CN113578310A - CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, and preparation method and application thereof - Google Patents
CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 22
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- 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
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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Abstract
The invention discloses a CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, a preparation method and application thereof, wherein the CdS @ ZnCr-LDHs heterojunction nano material is a composite material formed by growing zinc-chromium hydrotalcite on a CdS nanorod carrier by taking a CdS nanorod as the carrier, and the chemical general formula of the zinc-chromium hydrotalcite in the composite material is [ Zn ]2+ x1‑Cr3+ x (OH)2](CO3 2‑)x/2·mH2O]In which Zn is2+And [ Cr ]3+]The molar ratio of (1-x) x is more than or equal to 0.2 and less than or equal to 0.33, m is the quantity of crystal water, and m is more than or equal to 2 and less than or equal to 6. The zinc-chromium hydrotalcite and cadmium sulfide composite material is used for catalytically degrading tetracycline in wastewater, the reaction conditions are mild, the tetracycline removal rate is high, and the catalytically degraded composite material is easy to recycle.
Description
Technical Field
The invention relates to a CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, and a preparation method and application thereof.
Background
Antibiotics are secondary metabolites with antibiotic protomer or other activities generated by microorganisms such as bacteria, fungi, actinomycetes and the like or higher animals and plants in the life activity process. Tetracycline antibiotics (hereinafter referred to as TC) are widely applied antibiotics. In recent years, with the ever-increasing population and the rapid development of economy, China has become the world's largest antibiotic producing and consuming country, and improper use and even abuse of tetracycline antibiotics in medicine, livestock raising and the like have led to the tetracycline antibiotics entering the water environment, so that the environmental safety, ecosystem and human health are more and more seriously threatened. Conventional approaches to tetracycline disposal are biological and physical methods. Biological methods are susceptible to contaminant concentration limitations for their use in the treatment of tetracycline. In addition, because tetracycline itself has biological toxicity, the microbial activity is inhibited during biological processes, making the treatment less than ideal. In addition, the biological method is not an ideal method for treating tetracycline pollutants in wastewater due to the defects of high power loss, high cost, easy sludge bulking and the like. The physical method is only to transfer the organic pollutants in the sewage to another place, which can not completely remove the organic pollutants, and is easy to bring secondary pollution to the environment and very difficult to recycle. Thus, physical methods are also not effective methods for treating tetracycline contaminants in wastewater. Based on the limitations of the above two traditional approaches, many have focused on finding more efficient wastewater treatment strategies, including photocatalytic technologies, which may have promising new applications in environmental cleaning and energy conversion.
An ideal semiconductor photocatalyst should have good light trapping capability, high redox potential, and rapid photo-induced electron-hole (e-h) pair separation and transfer. To overcome these disadvantages, it has been proposed to construct a heterostructure photocatalytic system by compounding two semiconductors. The Z-type heterojunction is an effective method for reducing the recombination probability of carriers. The band arrangement and electron transfer mechanism of the Z-type heterojunction are mainly that electrons on the conduction band of semiconductor B and holes on the valence band of semiconductor a are recombined and annihilated, the remaining electrons mainly exist on the conduction band of semiconductor a and the holes mainly exist on the valence band of semiconductor B, and thus the electrons and the holes are efficiently separated in space. The Z-type heterojunction has an advantage in that electrons are accumulated at a higher energy level and holes are accumulated at a lower energy level, thereby having a stronger redox ability, relative to the type-ii heterojunction. At present, the preparation of cheap and efficient Z-scheme isomeric structure photocatalyst is still very difficult. Therefore, it is very desirable to develop a Z-scheme photocatalytic system based on semiconductor materials abundant on the earth and to explore its catalytic mechanism.
The structural formula of the layered double hydroxide LDHs is as follows:
the layered structure of the composite material is formed by cation laminates and interlayer anions. Because of the adjustable modification of the cation species and the interlayer anions in the cation laminate, the cation laminate is often used for introducing transition metal elements or organic anions with photocatalytic activity to modify the photocatalytic performance. The forbidden band width after modification is about 1.5-3.0eV according to the types of the introduced metal elements or the difference of organic anions. Under illumination within a specific wavelength range, valence electrons on the LDHs can be excited into a conduction band and generate electron-hole pairs, and the valence electrons participate in an oxidation-reduction reaction to promote a photocatalytic process. CdS has a band gap (Eg ═ 2.4eV) suitable for visible light absorption, and is simple to synthesize and inexpensive, but the photocatalytic activity of pure CdS is restricted due to the fact that its photogenerated carriers and vacancies are easily recombined and CdS is easily subjected to photo-corrosion under light irradiation. However, both phases can be excited by visible light, and energy bands are arranged in a cross manner, so that the heterojunction photocatalytic material can be constructed by adopting LDHs and CdS.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, and a preparation method and application thereof.
The CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline is characterized in that the CdS @ ZnCr-LDHs heterojunction nano material is a composite material formed by growing zinc-chromium hydrotalcite on a CdS nanorod carrier by taking a CdS nanorod as a carrier, wherein the chemical general formula of the zinc-chromium hydrotalcite in the composite material is [ Zn ]2+ 1-xCr3+ x(OH)2](CO3 2-)x/2·mH2O]In which Zn is2+And [ Cr ]3+]The molar ratio of (1-x) x is more than or equal to 0.2 and less than or equal to 0.33, m is the quantity of crystal water, and m is more than or equal to 2 and less than or equal to 6.
The CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline is characterized in that the molar ratio of cadmium to chromium of cadmium sulfide to zinc-chromium hydrotalcite in the composite material is 0.1:1-9:1, and preferably 1: 0.6-0.8.
The preparation method of the CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline is characterized by comprising the following steps of:
dissolving cadmium sulfide, zinc nitrate, chromium nitrate and urea in deionized water, uniformly mixing and dispersing, adding the obtained dispersion into a polytetrafluoroethylene reaction kettle, then placing the polytetrafluoroethylene reaction kettle in an oven to react at 92-97 ℃ for 10-15h, then taking out the polytetrafluoroethylene reaction kettle, naturally cooling to room temperature, centrifuging the reaction liquid, washing the obtained solid with deionized water and absolute ethyl alcohol in sequence, and drying to obtain the CdS @ ZnCr-LDHs heterojunction nano material.
The preparation method of the CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline is characterized in that the feeding molar ratio of cadmium sulfide to urea is 1: 2-8, and preferably 1: 5-6.
The CdS @ ZnCr-LDHs heterojunction nano material is applied to catalyzing and degrading tetracycline in wastewater.
The application of the CdS @ ZnCr-LDHs heterojunction nano material in catalyzing and degrading tetracycline in wastewater is characterized in thatThe application process comprises the following steps: placing CdS @ ZnCr-LDHs in tetracycline wastewater, irradiating for 0.5-4.0 h by a 500W xenon lamp at the temperature of 10-50 ℃ and the pH value of 4.0-10.0, and stirring to degrade tetracycline; the mass concentration of the tetracycline in the wastewater is 10-50 mg.L-1The dosage of the CdS @ ZnCr-LDHs in tetracycline wastewater is 10-50 mg.L-1。
Compared with the prior art, the invention has the following beneficial effects: the invention discloses a heterojunction photocatalytic material CdS @ ZnCr-LDHs which takes a CdS nanorod as a carrier and ZnCr hydrotalcite as a load material, wherein the CdS @ ZnCr-LDHs composite material has stronger thermal stability and photochemical stability, and CdS with photocatalytic performance is combined in the hydrotalcite, so that the defect that the traditional CdS is difficult to recover is overcome, and the photocatalytic performance is improved.
Drawings
FIG. 1 is a comparison of XRD characterization results of ZnCr-LDHs material prepared in example 1, CdS material prepared in example 2, and CdS @ ZnCr-LDHs composite material prepared in example 3;
FIG. 2 is a graph comparing the UV-vis characterization results of the ZnCr-LDHs material prepared in example 1, the CdS material prepared in example 2, and the CdS @ ZnCr-LDHs composite material prepared in example 3;
FIG. 3 is a comparison of electron microscope characterization of the ZnCr-LDHs material prepared in example 1, the CdS material prepared in example 2, and the CdS @ ZnCr-LDHs composite material prepared in example 3;
FIG. 4 is an XPS plot of CdS @ ZnCr-LDHs composites prepared in example 3;
FIG. 5 is a graph showing the comparative results of the change of the concentration of tetracycline after degradation with the degradation time under blank control conditions, in which the ZnCr-LDHs material obtained in example 1, the CdS material obtained in example 2, and the CdS @ ZnCr-LDHs composite material obtained in example 3 are used as catalysts, respectively.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
EXAMPLE 1 Synthesis of ZnCr-LDHs Material
The method comprises the following specific steps: nitrogen protectionUnder the protection of atmosphere, 0.075mol (22.31g) of Zn (NO)3)2·6H2O and 0.025mol (10.00g) Cr (NO)3)3·9H2O was dissolved in 100ml of deionized water to prepare a solution A. Solution B was 1M sodium hydroxide solution. Stirring the liquid in the three-neck flask at room temperature (the rotating speed is 200r/min) in a three-neck flask filled with 50ml of deionized water, dropwise adding the solution A and the solution B into the three-neck flask, controlling the pH value of the mixed liquid in the three-neck flask to be 9.0-9.5, and stopping adding the solution B after the solution A is completely added within 30 min. Crystallizing the obtained mixed solution at 65 ℃ for 24h, centrifuging and washing to neutrality, drying in vacuum at 85 ℃ for 12h to finally obtain a sample ZnCr-NO3LDHs, noted as ZnCr-LDHs material.
Example 2CdS Synthesis
The method comprises the following specific steps: CdS synthesized by hydrothermal method mainly uses Cd (NO)3)2·4H2O, thiourea and ethylenediamine are taken as raw materials, and the synthesis process is as follows: 0.0197mol (6.0768g) of Cd (NO) at room temperature3)2·4H2Dissolving O and 0.0591mol (4.5g) of thiourea in 60ml of ethylenediamine, uniformly stirring, transferring to a 100ml of polytetrafluoroethylene reaction kettle, sealing the polytetrafluoroethylene reaction kettle, transferring the polytetrafluoroethylene reaction kettle to a 160 ℃ vacuum oven for reaction for 48 hours, naturally cooling to room temperature, centrifuging out yellow precipitate in reaction liquid, washing the yellow precipitate twice with deionized water and ethanol respectively, and drying at 65 ℃ for 10 hours to obtain the nano CdS product.
Example 3 Synthesis of CdS @ ZnCr-LDHs composite Material
The synthesis of the CdS @ ZnCr-LDHs material adopts over-boiling water to avoid influencing dissolved carbon dioxide, and comprises the following steps: 0.007mol (100mg) of cadmium sulfide (CdS), 0.0147mol (4.373g) of Zn (NO)3)2·6H2O，0.0049mol(1.961g)Cr(NO3)3·9H2O, and 0.037mol (2.248g) of urea were dissolved in 100ml of deionized water, and the resulting solution was subjected to ultrasonic treatment for 15min and further stirred for 30min to disperse the reaction system uniformly. Transferring the solution into a polytetrafluoroethylene reaction kettle, sealing the polytetrafluoroethylene reaction kettle, and placing the polytetrafluoroethylene reaction kettle in a sealed stateAnd (3) placing the mixture in an oven at the temperature of 95 ℃ for 12h for reaction, taking out the mixture, naturally cooling the mixture to room temperature, centrifuging the reaction solution, and washing the obtained precipitated solid for 2 times by using deionized water and absolute ethyl alcohol respectively. After vacuum drying for 12h at 50 ℃, the product is a composite material of CdS and ZnCr-LDHs, and is recorded as CdS @ ZnCr-LDHs composite material. In the CdS @ ZnCr-LDHs composite material prepared in example 3, the molar ratio of Cr to Zn is 1: 3.
Example 4 XRD characterization of CdS @ ZnCr-LDHs composites
A Shimadzu XRD-6000X-ray powder diffractometer is adopted, wherein the characterization parameters are set as follows: and (3) determining the crystal structure of the sample by using a Cu target and a Kalpha ray with the lambda of 0.1542nm and the angle range of 5-80 degrees. XRD characterization is carried out on the ZnCr-LDHs material prepared in the example 1, the CdS material prepared in the example 2 and the CdS @ ZnCr-LDHs composite material prepared in the example 3 respectively, and a comparison graph of test results is shown in figure 1.
As can be seen from the XRD spectrogram in fig. 1, characteristic peaks of (003), (006) and (009) crystal planes of the hydrotalcite ZnCr-LDHs are obvious, but the half-peak width is wide, which is presumed to be that the stability of the hydrotalcite cation lamina is weakened due to the zingiber effect of trivalent chromium contained in the cation lamina, thereby affecting the stability of the hydrotalcite crystal form, and the interlayer spacing of the hydrotalcite is 8.6nm as calculated from the 2 θ angle corresponding to the (003) diffraction peak. From an XRD (X-ray diffraction) pattern of the CdS @ ZnCr-LDHs composite material, the characteristic peak of cadmium sulfide in the composite material is sharp and long, which shows that a nuclear crystal form of cadmium sulfide in a core-shell structure of the CdS @ ZnCr-LDHs composite material is not damaged, and the characteristic peak (003) peak of hydrotalcite has a weaker signal compared with the characteristic peak of cadmium sulfide, which is related to the main position of cadmium sulfide in the CdS @ ZnCr-LDHs composite material, and is inserted on the surface of rod-shaped CdS as a sheet structure, and simultaneously, under the influence of the CdS core-shell structure, a 2 theta angle shifts to a high angle, and the interlayer spacing is reduced.
Example 5 UV-vis characterization of CdS @ ZnCr-LDHs composites
The ZnCr-LDHs material prepared in the embodiment 1, the CdS material prepared in the embodiment 2 and the CdS @ ZnCr-LDHs composite material prepared in the embodiment 3 are respectively subjected to UV-vis characterization, and the characterization comprises the following operation steps: taking 2000mg of a material to be detected, scanning the material in an ultraviolet-visible spectrophotometer (2550 type, Shimadzu), measuring the wavelength range of 200-800 nm, measuring the diffuse reflection spectrum of the material, obtaining the wavelength of an absorption edge according to the absorption edge of the measured spectrogram, and calculating the band gap energy according to the formula Eg which is 1240/lambada g (Eg is the band gap energy, and lambada g is the wavelength of the absorption edge).
The comparative graph of the UV-vis characterization results of the ZnCr-LDHs material prepared in example 1, the CdS material prepared in example 2 and the CdS @ ZnCr-LDHs composite material prepared in example 3 is shown in FIG. 2, and it can be seen from FIG. 2 that the forbidden bandwidth of the CdS @ ZnCr-LDHs composite material is 2.27 eV.
Example 6 XPS characterization of CdS @ ZnCr-LDHs composites
The CdS @ ZnCr-LDHs composite material prepared in example 3 was taken, XPS characterization was performed on the catalyst using a thermo fischer ESCALAB250Xi instrument, the chemical composition and valence state of the material were analyzed, the excitation source used Alk α rays, the operating voltage 12.5kV, the filament current 16mA, and the charge correction was performed using the binding energy of C1s ═ 284.8eV as the energy standard. The XPS full spectrum of the CdS @ ZnCr-LDHs composite material is shown in FIG. 4, and the XPS full spectrum of ZnCr @ CdS confirms that main elements in a sample are Zn, Cr, Cd, S and O, which are consistent with the characterization result of XRD, and shows that CdS @ ZnCr-LDHs are successfully synthesized.
Example 7 Electron microscopy (SEM, TEM) characterization of CdS @ ZnCr-LDHs composites
The ZnCr-LDHs material prepared in the example 1, the CdS material prepared in the example 2 and the CdS @ ZnCr-LDHs composite material prepared in the example 3 are characterized by corresponding electron microscopes, and the results are summarized in FIG. 3. In FIG. 3, (a) a transmission electron micrograph of CdS; (b) a scanning electron microscope image of ZnCr-LDHs; (c) a transmission electron microscope image of CdS @ ZnCr-LDHs; (d) scanning electron microscope image of CdS @ ZnCr-LDHs.
As can be seen from FIG. 3, the synthesized ZnCr @ CdS core-shell structure takes a regular CdS nanorod core as a main body, ZnCr-LDHs is loaded on a CdS framework, and lattice interfaces of the two materials are in contact with each other to form the core-shell structure composite material.
Example 8 photocatalytic performance study of CdS @ ZnCr-LDHs composite Material
The ZnCr-LDHs material obtained in example 1, the CdS material obtained in example 2 and the CdS @ ZnCr-LD material obtained in example 3 were mixedHs composite material, respectively carrying out photocatalytic performance research, wherein the catalytic process is as follows: 50mg of catalytic material is added to 50ml of 20 mg.L-1The photocatalytic degradation experiment was carried out in an aqueous tetracycline solution at a temperature of 25 ℃ and a pH of 7.0 under 500W xenon lamp irradiation. In the photocatalysis process, sampling analysis is carried out every 15min, and each sampling analysis process comprises the following steps: 2mL of tetracycline solution is taken from the reaction system, then is filtered by 0.45 mu m quickly, and is analyzed and tested at the maximum absorption wavelength (357nm) of the tetracycline by adopting a UV-Vis spectrometer (Shimadzu UV-2600), the content of the tetracycline is determined by the absorbance at the maximum absorption wavelength (357nm), and the concentration of the tetracycline in the reaction system is further calculated.
By adopting the above catalytic degradation process, the results of comparing the concentration of tetracycline after degradation with the change of degradation time when the ZnCr-LDHs material prepared in example 1, the CdS material prepared in example 2 and the CdS @ ZnCr-LDHs composite material prepared in example 3 are used as catalysts are shown in FIG. 5.
In addition, a blank control experiment was set up with reference to the above catalytic degradation process, and the concentration was 20 mg.L for 50ml-1The tetracycline aqueous solution was directly subjected to photocatalytic degradation at 25 ℃ under a condition of pH 7.0 under 500W xenon lamp irradiation. In the photocatalysis process, sampling analysis is carried out every 15min, and the change relation result of the concentration of the degraded tetracycline along with the degradation time in the blank control experiment is summarized in figure 5.
As can be seen from FIG. 5, with the increase of the reaction time, the degradation rate of the CdS @ ZnCr-LDHs composite material and the CdS material to tetracycline is as high as 93.03%, but the catalytic degradation speed of the CdS @ ZnCr-LDHs composite material is faster.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (6)
1. The CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline is characterized in that CdS @ ZnCr-LDHs heterojunction nano material takes CdS nanorods as carriersThe composite material is formed by growing zinc-chromium hydrotalcite on a CdS nanorod carrier, and the chemical general formula of the zinc-chromium hydrotalcite in the composite material is [ Zn ]2+ x1-Cr3+ x (OH)2](CO3 2-)x/2·mH2O]In which Zn is2+And [ Cr ]3+]The molar ratio of (1-x) x is more than or equal to 0.2 and less than or equal to 0.33, m is the quantity of crystal water, and m is more than or equal to 2 and less than or equal to 6.
2. The CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline as claimed in claim 1, wherein the cadmium-chromium molar ratio of cadmium sulfide to zinc-chromium hydrotalcite in the composite material is 0.1:1-9:1, preferably 1: 0.6-1.0.
3. The preparation method of the CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline as claimed in claim 1, characterized by comprising the following steps:
dissolving cadmium sulfide, zinc nitrate, chromium nitrate and urea in deionized water, uniformly mixing and dispersing, adding the obtained dispersion into a polytetrafluoroethylene reaction kettle, then placing the polytetrafluoroethylene reaction kettle in an oven to react at 92-97 ℃ for 10-15h, then taking out the polytetrafluoroethylene reaction kettle, naturally cooling to room temperature, centrifuging the reaction liquid, washing the obtained solid with deionized water and absolute ethyl alcohol in sequence, and drying to obtain the CdS @ ZnCr-LDHs heterojunction nano material.
4. The preparation method of the CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline as claimed in claim 3, wherein the feeding molar ratio of the cadmium sulfide to the urea is 1: 2-8, preferably 1: 5-6.
5. The use of the CdS @ ZnCr-LDHs heterojunction nanomaterial of claim 1 in catalytic degradation of tetracycline in wastewater.
6. The CdS @ ZnCr-LDHs heterojunction nano-material as defined in claim 5, in the presence of catalystThe application of the tetracycline in the wastewater is characterized in that the application process is as follows: placing CdS @ ZnCr-LDHs in tetracycline wastewater, irradiating for 0.5-4.0 h by a 500W xenon lamp at the temperature of 10-50 ℃ and the pH value of 4.0-10.0, and stirring to degrade tetracycline; the mass concentration of the tetracycline in the wastewater is 10-50 mg.L-1The dosage of the CdS @ ZnCr-LDHs in tetracycline wastewater is 10-50 mg.L-1。
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| CN116099552A (en) * | 2023-02-20 | 2023-05-12 | 常州大学 | ZnIn 2 S 4 Preparation method and application of/Ni-Al LDHs/CDs composite photocatalyst |
| CN116139868A (en) * | 2023-02-20 | 2023-05-23 | 常州大学 | Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116099552A (en) * | 2023-02-20 | 2023-05-12 | 常州大学 | ZnIn 2 S 4 Preparation method and application of/Ni-Al LDHs/CDs composite photocatalyst |
| CN116139868A (en) * | 2023-02-20 | 2023-05-23 | 常州大学 | Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst |
| CN116099552B (en) * | 2023-02-20 | 2024-02-13 | 常州大学 | ZnIn 2 S 4 Preparation method and application of/Ni-Al LDHs/CDs composite photocatalyst |
| CN116139868B (en) * | 2023-02-20 | 2024-02-13 | 常州大学 | Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst |
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