CN111203233B - CdIn2S4nanoparticle/BiVO4Preparation method and application of nanorod composite structure - Google Patents
CdIn2S4nanoparticle/BiVO4Preparation method and application of nanorod composite structure Download PDFInfo
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- 150000004686 pentahydrates Chemical class 0.000 claims 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract 1
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- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
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- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the technical field of nano composite materials, and discloses CdIn2S4nanoparticle/BiVO4A preparation method and application of a nano-rod composite structure. Firstly hydrothermally synthesizing BiVO4Nanorod, and then preparing BiVO4Nanorod and CdIn2S4Suspension of nano particles, and finally, hydrothermal method is adopted to prepare BiVO4Nanorod and CdIn2S4Nano particle composite preparation of CdIn2S4nanoparticle/BiVO4And (3) a nanorod composite structure. The prepared composite structure can be applied to catalytic degradation of tetracycline hydrochloride and oxytetracycline hydrochloride under visible light. The invention has rich raw material sources, simple and convenient operation process and mild reaction conditions. BiVO (bismuth oxide) is added4Nanorod and CdIn2S4The nano particles are compounded, and the characteristics of ultrasonic dispersion and a hydrothermal method are fully utilized, so that the nano particles and the hydrothermal method are in close contact, the effective transmission and separation of photoproduction electrons are realized, and the electron transmission capability in the composite material is improved; the band gap matched with the single photocatalyst is utilized, the light absorption range of the single photocatalyst is widened, so that the integral photocatalytic activity is improved, and the method has important and wide application prospects in the aspect of environmental management.
Description
Technical Field
The invention relates to CdIn2S4nanoparticle/BiVO4Preparation of nanorod composite structuresThe method belongs to the preparation of the nano composite material and the application thereof in the field of environmental protection.
Background
With the continuous improvement of the economic level and the rapid improvement of the industrialization degree of China, the environmental problems have been paid extensive attention, and the importance of the technical development of sewage treatment as a means for reducing the water body pollution is self-evident. Because the traditional sewage treatment method has the defects of low removal efficiency, high cost, secondary pollution and the like, the sewage treatment technology utilizing photocatalytic oxidation is attracted by extensive attention, and the corresponding semiconductor material also becomes a research hotspot in the material field. However, the processing effect of the semiconductor material is greatly limited due to the characteristics of the semiconductor material, such as easy recombination of photo-generated electrons and holes, poor visible light response capability, and the like. Therefore, the development of novel photocatalytic semiconductor materials is necessary, and the development of sewage treatment technology is greatly promoted.
CdIn2S4The material is a spinel-structured ternary sulfur compound, the forbidden band width of the ternary sulfur compound is about 2.1eV, the material has excellent light absorption performance in a visible light range, and simultaneously has good photocatalytic activity and photochemical stability, so that the material is very suitable for being used as a photocatalyst. However, single-component CdIn2S4The practical application of the material is limited due to the defects of weaker electron transport capacity, lower photon-generated carrier separation rate and the like. Therefore, CdIn is improved by constructing a composite multi-element structure2S4The photocatalytic effect of (2) is the research direction of our.
BiVO4The yellow dye is a well-known yellow dye, has low preparation cost and no toxicity, can stably exist in water, does not change the pH value of a system, and has wide application prospect in the aspects of environmental protection and sewage treatment. BiVO4Belongs to an n-type semiconductor, the narrow forbidden band width (the band gap is about 2.4V) of the n-type semiconductor enables the n-type semiconductor to respond in a visible light region, and the n-type semiconductor is considered to be a better photocatalyst, but the n-type semiconductor has the defects of low electron-hole separation efficiency, limited response capability in the visible light region and the like, and limits the n-type semiconductorFurther popularization and application. Therefore, the visible light response range is widened, the electron hole separation efficiency is improved, and the BiV O is treated4The performance improvement has positive significance, and BiVO can be relieved by compounding with other materials4Has the defects of improving the whole photocatalysis effect.
CdIn2S4The valence band of (A) is 1.58eV, and the conduction band is-0.5 eV; BiVO4Has a valence band of 2.74eV and a conduction band of 0.34eV, both apparently having matched band structures. Comprehensive consideration of CdIn2S4And BiVO4Has the advantages and disadvantages that CdIn is prepared from2S4And BiVO4The composite construction of the heterojunction can obviously enhance the response capability of the light absorption capability of the system in a visible light region, can realize the high-efficiency transmission and separation of photo-generated electrons, improve the quantum efficiency of the whole material and finally realize the great improvement of the photocatalytic activity.
By inspection, no CdIn has been found2S4nanoparticle/BiVO4The preparation of the nanorod composite structure and related reports of the nanorod composite structure used for degrading tetracycline hydrochloride (TC) and oxytetracycline hydrochloride (OTC).
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel composite material, namely CdIn2S4nanoparticle/BiVO4The nanorod composite structure and the preparation method thereof are used for the visible light catalytic degradation of tetracycline hydrochloride (TC) and oxytetracycline hydrochloride (OTC) for the first time.
The invention provides a CdIn2S4nanoparticle/BiVO4The method for preparing the nano-rod composite structure adopts an ultrasonic dispersion hydrothermal method to prepare the CdIn2S4/BiVO4The composite structure comprises the following specific steps:
(1) weighing a certain volume of ethanol in a beaker, and weighing bismuth nitrate pentahydrate Bi (NO) according to a certain mass ratio3)3·5H2Adding O and polyvinylpyrrolidone PVP into ethanol, and ultrasonically dispersing for 20-40min to obtain uniform dispersion A;
weighing a certain amount of the materialsSodium metavanadate NaVO3Adding a certain volume of water, and performing ultrasonic treatment for 10-20min to obtain a dispersion liquid B;
slowly dripping B into A, stirring for 30-40min, transferring into a hydrothermal kettle, performing hydrothermal reaction at a certain temperature for several hours, naturally cooling to room temperature, washing, drying and grinding, and finally adding the ground sample into a tube furnace for calcination reaction to obtain BiVO4And (4) nanorods.
(2) Weighing a certain mass of BiVO obtained according to the step (1)4Dispersing the nano-rods in methanol and water solution with a certain proportion, performing ultrasonic treatment for 10-20min, stirring for 10-20min, repeating for 3-6 times to obtain uniformly dispersed BiVO4Suspension of the nano-rods;
weighing a certain mass of CdIn2S4The nano particles are dispersed in BiVO4Performing ultrasonic treatment for 10-20min in the nanorod suspension, stirring for 10-20min, repeating for 3-6 times, adding the uniformly dispersed suspension into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating to a certain temperature, reacting for a period of time, naturally cooling to room temperature, washing, drying, and collecting a sample to obtain CdIn2S4nanoparticle/BiVO4And (3) a nanorod composite structure.
In the step (1), ethanol and Bi (NO)3)3·5H2O、PVP、NaVO3And the dosage ratio of water is as follows: 25-75 mL: 0.3-0.9 mmol:1g-3g:0.5-1.5mmol:15-45 mL;
the temperature of the hydrothermal reaction is 140 ℃ and 180 ℃, and the reaction time is 8-16 h.
The calcination temperature of the tubular furnace is 400-480 ℃, the calcination time is 1-3h, and the heating rate is 1.5-3 ℃/min.
BiVO prepared in step (1)4The diameter of the nano rod is 5-20nm, and the length is 150-250 nm.
In step (2), BiVO4The dosage ratio of the nano-rods to the methanol and the water is 0.5-1.5mmol:15-45mL:15-45mL,
the temperature of the hydrothermal reaction is 80-120 ℃, and the reaction time is 1-2.5 h.
BiVO4Nanorod in CdIn2S4nanoparticle/BiVO4Nano-rod compositeThe mass percentage of the composite structure is 5-15%.
The CdIn prepared by the invention2S4nanoparticle/BiVO4The nanorod composite structure is applied to removing tetracycline hydrochloride (TC) and oxytetracycline hydrochloride (OTC) in sewage under visible light, and provides a new effective way for sewage treatment.
The invention has the beneficial effects that:
(1) the invention provides a CdIn2S4nanoparticle/BiVO4Nanorod composite structures for CdIn2S4The material has the defect of low separation efficiency of a photon-generated carrier, and the material is subjected to composite modification, so that the separation rate of the photon-generated carrier is greatly improved, and the recombination of the photon-generated carrier is inhibited, and the integral photocatalytic performance of a catalytic system is greatly improved.
(2) This patent first proposed using the ultrasonic dispersion water method with BiVO4Nanorod doping to CdIn2S4In the nano particles, the photo-generated electrons and the holes are tightly compounded by a hydrothermal method, so that the recombination of the photo-generated electrons and the holes can be greatly reduced, the electron transmission capability is improved, and the novel composite photocatalyst with wide spectral response is obtained.
(3) The synthesis process used in the invention is simple, the raw materials are low in cost and easy to obtain, the reaction conditions are mild and easy to control, and the feasibility of industrial and large-scale production is realized in the future.
(4) Synthesized CdIn2S4nanoparticle/BiVO4The nanorod composite structure has low toxicity, has a very good effect on degradation of tetracycline hydrochloride and oxytetracycline, has a high TOC removal rate, and has a very good application prospect in the aspect of wastewater treatment.
Drawings
FIG. 1 shows CdIn prepared in examples 1-32S4nanoparticle/BiVO4XRD pattern of nanorod composite structure.
FIG. 2 shows BiVO prepared in example 14Nanorods (a) and CdIn2S4nanoparticle/BiVO4SEM image of nanorod composite structure (b).
FIG. 3 is a schematic view ofExamples 1-3 preparation of CdIn2S4nanoparticle/BiVO4Degradation diagram of the nanorod composite structure to tetracycline hydrochloride (TC).
FIG. 4 shows CdIn prepared in examples 1-32S4nanoparticle/BiVO4Degradation pattern of nanorod composite structure to oxytetracycline hydrochloride (OTC).
FIG. 5 shows CdIn obtained in example 12S4nanoparticle/BiVO4Graph of TOC (Total organic carbon) as a function of time when the nanorod composite structure degrades oxytetracycline hydrochloride (OTC).
FIG. 6 shows CdIn obtained in example 22S4nanoparticle/BiVO4PL diagram of nanorod composite structure.
FIG. 7 shows CdIn obtained in example 32S4nanoparticle/BiVO4UV-VIS DRS diagram of nanorod composite structure.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
(1) The proportion is 0.3 mmol:1 g:0.5 mmol Bi (NO) was weighed3)3·5H2O、PVP、NaVO3Adding Bi (NO)3) 3·5H2Adding O and PVP into 25mL of ethanol, and performing ultrasonic dispersion for 20min to obtain a uniform dispersion liquid A;
15mL of water is measured and added with NaVO3And performing ultrasonic treatment for 10min to obtain dispersion liquid B.
Slowly dripping B into A, stirring for 30min, transferring into a hydrothermal kettle, reacting for 16h at 140 ℃, naturally cooling to room temperature, washing, drying and grinding, adding the ground sample into a tube furnace for calcining, wherein the temperature rise rate is 3 ℃/min, the calcining temperature is 450 ℃, and the calcining time is 1h, thus obtaining BiVO4And (4) nanorods.
(2) BiVO obtained in the step (1)4Dispersing 0.5mmol (0.1620 g mass) of nano rod in a mixed solvent of 15mL of methanol and 15mL of water, performing ultrasonic treatment for 10min, stirring for 10min, and repeating the ultrasonic treatment and stirring for 3 times to obtain uniformly dispersed BiVO4Suspension of the nano-rods;
3.0772g of CdIn2S4The nano particles are dispersed in BiVO4And (3) performing ultrasonic treatment for 10min and stirring for 10min in the nanorod suspension, and repeating the ultrasonic treatment and stirring for 3 times to obtain uniformly dispersed suspension. Adding the mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven, heating the hydrothermal kettle to 80 ℃, reacting for 2.5 hours, naturally cooling the hydrothermal kettle to room temperature, washing, drying and collecting a sample to obtain the CdIn2S4nanoparticle/BiVO4Nanorod composite structure, in which BiVO4The mass percentage of the nano rod in the composite structure is 5 percent.
As shown in FIG. 1, XRD diffraction peak and CdIn of the sample synthesized in example 12S4Due to BiVO4The content of (A) is lower, and obvious BiVO is found4Characteristic peaks appear.
As shown in FIG. 2, in the SEM image, diagram a shows BiVO in the synthesis process4Nanorod, graph b is CdIn2S4nanoparticle/BiVO4The nanorod composite structure can be seen, and the existing CdIn in the figure is shown2S4The nanoparticles also have BiVO4Nanorods appeared, and the two monomers were mixed together homogeneously, in which BiVO4The length of the nano rod is 150-250nm, and the diameter is 5-20 nm.
As shown in FIG. 3, after the visible light is irradiated for 180min, the photocatalytic degradation efficiency of TC reaches 87.79 percent, which is much higher than Cdn2S4Degradation effect of nanoparticles on TC.
As shown in FIG. 4, after 120min of visible light irradiation, the photocatalytic degradation efficiency of OTC reaches 83.31%, which is much higher than CdIn2S4The degradation efficiency of (a).
FIG. 5 is a graph showing the change of TOC with time in the process of oxytetracycline hydrochloride (OTC) degradation, and the TO C removal rate reaches 61.51% after 120min reaction, which shows that the composite catalyst has good mineralization effect on oxytetracycline hydrochloride (OTC).
Example 2
(1) According to the proportion of 0.6 mmol: 2 g: 1.0mmol Bi (NO) was weighed3)3·5H2O、PVP、NaVO3Adding Bi (NO)3)3·5 H2O, PVP into 50mL ethanol, and sonicatingDispersing for 30min to obtain uniform dispersion A;
30mL of water is measured and added with NaVO3And carrying out ultrasonic treatment for 15min to obtain dispersion B.
Slowly dripping B into A, stirring for 30min, transferring into a hydrothermal kettle, reacting at 160 ℃ for 12 hours, naturally cooling to room temperature, washing, drying and grinding, adding the ground sample into a tube furnace for calcination, wherein the heating rate is 3 ℃/min, the calcination temperature is 400 ℃, and the calcination time is 3 hours, thus obtaining BiVO4And (4) nanorods.
(2) BiVO obtained in the step (1)4Dispersing 1.0mmol (0.3240 g mass) of nano rod in a mixed solvent of 45mL of methanol and 30mL of water, performing ultrasonic treatment for 10min, stirring for 10min, and repeating the ultrasonic treatment and stirring for 5 times to obtain uniformly dispersed BiVO4Suspension of the nano-rods;
2.9160g of CdIn2S4The nano particles are dispersed in BiVO4And (3) performing ultrasonic treatment for 15min, stirring for 20min, and repeating the ultrasonic treatment and stirring for 5 times in the nanorod suspension to obtain uniformly dispersed suspension. Adding the mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven, heating the hydrothermal kettle to 100 ℃, reacting for 2 hours, naturally cooling the hydrothermal kettle to room temperature, washing, drying and collecting a sample to obtain the CdIn2S4nanoparticle/BiVO4Nanorod composite structure, in which BiVO4The mass percentage of the nano-rod in the composite structure is 10%.
In the XRD pattern of the sample synthesized in example 2 in FIG. 1, not only CdIn is present in the composite structure2S4The characteristic diffraction peak of the compound is shown to be in BiVO at 18.7 degrees and 28.8 degrees4The diffraction peak of (a) indicates that the composite structure has been successfully synthesized.
Fig. 3 shows that the photocatalytic degradation efficiency of the sample on TC within 180min is 66.38%, and in fig. 4, the degradation of the sample on OTC within 120min reaches 74.35%, and the sample has a good removal effect on TC and OTC at the same time.
Fig. 6 is a PL diagram of a composite structure sample prepared according to example 2, and it can be seen that the PL strength of the composite structure is significantly reduced, which proves that the heterojunction formed by the two can effectively prevent the recombination of electrons and holes, and greatly improve the overall separation efficiency of photogenerated carriers.
Example 3
(1) According to the proportion of 0.9 mmol: 3g: 1.5mmol Bi (NO) was weighed3)3·5H2O、PVP、NaVO3Adding Bi (NO)3)3·5 H2O, PVP adding into 75mL ethanol, and ultrasonic dispersing for 40min to obtain uniform dispersion A;
45mL of water is measured and NaVO is added3And performing ultrasonic treatment for 20min to obtain dispersion liquid B.
Slowly dripping B into A, stirring for 40min, transferring into a hydrothermal kettle, reacting for 8 hours at 180 ℃, naturally cooling to room temperature, washing, drying and grinding, adding the ground sample into a tube furnace for calcining, wherein the heating rate is 1.5 ℃/min, the calcining temperature is 480 ℃, and the calcining time is 2 hours, thus obtaining BiVO4And (4) nanorods.
(2) BiVO obtained in the step (1)4Dispersing 1.5mmol (0.4860 g mass) of nano rod in a mixed solvent of 45mL of methanol and 45mL of water, performing ultrasonic treatment for 20min, stirring for 20min, and repeating ultrasonic treatment and stirring for 6 times to obtain uniformly dispersed BiVO4Suspension of the nano-rods;
2.754g of CdIn2S4The nano particles are dispersed in BiVO4And (3) performing ultrasonic treatment for 20min, stirring for 20min, and repeating ultrasonic treatment and stirring for 6 times in the nanorod suspension to obtain uniformly dispersed suspension. Adding the mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven, heating the hydrothermal kettle to 120 ℃, reacting for 1h, naturally cooling the hydrothermal kettle to room temperature, washing, drying and collecting a sample to obtain the CdIn2S4nanoparticle/BiVO4Nanorod composite structure, in which BiVO4The mass percentage of the nano-rod in the composite structure is 15%.
Similar to example 2, in the XRD pattern of the sample according to example 3 in FIG. 1, the CdIn attributed to the composite structure is simultaneously present2S4Characteristic diffraction peak of (A) and BiVO4But belongs to BiVO4Is slightly higher than that of example 2, mainly due to BiVO4Due to the increase of the content of (b).
Fig. 3 shows that the photocatalytic degradation efficiency of the sample to TC within 180min is 68.92%, and in fig. 4, the sample degrades OTC within 120min to 77.54%, and has good removal effect to both TC and OTC.
FIG. 7 is a DRS graph of a sample of a composite structure prepared according to example 3, from which it can be seen that the visible light absorption performance of the composite structure is significantly higher than that of CdIn2S4And (4) enhancing.
All the above degradation experiments were carried out in a model GHX-3 photochemical reaction apparatus, using a 250W xenon lamp to simulate a solar light source, and using lambda>The CdIn prepared by the invention is evaluated by filtering out ultraviolet light with a 420nm filter2S4nanoparticle/BiVO4The degradation effect of the nanorod composite structure on tetracycline hydrochloride and oxytetracycline hydrochloride. The method comprises the following specific steps: adding 50mL (10mg/L) of medical tetracycline hydrochloride (TC)/oxytetracycline hydrochloride (OTC) into a reactor, measuring the initial value, then adding 20mg (in TC solution)/50 mg (in OTC solution) of a composite photocatalyst, carrying out dark reaction for 60min (in TC solution)/40 min (in OTC solution) to reach adsorption-desorption equilibrium, illuminating for 180min (in TC solution)/120 min (in OTC solution), sampling at intervals, taking supernatant after centrifugal separation, and measuring the absorbance (lambda) of the maximum absorption wavelength in an ultraviolet-visible spectrophotometerTC=360nm,λOTC356 nm). Calculating the degradation rate eta of the organic pollutants according to the change of the absorbance before and after the illumination (C)0–Ct)/C0X 100% (wherein C)0Absorbance of the sample at the very beginning of the light irradiation, CtAs absorbance of the sample after a certain period of light).
All the above-mentioned embodiments are only some of the embodiments of the present invention, and therefore, the scope of the present invention should not be limited thereby, and the methods and equivalents thereof described in the claims and the description of the present invention are all covered by the present invention.
Claims (8)
1. CdIn2S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized by comprising the following steps of:
(1) weighing bismuth nitrate (Bi (NO) pentahydrate according to a certain mass ratio3)3·5H2Adding ethanol into O and polyvinylpyrrolidone PVPPerforming ultrasonic dispersion for 20-40min to obtain uniform dispersion liquid A;
weighing sodium metavanadate NaVO with a certain amount3Adding into water, and performing ultrasonic treatment for 10-20min to obtain dispersion B;
slowly dripping B into A, stirring for 30-40min, transferring into a hydrothermal kettle, performing hydrothermal reaction at a certain temperature for several hours, naturally cooling to room temperature, washing, drying and grinding, and finally adding the ground sample into a tube furnace for calcination reaction to obtain BiVO4A nanorod;
(2) weighing a certain mass of BiVO obtained according to the step (1)4Dispersing the nano-rods in methanol and water solution with a certain proportion, ultrasonically stirring for 10-20min, repeating for 3-6 times to obtain uniformly dispersed BiVO4Suspension of the nano-rods;
weighing a certain mass of CdIn2S4Nanoparticles dispersed in BiVO4Performing ultrasonic treatment for 10-20min in the nanorod suspension, stirring for 10-20min, repeating for 3-6 times, adding the uniformly dispersed suspension into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating to a certain temperature, reacting for a period of time, naturally cooling to room temperature, washing, drying, and collecting a sample to obtain CdIn2S4nanoparticle/BiVO4And (3) a nanorod composite structure.
2. The CdIn of claim 12S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized in that in the step (1), ethanol and Bi (NO) are added3)3·5H2O、PVP、NaVO3And the dosage ratio of water is as follows: 25-75 mL: 0.3-0.9 mmol: 1-3 g:0.5-1.5mmol:15-45 mL.
3. The CdIn of claim 12S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized in that in the step (1), the temperature of the hydrothermal reaction is 140-180 ℃, and the reaction time is 8-16 h; the heating rate of the tubular furnace for calcination is 1.5-3 ℃/min, the calcination temperature is 400-480 ℃, and the calcination time is 1-3 h.
4. The CdIn of claim 12S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized in that the BiVO prepared in the step (1)4The diameter of the nano rod is 5-20nm, and the length is 150-250 nm.
5. The CdIn of claim 12S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized in that in the step (2), BiVO4The dosage ratio of the nano-rods to the methanol and the water is 0.5-1.5mmol:15-45mL:15-45 mL.
6. The CdIn of claim 12S4nanoparticle/BiVO4The preparation method of the nanorod composite structure is characterized in that in the step (2), the temperature of the hydrothermal reaction is 80-120 ℃, and the reaction time is 1-2.5 h.
7. CdIn2S4nanoparticle/BiVO4Nanorod composite structures, characterized in that they are obtained by the method of any one of claims 1 to 6, wherein BiVO4Nanorod in CdIn2S4nanoparticle/BiVO4The mass percentage of the nano-rod composite structure is 5-15%.
8. The CdIn of claim 72S4nanoparticle/BiVO4The application of the nanorod composite structure is characterized in that the nanorod composite structure is used for catalytic degradation of tetracycline hydrochloride TC and oxytetracycline hydrochloride OTC under visible light.
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