volume Analyzer (BELSORP-mini II, microtracBEL, japan) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Is 83.84m 2 /g，Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The specific surface area of the Sepiolite composite photocatalyst is 132.41m 2 And/g. Fe was measured using a model 6000 physical property measurement system (Quantum Design Co., america) with a Vibrating Sample Magnetometer (VSM) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 And Fe (Fe) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The saturation magnetization of the composite photocatalyst of the Sepiolite is 48.6 emu/g and 20.1emu/g respectively, which shows that the composite photocatalyst is matched with the magnetic core Fe 3 O 4 @SiO 2 The composition endows the photocatalyst with good magnetism; compounding with sepiolite increases the proportion of non-magnetic substances and therefore reduces the saturation magnetization. The diffuse reflection ultraviolet-visible spectrum (UV-vis DRS) was measured by a UV-2550 scanning ultraviolet-visible spectrophotometer (Shimadzu, japan), and Fe was calculated 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 And Fe (Fe) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Band gap E of Sepiolite composite photocatalyst g 3.27eV and 3.11eV, respectively, indicate Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Fe compounded with sepiolite 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 E of Sepiolite composite photocatalyst g Obviously reduce Bi 2 O 2 CO 3 The existence of the (C) obviously improves the structure of the composite photocatalyst and reduces the energy band gap of the composite photocatalyst.
Example 4
(1) Adding 5.83g of cetyltrimethylammonium bromide into 64mL of ethylene glycol, and stirring ultrasonically for 40min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.25 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.36g of ferric nitrate nonahydrate with the content of 98.5 percent, adding into 194mL of deionized water at the same time, and stirring ultrasonically for 25min to dissolve Bi 3+ The concentration is 0.033mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.030 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 30min, then adjusting the pH to 9.5 by using a 9mol/L KOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) 1.26g of Fe with a particle size of about 400nm was taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 60min by ultrasonic waves; then adding 0.79g of purified sepiolite, and stirring for 55min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 200 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ to constant weight to obtain 3.62g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 5
(1) Adding 5.83g of cetyltrimethylammonium bromide into 110mL of ethylene glycol, and stirring ultrasonically for 30min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.145 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.57g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 280mL of deionized water at the same time, and dissolving the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi by ultrasonic stirring for 35min 3+ The concentration is 0.023mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.022 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10 by using 8mol/L NaOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) 1.00g of Fe with the granularity of about 350nm is taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 50min by ultrasonic waves; then adding 1.29g of purified sepiolite, and stirring for 50min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 190 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 2 times respectively, and drying at 100 ℃ to constant weight to obtain 3.85g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 6
(1) Adding 5.83g of cetyltrimethylammonium bromide into 100mL of ethylene glycol, and stirring ultrasonically for 30min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.16 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.49g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 280mL of deionized water at the same time, and dissolving the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi by ultrasonic stirring for 35min 3+ The concentration is 0.021mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15min, then adjusting the pH to 10.3 by using a 12mol/L NaOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) 1.73g of Fe with the particle size of about 450nm is taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 40min by ultrasonic waves; then adding 1.26g of purified sepiolite, and stirring for 40min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 4 times respectively, and drying at 105 ℃ to constant weight to obtain 4.49g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 7
(1) Adding 5.83g of cetyltrimethylammonium bromide into 100mL of ethylene glycol, and stirring ultrasonically for 30min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.18 mol/L;
(2) Respectively taking 3.14g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.44g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 220mL of deionized water at the same time, and stirring for 40min by ultrasonic to dissolve the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi 3+ The concentration is 0.029mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.027 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10.3 by using 12mol/L KOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) 1.16g of Fe with a particle size of about 500nm was taken 3 O 4 @SiO 2 Adding the microspheres into the mixture C, and stirring for 60min by ultrasonic waves; then adding 0.94g of purified sepiolite, and stirring for 80min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 220 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ to constant weight to obtain 3.65g of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst.
Examples 8 to 10 are examples of photocatalytic degradation performance tests
Example 8
The photocatalytic performance test conditions were as follows: the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst (Fe) prepared in example 3 was used as a light source at room temperature using a 300W xenon lamp 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite，m(Bi 2 O 2 CO 3 ) Magnetic core-shell bismuth oxide carbonate (Fe) prepared under the same conditions in the presence of m (Sepilolite) =1:0.4) 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 ) The degradation rate of rhodamine B (RhB) was used as an evaluation index for the test sample. The specific operation steps are as follows: a clean 100mL jacketed beaker was charged with 50mg of photocatalyst sample and 50mL of 60mg/L RhB solution, each kept at equal distance from the light source. Standing for 30min in the dark to ensure that the adsorption and desorption of RhB on the surface of the sample reach equilibrium; degradation is carried out under 300W xenon lamp illumination, and sampling is carried out every 15min in the degradation process, and the sampling volume is 2mL. The photocatalyst was separated by magnet attraction from the samples, and the concentration of the supernatant was measured at 554nm with a UV-3600 ultraviolet-visible spectrophotometer (Shimazu, japan), and the degradation rates at different degradation times were calculated and plotted as degradation graphs with respect to time, as shown in FIG. 4. Taking a water sample with illumination for 90min, measuring total organic carbon in a TOC-LCPH type total organic carbon analyzer (Shimadzu, japan), and calculating the degradation rate of the total organic carbon.
As can be seen from fig. 4, the adsorption/desorption equilibrium is reached in the dark room for 30min, the RhB concentration is reduced by about 5.8%; the light is irradiated for 90min when no photocatalyst is added, and the self-degradation rate is very small; by Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) is catalyst illumination 90min, and the degradation rate of RhB reaches 99.6%; and Fe as 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 As a catalyst, the degradation rate of RhB reaches 57.8% after 90min of irradiation. Thus Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) has excellent photocatalytic degradation performance on RhB.
Measuring Fe after 90min of irradiation 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) and Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The Total Organic Carbon (TOC) removal rates were 82.17% and 31.21%, respectively. Thus Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) has excellent mineralization ability to RhB.
Example 9
To degrade Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The Sepiolite composite photocatalyst was recovered by magnet separation and used as the photocatalyst for the next round of experiments. The experimental conditions and procedures and test methods were the same as in example 8. The cycle was repeated 5 times, and the change in degradation rate was as shown in FIG. 5.
As can be seen from FIG. 5, fe is recycled 5 times 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The catalytic degradation rate of the composite photocatalyst of the/Sepiolite on the RhB is reduced from 99.6% of the 1 st time to 97.0% of the 5 th time, and the catalytic degradation rate is reduced by only 2.6%. The results show that the Fe prepared by the invention 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 The Sepiolite composite photocatalyst has excellent magnetic separation recovery and recycling performance.
Example 10
This example is an example of photocatalytic decoloring performance. The test conditions were as follows: 10mg of Methyl Red (MR), methylene Blue (MB) and Fluorescein (FS) were dissolved in 1L of distilled water to prepare a simulated mixed solution (MR-MB-FS), respectively, to prepare a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst (Fe) prepared in example 3 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite，m(Bi 2 O 2 CO 3 )∶m(Sepilolite)=1:0.4) and magnetic core-shell bismuth oxide carbonate (Fe) prepared under the same conditions in the absence of sepiolite 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 ) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of the photocatalyst sample and 100mL of MR-MB-FS solution. Standing in the dark for 30min, then carrying out degradation under 300W xenon lamp illumination, sampling every 15min in the degradation process, sampling 2mL in volume, and measuring the chromaticity of the solution by a dilution fold method after magnet adsorption separation, wherein the results are shown in Table 1.
TABLE 1 variation of solution chromaticity with time of illumination
The results in Table 1 show that Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) The dye has excellent photocatalytic decoloring capability for mixed dye solution with the ratio of m (sepiolite) =1:0.4, can be completely decolored after being irradiated for 75min, and is obviously superior to Fe without sepiolite 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 。
The foregoing is only a preferred embodiment of the invention, and various modifications and changes may be made thereto by those skilled in the art in light of the above teachings, for example, combinations of ratios and process conditions may be made within the scope of the invention as defined by the appended claims, and similar such changes and modifications are intended to be included within the spirit of the invention.
Claims (8)
1. A magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst is characterized in that magnetic core-shell type ferroferric oxide @ silicon dioxide, namely Fe 3 O 4 @SiO 2 The microsphere is taken as a core, a layer of bismuth oxide carbonate is coated on the surface, and bismuth oxide carbonate/sepiolite composite material which is Bi is generated on line in the presence of sepiolite is coated on the surface 2 O 2 CO 3 Sepiolite-forming core-shell composite photocatalyst, denoted Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 Sepiolite wherein the magnetic core Fe 3 O 4 @SiO 2 The grain diameter of the microsphere is 350-500 nm, and the magnetic core Fe 3 O 4 @SiO 2 、Bi 2 O 2 CO 3 The mass ratio of the sepiolite to the sepiolite is 0.62-1.10:1:0.16-0.78;
the preparation method of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst is characterized by comprising the following steps of:
(1) Adding cetyl trimethyl ammonium bromide into ethylene glycol, and stirring ultrasonically for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking the solution as a solution A;
(2) Bismuth nitrate pentahydrate and ferric nitrate nonahydrate are simultaneously added into deionized water according to the mol ratio of 1:0.9-1.0, and are ultrasonically stirred for 20-40 min to be dissolved and prepared into bismuth nitrate-ferric nitrate mixed solution, which is marked as solution B, wherein Bi is contained in the solution B 3+ The concentration is 0.02-0.033 mol/L, fe 3+ The concentration is 0.018-0.033 mol/L;
(3) Slowly dripping the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH to 9.5-10.5, and continuously ultrasonically stirring at room temperature for 3-4 h to obtain a mixture C;
(4) In the mixture C obtained in the step (3), according to Fe 3 O 4 @SiO 2 The mass ratio of the microsphere to the bismuth nitrate pentahydrate is 0.32-0.57:1, and Fe is added 3 O 4 @SiO 2 Microspheres, and stirring for 40-80 min by ultrasonic waves; then adding purified sepiolite according to the mass ratio of the sepiolite to the bismuth nitrate pentahydrate of 0.082-0.41:1, and carrying out ultrasonic stirring for 40-80 min to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst, namely Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite。
2. The preparation method of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) Adding cetyl trimethyl ammonium bromide into ethylene glycol, and stirring ultrasonically for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking the solution as a solution A;
(2) Bismuth nitrate pentahydrate and ferric nitrate nonahydrate are simultaneously added into deionized water according to the mol ratio of 1:0.9-1.0, and are ultrasonically stirred for 20-40 min to be dissolved and prepared into bismuth nitrate-ferric nitrate mixed solution, which is marked as solution B, wherein Bi is contained in the solution B 3+ The concentration is 0.02-0.033 mol/L, fe 3+ The concentration is 0.018-0.033 mol/L;
(3) Slowly dripping the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH to 9.5-10.5, and continuously ultrasonically stirring at room temperature for 3-4 h to obtain a mixture C;
(4) In the mixture C obtained in the step (3), according to Fe 3 O 4 @SiO 2 The mass ratio of the microsphere to the bismuth nitrate pentahydrate is 0.32-0.57:1, and Fe is added 3 O 4 @SiO 2 Microspheres, and stirring for 40-80 min by ultrasonic waves; then adding purified sepiolite according to the mass ratio of the sepiolite to the bismuth nitrate pentahydrate of 0.082-0.41:1, and carrying out ultrasonic stirring for 40-80 min to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst, namely Fe 3 O 4 @SiO 2 @Bi 2 O 2 CO 3 /Sepiolite。
3. The preparation method of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (3), a strong alkali solution with the pH of 8-12 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
4. The method for preparing a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (4), the Fe is as follows 3 O 4 @SiO 2 The particle size of the microsphere is 350-500 nm.
5. The method for preparing the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (4), the purified sepiolite is treated by the following method: grinding sepiolite, sieving with a 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85 ℃ under reflux for 0.5-1 h, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide, namely CTAB solution with the solid-to-liquid ratio of 1:40-60 g/mL, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000 mesh sieve, and taking the undersize for later use.
6. The method for preparing the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene lining high-pressure reaction kettle.
7. The preparation method of the magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 2, wherein the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
8. The method for preparing a magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst according to any one of claims 2 to 7, wherein the reagents used are cetyl trimethylammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol and hydrochloric acid.
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