CN112808287A - Magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof - Google Patents
Magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 121
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 110
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 106
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 39
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 73
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- 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 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 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 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
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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 15
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- 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 9
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- 241001198704 Aurivillius Species 0.000 description 1
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- 239000011777 magnesium 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
-
- B01J35/33—
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- B01J35/39—
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- B01J35/396—
-
- B01J35/40—
-
- B01J35/615—
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof. Cetyl trimethyl ammonium bromide CTAB is dissolved in ethylene glycol EG to prepare CTAB-EG solution which is taken as a template agent and a reducing agent, bismuth nitrate-ferric nitrate solution is taken as a raw material, the pH value is adjusted, and then magnetic core-shell type Fe is sequentially added3O4@SiO2Fully mixing the microspheres and the purified sepiolite, and then carrying out hydrothermal reaction to generate shape-controllable core-shell carbonBismuth oxyoxalate/sepiolite composite photocatalyst. By means of oxidative decomposition of EG or CTAB under hydrothermal conditions to generate carbonate, and by means of surface activity and template action of CTAB and the interface effect of sepiolite, the structure and morphology of the product are effectively controlled, the energy band gap and the recombination rate of photon-generated carriers are reduced, the visible light absorption utilization rate and the adsorption performance of organic matters are improved, the catalyst is endowed with excellent magnetic separation performance, and therefore the photocatalytic activity and the 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 type bismuth oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof.
Background
Organic matters such as organic dyes, antibiotics and the like discharged into the environment cause serious pollution to the ecological environment, and increasingly serious threats to human health become a serious global environmental problem. In response to these pollution, various treatment methods such as adsorption, ion exchange, reverse osmosis, biodegradation, chemical oxidation, advanced oxidation, photocatalytic degradation, and the like have been developed. The photocatalytic degradation method is an organic pollution treatment method which utilizes light energy to excite a catalyst to generate a photon-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 and convenient operation, and has the most popularization and application values and application prospects. The effect of the photocatalytic degradation method depends mainly on the performance of the photocatalyst. Conventional photocatalysts, such as titanium dioxide and zinc oxide, can only exhibit photocatalytic activity under irradiation of ultraviolet light (λ.387.5 nm) due to their high band gaps (both above 3.2 eV). The ultraviolet content of solar radiation only accounts for about 5% of the total solar radiation, and the effective utilization rate of solar energy by taking natural light as a light source is too low. Therefore, there is a need to develop a novel visible light driven photocatalyst. Among the developed visible light photocatalyst, bismuth oxycarbonate (Bi)2O2CO3) Is a typical Aurivillius type oxide, belongs to a tetragonal system, and has a unique composition of [ Bi2O2]2+And CO3 2-The layered structure composed of alternating layers, the internal electric field generated by polarization facilitates the separation of photoelectrons from holes, so Bi2O2CO3Has high photocatalytic performance. But Bi2O2CO3The defects of high energy band gap (3.2-3.5 eV), low visible light absorption rate, high recombination rate of photo-generated electron/hole pairs and the like still exist, the catalytic degradation effect is limited, the separation and recovery of the photocatalyst after treatment are difficult, and the recycling performance is poor, so that the structure and the performance of the photocatalyst must be further improved and improved in popularization and application.
The photocatalyst with excellent performance has the advantages of proper energy band gap, high light absorption rate and quantum efficiency, low recombination rate of photon-generated carriers, excellent structural morphology, good pollutant adsorption performance, high photocatalytic degradation efficiency, low cost and good separation, recovery and recycling performance. This requires that the photocatalysis has an optimized composition, a large specific surface area, a stable structure and morphology for light absorption, and performance for separation and recovery after degradation. The common method for improving the performance of the photocatalyst mainly comprises the regulation and control of the structure and the appearance of the photocatalyst, doping, heterojunction and compounding 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 has a large number of acid-base centers, thereby being beneficial to the formation and growth of other materials supported on the Sepiolite. The photocatalyst is used as a template or support for the generation of other photocatalysts, can provide active sites for the generation of the photocatalysts, and influences the structure and the appearance of the photocatalysts, so that the aim of regulating and controlling the structure and the appearance of the material is fulfilled. 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 improved so as to improve the performance of precipitation separation or filtration separation; (2) the photocatalyst is endowed with magnetism, and magnetic separation is carried out through an external magnetic field, so that the continuous and automatic control of the photocatalytic degradation process is conveniently realized.
Disclosure of Invention
In view of Bi2O2CO3Disclosure of the inventionto solve the above problems, it is an object of the present invention to provide a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (Fe)3O4@SiO2@Bi2O2CO3/Sepiolite) with a magnetic core-shell ferroferric oxide @ silicon dioxide (Fe)3O4@SiO2) The microsphere is used as a core, and the surface of the microsphere is coated with a layer of bismuthyl carbonate/sepiolite composite material (Bi) generated by on-line production of bismuthyl carbonate in the presence of sepiolite2O2CO3Sepiolite) to form a core-shell type composite photocatalyst, noted as Fe3O4@SiO2@Bi2O2CO3/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、Bi2O2CO3The mass ratio of the silica to the 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 Bi2O2CO3The visible light catalytic activity is not high, the separation and recovery are difficult and the recycling performance is not good.
Another object of the present invention is to provide a magnetic core-shell type Fe3O4@SiO2@Bi2O2CO3Preparation method of/Sepiolite composite photocatalyst in Fe3O4@SiO2In-situ generation of Bi in the presence of sepiolite2O2CO3To Bi2O2CO3The structure and the appearance of the Bi are effectively controlled and the Bi is enabled to be2O2CO3The sepiolite compound is uniformly and firmly coated on the Fe3O4@SiO2Forming a core-shell structure on the surface of the microsphere; the method specifically comprises the following steps:
(1) adding cetyl trimethyl ammonium bromide into ethylene glycol, and ultrasonically stirring 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 as a solution A;
(2) adding bismuth nitrate pentahydrate and ferric nitrate nonahydrate into deionized water according to the molar ratio of 1: 0.9-1.0, ultrasonically stirring for 20-40 min to dissolve and prepare a bismuth nitrate-ferric nitrate mixed solution, marking as a solution B, wherein Bi is3+The concentration of the Fe is 0.02-0.033 mol/L3+The concentration is 0.018-0.033 mol/L;
(3) slowly dropwise adding 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 value to 9.5-10.5, and continuously ultrasonically stirring for 3-4 h at room temperature to obtain a mixture C;
(4) in the mixture C obtained in step (3), as Fe3O4@SiO2Adding Fe into the microspheres and the bismuth nitrate pentahydrate at a mass ratio of 0.32-0.57: 13O4@SiO2Carrying out ultrasonic stirring on microspheres for 40-80 min; 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 for 2-5 times by using deionized water and ethanol respectively, and drying at 100-120 ℃ to constant weight to obtain the magnetic core-shell type bismuthyl carbonate/sepiolite composite photocatalyst, namely Fe3O4@SiO2@Bi2O2CO3/Sepiolite。
Further, in the step (3), a strong alkali solution of 8-12 mol/L is adopted for adjusting the pH, and the used strong alkali is KOH or NaOH.
Further, in the step (4), Fe3O4@SiO2The particle size of the microspheres is 350-500 nm.
Further, in the step (4), 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), the high-pressure reaction kettle is a polytetrafluoroethylene-lined high-pressure reaction kettle.
Furthermore, the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
Furthermore, the reagents used, cetyl trimethyl ammonium 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 type bismuth oxycarbonate/sepiolite composite photocatalyst. Firstly, cetyl trimethyl ammonium bromide is dissolved in ethylene glycol to prepare a template-reducing agent solution, then a bismuth nitrate-ferric nitrate mixed solution is dropwise added into the template-reducing agent solution, and a strong base solution is used for adjusting the pH value of the mixed solution to obtain a mixture; then Fe3O4@SiO2Adding the microspheres and the treated purified sepiolite into the mixture respectively, fully mixing, transferring the mixture into a polytetrafluoroethylene-lined high-pressure kettle for hydrothermal reaction to generate Fe3O4@SiO2As a nucleus, Bi2O2CO3Magnetic core-shell type Fe with coating layer made of/Sepiolite composite material3O4@SiO2@Bi2O2CO3A Sepiolite composite photocatalyst. The ethylene glycol or hexadecyl trimethyl ammonium bromide is oxidatively decomposed by bismuth nitrate and ferric nitrate under hydrothermal conditions to generate carbonate radical, and the carbonate radical is reacted with Bi3+Bismuth oxycarbonate is generated under alkaline conditions; the generated Bi is generated under the comprehensive action of the surface activity and the template action of hexadecyl trimethyl ammonium bromide and the strong interface effect of sepiolite2O2CO3Formation of Bi by taking sepiolite as support2O2CO3Sepiolite and firmly and uniformly coated Fe3O4@SiO2The surface of the microsphere solves Bi2O2CO3Generation rate of (2) and coating layer Bi2O2CO3Effective regulation and control of/Sepiolite structure and morphology and coating layer Bi2O2CO3Sepiolite and magnetic core Fe3O4@SiO2The fusion problem of (2) is overcome 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 photon-generated carriers, improving the absorption utilization rate of visible light and the adsorption performance to organic matters, obviously improving the photocatalytic degradation performance to organic pollution, and endowing the photocatalyst with excellent magnetic separation performance.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the carbonate is obtained by oxidizing and decomposing hexadecyl trimethyl ammonium bromide or ethylene glycol by bismuth nitrate and ferric nitrate under the hydrothermal condition, and the amount of the carbonate is controlled by the oxidizing and decomposing reaction speed, so that Bi can be effectively regulated and controlled by the reaction condition2O2CO3The generation speed of (2); the surface activity or template action of cetyl trimethyl ammonium bromide and ethylene glycol and the interface action of sepiolite are used to realize the Bi of the coating layer2O2CO3Effective regulation and control of structure and morphology of/Sepiolite.
(2) Fe prepared by the invention3O4@SiO2@Bi2O2CO3the/Sepiolite composite photocatalyst is of a core-shell structure and a coating layer Bi2O2CO3the/Sepiolite is in Fe3O4@SiO2Generated on line in the presence of magnetic microspheres, magnetic core shell layer SiO2The surface is rich in active oxygen-containing groups such as-OH, -O-and the like, and is beneficial to Bi2O2CO3the/Sepiolite is loaded and grows on the surface of the core-shell material, so that the coating layer and the shell layer have better fusion, and the prepared core-shell material has better stability.
(3) F prepared by the inventione3O4@SiO2@Bi2O2CO3The surface layer of the/Sepiolite composite photocatalyst is of a porous structure, and the specific surface area ratio of the porous structure is BFe generated in the absence of Sepiolite3O4@SiO2@Bi2O2CO3Obviously increased by sepiolite and magnetic core Fe3O4@SiO2The rich oxygen-containing groups on the surface and the interface action promote the coating layer Bi2O2CO3The formation of the/Sepiolite structure increases the adsorption performance to organic pollutants and the absorption capacity to light.
(4) BFe prepared by the invention3O4@SiO2@Bi2O2CO3The Sepiolite promotes and controls Bi loaded on the Sepiolite by a special pore channel structure2O2CO3The structure and the appearance of the photocatalyst are formed, so that the energy band gap and the recombination rate of photon-generated carriers are reduced, and the photocatalytic degradation performance of organic pollutants is improved; and BFe prepared3O4@SiO2@Bi2O2CO3the/Sepiolite composite photocatalyst has excellent magnetic separation performance and recycling performance, and is beneficial to continuous operation and automatic control in the process of degrading organic pollutants by photocatalysis.
(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 polluted wastewater.
(5) The method has the advantages of simple preparation process, easy control of the process, less discharge of three wastes, lower manufacturing cost, conventional equipment as required, easy realization of industrial production and wide application prospect.
Drawings
Fig. 1 is a synthesis route diagram of a magnetic core-shell bismuth oxycarbonate/sepiolite composite photocatalyst.
FIG. 2 shows a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3)∶m(Sepilolite)＝10.4).
FIG. 3 shows a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) SEM image of m (Sepilolite) 1: 0.4).
FIG. 4 shows a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) Graph of photocatalytic degradation efficiency for m (Sepilolate) 1: 0.4).
FIG. 5 shows a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (m (Bi)2O2CO3) Graph of effect of recycling m (Sepilolate) 1: 0.4)
Note: m (Bi)2O2CO3) M (Sepilolite) is the mass ratio of bismuth subcarbonate 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) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 128mL of ethylene glycol, and ultrasonically stirring for 20min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.125 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.62g of 98.5% ferric nitrate nonahydrate into 320mL of deionized water, and ultrasonically stirring for 20min to dissolve into Bi3+The concentration is 0.020mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) slowly dropwise adding 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 a particle size of about 500nm are taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 80 min; then adding 0.47g of purified sepiolite, and carrying out ultrasonic stirring for 80min 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 250 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 3 times by using deionized water and ethanol respectively, and drying at 110 ℃ to constant weight to obtain 3.83g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 2
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 107mL of ethylene glycol, and ultrasonically stirring for 25min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.57g of 98.5% ferric nitrate nonahydrate into 256mL of deionized water, and ultrasonically stirring for 25min to obtain Bi3+The concentration is 0.025mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.024 mol/L;
(3) slowly dropwise adding 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 were taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 70 min; then adding 0.26g of purified sepiolite, and carrying out ultrasonic stirring for 70min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 4 times by using deionized water and ethanol respectively, and drying at 115 ℃ to constant weight to obtain 3.37g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 3
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 80mL of ethylene glycol, and ultrasonically stirring for 30min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.20 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.49g of 98.5% ferric nitrate nonahydrate into 213mL of deionized water, and ultrasonically stirring for 25minBi3+The concentration is 0.030mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.029 mol/L;
(3) slowly dropwise adding 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 for 3h at room temperature to obtain a mixture C;
(4) 1.41g of Fe with a particle size of about 450nm were taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 60 min; then adding 0.63g of purified sepiolite, and carrying out ultrasonic stirring for 65min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 5 times by using deionized water and ethanol respectively, and drying at 120 ℃ to constant weight to obtain 3.59g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
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, the diffraction peaks and Fe at 2 θ of 30.2 °, 35.5 °, 43.1 °, 53.2 °, 57.1 ° and 62.8 ° are3O4(JCPDS No.19-0629) (220), (311), (400), (422), (511), and (440) the standard diffraction peaks corresponded, demonstrating that the samples all contained Fe3O4. The diffraction peak at 25 ° is typical of amorphous silica, indicating Fe3O4The microspheres were successfully coated with a layer of amorphous silica. Sample Fe3O4@SiO2@Bi2O2CO3-Sepiolite XRD pattern with the exception of Fe3O4And SiO2The newly appeared diffraction peaks of 23.9 degrees, 30.3 degrees, 32.7 degrees and 48.9 degrees and Bi are outside the diffraction peaks corresponding to the standard peaks2O2CO3The standard peak (JCPDS No.41-1488) is consistent, indicating that Bi2O2CO3Has been formed and coated on Fe3O4@SiO2The above. The new diffraction peak at 26.6 ° corresponds to the (080) face of sepiolite, indicating that it is a true productThe product contains sepiolite. The above results all show that the sample is Fe3O4@SiO2@Bi2O2CO3Fe from Sepiolite3O4、SiO2、Bi2O2CO3And 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@Bi2O2CO3And the morphology of the sample of this example, the results are shown in FIG. 3. FIG. 3(a) shows Fe3O4@SiO2@Bi2O2CO3Is 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 sepiolite3O4@SiO2@Bi2O2CO3the/Sepiolite composite photocatalyst is formed by coating larger irregular-shaped particles on the outer surface of a ball to form a porous coating layer. This indicates that the presence of sepiolite changes the coating layer Bi2O2CO3The crystal structure of the photocatalyst is beneficial to improving the photoelectrochemical properties of the photocatalyst (improving the absorption performance of light, reducing the energy band gap and the recombination rate of photo-generated electrons and holes) and the adsorption capacity of pollutants.
Fe was measured using a specific surface area-pore volume analyzer (BELSORP-mini II, MicrotracBEL, Japan)3O4@SiO2@Bi2O2CO3Has a specific surface area of 83.84m2/g，Fe3O4@SiO2@Bi2O2CO3Specific surface area of/Sepiolite composite photocatalyst is 132.41m2(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@Bi2O2CO3And Fe3O4@SiO2@Bi2O2CO3The saturation magnetization of the/Sepiolite composite photocatalyst is 48.6 emu/g and 20.1emu/g respectively, which shows that the composite photocatalyst is Fe with a magnetic core3O4@SiO2The composite is carried out by compounding,endowing the photocatalyst with good magnetism; 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@Bi2O2CO3And Fe3O4@SiO2@Bi2O2CO3Energy band gap E of/Sepiolite composite photocatalystg3.27eV and 3.11eV, respectively, indicating Fe3O4@SiO2@Bi2O2CO3Fe compounded with sepiolite3O4@SiO2@Bi2O2CO3E of/Sepiolite composite photocatalystgSignificantly reduced in Bi2O2CO3The composite photocatalyst has the advantages that the structure of the composite photocatalyst is obviously improved, and the energy band gap of the composite photocatalyst is reduced.
Example 4
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 64mL of ethylene glycol, and ultrasonically stirring for 40min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.25 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.36g of 98.5% ferric nitrate nonahydrate into 194mL of deionized water, and ultrasonically stirring for 25min to dissolve into Bi3+The concentration is 0.033mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.030 mol/L;
(3) slowly dropwise adding 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 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 were taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 60 min; then adding 0.79g of purified sepiolite, and carrying out ultrasonic stirring for 55min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 3 times by using deionized water and ethanol respectively, and drying at 110 ℃ to constant weight to obtain 3.62g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 5
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 110mL of ethylene glycol, and ultrasonically stirring for 30min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.145 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.57g of 98.5% ferric nitrate nonahydrate into 280mL of deionized water, and ultrasonically stirring for 35min to dissolve into Bi3+The concentration is 0.023mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.022 mol/L;
(3) slowly dropwise adding 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 a particle size of about 350nm was taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 50 min; then adding 1.29g of purified sepiolite, and carrying out ultrasonic stirring for 50min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 2 times by using deionized water and ethanol respectively, and drying at 100 ℃ to constant weight to obtain 3.85g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 6
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 100mL of ethylene glycol, and ultrasonically stirring for 30min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.16 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.49g of 98.5% ferric nitrate nonahydrate into 280mL of deionized water, and ultrasonically stirring for 35min to dissolve into Bi3+The concentration is 0.021mol/L, Fe3+A bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) slowly dropwise adding 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 a particle size of about 450nm were taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 40 min; then adding 1.26g of purified sepiolite, and carrying out ultrasonic stirring for 40min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 4 times by using deionized water and ethanol respectively, and drying at 105 ℃ to constant weight to obtain 4.49g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Example 7
(1) Adding 5.83g of hexadecyl trimethyl ammonium bromide into 100mL of ethylene glycol, and ultrasonically stirring for 30min to prepare a hexadecyl trimethyl ammonium bromide-ethylene glycol solution A with the concentration of 0.18 mol/L;
(2) respectively adding 3.14g of 99.0% bismuth nitrate pentahydrate and 2.44g of 98.5% ferric nitrate nonahydrate into 220mL of deionized water, and ultrasonically stirring for 40min to obtain Bi3+The concentration is 0.029mol/L, Fe3+0.027mol/L bismuth nitrate-ferric nitrate mixed solution B;
(3) slowly dropwise adding 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 a KOH solution of 12mol/L, 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 were taken3O4@SiO2Adding the microspheres into the mixture C, and ultrasonically stirring for 60 min; then adding 0.94g of purified sepiolite, and carrying out ultrasonic stirring for 80min 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 ℃; and cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 3 times by using deionized water and ethanol respectively, and drying at 110 ℃ to constant weight to obtain 3.65g of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst.
Examples 8 to 10 are photocatalytic degradation performance test examples
Example 8
The photocatalytic performance test conditions were as follows: the magnetic core-shell bismuth oxycarbonate/sepiolite composite photocatalyst prepared in example 3 (Fe) was used as a light source at room temperature under a 300W xenon lamp3O4@SiO2@Bi2O2CO3/Sepiolite，m(Bi2O2CO3) M (Sepilolite) 1: 0.4 and magnetic core-shell bismuth subcarbonate (Fe) prepared under the same conditions in the absence of sepiolite3O4@SiO2@Bi2O2CO3) As a test sample, the degradation rate of rhodamine B (RhB) is used as an evaluation index. The specific operation steps are as follows: a clean 100mL jacketed beaker was charged with 50mg photocatalyst sample and 50mL of 60mg/L RhB solution, each at equal distances 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 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 photocatalyst was separated by attracting the sample with a magnet, the concentration of the clear solution was measured at 554nm in a UV-3600 ultraviolet-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 at 30min in the dark room, with a decrease in RhB concentration of about 5.8%; when no photocatalyst is added, the light is irradiated for 90min, and the self-degradation rate is very low; with Fe3O4@SiO2@Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (Sepilolite) is 1: 0.4) as a catalyst, the irradiation is carried out for 90min, and the degradation rate of RhB reaches 99.6 percent; to therebyFe3O4@SiO2@Bi2O2CO3As a catalyst, the degradation rate of RhB is only 57.8 percent after the irradiation for 90 min. Thus, Fe3O4@SiO2@Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (sepiolite) 1: 0.4) has excellent photocatalytic degradation properties for RhB.
Determination of Fe after 90min of irradiation3O4@SiO2@Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (Sepilolite) 1: 0.4) and Fe3O4@SiO2@Bi2O2CO3The Total Organic Carbon (TOC) removal was 82.17% and 31.21%, respectively. Thus, Fe3O4@SiO2@Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (sepiolite) 1: 0.4) has excellent mineralization ability on RhB.
Example 9
Degrading the degraded Fe3O4@SiO2@Bi2O2CO3the/Sepiolite composite photocatalyst is separated and recovered by a magnet and is used as the photocatalyst for the next round of experiment. The experimental conditions and procedures and test methods were the same as in example 8. 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@Bi2O2CO3The catalytic degradation rate of the/Sepiolite composite photocatalyst to RhB is reduced from 99.6% at the 1 st time to 97.0% at the 5 th time, and is only reduced by 2.6%. The results show that the Fe prepared by the invention3O4@SiO2@Bi2O2CO3the/Sepiolite composite photocatalyst has excellent magnetic separation recovery and recycling performance.
Example 10
This example is an example of photocatalytic bleaching performance. The test conditions were as follows: 10mg of Methyl Red (MR), Methylene Blue (MB) and Fluorescein (FS) were dissolved in 1L of distilled waterA simulated mixed solution (MR-MB-FS) was prepared, and the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst (Fe) prepared in example 3 was used3O4@SiO2@Bi2O2CO3/Sepiolite，m(Bi2O2CO3) M (Sepilolite) 1: 0.4 and magnetic core-shell bismuth subcarbonate (Fe) prepared under the same conditions in the absence of sepiolite3O4@SiO2@Bi2O2CO3) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of photocatalyst sample and 100mL of MR-MB-FS 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@Bi2O2CO3/Sepiolite(m(Bi2O2CO3) M (Sepilolite) 1: 0.4) 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@Bi2O2CO3。
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 (8)
1. The magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst is characterized by comprising magnetic core-shell type ferroferric oxide @ dioxideSilicon, i.e. Fe3O4@SiO2The microsphere is a core, and the surface of the microsphere is coated with a layer of bismuthyl carbonate/sepiolite composite material, namely Bi, which is generated on line by bismuthyl carbonate in the presence of sepiolite2O2CO3Core-shell type composite photocatalyst formed by/Sepiolite and marked as Fe3O4@SiO2@Bi2O2CO3/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、Bi2O2CO3The mass ratio of the sepiolite powder to the sepiolite powder is 0.62-1.10: 1: 0.16-0.78.
2. The preparation method of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst of claim 1, which is characterized by comprising the following steps:
(1) adding cetyl trimethyl ammonium bromide into ethylene glycol, and ultrasonically stirring 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 as a solution A;
(2) adding bismuth nitrate pentahydrate and ferric nitrate nonahydrate into deionized water according to the molar ratio of 1: 0.9-1.0, ultrasonically stirring for 20-40 min to dissolve and prepare a bismuth nitrate-ferric nitrate mixed solution, marking as a solution B, wherein Bi is3+The concentration of the Fe is 0.02-0.033 mol/L3+The concentration is 0.018-0.033 mol/L;
(3) slowly dropwise adding 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 value to 9.5-10.5, and continuously ultrasonically stirring for 3-4 h at room temperature to obtain a mixture C;
(4) in the mixture C obtained in step (3), as Fe3O4@SiO2Adding Fe into the microspheres and the bismuth nitrate pentahydrate at a mass ratio of 0.32-0.57: 13O4@SiO2Carrying out ultrasonic stirring on microspheres for 40-80 min; 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 kettleThe reaction time is 3-6 h at 180-250 ℃; cooling to room temperature, performing adsorption separation by using a magnet, washing the collected solid matters for 2-5 times by using deionized water and ethanol respectively, and drying at 100-120 ℃ to constant weight to obtain the magnetic core-shell type bismuthyl carbonate/sepiolite composite photocatalyst, namely Fe3O4@SiO2@Bi2O2CO3/Sepiolite。
3. The preparation method of the magnetic core-shell bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (3), a strong alkaline solution of 8-12 mol/L is adopted for adjusting the pH, and the strong alkaline is KOH or NaOH.
4. The method for preparing the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (4), the Fe is3O4@SiO2The particle size of the microspheres is 350-500 nm.
5. The preparation method of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (4), 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.
6. The method for preparing the magnetic core-shell bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene-lined high-pressure reaction kettle.
7. The preparation method of the magnetic core-shell bismuth oxycarbonate/sepiolite composite photocatalyst according to claim 2, wherein ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
8. The preparation method of the magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst according to any one of claims 2 to 7, wherein the reagents used are cetyl trimethyl ammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, NaOH, ethanol and hydrochloric acid, all of which are analytically pure.
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