CN112892545A - Magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst and preparation method thereof - Google Patents
Magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst and preparation method thereof Download PDFInfo
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- CN112892545A CN112892545A CN202110132656.9A CN202110132656A CN112892545A CN 112892545 A CN112892545 A CN 112892545A CN 202110132656 A CN202110132656 A CN 202110132656A CN 112892545 A CN112892545 A CN 112892545A
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 120
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 112
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 50
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011258 core-shell material Substances 0.000 title claims abstract description 43
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 title claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 67
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 67
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 67
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 57
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- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
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- 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 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 6
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical group [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 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 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 150000002505 iron Chemical class 0.000 abstract 2
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- 238000006731 degradation reaction Methods 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 14
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 239000002957 persistent organic pollutant Substances 0.000 description 9
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 4
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 4
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- 229910001868 water Inorganic materials 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
- 239000002585 base Substances 0.000 description 2
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- 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
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- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 2
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012491 analyte Substances 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
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 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 1
- 230000006872 improvement Effects 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- 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 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
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Abstract
The invention relates to a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst and a preparation method thereof. It uses soluble bismuth salt and iron salt as raw material, after the bismuth salt and iron salt solution are fully mixed, uses strong alkali to regulate pH value, then adds magnetic core-shell type Fe respectively3O4@SiO2Mixing the microsphere and purified sepiolite by ultrasonic stirring, and performing hydrothermal reaction on sepiolite and Fe3O4@SiO2Bismuth ferrite is generated on line under the combined action of rich oxygen-containing groups on the surface of the magnetic core and an interface effect and is firmly coated on the surface of the magnetic core, so that the effective regulation and control of the structure and the appearance of a coating layer and the effective regulation and control of the coating layer and the Fe of the magnetic core are realized3O4@SiO2The fusion of the microspheres and the use stability in an acid environment and the like, reduces the energy band gap and the recombination rate of photo-generated electrons and holes, and improves the adsorption performance to organic matters and the absorption utilization rate of visible light. The product of the invention has excellent photocatalytic degradation activity, magnetic separation recovery and recycling performance.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation treatment of organic pollutants, and particularly relates to a magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst and a preparation method thereof.
Background
The increasing discharge of organic matters such as organic dyes, antibiotics and the like can cause serious pollution to the ecological natural environment, and pose a potential threat to human bodies. Water pollution caused by organic contaminants such as organic dyes and antibiotics has become a serious global environmental problem. The research and development of the efficient, economic, environment-friendly and practical wastewater treatment method has important significance for solving the organic wastewater pollution, promoting the ecological environment construction and protecting the health of people.
Compared with other organic wastewater treatment methods, the photocatalytic degradation technology has high degradation degree on pollutants, and can even thoroughly mineralize organic pollutants into CO2、H2O and other inorganic small molecules; the reaction condition is mild, and the operation is simple and convenient; the treatment cost is lower, and particularly, the energy is saved and the cost is lower when natural light is used for degradation; strong adaptability and no special selectivity to wastewater; the treatment method does not bring other pollution, and is one of the methods which have most popularization and application values for treating the organic dye wastewater. Numerous photocatalysts have been developed, including nano-metal oxides, metal sulfides, nano-semiconductor photocatalysts, surface-supported noble nano-metal photocatalysts, perovskite oxide photocatalysts, and the like. Among developed photocatalysts, the perovskite photocatalyst has the advantages of good visible light absorption capacity, high catalytic activity, low price, environmental friendliness and the like. Bismuth ferrite (BiFeO)3) Is a typical bismuth-based perovskite material, has a narrow band gap of only about 2.5eV, and can excite photoproduced electrons and holes under the irradiation of visible light to generate O2 -OH and h+The active species are used for decomposing organic pollutant molecules, the stability in an acid environment is good, the toxicity is low, new pollution cannot be caused, and a plurality of research reports for applying the organic pollutant molecules to organic pollutant treatment exist. But BiFeO3As the photocatalyst, the following problems still exist, and the photocatalyst is far from practical application: (1) the prepared specific surface area is small, the adsorption performance to pollutants is poor, and the absorption utilization rate to light is low; (2) the recombination of the photoproduction electron/hole pair is faster, and the photocatalytic degradation rate is not too high; (3) the separation and recovery of the catalyst after the pollutants are degraded are not convenient enough, and the like. Therefore, for BiFeO3The photocatalyst reaches the practical level and is popularized and applied in the actual organic wastewater treatment, and the structure and the performance of the photocatalyst must be further improved and improved.
Sepiolite (Sepiolite) is a porous inosilicate mineral containing magnesium, and is added to BiFeO in view of unique nano-structured pore diameter, large pore volume, large specific surface area and good chemical stability, particularly in the presence of a large number of acid-base centers3In the process of (2), BiFeO is produced3Takes active sites on the sepiolite as base points and depends on the active sites, and the action of the strong interface effect on the BiFeO3The structure and the appearance of the film are controlled. Magnetic separation properties can be imparted to the prepared material by compounding with magnetic particle materials, such as Fe3O4、γ-Fe2O3And NiFe2O4And the prepared photocatalyst can be conveniently separated through an external magnetic field, so that the continuous and automatic control of the organic polluted wastewater treatment process is realized.
Disclosure of Invention
In view of BiFeO3And it is an object of the present invention to provide a magnetic core-shell bismuth ferrite/sepiolite composite visible light photocatalyst (Fe)3O4@SiO2@BiFeO3Sepiolite) having a morphologyRegular core-shell spherical structure, good visible light response performance and magnetic separation performance, and solves the problem of BiFeO3The visible light catalytic activity is not high, the separation and recovery are difficult and the recycling performance is not good.
The invention also aims to provide a preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst, and the method is used for preparing the Fe-based composite visible light catalyst3O4@SiO2In-situ generation of BiFeO in the presence of sepiolite3For BiFeO3The structure and the appearance of the BiFeO are effectively regulated and controlled, and the BiFeO is enabled to be3the/Sepiolite compound is uniformly and firmly coated on the Fe3O4@SiO2The preparation method is simple and convenient, the process is easy to control, the discharge of three wastes is less, the manufacturing cost is lower, and the industrial production is easy to realize; the method specifically comprises the following steps:
(1) soluble bismuth salt and ferric salt are prepared into bismuth salt and ferric salt solution respectively by deionized water or dilute acid according to the mol ratio of 1: 0.9-1.0, and Bi3+The concentration is 0.05-0.067 mol/L, Fe3+The concentration is 0.045-0.067 mol/L; then mixing the two solutions, and ultrasonically stirring for 1-2 hours to obtain a bismuth salt-iron salt solution which is marked as solution A;
(2) adjusting the pH value of the solution A obtained in the step (1) to 12.6-13.5, and continuing to stir ultrasonically at room temperature for 1-2 hours to obtain a mixture B;
(3) in the mixture B obtained in step (2), as Fe3O4@SiO2Adding Fe into the microspheres with the mass ratio of the microspheres to the bismuth salt of 0.32-0.49: 13O4@SiO2Carrying out ultrasonic stirring on microspheres for 30-60 min; adding purified sepiolite according to the mass ratio of the sepiolite to the bismuth salt of 0.082-0.41: 1, and carrying out ultrasonic stirring for 2-3 h to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 4-8 h at 150-200 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matter with deionized water and ethanol for 2-5 times respectively, and drying at 60-80 ℃ to constant weight to obtain the magnetic core-shell type bismuth ferrite/sepiolite composite visible light catalyst, which is marked as Fe3O4@SiO2@BiFeO3/Sepiolite;
(5) And (4) adjusting the pH value of the waste liquid remained in the magnet adsorption separation in the step (4) to 8.0-9.0, precipitating for 1-2 h, filtering, discharging filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
Further, in the step (1), the soluble bismuth salt is bismuth sulfate, bismuth chloride or bismuth nitrate pentahydrate; the soluble ferric salt is ferric sulfate, ferric trichloride hexahydrate or ferric nitrate nonahydrate.
Further, in the step (1), the diluted acid is hydrochloric acid or nitric acid with the concentration of 0.1-0.2 mol/L.
Further, in the step (2), a strong alkali solution of 5-8 mol/L is adopted for adjusting the pH, and the used strong alkali is KOH or NaOH.
Further, in the step (3), Fe3O4@SiO2The particle size of the microspheres is 350-500 nm.
Further, in the step (3), the purified sepiolite is processed by the following method: grinding sepiolite, sieving with a 200-300-mesh sieve, soaking in 1-2 mol/L hydrochloric acid at 75-85 ℃ for refluxing for 0.5-1 h, filtering, and washing with distilled water to be neutral; then preparing a mixture of sepiolite and 8-10 mmol/L Cetyl 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 at 80-100 ℃ to constant weight, grinding and sieving with a 800-1000-mesh sieve, and taking undersize for later use.
Further, in the step (5), sulfuric acid with the pH value of 6-8 mol/L is adopted for adjusting the pH value.
Furthermore, the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
Furthermore, the reagents used, bismuth nitrate pentahydrate, bismuth sulfate, bismuth chloride, ferric sulfate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, KOH, NaOH, ethanol, sulfuric acid and hydrochloric acid, were analytically pure.
The invention relates to a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst and a preparation method thereof. It is prepared through preparing solution of bismuth nitrate and ferric nitrate, mixing, regulating pH value with strong alkali solutionFully stirring; then the magnetic core-shell type Fe3O4@SiO2Adding microspheres and purified sepiolite into the mixture in sequence, ultrasonically stirring for a period of time, transferring into a polytetrafluoroethylene-lined high-pressure kettle, and performing hydrothermal reaction to obtain the magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst (Fe) with excellent morphology3O4@SiO2@BiFeO3/Sepiolite). According to the technical scheme, under the comprehensive action of rich oxygen-containing active groups on the surface of sepiolite and strong interface effect, BiFeO is generated through hydrothermal reaction3The sepiolite is used as the support to form and grow, and firmly and uniformly coats the Fe3O4@SiO2The surface of the microsphere is endowed with excellent magnetic separation performance of the photocatalyst, and the problem of coating BiFeO is solved3Effective regulation and control of/Sepiolite structure and morphology and coating layer BiFeO3Sepiolite and magnetic core Fe3O4@SiO2The problem of microsphere fusion is solved by adopting other magnetic cores such as Fe3O4And gamma-Fe2O3Not stable enough in acid environment and Fe3O4The core is easy to form heterojunction with the outer photocatalyst to accelerate the recombination of electron-hole pairs, thereby causing the defect of reduced photocatalytic efficiency, reducing the energy band gap and the recombination rate of photoproduction electrons and holes, improving the adsorption performance and the visible light absorption utilization rate of organic matters, and improving the photocatalytic degradation performance of organic pollution.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the technical scheme of the invention is that Fe is adopted3O4@SiO2On-line generation of BiFeO by hydrothermal reaction in the presence of microspheres and sepiolite3Under the influence of rich active groups on the surface of the sepiolite and the action of strong interface effect, BiFeO is generated3The structure and the appearance of the BiFeO are effectively regulated and controlled, and the BiFeO generated on line3The compound photocatalyst BiFeO prepared by taking sepiolite as a support for formation and growth3The sepiolite is well fused; formed BiFeO3/Sepiolite composite in Fe3O4@SiO2Microsphere surface richThe BiFeO is loaded on the surface of the material on line under the action of rich oxygen-containing activity, so that the BiFeO is improved3Sepiolite coating layer and magnetic kernel Fe3O4@SiO2The fusion property, the coating uniformity and the bonding firmness of the composite photocatalyst are improved, so that the stability of the prepared composite photocatalyst is improved.
(2) Fe prepared by the invention3O4@SiO2@BiFeO3the/Sepiolite composite visible light catalyst is a porous structure, and has specific surface area ratio of core-shell type Fe generated without Sepiolite3O4@SiO2@BiFeO3The increase is obvious; through the synergistic effect with the sepiolite, the adsorption capacity and the light absorption utilization rate of organic matters are increased, and the catalytic degradation effect on organic pollutants is promoted; and the product has higher saturation magnetization and excellent magnetic separation performance, and is beneficial to realizing continuous operation and automatic control of the photocatalytic process.
(3) Fe prepared by the invention3O4@SiO2@BiFeO3Sepiolite in Sepiolite composite visible light catalyst not only promotes and regulates BiFeO loaded on Sepiolite by virtue of special pore channel structure3The structure and the appearance of the composite photocatalyst lead the coating layer BiFeO of the prepared composite photocatalyst to be3the/Sepiolite is beneficial to the adsorption of organic pollutants and the absorption and utilization rate of light, and reduces the energy band gap and the recombination rate of photoproduction electrons and holes, thereby improving the photocatalytic degradation performance of the 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, is convenient to recover and good in recycling performance, and is suitable for treating various organic polluted wastewater; the method has the advantages of simple process, low water treatment cost, easy operation and control, and continuous and automatic control.
(5) The method has the advantages of simple synthesis process, easy and convenient operation control in the preparation process, low manufacturing cost, conventional equipment required, easy realization of large-scale production and wide application prospect.
Drawings
Fig. 1 is a synthesis route diagram of a magnetic core-shell bismuth ferrite/sepiolite composite visible light photocatalyst.
FIG. 2 shows a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst (m (BiFeO)3) M (Sepilolite) 1: 0.3) XRD pattern.
FIG. 3 shows a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst (m (BiFeO)3) M (Sepilolite) 1: 0.3) SEM image.
FIG. 4 shows a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst (m (BiFeO)3) Graph of photocatalytic degradation efficiency for m (Sepilolate) 1: 0.3).
FIG. 5 shows a magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst (m (BiFeO)3) M (Sepilolate) 1: 0.3).
Note: m (BiFeO)3) M (Sepilolite) is the mass ratio of bismuth ferrite to sepiolite.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited thereto.
Example 1
(1) 3.31g of 99.0 percent bismuth nitrate pentahydrate are dissolved in 100mL of deionized water to prepare Bi3+The concentration is 0.067mol/L solution, 2.77g of ferric nitrate with the content of 98.5 percent is dissolved in 100mL of deionized water to prepare Fe3+The concentration is 0.067mol/L solution; mixing the two solutions, and ultrasonically stirring for 2 hours to obtain a bismuth nitrate-ferric nitrate solution A;
(2) adjusting the pH value to 13 by using 8mol/L KOH solution, and continuing to stir for 2 hours at room temperature by ultrasound to obtain a mixture B;
(3) 1.16g of Fe with a particle size of about 500nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 60 min; then adding 0.50g of purified sepiolite, and carrying out ultrasonic stirring for 3 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) 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 matter for 3 times by using deionized water and ethanol respectively, and drying at 80 ℃ to constant weight to obtain 3.68g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 8mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.5, precipitating for 2 hours, filtering, discharging the filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
Example 2
(1) 3.31g of 99.0 percent bismuth nitrate pentahydrate are dissolved in 113mL of deionized water to prepare Bi3+The concentration is 0.060mol/L solution, 2.71g ferric nitrate with the content of 98.5 percent is dissolved in 132mL deionized water to prepare Fe3+The concentration is 0.050mol/L solution; mixing the two solutions, and ultrasonically stirring for 1.5h to obtain a bismuth nitrate-ferric nitrate solution A;
(2) regulating the pH value to 13.5 by using 8mol/L KOH solution, and continuing to stir for 1.5 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 1.32g of Fe with a particle size of about 500nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 50 min; then adding 0.66g of purified sepiolite, and carrying out ultrasonic stirring for 2.5 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 7 hours at 190 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matter for 3 times by using deionized water and ethanol respectively, and drying at 75 ℃ to constant weight to obtain 3.99g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 8mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.9, precipitating for 1.5h, filtering, discharging the filtrate, collecting filter residues, and intensively treating and recycling valuable components.
The phase was determined on a D8 Advance X-powder diffractometer (40kV,40mA, Bruker 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 30.2 °, 35.5 °, 43.1 °, 53.2 °, 57.1 ° and 62.8 ° were observed for Fe3O4(JCPDS No.19-0629) (220), (311), (400), (422), (511), and (440) the standard diffraction peaks matched well, indicating that the sample wasAll products contain Fe3O4(ii) a The diffraction peak at 25 ℃ is typical of amorphous silica and is Fe3O4@SiO2A layer of amorphous silica on the surface of the microspheres; diffraction peaks at 22.5 °, 31.8 °, 32.1 °, 39.5 °, 45.8 °, 51.4 ° and 57.0 ° with BiFeO3Diffraction peaks on a standard card (JCPDS No.20-0169) are consistent, which indicates that BiFeO exists in the product3Phase, the diffraction peak at 26.6 ° is in good agreement with the sepiolite (080) crystal face, indicating the presence of sepiolite in the sample. The above results show that the prepared sample is made of Fe3O4、SiO2、BiFeO3And sepiolite.
Fe prepared in the absence of sepiolite was determined using a field emission scanning electron microscope (FESEM, Hitachi Co., Japan) model S-48003O4@SiO2@BiFeO3And the morphology of the sample of this example, the results are shown in FIG. 3. FIG. 3(a) shows Fe3O4@SiO2@BiFeO3Is in a flower-shaped spherical shape consisting of a plurality of flakes with different shapes and uneven surfaces; FIG. 3(b) shows Fe produced in the presence of sepiolite3O4@SiO2@BiFeO3the/Sepiolite composite photocatalyst is formed by coating larger irregular-shaped particles on the outer surface of a ball to form a surface porous coating layer. This indicates that the existence of sepiolite changes the coating layer BiFeO3The crystal structure of the photocatalyst is beneficial to improving the photoelectrochemical properties of the photocatalyst, such as improving the absorption performance of light, reducing the energy band gap, the recombination rate of photo-generated electrons and holes and the like, and improving the adsorption capacity of pollutants.
Fe was measured using a specific surface area-pore volume analyzer (BELSORP-mini II, MicrotracBEL, Japan)3O4@SiO2@BiFeO3Has a specific surface area of 99.93m2/g,Fe3O4@SiO2@BiFeO3Specific surface area of/Sepiolite composite photocatalyst is 126.68m2(ii) in terms of/g. Fe was measured using a 6000 type physical property measuring system (Quantum Design Co., America) with a Vibrating Sample Magnetometer (VSM)3O4@SiO2@BiFeO3And Fe3O4@SiO2@BiFeO3The saturation magnetization of the/Sepiolite composite photocatalyst is 40.8 emu/g and 18.2emu/g respectively, which shows that the composite photocatalyst is Fe with a magnetic core3O4@SiO2The photocatalyst is endowed with good magnetism through compounding; compounding with sepiolite increases the proportion of non-magnetic material, and therefore the saturation magnetization is reduced. Measuring diffuse reflection ultraviolet-visible spectrum (UV-vis DRS) by using UV-2550 scanning ultraviolet-visible spectrophotometer (Shimadzu, Japan), and calculating to obtain Fe3O4@SiO2@BiFeO3And Fe3O4@SiO2@BiFeO3Energy band gap E of/Sepiolite composite photocatalyst sampleg2.23eV and 2.09eV, respectively, indicating Fe3O4@SiO2@BiFeO3Fe compounded with sepiolite3O4@SiO2@BiFeO3E of/Sepiolite composite photocatalystgObviously reduces the content of the sepiolite, obviously improves the structure of the composite photocatalyst and reduces the energy band gap of the composite photocatalyst.
Example 3
(1) 3.31g of 99.0 percent bismuth nitrate pentahydrate are dissolved in 123mL0.1mol/L dilute nitric acid to prepare Bi3+The solution with the concentration of 0.055mol/L is dissolved in 2.63g of ferric nitrate with the content of 98.5 percent in 116mL0.1mol/L dilute nitric acid to prepare Fe3+The concentration is 0.055mol/L solution; mixing the two solutions, and ultrasonically stirring for 1h to obtain a bismuth nitrate-ferric nitrate solution A;
(2) regulating the pH value to 12.9 by using 6mol/L KOH solution, and continuing to stir for 1.5 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 1.06g of Fe with a particle size of about 450nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 40 min; then adding 0.27g of purified sepiolite, and carrying out ultrasonic stirring for 2 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at 180 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matter for 4 times by using deionized water and ethanol respectively, and drying at 70 ℃ to constant weight to obtain 3.35g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 7mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 9.0, precipitating for 1h, filtering, discharging the filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
Example 4
(1) 3.31g of 99.0 percent bismuth nitrate pentahydrate are dissolved in 127mL of deionized water to prepare Bi3+The concentration is 0.053mol/L solution, 2.63g of ferric nitrate with the content of 98.5 percent is dissolved in 101mL of deionized water to prepare Fe3+The concentration is 0.060mol/L solution; mixing the two solutions, and ultrasonically stirring for 1h to obtain a bismuth nitrate-ferric nitrate solution A;
(2) regulating the pH value to 12.7 by using 5mol/L KOH solution, and continuing to stir for 1 hour by ultrasound at room temperature to obtain a mixture B;
(3) 1.49g of Fe with a particle size of about 400nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 30 min; then adding 0.83g of purified sepiolite, and carrying out ultrasonic stirring for 3 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 7 hours at 160 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matter for 5 times by using deionized water and ethanol respectively, and drying at 80 ℃ to constant weight to obtain 4.37g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 6mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.2, precipitating for 2 hours, filtering, discharging the filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
Example 5
(1) 2.42g of 98.5 percent bismuth sulfate is dissolved in 135mL0.1mol/L dilute hydrochloric acid to prepare Bi3+Dissolving 0.050mol/L solution of iron sulfate (1.27 g) with 99.0% concentration in 121mL0.1mol/L dilute hydrochloric acid to obtain Fe3+The concentration is 0.052mol/L solution; mixing the two solutions, and ultrasonically stirring for 2 hours to obtain a bismuth sulfate-ferric sulfate solution A;
(2) adjusting the pH value to 13.2 by using a 5mol/L NaOH solution, and continuing to stir for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 1.18g of the powder with the particle size of aboutFe of 350nm3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 60 min; then adding 0.99g of purified sepiolite, and then carrying out ultrasonic stirring for 2.5h to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 8 hours at 150 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters by using deionized water and ethanol for 2 times respectively, and drying at 80 ℃ to constant weight to obtain 4.15g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light catalyst.
(5) And (4) adding 6.5mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.0, precipitating for 1.5h, filtering, discharging the filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
Example 6
(1) 2.42g of 98.5 percent bismuth sulfate is dissolved in 116mL0.2mol/L dilute nitric acid to prepare Bi3+The concentration is 0.058mol/L solution, 1.31g of ferric sulfate with the content of 98.5 percent is dissolved in 135mL0.2mol/L dilute nitric acid to prepare Fe3+The concentration is 0.048mol/L solution; mixing the two solutions, and ultrasonically stirring for 2 hours to obtain a bismuth sulfate-ferric sulfate solution A;
(2) adjusting the pH value to 13.0 by using 8mol/L NaOH solution, and continuing to stir for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 1.09g of Fe with a particle size of about 500nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 55 min; then adding 0.85g of purified sepiolite, and carrying out ultrasonic stirring for 3 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 4 hours at 200 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matters for 4 times by using deionized water and ethanol respectively, and drying at 60 ℃ to constant weight to obtain 3.98g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light catalyst.
(5) And (4) adding 6mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.3, precipitating for 1.5h, filtering, discharging the filtrate, collecting filter residues, and intensively treating and recycling valuable components.
Example 7
(1) 2.17g of 98.0 percent bismuth chloride is dissolved in 120mL0.1mol/L dilute hydrochloric acid to prepare Bi3+0.056mol/L solution, dissolving 1.69g of 99.5 percent ferric trichloride hexahydrate in 115mL0.1mol/L dilute hydrochloric acid to prepare Fe3+The concentration is 0.054mol/L solution; mixing the two solutions, and ultrasonically stirring for 2 hours to obtain a bismuth chloride-ferric trichloride solution A;
(2) regulating the pH value to 12.6 by using 8mol/L KOH solution, and continuing to stir for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 0.87g of Fe with a particle size of about 500nm is taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 60 min; then adding 0.65g of purified sepiolite, and carrying out ultrasonic stirring for 2.5h to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) 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 matter for 3 times by using deionized water and ethanol respectively, and drying at 70 ℃ to constant weight to obtain 3.57g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 6.5mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.7, precipitating for 2 hours, filtering, discharging the filtrate, collecting filter residues, and intensively treating and recycling valuable components.
Example 8
(1) 2.17g of 98.0 percent bismuth chloride is dissolved in 130mL0.1mol/L dilute hydrochloric acid to prepare Bi3+Dissolving 0.052mol/L solution of ferric chloride hexahydrate with the content of 99.5 percent by 1.78g in 125mL0.1mol/L dilute hydrochloric acid to prepare Fe3+The concentration is 0.052mol/L solution; mixing the two solutions, and ultrasonically stirring for 2 hours to obtain a bismuth chloride-ferric trichloride solution A;
(2) regulating the pH value to 12.9 by using 8mol/L KOH solution, and continuing to stir for 2 hours at room temperature by ultrasonic waves to obtain a mixture B;
(3) 0.76g of Fe with a particle size of about 500nm was taken3O4@SiO2Adding the microspheres into the mixture B, and ultrasonically stirring for 55 min; then adding 0.54g of purified sepiolite, and carrying out ultrasonic stirring for 3 hours to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at 200 ℃; cooling to room temperature, carrying out adsorption separation by using a magnet, washing the collected solid matter for 3 times by using deionized water and ethanol respectively, and drying at 80 ℃ to constant weight to obtain 3.34g of the magnetic core-shell type bismuth ferrite/sepiolite composite visible light photocatalyst.
(5) And (4) adding 6.5mol/L sulfuric acid into the waste liquid remaining after the magnet separation in the step (4) to adjust the pH value to 8.9, precipitating for 1.5h, filtering, discharging the filtrate, collecting filter residues, and carrying out centralized treatment to recover valuable components.
Examples 9 to 12 are photocatalytic degradation performance test examples
Example 9
The photocatalytic performance test conditions were as follows: at room temperature, a 300W xenon lamp was used as a light source, and the magnetic core-shell bismuth ferrite/sepiolite composite visible light photocatalyst (Fe) prepared in example 2 was used3O4@SiO2@BiFeO3/Sepiolite,m(BiFeO3) M (Sepilolite) 1: 0.3 and in the absence of sepiolite under the same conditions to prepare magnetic core-shell bismuth ferrite (Fe)3O4@SiO2@BiFeO3) For the test samples, the degradation rate of Methylene Blue (MB) was used as an evaluation index. The specific operation steps are as follows: a clean 100mL jacketed beaker was charged with 50mg of photocatalyst sample and 50mL of 60mg/L MB solution, each at equal distances from the light source. Standing in the dark for 30min to ensure that MB is adsorbed and desorbed on the surface of the sample to reach balance; and (3) degrading under the illumination of a 300W xenon lamp, and sampling once every 15min in the degradation process, wherein the sampling volume is 2 mL. The sampled sample was injected into a centrifuge tube and centrifuged to take out the supernatant, the concentration was measured at 665nm in a UV-3600 UV-visible spectrophotometer (Shimazu, Japan), the degradation rates at different degradation times were calculated, and a degradation curve was obtained by plotting the degradation rates against time, as shown in fig. 4. A water sample with illumination for 90min is taken to determine the total organic carbon in a TOC-LCPH type total organic carbon analyzer (Shimadzu, Japan), and the degradation rate of the total organic carbon is calculated.
As can be seen from fig. 4, the adsorption/desorption equilibrium was reached in the dark room for 30min, with a reduction in MB concentration of about 6.7%; the light irradiation is carried out for 90min without adding the photocatalyst, and the self-degradation rate is very low; as followsProduct Fe3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (Sepilolite) is 1: 0.3) is taken as a catalyst, the light irradiation is carried out for 90min, and the degradation rate of MB reaches 99.8 percent; and with Fe3O4@SiO2@BiFeO3As a catalyst, after irradiating for 90min, the degradation rate of MB is only 60.8%. Thus, Fe3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (sepiolite) 1: 0.3) has excellent photocatalytic degradation properties for MB.
Determination of Fe after 90min of irradiation3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (Sepilolite) 1: 0.3) and Fe3O4@SiO2@BiFeO3The Total Organic Carbon (TOC) removal was 92.3% and 43.03%, respectively. Thus, Fe3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (sepiolite) 1: 0.3) has excellent mineralization ability to MB.
Example 10
Degrading the degraded Fe3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (sepiolite) 1: 0.3) composite photocatalyst was separated and recovered by magnet and used as photocatalyst for the next round of experiment. The experimental conditions and procedures and test methods were the same as in example 9. The degradation rate was varied by 5 cycles as shown in FIG. 5.
As can be seen from FIG. 5, Fe was used for 5 times3O4@SiO2@BiFeO3The catalytic degradation rate of the/Sepiolite composite photocatalyst to MB is reduced from 99.8% at the 1 st time to 98.6% at the 5 th time, and is only reduced by 1.2%. The results show that the Fe prepared by the invention3O4@SiO2@BiFeO3the/Sepiolite composite photocatalyst has excellent magnetic separation recovery and recycling performance and wide popularization and application prospects.
Example 11
This example is an example of photocatalytic bleaching performance, with the following test conditions: 10mg of Methyl Red (MR), Methylene Blue (MB) and rhodamine (RhB) are respectively dissolved in 1L of steamA simulated mixed solution (MR-MB-RhB) was prepared from distilled water, and the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst (Fe) prepared in example 2 was used3O4@SiO2@BiFeO3/Sepiolite,m(BiFeO3) M (Sepilolite) 1: 0.3 and magnetic core-shell bismuth subcarbonate (Fe) prepared under the same conditions in the absence of sepiolite3O4@SiO2@BiFeO3) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of photocatalyst sample and 100mLMR-MB-RhB solution. Standing in the dark for 30min, then degrading under the illumination of a 300W xenon lamp, sampling once every 15min in the degradation process, wherein the sampling volume is 2mL, and measuring the solution chromaticity by a dilution multiple method after magnetic adsorption separation, wherein the results are shown in Table 1.
TABLE 1 change in solution color with time of illumination
The results in Table 1 show that Fe3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (Sepilolite) 1: 0.3) has excellent photocatalytic decolorizing capability on mixed dye solution, can be completely decolorized after being irradiated for 75min, and is obviously superior to Fe without sepiolite3O4@SiO2@BiFeO3。
Example 12
This example is an example of the catalytic degradation performance of the prepared samples to antibiotics. The photocatalyst and experimental conditions used were the same as in example 9, and the degradation subjects were the common antibiotics Ciprofloxacin (CIP), Norfloxacin (NFX) and tetracycline hydrochloride (TC-H). Preparing CIP, NFX and TC-H into 10mg/L solution, performing degradation test according to the method and the steps in the embodiment 9, after irradiating for 90min, sampling, measuring the concentrations of the CIP, the NFX and the TC-H at 272nm, 273nm and 357nm on a UV-3600 ultraviolet-visible spectrophotometer (Shimazu, Japan), and calculating the degradation rate of irradiating for 90 min; meanwhile, the total organic carbon was measured by a TOC-LCPH type total organic carbon analyzer (Shimadzu, Japan), and the degradation rate of the total organic carbon was calculated, and the results are shown in Table 2.
TABLE 2 degradation Effect of the photocatalysts prepared in the following Table on antibiotics
Table 2 results show that Fe was produced3O4@SiO2@BiFeO3/Sepiolite(m(BiFeO3) M (Sepilolite) 1: 0.3 has higher degradation rate and mineralization rate for 3 antibiotics, which are obviously better than Fe3O4@SiO2@BiFeO3. Therefore, the sepiolite has obvious improvement on the performance of preparing the photocatalyst.
The above is only a preferred embodiment of the present invention, and various modifications and changes can be made by those skilled in the art based on the above concept of the present invention, for example, combinations and changes of the ratio and the process conditions within the scope of the ratio and the process conditions given in the present invention, and such changes and modifications are within the spirit of the present invention.
Claims (10)
1. A magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst is characterized in that magnetic core-shell ferroferric oxide @ silicon dioxide, namely Fe3O4@SiO2The microsphere is used as a core, and the surface of the microsphere is coated with a layer of bismuth ferrite/sepiolite composite material, namely BiFeO, generated on line by bismuth ferrite in the presence of sepiolite3Core-shell type composite photocatalyst formed by/Sepiolite and marked as Fe3O4@SiO2@BiFeO3/Sepiolite, in which the magnetic core is Fe3O4@SiO2The particle size of the microsphere is 350-500 nm, and the magnetic core is Fe3O4@SiO2、BiFeO3The mass ratio of the silica to the Sepiolite is 0.51-0.76: 1: 0.12-0.63.
2. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst of claim 1, which is characterized by comprising the following steps:
(1) Soluble bismuth salt and ferric salt are prepared into bismuth salt and ferric salt solution respectively by deionized water or dilute acid according to the mol ratio of 1: 0.9-1.0, and Bi3+The concentration is 0.05-0.067 mol/L, Fe3+The concentration is 0.045-0.067 mol/L; then mixing the two solutions, and ultrasonically stirring for 1-2 hours to obtain a bismuth salt-iron salt solution which is marked as solution A;
(2) adjusting the pH value of the solution A obtained in the step (1) to 12.6-13.5, and continuing to stir ultrasonically at room temperature for 1-2 hours to obtain a mixture B;
(3) in the mixture B obtained in step (2), as Fe3O4@SiO2Adding Fe into the microspheres with the mass ratio of the microspheres to the bismuth salt of 0.32-0.49: 13O4@SiO2Carrying out ultrasonic stirring on microspheres for 30-60 min; adding purified sepiolite according to the mass ratio of the sepiolite to the bismuth salt of 0.082-0.41: 1, and carrying out ultrasonic stirring for 2-3 h to obtain a mixture C;
(4) transferring the mixture C prepared in the step (3) into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 4-8 h at 150-200 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matter with deionized water and ethanol for 2-5 times respectively, and drying at 60-80 ℃ to constant weight to obtain the magnetic core-shell type bismuth ferrite/sepiolite composite visible light catalyst, which is marked as Fe3O4@SiO2@BiFeO3/Sepiolite;
(5) And (4) adjusting the pH value of the waste liquid remained in the magnet adsorption separation in the step (4) to 8.0-9.0, precipitating for 1-2 h, filtering, discharging filtrate, collecting filter residues, performing centralized treatment and recovering valuable components.
3. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (1), the soluble bismuth salt is bismuth sulfate, bismuth chloride or bismuth nitrate pentahydrate; the soluble ferric salt is ferric sulfate, ferric trichloride hexahydrate or ferric nitrate nonahydrate.
4. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (1), the dilute acid is 0.1-0.2 mol/L hydrochloric acid or nitric acid.
5. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (2), a strong alkali solution of 5-8 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
6. The method for preparing the magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst according to claim 2, wherein in the step (3), the Fe is3O4@SiO2The particle size of the microspheres is 350-500 nm.
7. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (3), the purified sepiolite is processed by the following method: grinding sepiolite, sieving with a 200-300-mesh sieve, soaking in 1-2 mol/L hydrochloric acid at 75-85 ℃ for refluxing for 0.5-1 h, filtering, and washing with distilled water to be neutral; then preparing a mixture of sepiolite and 8-10 mmol/L Cetyl Trimethyl Ammonium Bromide (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 at 80-100 ℃ to constant weight, grinding and sieving with a 800-1000-mesh sieve, and taking undersize for later use.
8. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to claim 2, wherein in the step (5), sulfuric acid with the pH value of 6-8 mol/L is adopted for adjusting the pH value.
9. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible-light-driven photocatalyst according to claim 2, wherein ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
10. The preparation method of the magnetic core-shell bismuth ferrite/sepiolite composite visible light catalyst according to any one of claims 2 to 9, wherein the reagents used are bismuth nitrate pentahydrate, bismuth sulfate, bismuth chloride, ferric sulfate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, KOH, NaOH, ethanol, sulfuric acid and hydrochloric acid, all of which are analytically pure.
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CN106944064A (en) * | 2017-03-15 | 2017-07-14 | 辽宁大学 | Ferrite cladding sepiolite composite catalyst and its preparation method and application |
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---|
GANG SU等: "Magnetic Fe3O4@SiO2@BiFeO3/rGO composite for the enhanced visible-light catalytic degradation activity of organic pollutants", 《CERAMICS INTERNATIONAL》 * |
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