CN109675578B - BiFeO3-ZrO2Composite material, preparation method and application thereof - Google Patents
BiFeO3-ZrO2Composite material, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 183
- 239000002131 composite material Substances 0.000 claims abstract description 128
- 229910002902 BiFeO3 Inorganic materials 0.000 claims abstract description 64
- 239000011941 photocatalyst Substances 0.000 claims abstract description 60
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000003980 solgel method Methods 0.000 claims abstract description 31
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 230000001699 photocatalysis Effects 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 17
- 239000011165 3D composite Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 15
- 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 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 235000002906 tartaric acid Nutrition 0.000 claims description 8
- 239000011975 tartaric acid Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 3
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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 2
- 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 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 8
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- 239000003054 catalyst Substances 0.000 description 11
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- 239000000203 mixture Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
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- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/38—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
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- C02F2305/10—Photocatalysts
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Abstract
The invention discloses BiFeO3‑ZrO2Composite material, preparation method and application thereof, and BiFeO prepared by using composite material3Is added to the synthesized ZrO2The precursor solution is fully stirred, the pH is adjusted by ammonia water solution, and the supported visible light photocatalyst BiFeO is prepared by a sol-gel method3‑ZrO2A composite material. The prepared supported BiFeO3‑ZrO2The shape of the composite material is blocky, and BiFeO3ZrO uniformly distributed on the carrier2The above. The supported composite photocatalyst has high catalytic activity, has the degradation rate of 98% on rhodamine B, has good stability and reusability, and is simple in preparation process, low in energy consumption and easy for large-scale production.
Description
Technical Field
The invention relates to a photocatalyst, a preparation method and application thereof, in particular to a visible light photocatalyst BiFeO loaded3The composite material, the preparation method and the application thereof, and also relates to a method for degrading a persistent organic pollutant rhodamine in water, which is applied to the technical field of photocatalytic materials.
Background
Currently, with the progress of scientific technology, the rapid development of industries, and the increasing population, the problems of environmental pollution and energy shortage are gradually highlighted and increasingly seriousAnd is sharp, so that the method becomes one of the bottlenecks for restricting social development and improving life quality. Organic pollutants are an important component of the problem of environmental pollution and are one of the major difficulties in treatment. A considerable portion of organic pollutants are structurally stable, are difficult to degrade under natural conditions and exist for a long time, are widely dispersed through various routes, and have lasting harmful effects on animals, plants and even human beings. Although conventional methods for treating such contaminants by various physical and chemical methods have been developed and widely used, they generally have problems of incomplete degradation, low efficiency, etc., and may cause secondary pollution, and thus, there is a need for a more effective method. Photocatalysis is an emerging technology and has wide prospect in the aspect of treating organic pollutants. Photocatalytic reactions are generally carried out by relatively simple equipment under mild conditions which are easy to control and decompose organic pollutants into CO by advanced oxidation2、H2O and other non-toxic and harmless inorganic matters, and the secondary pollution is rarely generated. The advantages of low cost, wide application range and the like draw wide attention in the aspect of environmental pollution treatment.
BiFeO3Is an important visible light response type semiconductor material, the forbidden band width is 2.3eV, and the specific energy is TiO2It is slightly narrow, so it has strong light absorption in visible light region, and it is not easy to produce light corrosion, and has good light stability. However, BiFeO3When the photocatalyst is used alone, the generated photoproduction electron-hole are easy to recombine, so that the corresponding photocatalytic reaction efficiency is inhibited; nanoparticle BiFeO3The photocatalyst is easy to have particle agglomeration, so that the monomer BiFeO3It is difficult to be directly applied to actual wastewater. Further, BiFeO3The recovery and reutilization of the photocatalytic material in a heterogeneous catalytic reaction system is also an existing technical problem, so that the photocatalytic reaction process has high cost and is difficult to popularize and apply.
ZrO2Is the only metal oxide semiconductor integrating acid-base property and oxidation-reduction property, and has a more negative conduction band (-1.0V vs NHE) and a more positive valence band (4.0V vs NHE) than titanium dioxide and zinc oxide. Moreover, it has a relatively large specific surface area, and can be used forActing as a carrier. Research has proved its superiority and feasibility as carrier in composite material catalyst. However, the zirconium oxychloride and BiFeO are not found through the research and investigation of the literature3Preparing BiFeO by using a sol-gel method as a raw material3-ZrO2Patent applications and literature reports on methods for visible photocatalytic materials.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide BiFeO3-ZrO2Composite material, preparation method and application thereof, and BiFeO is prepared by improved sol-gel method3-ZrO2New material of BiFeO3Is uniformly distributed in ZrO2The forbidden bands of the two components of the material are coupled, so that the response range of the whole composite material to visible light is widened, and the photocatalytic activity of the composite material under the visible light is increased; the invention determines BiFeO with excellent visible light photocatalytic performance by evaluating the performance of the catalyst3-ZrO2The preparation method of the composite material prepares a novel supported visible light photocatalyst with high efficiency and stability.
In order to achieve the purpose, the following invention conception is adopted:
by controlling the component BiFeO in the composite material3And ZrO2The composite material with high visible light photocatalytic activity and stability is prepared according to the mass ratio of the components, so that the supported visible light photocatalyst BiFeO with excellent performance is provided3-ZrO2A method for preparing a composite material.
According to the inventive concept, the invention adopts the following technical scheme:
BiFeO3-ZrO2Composite material of BiFeO3ZrO uniformly distributed in the carrier material2To form a supported visible light photocatalyst BiFeO3-ZrO2Composite material of BiFeO3And ZrO2The mass ratio of (0.25-0.67): 1, and is made of BiFeO3And ZrO2The interface region where the two different semiconductor materials contact forms a heterostructure.
As a preferred technical scheme of the invention, BiFeO3And ZrO2The mass ratio of (0.38-0.67) to (1).
As a preferable technical scheme of the invention, the supported visible light photocatalyst BiFeO3-ZrO2The micro-morphology of the composite material is a block particle shape with the particle diameter not more than 4 mu m, in ZrO2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm.
The BiFeO of the invention3-ZrO2The preparation method of the composite material comprises the following steps:
a. according to the proportion of bismuth nitrate: iron nitrate: the molar ratio of tartaric acid is 1: 1: 2, respectively weighing bismuth nitrate, ferric nitrate and tartaric acid; the bismuth nitrate is preferably pentahydrate bismuth nitrate; the ferric nitrate is preferably ferric nitrate nonahydrate;
b. dissolving the bismuth nitrate weighed in the step a in distilled water, dropwise adding dilute nitric acid with the concentration not higher than 40 wt.% in the magnetic stirring process until the bismuth nitrate is completely dissolved and is clear and transparent, and preparing a bismuth nitrate solution; b, dissolving the ferric nitrate and the tartaric acid weighed in the step a into the bismuth nitrate solution, and fully stirring to obtain a mixed solution; then the mixed solution is put into an oven with the temperature not higher than 140 ℃ for drying for at least 12 hours to obtain BiFeO3A precursor; the BiFeO obtained is subjected to3Grinding the precursor to obtain BiFeO3Precursor powder, then BiFeO3Putting precursor powder into a crucible with a cover, covering the crucible with the cover, putting the crucible into a muffle furnace, heating to a target temperature of not lower than 500 ℃, preserving heat for at least 1 hour at the target temperature, and cooling a product obtained by heat treatment to room temperature to obtain a brown yellow nano material BiFeO3(ii) a Preferably, according to the mixing ratio of 0.01mol of bismuth nitrate and not more than 100ml of distilled water, dissolving the bismuth nitrate in the distilled water to prepare a bismuth nitrate solution;
c. zirconium oxychloride is adopted as an original reactant raw material, and is dissolved in distilled water according to the proportion of mixing 0.01mol of zirconium oxychloride with not more than 10ml of distilled water, so as to prepare a zirconium oxychloride solution; the zirconium oxychloride raw material preferably adopts zirconium oxychloride octahydrate;
d. c, magnetically stirring the zirconium oxychloride solution obtained in the step c, and adjusting the pH of the zirconium oxychloride mixed solution to 10 by using an ammonia water solution to obtain ZrO2A precursor solution; preferably, the concentration of the ammonia water solution is not higher than 2 mol/L;
e. by sol-gel method according to BiFeO3And ZrO2The mass ratio of (0.25-0.67) to 1, and the BiFeO prepared in the step b3Is added to the ZrO prepared in said step d2Continuing stirring the precursor solution in a water bath kettle at the temperature of not lower than 75 ℃ for at least 4 hours until gel is obtained, then transferring the gel into a drying oven at the temperature of not lower than 110 ℃ for drying for at least 12 hours to obtain dry gel; preferably by adjusting BiFeO3And ZrO2Preparing a series of catalysts BiFeO by the mass ratio of the two monomers and the reaction conditions of the sol-gel method3-ZrO2A composite material;
f. e, grinding the dry gel obtained in the step e into powder, using the powder as a composite material roasting precursor, transferring the dry gel powder into a crucible, placing the crucible into a muffle furnace, controlling the temperature to be not lower than 500 ℃, roasting the dry gel powder for at least 3 hours, cooling the roasted product to room temperature, and finally obtaining a product BiFeO3-ZrO2A composite material.
The BiFeO of the invention3-ZrO2Application of composite material as supported visible light photocatalyst in photocatalytic reactor under visible light condition and BiFeO3-ZrO2And degrading the refractory organic rhodamine B in the solution to be treated under the coexistence condition of the composite material.
Polymer-BiFeO3-ZrO2The three-dimensional composite material takes a polymer as a carrier matrix and takes BiFeO of the invention3-ZrO2Solidifying the bonding interface of the local composite material block particles and the surface of the polymer material to obtain the BiFeO3-ZrO2Composite material block particles as visible light photocatalystA neutral point material, BiFeO3-ZrO2The composite material block particles are uniformly dispersed, distributed and connected and fixed on the surface of the polymer, so that an active site array surface interface of the visible light photocatalyst is formed on the surface of the polymer.
The polymer of the invention, BiFeO3-ZrO2The preparation method of the three-dimensional composite material comprises the step of mixing BiFeO3-ZrO2Solidifying the bonding interface of the local composite material blocky particles and the surface of the polymer material to obtain the polymer-BiFeO3-ZrO2A three-dimensional composite material initial product; then, the polymer-BiFeO was treated with distilled water3-ZrO2Washing the three-dimensional composite material initial product, and performing ultrasonic treatment for at least 60 minutes to remove BiFeO which is not firmly connected on the surface of the polymer material3-ZrO2Nano-powder particles; finally, putting the product into the oven again, drying the product for at least 30 minutes at the temperature of not higher than 60 ℃, and cooling the product to room temperature to obtain the final product polymer-BiFeO3-ZrO2A three-dimensional composite material.
The visible light photocatalyst BiFeO of the invention3-ZrO2The mechanism of the composite material for catalyzing and degrading the refractory organic matters is as follows:
under the excitation of visible light, the semiconductor BiFeO3Electron e in valence band-Transitions to its conduction band, thereby generating photogenerated electron-hole pairs. Because of the difference of forbidden band widths of two semiconductor components in the composite material and the deviation of valence band and conduction band positions, photo-generated electrons can be transferred to the carrier ZrO2The efficient separation of photogenerated electrons and holes is caused; at the same time, the photoproduction electrons can be O in water2Capture, generation O2 -Free radicals, and photogenerated holes can be associated with OH in water-/H2O reacts to form OH radicals, holes, O2 -And OH can react with organic matters to decompose the organic matters into small organic molecules and even mineralize the organic molecules into CO2And H2And O and other inorganic small molecules.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the visible light photocatalyst BiFeO of the invention3-ZrO2The composite material can efficiently catalyze and degrade refractory organic pollutants, and the prepared photocatalyst is ZrO2As a carrier, BiFeO3The photocatalyst is uniformly distributed on the surface of the substrate, and the heterojunction is formed to inhibit the recombination of photo-generated electrons and holes, expand the absorption range of visible light, improve the efficiency of photocatalytic reaction, overcome the defect of poor photocatalytic performance of a single semiconductor, and further have good stability and reusability;
2. the invention can effectively improve the photocatalytic activity of the nano monomer and enhance the stability of the composite material by compounding the two semiconductor materials; in addition, the invention uses BiFeO3The nano photocatalyst is fixed on the carrier, and the difficult problems of recycling and reutilization of the photocatalytic material in a heterogeneous catalytic reaction system can be solved.
Drawings
FIG. 1 shows BiFeO obtained in examples one to four of the present invention3-ZrO2XRD pattern of visible photocatalytic material. Wherein curve a is BiFeO obtained in the first example of the present invention3-ZrO2XRD curve of visible light catalytic material, curve b is BiFeO obtained in example two3-ZrO2XRD profile of visible photocatalytic material, where profile c is BiFeO obtained in example three3-ZrO2XRD profile of visible light catalytic material, curve d is BiFeO obtained in example four3-ZrO2XRD profile of visible photocatalytic material.
FIG. 2 shows a visible-light photocatalyst BiFeO according to an embodiment of the present invention3-ZrO2SEM image of the composite material.
FIG. 3 shows four visible-light photocatalysts BiFeO according to the first to the second embodiments of the present invention3-ZrO2And respectively comparing the degradation rate curves of the composite material and the visible light under the coexistence condition on the organic rhodamine B in water. Wherein curve a is BiFeO obtained in the first example of the present invention3-ZrO2The degradation rate curve of the composite material to organic rhodamine B in water under the condition of coexistence with visible light respectively, and the curve B is the curve of the second embodimentBiFeO obtained3-ZrO2The degradation rate curve of the composite material on organic rhodamine B in water under the condition of coexistence with visible light respectively, wherein the curve c is BiFeO obtained in the third embodiment3-ZrO2The degradation rate curve of the composite material to organic rhodamine B in water under the condition of coexistence with visible light respectively, and the curve d is BiFeO obtained in example four3-ZrO2Respectively carrying out degradation rate curve on organic rhodamine B in water under the condition of coexistence of the composite material and visible light.
FIG. 4 shows a visible-light photocatalyst BiFeO according to an embodiment of the present invention3-ZrO2A degradation curve diagram of organic rhodamine B in water in the process of continuous 5-time recycling of the composite material.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this example, a BiFeO3-ZrO2Composite material, BiFeO3ZrO uniformly distributed in the carrier material2To form a supported visible light photocatalyst BiFeO3-ZrO2Composite material of BiFeO3And ZrO2Is 0.43:1 in terms of mass ratio and is formed from BiFeO3And ZrO2The interface region where the two different semiconductor materials contact forms a heterostructure. This example is a supported visible light photocatalyst BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm.
BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. 0.01mol of Bi (NO) was weighed out separately3)3·5H2O, 0.01mol of Fe (NO)3)3·9H2O, 0.02mol of tartaric acid;
b. according to 0.01mol of Bi (NO)3)3With distillation of 100mlMixing water according to the proportion, and weighing Bi (NO) in the step a3)3·5H2Dissolving O in distilled water, dropwise adding dilute nitric acid with the concentration of 40 wt.% in the magnetic stirring process until bismuth nitrate is completely dissolved and is clear and transparent, and preparing a bismuth nitrate solution; b, dissolving the ferric nitrate and the tartaric acid weighed in the step a into the bismuth nitrate solution, and fully stirring to obtain a mixed solution; then the mixed solution is put into a drying oven with the temperature of 140 ℃ for drying for 12 hours to obtain BiFeO3A precursor; then the BiFeO obtained is used3Grinding the precursor to obtain BiFeO3Precursor powder, then BiFeO3Putting precursor powder into a ceramic crucible with a cover, covering the ceramic crucible with the cover, putting the ceramic crucible into a muffle furnace, heating to a target temperature of 500 ℃, preserving heat for 1 hour at the target temperature, and cooling a product obtained by heat treatment to room temperature to obtain a brown yellow nano material BiFeO3；
c. Adopting zirconium oxychloride octahydrate as an original reactant raw material, and mixing 0.01mol of zirconium oxychloride in 10mL of distilled water to prepare a zirconium oxychloride solution;
d. c, magnetically stirring the zirconium oxychloride solution obtained in the step c, and adjusting the pH of the zirconium oxychloride mixed solution to 10 by using an ammonia water solution with the concentration of 2mol/L to obtain ZrO2A precursor solution;
e. 0.53g of BiFeO prepared in the step b is added by a sol-gel method3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.43:1, and xerogel is prepared by a sol-gel method;
f. e, grinding the dry gel obtained in the step e into powder, using the powder as a composite material roasting precursor, transferring the dry gel powder into a crucible, placing the crucible into a muffle furnace, controlling the temperature to be 500 ℃, roasting the dry gel powder for 3 hours, and then roasting the dry gel powderCooling the roasted product to room temperature to finally obtain a product BiFeO3-ZrO2A composite material.
The supported visible-light photocatalyst BiFeO prepared by the above process steps of this example3-ZrO2The composite material was analyzed by X-ray diffraction, and as shown in FIG. 1, it was found to have a composition of BiFeO3And ZrO2Two kinds of crystals. The supported visible-light photocatalyst BiFeO prepared by the above process steps of this example3-ZrO2The composite material is tested and analyzed by a scanning electron microscope, and as shown in figure 2, the supported visible light photocatalyst BiFeO can be known3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm.
BiFeO prepared in this example3-ZrO2The composite material can be used as a supported visible light photocatalyst in a photocatalytic reactor under the condition of visible light and BiFeO3-ZrO2And degrading the refractory organic rhodamine B in the solution to be treated under the coexistence condition of the composite material. The novel BiFeO prepared by the above process steps of this example3-ZrO2A test that the composite material is subjected to catalytic degradation of rhodamine B solution under visible light shows that BiFeO prepared by the method is shown in figure 33-ZrO2Under the action of the composite material as a catalyst, the rhodamine B in the water can reach the degradation rate of 98 percent. BiFeO prepared in this example3-ZrO2After the composite material is used as a catalyst and continuously recycled for 5 times, as shown in figure 4, the degradation rate of organic rhodamine B in water can still reach 91%. The visible-light photocatalyst BiFeO prepared in this example3-ZrO2The composite material can efficiently catalyze and degrade refractory organic pollutants, and the prepared photocatalyst is ZrO2As a carrier, BiFeO3Uniformly distributed on the surface, and forms heterojunction to inhibit the recombination of photo-generated electrons and holes, expand the absorption range of visible light, improve the efficiency of photocatalytic reaction, and overcome the defect of poor photocatalytic performance of single semiconductorThe prepared photocatalyst has the defects of good stability and reusability. Under the excitation of visible light, the semiconductor BiFeO3Electron e in valence band-Transitions to its conduction band, thereby generating photogenerated electron-hole pairs. Because of the difference of forbidden band widths of two semiconductor components in the composite material and the deviation of valence band and conduction band positions, photo-generated electrons can be transferred to the carrier ZrO2The efficient separation of photogenerated electrons and holes is caused; at the same time, the photoproduction electrons can be O in water2Capture, generation O2 -Free radicals, and photogenerated holes can be associated with OH in water-/H2O reacts to form OH radicals, holes, O2 -And OH can react with organic matters to decompose the organic matters into small organic molecules and even mineralize the organic molecules into CO2And H2And O and other inorganic small molecules.
BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst BiFeO by using a sol-gel method3-ZrO2A composite material. In this example, BiFeO was used as the starting material in the preparation process3And ZrO2The mass ratio of (1) to (2) is 0.43:1, xerogel is prepared by a sol-gel method, and finally the prepared supported BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm. The supported composite photocatalyst prepared by the embodiment has high catalytic activity, good stability and reusability, simple preparation process, low energy consumption and easy large-scale production.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. the step is the same as the first embodiment;
b. the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. 0.41g of BiFeO prepared in the step b is added by a sol-gel method3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.33:1, and xerogel is prepared by a sol-gel method;
f. the procedure is the same as in the first embodiment.
The novel BiFeO prepared by the above process steps of this example3-ZrO2The composite material was analyzed by X-ray diffraction, and as shown in FIG. 1, it was found to have a composition of BiFeO3And ZrO2Two kinds of crystals. BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst BiFeO by using a sol-gel method3-ZrO2A composite material. In the preparation process of this example, the followingBiFeO3And ZrO2The mass ratio of (1) to (2) is 0.33:1, xerogel is prepared by a sol-gel method, and finally the prepared supported BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm. As shown in fig. 3, the supported composite photocatalyst prepared by the embodiment has high catalytic activity, has a rhodamine B degradation rate of 85.0%, and also has good stability and reusability, and the preparation method is simple, low in energy consumption and easy for large-scale production.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. the step is the same as the first embodiment;
b. the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. 0.66g of BiFeO prepared in the step b is added by a sol-gel method3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.54:1, and xerogel is prepared by a sol-gel method;
f. the procedure is the same as in the first embodiment.
The novel BiFeO prepared by the above process steps of this example3-ZrO2X-ray diffraction analysis of the compositeAs shown in FIG. 1, it was found that its composition was BiFeO3And ZrO2Two kinds of crystals. BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst BiFeO by using a sol-gel method3-ZrO2A composite material. In this example, BiFeO was used as the starting material in the preparation process3And ZrO2The mass ratio of the supported BiFeO to the supported BiFeO is 0.54:1, xerogel is prepared by a sol-gel method, and the supported BiFeO is finally prepared3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm. As shown in fig. 3, the supported composite photocatalyst prepared by the embodiment has high catalytic activity, has a rhodamine B degradation rate of 94.0%, and also has good stability and reusability, and the preparation method is simple, low in energy consumption and easy for large-scale production.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. the step is the same as the first embodiment;
b. the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. using a sol-gel method, 0.82g of BiF prepared in step b is addedeO3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.67:1, and xerogel is prepared by a sol-gel method;
f. the procedure is the same as in the first embodiment.
The novel BiFeO prepared by the above process steps of this example3-ZrO2The composite material was analyzed by X-ray diffraction, and as shown in FIG. 1, it was found to have a composition of BiFeO3And ZrO2Two kinds of crystals. BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst BiFeO by using a sol-gel method3-ZrO2A composite material. In this example, BiFeO was used as the starting material in the preparation process3And ZrO2The mass ratio of (1) to (2) is 0.67:1, xerogel is prepared by a sol-gel method, and finally the prepared supported BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm. As shown in fig. 3, the supported composite photocatalyst prepared by the embodiment has high catalytic activity, has a degradation rate of 92.0% for rhodamine B, has good stability and reusability, and is simple in preparation process, low in energy consumption and easy for large-scale production.
Example five:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. the step is the same as the first embodiment;
b. the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. 0.31g of BiFeO prepared in the step b is added by a sol-gel method3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.25:1, and xerogel is prepared by a sol-gel method;
f. the procedure is the same as in the first embodiment.
BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst BiFeO by using a sol-gel method3-ZrO2A composite material. In this example, BiFeO was used as the starting material in the preparation process3And ZrO2The mass ratio of (1) to (2) is 0.25:1, xerogel is prepared by a sol-gel method, and finally the prepared supported BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFe supported on surfaceO3The nanoparticles have an average particle size of no greater than 150 nm. The supported composite photocatalyst prepared by the embodiment has high catalytic activity, has the degradation rate of 78.0% on rhodamine B, has good stability and reusability, and is simple in preparation process, low in energy consumption and easy for large-scale production.
Example six:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material comprises the following steps:
a. the step is the same as the first embodiment;
b. the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. 0.47g of BiFeO prepared in the step b is added by a sol-gel method3To 0.01mol of ZrO prepared in step d2Continuing stirring the precursor solution in a water bath kettle at 75 ℃ for 4 hours until gel is obtained, and then transferring the gel into a drying oven at 110 ℃ for drying for 12 hours to obtain dry gel; this example is in accordance with BiFeO3And ZrO2The mass ratio of (1) to (2) is 0.38:1, and xerogel is prepared by a sol-gel method;
f. the procedure is the same as in the first embodiment.
BiFeO prepared in this example3-ZrO2The composite material is used as a novel efficient and stable visible light photocatalyst, and is a supported composite material BiFeO3Is uniformly distributed in ZrO2The above. The composite BiFeO prepared in the example is subjected to visible light in a photocatalytic reactor3-ZrO2Under the coexistence condition, the refractory organic rhodamine B in the reaction solution can be effectively degraded. This example will prepare BiFeO3Is added to ZrO2Fully stirring the precursor solution, adjusting the pH value by using an ammonia water solution, and preparing the supported visible light photocatalyst by using a sol-gel methodReagent BiFeO3-ZrO2A composite material. In this example, BiFeO was used as the starting material in the preparation process3And ZrO2The mass ratio of (1) to (2) is 0.38:1, xerogel is prepared by a sol-gel method, and finally the prepared supported BiFeO3-ZrO2The micro-morphology of the composite material is in the shape of block-shaped particles, the particle size of the block-shaped particles is not more than 4 mu m, and the particles are in ZrO state2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm. The supported composite photocatalyst prepared by the embodiment has high catalytic activity, has a degradation rate of 91.0% on rhodamine B, has good stability and reusability, and is simple in preparation process, low in energy consumption and easy for large-scale production.
Example seven:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, BiFeO in this example3-ZrO2The preparation method of the composite material is realized by adjusting BiFeO3And ZrO2Preparing a series of catalysts BiFeO by the mass ratio of the two monomers and the reaction conditions of the sol-gel method3-ZrO2A composite material. According to the formula of BiFeO3-ZrO2The method is convenient to control and easy to realize, can realize selection and optimization of different target product preparation processes by introducing an automatic control means and a high-flux preparation process, and realizes rapid preparation of the catalyst BiFeO3-ZrO2Composite materials and process cost control for product manufacturing.
Example eight:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a polymer-BiFeO3-ZrO2The preparation method of the three-dimensional composite material comprises the step of mixing BiFeO3-ZrO2Solidifying the bonding interface of the local composite material blocky particles and the surface of the polymer material to obtain the polymer-BiFeO3-ZrO2A three-dimensional composite material initial product; then, the polymer-BiFeO was treated with distilled water3-ZrO2Washing the three-dimensional composite material initial product, and then carrying out ultrasonic treatment for 60 minutes to remove BiFeO which is not firmly connected on the surface of the polymer material3-ZrO2Nano-powder particles; finally, putting the product into the oven again, drying the product for 30 minutes at the temperature of 60 ℃, and cooling the product to room temperature to obtain the final product polymer-BiFeO3-ZrO2A three-dimensional composite material. The polymer prepared in the embodiment, BiFeO3-ZrO2The three-dimensional composite material takes a polymer as a carrier matrix and takes BiFeO of the invention3-ZrO2Solidifying the bonding interface of the local composite material block particles and the surface of the polymer material to obtain the BiFeO3-ZrO2The composite material block particles are used as an active point position material of the visible light photocatalyst, and BiFeO is prepared by mixing3-ZrO2The composite material block particles are uniformly dispersed, distributed and connected and fixed on the surface of the polymer, so that an active site array surface interface of the visible light photocatalyst is formed on the surface of the polymer. ZrO (ZrO)2With BiFeO3The compound formation can greatly inhibit the recombination of photo-generated electron-hole pairs and reduce the BiFeO nanoparticles3Thereby improving the photocatalytic activity. Further adding BiFeO3-ZrO2The composite bulk particles are bound to the polymer matrix, eliminating the problems of powder catalysts: the traditional powder catalyst is easy to run off, so that material waste and harm to the environment are caused, the nano powder catalyst is easy to agglomerate and difficult to separate and recycle, and the catalyst is difficult to realize in repeated use and poor in practical applicability. In addition, the embodiment is suitable for the immobilization of various powdered photocatalysts of organic, inorganic and organic-inorganic hybrid nanopowder, and the matrix material for immobilization also comprises one or a mixture of polymers such as PP (polypropylene), PS (polystyrene) and PVC (polyvinyl chloride), so as to provide feasible technical support for preparing the visible light photocatalyst which is easy to separate and recycle, thereby promoting the application of the photocatalytic technology in water and wastewater treatment. The three-dimensional composite photocatalyst has the advantages of simple preparation method and applicationUnder the condition, the method has the advantages of high chemical and thermal stability, environmental friendliness, low cost and macroscopic form.
BiFeO to be prepared in the above-mentioned embodiment of the invention3Is added to the synthesized ZrO2The precursor solution is fully stirred, the pH is adjusted by ammonia water solution, and the supported visible light photocatalyst BiFeO is prepared by a sol-gel method3-ZrO2A composite material. The prepared supported BiFeO3-ZrO2The shape of the composite material is blocky, and BiFeO3ZrO uniformly distributed on the carrier2The above. BiFeO is synthesized according to the above embodiment of the present invention3The nano photocatalyst is fixed on the carrier, which can solve the problem of recycling and reusing of the photocatalytic material in a heterogeneous catalytic reaction system, and ZrO2With BiFeO3The compound formation can greatly inhibit the recombination of photo-generated electron-hole pairs and reduce the BiFeO nanoparticles3Thereby improving the photocatalytic activity. By adjusting the reaction conditions, the grain size and the morphology of the product can be controlled, the microstructure, the phase composition and the chemical properties of the material are changed, and the method has obvious industrial application value. The supported composite photocatalyst disclosed by the embodiment of the invention has high catalytic activity, has a rhodamine B degradation rate of 98%, and also has good stability and reusability, and the preparation process is simple, low in energy consumption and easy for large-scale production.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, but various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions as long as the purpose of the present invention is met without departing from the BiFeO of the present invention3-ZrO2The composite material, the preparation method and the applied technical principle and the inventive concept thereof all belong to the protection scope of the invention.
Claims (11)
1. BiFeO3-ZrO2A composite material characterized by: BiFeO3ZrO uniformly distributed in the carrier material2Upper, shapeSupported visible light photocatalyst BiFeO3-ZrO2Composite material of BiFeO3And ZrO2The mass ratio of (0.25-0.67): 1, and is made of BiFeO3And ZrO2The interface region where the two different semiconductor materials contact forms a heterostructure.
2. BiFeO according to claim 13-ZrO2A composite material characterized by: BiFeO3And ZrO2The mass ratio of (0.38-0.67) to (1).
3. BiFeO according to claim 1 or 23-ZrO2A composite material characterized by: supported visible-light photocatalyst BiFeO3-ZrO2The micro-morphology of the composite material is a block particle shape with the particle diameter not more than 4 mu m, in ZrO2BiFeO loaded on surface3The nanoparticles have an average particle size of no greater than 150 nm.
4. BiFeO according to claim 13-ZrO2The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
a. according to the proportion of bismuth nitrate: iron nitrate: the molar ratio of tartaric acid is 1: 1: 2, respectively weighing bismuth nitrate, ferric nitrate and tartaric acid;
b. dissolving the bismuth nitrate weighed in the step a in distilled water, dropwise adding dilute nitric acid with the concentration not higher than 40 wt.% in the magnetic stirring process until the bismuth nitrate is completely dissolved and is clear and transparent, and preparing a bismuth nitrate solution; b, dissolving the ferric nitrate and the tartaric acid weighed in the step a into the bismuth nitrate solution, and fully stirring to obtain a mixed solution; then the mixed solution is put into an oven with the temperature not higher than 140 ℃ for drying for at least 12 hours to obtain BiFeO3A precursor; the BiFeO obtained is subjected to3Grinding the precursor to obtain BiFeO3Precursor powder, then BiFeO3Placing the precursor powder into a crucible with a cover, covering the crucible with the cover, placing the crucible in a muffle furnace, and heating to a target temperature of not lower than 500 deg.CThen, preserving the heat for at least 1 hour at the target temperature, and then cooling the product obtained by heat treatment to room temperature to obtain the brown yellow nano material BiFeO3；
c. Zirconium oxychloride is adopted as an original reactant raw material, and is dissolved in distilled water according to the proportion of mixing 0.01mol of zirconium oxychloride with not more than 10ml of distilled water, so as to prepare a zirconium oxychloride solution;
d. c, magnetically stirring the zirconium oxychloride solution obtained in the step c, and adjusting the pH of the zirconium oxychloride mixed solution to 10 by using an ammonia water solution to obtain ZrO2A precursor solution;
e. by sol-gel method according to BiFeO3And ZrO2The mass ratio of (0.25-0.67) to 1, and the BiFeO prepared in the step b3Is added to the ZrO prepared in said step d2Continuing stirring the precursor solution in a water bath kettle at the temperature of not lower than 75 ℃ for at least 4 hours until gel is obtained, then transferring the gel into a drying oven at the temperature of not lower than 110 ℃ for drying for at least 12 hours to obtain dry gel;
f. e, grinding the dry gel obtained in the step e into powder, using the powder as a composite material roasting precursor, transferring the dry gel powder into a crucible, placing the crucible into a muffle furnace, controlling the temperature to be not lower than 500 ℃, roasting the dry gel powder for at least 3 hours, cooling the roasted product to room temperature, and finally obtaining a product BiFeO3-ZrO2A composite material.
5. BiFeO according to claim 43-ZrO2The preparation method of the composite material is characterized by comprising the following steps: in the step a, the bismuth nitrate adopts pentahydrate bismuth nitrate; the ferric nitrate is ferric nitrate nonahydrate.
6. BiFeO according to claim 43-ZrO2The preparation method of the composite material is characterized by comprising the following steps: in the step b, according to the mixing ratio of 0.01mol of bismuth nitrate and not more than 100ml of distilled water, dissolving the bismuth nitrate in the distilled water to prepare the nitric acidAnd (3) bismuth solution.
7. BiFeO according to claim 43-ZrO2The preparation method of the composite material is characterized by comprising the following steps: in the step c, the zirconium oxychloride raw material adopts zirconium oxychloride octahydrate.
8. BiFeO according to claim 43-ZrO2The preparation method of the composite material is characterized by comprising the following steps: in the step d, the concentration of the ammonia water solution is not higher than 2 mol/L.
9. BiFeO according to claim 13-ZrO2The application of the composite material is characterized in that: as a supported visible light photocatalyst, in a photocatalytic reactor, under visible light conditions and BiFeO3-ZrO2And degrading the refractory organic rhodamine B in the solution to be treated under the coexistence condition of the composite material.
10. Polymer-BiFeO3-ZrO2A three-dimensional composite characterized by: BiFeO according to claim 1, using a polymer as a carrier matrix3-ZrO2Solidifying the bonding interface of the local composite material block particles and the surface of the polymer material to obtain the BiFeO3-ZrO2The composite material block particles are used as an active point position material of the visible light photocatalyst, and BiFeO is prepared by mixing3-ZrO2The composite material block particles are uniformly dispersed, distributed and connected and fixed on the surface of the polymer, so that an active site array surface interface of the visible light photocatalyst is formed on the surface of the polymer.
11. A polymer of claim 10-BiFeO3-ZrO2The preparation method of the three-dimensional composite material is characterized by comprising the following steps: BiFeO is subjected to3-ZrO2Solidifying the bonding interface of the local composite material blocky particles and the surface of the polymer material to obtain the polymer-BiFeO3-ZrO2A three-dimensional composite material initial product; then, the polymer-BiFeO was treated with distilled water3-ZrO2Washing the three-dimensional composite material initial product, and performing ultrasonic treatment for at least 60 minutes to remove BiFeO which is not firmly connected on the surface of the polymer material3-ZrO2Nano-powder particles; finally, putting the product into the oven again, drying the product for at least 30 minutes at the temperature of not higher than 60 ℃, and cooling the product to room temperature to obtain the final product polymer-BiFeO3-ZrO2A three-dimensional composite material.
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| CN106807400A (en) * | 2017-03-13 | 2017-06-09 | 辽宁大学 | A kind of compound bismuth ferrite photocatalyst and its preparation method and application |
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| CN106807400A (en) * | 2017-03-13 | 2017-06-09 | 辽宁大学 | A kind of compound bismuth ferrite photocatalyst and its preparation method and application |
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