CN111298795A - Performance optimization method of strontium titanate magnetic photocatalyst - Google Patents
Performance optimization method of strontium titanate magnetic photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 55
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005457 optimization Methods 0.000 title claims abstract description 16
- 229910002771 BaFe12O19 Inorganic materials 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 claims abstract description 58
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 49
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 32
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 16
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000010842 industrial wastewater Substances 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 10
- 238000004448 titration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- -1 nitrate ions Chemical class 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 239000012088 reference solution Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000000696 magnetic material Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 27
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
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- 238000002835 absorbance Methods 0.000 description 6
- 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 6
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- 238000010521 absorption reaction Methods 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000000975 dye Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012803 optimization experiment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 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 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for optimizing the performance of a strontium titanate magnetic photocatalyst, belonging to the technical field of strontium titanate, which comprises the following steps: the optimization method comprises the following steps: the method comprises the following steps: preparing barium ferrite; step two: preparation of composite photocatalyst SrTiO3/BaFe12O19BaFe to be prepared12O19As a raw material of the composite photocatalyst; step three: the invention provides a method for optimizing the performance of a strontium titanate magnetic photocatalyst, and can prepare a novel composite magnetic photocatalytic material SrTiO with higher photocatalytic activity and better degradation effect3/BaFe12O19While increasing the light responseThe range is required, the utilization efficiency of light energy is improved, and the magnetic material has stronger magnetism and is convenient to recycle.
Description
Technical Field
The invention relates to the technical field of strontium titanate, in particular to a method for optimizing the performance of a strontium titanate magnetic photocatalyst.
Background
In the process of promoting the development of high-speed economy, human beings have exploited and waste existing resources on a large scale, and the large consumption of traditional energy inevitably pollutes the environment, and is accompanied by a series of problems such as environmental pollution and energy shortage. For our country, environmental governance has become the subject of the current hot door. With the intensive research on treatment theories and methods, the treatment modes become diversified. A technology which has no pollution to the environment and clean energy is provided, the photocatalysis technology can degrade organic matters and products are hydrogen and oxygen, and the technology becomes the key point of research of numerous experts and scholars at home and abroad.
Strontium titanate as a perovskite structure material shows certain activity in the process of photocatalysis, and draws attention and research of a plurality of scholars, and in the process, the strontium titanate is found to have wider forbidden bandwidth (3.2ev), the absorption wavelength is mainly distributed in the ultraviolet light range of light, the utilization rate of a light source is lower, and thus the photocatalytic effect of the light is low.
Although the research on the photodegradation of organic matters is relatively late, the photocatalytic degradation mechanism of China is rapidly developed, and a certain theoretical basis is provided for subsequent researchers. The performance optimization method for compounding the metal particles into the magnetic strontium titanate magnetic photocatalyst has good physical and chemical properties and stability in the physical aspect, and has excellent photocatalytic performance in degrading dye and photolyzing water in the chemical aspect. De-compositing metal particles with SrTiO having photocatalytic properties3The photoresponse range can be effectively enlarged, so that more light sources can be utilized, and the degradation rate is improved. Therefore, whether the photocatalysis technology can break through theoretical experiments and be applied to practice in the future needs to be diligently researched and diligent.
Although the existing industrial wastewater degradation methods are various and have different effects on the aspect of degrading organic matters, the existing industrial wastewater degradation methods have many defects, and other pollutants are added while the industrial organic wastewater is degraded, and the operation is difficult and difficult to apply in practice. Because the products of the photodegradation experiment are water and carbon dioxide and the light source is inexhaustible clean energy, the aim of treating industrial organic pollutants is towards the photocatalysis technology, but the theoretical research on the photocatalysis technology is not deep enough, and the degradation effect of a plurality of photocatalysts is not good.
With the continuous perfection of the photocatalytic technology, various novel photocatalysts come out in succession, but the problems of the photocatalytic technology are key problems which prevent the photocatalyst from being put into practice:
1. the absorption light source has less wavelength range. The photocatalyst strontium titanate can only absorb light sources distributed in an ultraviolet light range due to a wide forbidden band width, and the ultraviolet light is only a part of wavelengths in the wavelength range of the light sources and can only utilize a part of light sources, so that the photocatalytic effect of light is low.
2. The strontium titanate photocatalyst has fewer reaction active points, and because the strontium titanate photocatalyst easily generates photo-generated electron hole pairs on the surface to obstruct the photocatalytic reaction process, the active points participating in the reaction are reduced, thereby causing the degradation rate of the catalyst to be low.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, certain simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or other problems occurring in the prior art strontium titanate magnetic photocatalyst.
Therefore, the invention aims to provide a performance optimization method of a strontium titanate magnetic photocatalyst, which can prepare a novel composite magnetic photocatalytic material SrTiO with higher photocatalytic activity and better degradation effect3/ BaFe12O19Simultaneously, the optical response range is increased, and the light is improvedThe utilization efficiency of energy. And has stronger magnetism, and is convenient for recycling.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions:
the performance optimization method of the strontium titanate magnetic photocatalyst comprises the following steps:
the method comprises the following steps: preparing barium ferrite, preparing barium ferrite by sol-gel method, and preparing BaFe12O19The principle of (1) is as follows:
barium nitrate: iron nitrate: the stoichiometric ratio of citric acid is 1: 12: 19;
the preparation process can generate oxidation-reduction reaction, the reducing agent is citric acid, and the oxidizing agent is nitrate ions.
Step two: preparation of composite photocatalyst SrTiO3/BaFe12O19BaFe to be prepared12O19As a raw material of the composite photocatalyst, a sol-gel method is used to react with SrTiO3Forming complex compound, adjusting pH value at constant temperature, heating in water bath at constant temperature of 90 deg.C to form gel, baking in oven at 120 deg.C for 10 hr to form dry gel, and calcining in muffle furnace to obtain SrTiO3/BaFe12O19；
Step three: performing performance optimization on the composite strontium titanate magnetic photocatalyst, using a proper chemical reagent to simulate industrial wastewater as a reference solution of photocatalytic performance reaction, and preparing the novel composite magnetic photocatalytic material SrTiO by the technological process of synthesizing the photocatalytic material and detecting the degradation rate of the proper chemical reagent3/BaFe12O19。
As a preferable aspect of the method for optimizing the performance of the strontium titanate magnetic photocatalyst, the method comprises: preparing the composite photocatalyst SrTiO in the second step3/BaFe12O19The specific scheme is as follows:
the method comprises the following steps: different SrTiO materials are respectively taken and used in the preparation process3、BaFe12O19Quality, titration at the same pH and the same calcination temperature conditionsPreparation of SrTiO3/BaFe12O19The SrTiO with the best photocatalytic activity under the factor is prepared3/BaFe12O19A photocatalyst.
Step two: in the preparation process, SrTiO with best photocatalytic activity in the mass ratio factor and different pH values are respectively titrated3And BaFe12O19Preparation of SrTiO at the same calcination temperature and mass ratio3/ BaFe12O19The best SrTiO with the photocatalytic activity under the factor is prepared3/BaFe12O19A photocatalyst.
Step three: the SrTiO with the best determined photocatalytic activity is adopted3And BaFe12O19Preparing SrTiO at different calcination temperatures by using the pH values with the best mass ratio and photocatalytic activity3/BaFe12O19。
As a preferable aspect of the method for optimizing the performance of the strontium titanate magnetic photocatalyst, the method comprises: the photocatalysis principle in the third step is that light irradiates photocatalyst particles to generate electron-hole pairs, water adsorbed on the surface of the catalyst is decomposed into-OH free radicals by the holes, and the-OH free radicals and organic matters generate chemical reaction in the water.
Compared with the prior art: preparation of magnetic Carrier Material BaFe by comparison12O19The preparation method adopts a sol-gel method to prepare a magnetic carrier material BaFe12O19Preparing composite photocatalyst SrTiO under the same preparation mode3/BaFe12O19. The chemical of the coloring agent is utilized to simulate the industrial wastewater to carry out the photocatalytic degradation experiment, and SrTiO is compared3、BaFe12O19And the degree of photocatalytic degradation of the blank sample. SrTiO prepared under single factor discussed by photocatalytic degradation experiment3/BaFe12O19Influence on the photocatalytic activity, so that the composite photocatalyst SrTiO3/BaFe12O19The performance of (a) is further optimized to obtain the optimum factor level for the performance optimization. Finally, adopt the bestThe horizontal factors are used as a group of horizontal experiments, an appropriate horizontal spacing is selected for orthogonal interaction design, the influence of each component on the photocatalytic activity is discussed through a photocatalytic degradation experiment, and the composite photocatalyst SrTiO is achieved3/BaFe12O19For the purpose of performance optimization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail with reference to the accompanying drawings and detailed embodiments, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive labor. Wherein:
FIG. 1 is a schematic view of the flow structure of the method for optimizing the performance of a strontium titanate magnetic photocatalyst according to the present invention;
FIG. 2 is a diagram showing the adsorption effect of barium ferrite powder according to the method for optimizing the performance of a strontium titanate magnetic photocatalyst;
FIG. 3 is a flow chart of the preparation process of the method for optimizing the performance of the strontium titanate magnetic photocatalyst;
FIG. 4 is a process flow chart of the photocatalytic experiment of the method for optimizing the performance of the strontium titanate magnetic photocatalyst;
FIG. 5 is a graph of reaction time-degradation rate of different materials simulating industrial wastewater for the performance optimization method of strontium titanate magnetic photocatalyst of the present invention;
FIG. 6 is a graph of the reaction time-degradation rate of different composite mass ratios of SrTiO3 and BaFe12O19 according to the method for optimizing the performance of a strontium titanate magnetic photocatalyst;
FIG. 7 shows SrTiO of the method for optimizing the performance of a strontium titanate magnetic photocatalyst3With BaFe12O19Influence diagrams of different composite mass proportions on the catalytic efficiency;
FIG. 8 is a graph of reaction time versus degradation rate at different pH values for a method of optimizing the performance of a strontium titanate magnetic photocatalyst according to the present invention;
FIG. 9 is a graph showing the effect of different pH values on the catalytic efficiency of the method for optimizing the performance of a strontium titanate magnetic photocatalyst according to the present invention;
FIG. 10 is a graph of reaction time-degradation rate at different calcination temperatures for a method of optimizing the performance of a strontium titanate magnetic photocatalyst according to the present invention;
FIG. 11 is a graph showing the effect of different calcination temperatures on the catalytic efficiency of the method for optimizing the performance of a strontium titanate magnetic photocatalyst according to the present invention;
fig. 12 is a flowchart of an orthogonal experimental scheme of the performance optimization method of the strontium titanate magnetic photocatalyst of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Next, the present invention is described in detail with reference to the drawings, and in the detailed description of the embodiments of the present invention, the cross-sectional view showing the structure of the device is not partially enlarged in a general scale for convenience of explanation, and the drawings are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
The invention provides a performance optimization method of a strontium titanate magnetic photocatalyst, which is shown in figure 1 and comprises the following steps:
the method comprises the following steps: preparing barium ferrite, preparing barium ferrite by sol-gel method, and preparing BaFe12O19The principle of (1) is as follows:
barium nitrate: iron nitrate: the stoichiometric ratio of citric acid is 1: 12: 19;
the preparation process can generate oxidation-reduction reaction, the reducing agent is citric acid, and the oxidizing agent is nitrate ions.
Step two: preparation of composite photocatalyst SrTiO3/BaFe12O19BaFe to be prepared12O19As a raw material of the composite photocatalyst, the composite photocatalyst is prepared by a sol-gel method and SrTiO3Forming complex compound, adjusting pH value at constant temperature, heating in water bath at constant temperature of 90 deg.C to form gel, baking in oven at 120 deg.C for 10 hr to form dry gel, and calcining in muffle furnace to obtain SrTiO3/BaFe12O19；
Step three: performing performance optimization on the composite strontium titanate magnetic photocatalyst, using a proper chemical reagent to simulate industrial wastewater as a reference solution of photocatalytic performance reaction, and preparing the novel composite magnetic photocatalytic material SrTiO by the technological process of synthesizing the photocatalytic material and detecting the degradation rate of the proper chemical reagent3/BaFe12O19。
The specific scheme for preparing the barium ferrite in the first step is as follows:
1) weighing and mixing with the solution
Weighing 2.614g of barium nitrate, 48.48g of ferric nitrate and 39.926g of citric acid, mixing 100ml of distilled water with the barium nitrate, and placing the mixture on a stirrer to stir for half an hour to fully dissolve the mixture to form a solution.
2) Titration of pH value
The solution was titrated with concentrated ammonia with constant stirring and titration was complete when the titrated pH was reached.
3) Sol forming process
The titrated solution is stably placed into a constant-temperature water bath, a stirrer is placed into a beaker, and the mechanical stirring is carried out at the constant temperature of 90 ℃. When a sticky substance appears in the beaker, the water bath and stirring are stopped, and the sticky substance becomes gel.
4) Baking
And putting the sol into a corundum crucible, baking the sol in an oven at constant temperature of 120 ℃ for 15 hours, opening the oven and taking out the corundum crucible, wherein the sol becomes a precursor black brown xerogel.
5) Calcination of precursors
Moving the corundum crucible in which the sample is placed into a muffle furnace, setting the heating rate to be 5 ℃/min, and keeping the temperature for 1 hour when the temperature is raised to 210 ℃; heating to 600 deg.C, and maintaining for 1 hr; when the temperature is increased to 900 ℃, the temperature is kept for 3 hours. And (3) after the muffle furnace is cooled to the room temperature, taking out a sample, fully grinding the sample to obtain brick red barium ferrite powder as shown in figure 2.
Wherein, the composite photocatalyst SrTiO is prepared in the second step3/BaFe12O19The specific scheme is as follows:
mixing 4ml of ethylene glycol and 6.8ml (0.02mol) of butyl titanate uniformly to obtain solution A, and adding BaFe with different mass ratios into the solution A12O19(ii) a Respectively weighing 6.3g (0.03mol) of citric acid and 4.24g (0.02mol) of strontium nitrate by an electronic balance, adding 30ml of distilled water, stirring to form a solution B, uniformly mixing the solution B with the solution A, heating and stirring, titrating the pH value after the solutions are fully mixed, heating to be colloidal in a constant-temperature water bath at 90 ℃ under the condition of mechanical stirring, putting the colloidal substance into a corundum crucible, transferring the corundum crucible into an oven, roasting at 120 ℃ for 10 hours to form dry gel, finally putting the dried gel into a muffle furnace, roasting for 3 hours, and taking out SrTiO when the muffle furnace is cooled to room temperature3/BaFe12O19And (3) compounding a catalyst. Preparing composite photocatalyst SrTiO with different components under the same preparation process3/BaFe12O19。
The method comprises the following steps: different SrTiO materials are respectively taken and used in the preparation process3、BaFe12O19Quality, preparation of SrTiO at the same pH titration and same calcination temperature3/BaFe12O19The SrTiO with the best photocatalytic activity under the factor is prepared3/BaFe12O19A photocatalyst.
Step two: in the preparation process, SrTiO with best photocatalytic activity in the mass ratio factor and different pH values are respectively titrated3And BaFe12O19Mass ratio ofPreparation of SrTiO at the same calcination temperature3/BaFe12O19The best SrTiO with the photocatalytic activity under the factor is prepared3BaFe12O19A photocatalyst.
Step three: the SrTiO with the best determined photocatalytic activity is adopted3And BaFe12O19Preparing SrTiO at different calcination temperatures by using the pH values with the best mass ratio and photocatalytic activity3/BaFe12O19。
The preparation process flow is shown in figure 3.
The catalytic degradation process flow is as follows: taking 10mg/L of simulated industrial wastewater into a water-through beaker, and adding 0.1g of the prepared composite photocatalyst SrTiO3/BaFe12O19After mechanically stirring for 1 hour in the dark, the solution was irradiated under a xenon lamp for 75 minutes, 4ml of the solution was taken every 15 minutes, and centrifuged in a centrifuge (4000r/min) for 6 minutes to measure the absorbance (rhodamine B: λ max: 553nm, methylene blue: λ max: 664nm, λ max represents the maximum absorption wavelength). The catalytic degradation process flow is shown in figure 4.
Chemical agent selection for simulated wastewater
Respectively taking 10mg/L of rhodamine B and methylene blue as simulated industrial wastewater, adding 0.1g of composite photocatalyst SrTiO with the preparation process factors of 30 percent mass composite ratio, pH of 6 and roasting temperature of 700 into two same water-through beakers3/BaFe12O19. After mechanically stirring in the dark for 1 hour, the solution was irradiated with light under a xenon lamp for 75 minutes, 4ml of the solution was taken every 15 minutes, and centrifuged in a centrifuge (4000r/min) for 6 minutes to measure the absorbance of each solution (rhodamine B: λ max: 553nm, methylene blue: λ max: 664nm, λ max represents the maximum absorption wavelength). The absorbance data are shown in Table 1, and the reaction time degradation graph is shown in FIG. 5.
TABLE 1 Absorbance table of different dye wastewaters
By the formula of degradation rate:
degradation efficiency η ═ 1-Ct/C0
C0Is the absorbance of the solution before illumination;
Ctthe absorbance of the solution after different times of illumination;
through the chart analysis, the composite photocatalyst SrTiO3/BaFe12O19The degradation rate to 10mg/L rhodamine B and methylene blue is different, but the degradation rate to rhodamine B is only 5.04% in 75min, the degradation rate to methylene blue is 48.57%, and the degradation rate is higher. The degradation effect of the methylene blue simulated wastewater material obtained by comparing test results is better, and the methylene blue solution simulated wastewater is selected for optimization experiments in the later experiments.
The method comprises the following steps: single factor exploration of SrTiO3/BaFe12O19Effect on photocatalytic Activity
In the preparation of the composite photocatalyst SrTiO3/BaFe12O19In the preparation process, the used SrTiO3And BaFe12O19The composite mass proportion, the titrated pH value, the selected roasting temperature and other factors have certain influence on the performance of the prepared composite photocatalytic material. For the optimized preparation of the composite photocatalytic material SrTiO3/BaFe with better photocatalytic activity12O19And performing performance optimization experiments on three factors of mass proportion, pH value and roasting temperature in the preparation process.
Mass ratio of
Taking BaFe12O19The mass of the composite photocatalyst is 0.54g, the pH of the solution is adjusted to be 6, the solution is roasted at the roasting temperature of 700 ℃, and the composite photocatalyst SrTiO3/BaFe with the concentration of 30 percent is prepared by the preparation process flow12O19The sample is prepared into composite photocatalyst SrTiO3/BaFe with different composite mass ratios in the same way12O19The samples, as shown in fig. 6, were finally subjected to photocatalytic degradation experiments, and the results are shown in fig. 7.
With SrTiO3And BaFe12O19The proportion of the composite mass is improved, and the photocatalytic degradation rate is obviously improvedPotential in SrTiO3And BaFe12O19When the composite mass ratio is 20%, the photocatalytic degradation rate reaches the highest, the degradation rate reaches 50.22%, and SrTiO is continuously improved3And BaFe12O19The composite mass proportion reaches 30%, the photocatalytic degradation rate is reduced, and the photocatalytic degradation effect is reduced.
Therefore, under the condition that the titration pH value and the roasting temperature are the same, the composite photocatalyst SrTiO3/ BaFe12O19The optimal composite mass proportion is 20%.
pH value
Taking SrTiO3And BaFe12O19The composite mass proportion is 20 percent, the pH values are respectively titrated to 4, 5, 6, 7 and 8 in the solution, the solution is roasted at the roasting temperature of 700 ℃, and the composite photocatalyst SrTiO under different pH conditions is prepared by the preparation process3/BaFe12O19The samples, as shown in fig. 8, were finally subjected to photocatalytic degradation experiments, and the results are shown in fig. 9.
As the titrated pH increased, the sample exhibited a significantly increasing trend in photocatalytic degradation, reaching a maximum at titrated pH 6 with a degradation rate of 50.22%, continuing to titrate pH 8, and the measured photocatalytic degradation rate was found to exhibit a gradually decreasing trend at pH 8 with a degradation rate of 47.76%.
Therefore, composite photocatalysts SrTiO with different titration pH values are respectively prepared at the compounding ratio of 20% and the roasting temperature of 700 DEG C3/BaFe12O19The optimum titration pH was 6.
Temperature of calcination
Taking the best SrTiO3And BaFe12O19The composite mass proportion of 20 percent and the titration pH value of the solution are 6, the solution is respectively put into a muffle furnace and is calcined at the temperature of 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃, as shown in figure 10, and composite photocatalyst SrTiO3/BaFe under different pH conditions is prepared by the preparation process flow12O19And (3) sampling. The photocatalytic experiment was performed and the above data were obtained, and the photocatalytic degradation experiment results are shown in fig. 11.
When the roasting temperature is 500 ℃, the photocatalytic activity is better, and the degradation rate reaches 52.00 percent. With the increase of the roasting temperature, the photocatalytic degradation rate shows a slow descending trend. Although the calcination temperature is 700 ℃ and the rate of photocatalytic degradation tends to be slightly increased, the rate of photocatalytic degradation tends to be gradually decreased as a whole.
Therefore, the composite photocatalysts SrTiO3/BaFe with different roasting temperatures are respectively prepared under the conditions of optimal mass ratio and optimal titration pH value12O19The optimum calcination temperature is 500 ℃.
The second method comprises the following steps: research on SrTiO by orthogonal experimental method3/BaFe12O19Effect on photocatalytic Activity
Design of orthogonal experiments
Orthogonal experiment design is an experiment scheme of multi-factor multi-level interactive design, and test numbers can be evenly distributed in a comprehensive test number range by carrying out representative horizontal interactive experiments. Therefore, the orthogonal test numbers can be comprehensively analyzed to determine the optimal level group, and the specific flow is shown in fig. 12.
Determining levels of orthogonal experimental factors
In a single factor experiment, a plurality of factors influencing the experimental result are provided, and the influence of the factors on the experimental result is analyzed while the other factors are kept unchanged. Research on SrTiO through single-factor method3/BaFe12O19The optimum mass ratio was 20% under the same conditions of pH, calcination temperature and other factors, and was similarly obtained to an optimum pH of 6 and an optimum calcination temperature of 500 ℃. But all are the best composite photocatalyst SrTiO obtained under the same conditions3/BaFe12O19And the factors to be researched are partially blinded, so that only the optimal conditions of the factors to be researched under the condition that other factors are the same can be tested, and the influence of interaction among the factors on the experimental result cannot be obtained. Therefore, the mass ratio of 20%, pH 6 and calcination temperature of 500 ℃ under the optimum conditions in the above experiment were tested by the orthogonal experiment methodThe method comprises the steps of carrying out interactive design on factors and proper horizontal spacing, respectively selecting the mass ratio (17%, 20% and 23%), the pH value (5, 6 and 7) and the roasting temperature (400 ℃, 500 ℃ and 600 ℃), and designing a three-factor three-level orthogonal table with mixed interactive factors.
Orthogonal scheme performance optimization experiment and result analysis
After the samples are prepared, the photocatalytic experiment is carried out on all the samples, and the operation process flow is the same as the above. The data obtained were processed and analyzed, and the results of experimental analysis are shown in the following table.
TABLE 2 analysis of the results of the respective test numbers
The data chart analysis can obtain:
1) the composite photocatalyst SrTiO is prepared under the conditions that the mass ratio is 23%, the pH value is 7 and the roasting temperature is 500 DEG C3/BaFe12O19The sample has the highest degradation rate reaching 69.12% in the photocatalytic degradation experiment.
2) The photocatalytic degradation rate of most samples exceeded 53%.
3) From the extremely poor data, it was found that the largest influence of the calcination temperature in this orthogonal experimental method is an important factor affecting the performance of the prepared samples, and the pH value is the second one. Where the mass ratio has the least influence, it may be considered to be an insignificant factor under this experimental approach, in part because the horizontal spacing at the composite mass ratio is chosen to be small compared to the other horizontal spacings.
4) Among the horizontal factors, the mass ratio of 17%, pH 5 and firing temperature of 500 ℃ were found to be excellent levels under the mass ratio, pH and firing temperature factors.
5) Obtaining the composite photocatalyst SrTiO through the obtained excellent combination data3/BaFe12O19Best effort ofThe technological condition is SrTiO3And BaFe12O19The composite mass ratio is 17%, the pH value is 5, and the roasting temperature is 500 ℃.
In the process of carrying out a photocatalytic experiment, chemical dyes rhodamine B and methylene blue are adopted as industrial organic wastewater, and a composite photocatalyst SrTiO3/BaFe12O19Degrading to obtain the composite photocatalyst SrTiO3/BaFe12O19The methylene blue is better degraded, and the methylene blue is selected as industrial wastewater to carry out the following photocatalysis experiment. Then under the preparation process under the condition of single factor, the optimal preparation quality ratio obtained by the photocatalysis experiment is 20 percent, the pH value is 5, and the roasting temperature is 500 ℃. Finally, the optimal experiment level under the single factor is used as the level of the orthogonal experiment, the appropriate horizontal spacing is selected for orthogonal interaction, and the obtained test number is subjected to a preparation experiment and a photocatalysis experiment to obtain the composite photocatalyst SrTiO3/BaFe12O19The maximum factor of (1) is the roasting temperature, the optimal level combination mass proportion is 17%, the pH value is 5, the roasting temperature is 500 ℃, the degradation rate of an orthogonal test number in an experiment reaches 69.12%, and the composite photocatalyst SrTiO prepared under the condition of the non-optimal level combination3/BaFe12O19The photocatalytic performance is significantly higher than before. The orthogonal experiment numbers do not have the optimal level group, and the degradation rate of the optimal level group obtained by analyzing all data exceeds the highest degradation rate of all experiment numbers of the adopted orthogonal experiment scheme, and exceeds 69.12%. Shows that the composite photocatalyst SrTiO is explored in an orthogonal experiment3/BaFe12O19After the influence on the photocatalytic degradation effect, the composite photocatalyst SrTiO3/BaFe12O19The performance of the photocatalyst is well optimized, and the photocatalytic activity is obviously improved.
While the invention has been described above with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the various features of the disclosed embodiments of the invention may be used in any combination as long as there is no structural conflict, and the combination is not exhaustively described in this specification merely for the sake of brevity and resource conservation. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (3)
1. The performance optimization method of the strontium titanate magnetic photocatalyst is characterized by comprising the following steps: the optimization method comprises the following steps:
the method comprises the following steps: the barium ferrite is prepared by a sol-gel method, and is characterized in that: BaFe is prepared in the first step12O19The principle of (1) is as follows:
barium nitrate: iron nitrate: the stoichiometric ratio of citric acid is 1: 12: 19;
the preparation process can generate oxidation-reduction reaction, the reducing agent is citric acid, and the oxidizing agent is nitrate ions.
Step two: preparation of composite photocatalyst SrTiO3/BaFe12O19BaFe to be prepared12O19As the raw material of the composite photocatalyst, the composite photocatalyst is prepared by sol-gel method and SrTiO3Forming complex compound, adjusting pH value at constant temperature, heating in water bath at constant temperature of 90 deg.C to form gel, baking in oven at 120 deg.C for 10 hr to form dry gel, and calcining in muffle furnace to obtain SrTiO3/BaFe12O19；
Step three: performing performance optimization on the composite strontium titanate magnetic photocatalyst, using a proper chemical reagent to simulate industrial wastewater as a reference solution of photocatalytic performance reaction, and preparing the novel composite magnetic photocatalytic material SrTiO by the technological process of synthesizing the photocatalytic material and detecting the degradation rate of the proper chemical reagent3/BaFe12O19。
2. The method for optimizing the performance of the strontium titanate magnetic photocatalyst according to claim 1, characterized in that: the composite photocatalyst is prepared in the second stepOxidant SrTiO3/BaFe12O19The specific scheme is as follows:
the method comprises the following steps: different SrTiO materials are respectively taken and used in the preparation process3、BaFe12O19Quality, preparation of SrTiO at the same pH titration and same calcination temperature3/BaFe12O19The best SrTiO with the photocatalytic activity under the factor is prepared3/BaFe12O19A photocatalyst.
Step two: in the preparation process, different pH values are respectively titrated, and the SrTiO with the best photocatalytic activity in mass ratio factors3And BaFe12O19Preparation of SrTiO at the same calcination temperature and mass ratio3/BaFe12O19The best SrTiO with the photocatalytic activity under the factor is prepared3/BaFe12O19A photocatalyst.
Step three: the SrTiO with the best determined photocatalytic activity is adopted3And BaFe12O19Preparing SrTiO at different calcination temperatures by using the pH values with the best mass ratio and photocatalytic activity3/BaFe12O19。
3. The method for optimizing the performance of the strontium titanate magnetic photocatalyst according to claim 1, characterized in that: the photocatalysis principle in the third step is that light irradiates photocatalyst particles to generate electron-hole pairs, water adsorbed on the surface of the catalyst is decomposed into-OH free radicals by the holes, and the-OH free radicals and organic matters generate chemical reaction in the water.
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