CN111495432A - Polypyrrole/cadmium sulfide imprinted composite photocatalyst and preparation method and application thereof - Google Patents
Polypyrrole/cadmium sulfide imprinted composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN111495432A CN111495432A CN202010505248.9A CN202010505248A CN111495432A CN 111495432 A CN111495432 A CN 111495432A CN 202010505248 A CN202010505248 A CN 202010505248A CN 111495432 A CN111495432 A CN 111495432A
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- sparfloxacin
- polypyrrole
- cadmium sulfide
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 100
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 81
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229960004954 sparfloxacin Drugs 0.000 claims abstract description 80
- DZZWHBIBMUVIIW-DTORHVGOSA-N sparfloxacin Chemical compound C1[C@@H](C)N[C@@H](C)CN1C1=C(F)C(N)=C2C(=O)C(C(O)=O)=CN(C3CC3)C2=C1F DZZWHBIBMUVIIW-DTORHVGOSA-N 0.000 claims abstract description 80
- 230000000593 degrading effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000004729 solvothermal method Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 description 8
- 229960003702 moxifloxacin Drugs 0.000 description 8
- FABPRXSRWADJSP-MEDUHNTESA-N moxifloxacin Chemical compound COC1=C(N2C[C@H]3NCCC[C@H]3C2)C(F)=CC(C(C(C(O)=O)=C2)=O)=C1N2C1CC1 FABPRXSRWADJSP-MEDUHNTESA-N 0.000 description 8
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008684 selective degradation Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229960002422 lomefloxacin Drugs 0.000 description 1
- ZEKZLJVOYLTDKK-UHFFFAOYSA-N lomefloxacin Chemical compound FC1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNC(C)C1 ZEKZLJVOYLTDKK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- 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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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- 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
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Abstract
The invention discloses a polypyrrole/cadmium sulfide imprinted composite photocatalyst, which comprises a crystalline cadmium sulfide photocatalyst serving as a carrier and a polypyrrole imprinted layer formed on the surface of the carrier, wherein a cavity formed by using sparfloxacin as a template molecule is formed in the polypyrrole imprinted layer. The invention also discloses a preparation method and application of the photocatalyst, and a method for degrading sparfloxacin. The polypyrrole/cadmium sulfide imprinted composite photocatalyst has strong stability and can selectively and effectively degrade sparfloxacin.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a polypyrrole/cadmium sulfide imprinted composite photocatalyst as well as a preparation method and application thereof.
Background
The fluoroquinolone antibiotics are widely applied to the fields of clinical treatment of various infectious diseases, aquaculture, fruit and vegetable planting and the like. Sparfloxacin (Sparfloxacin) belongs to artificially synthesized fluoroquinolone antibiotics, and the medicaments also comprise lomefloxacin, norfloxacin, ciprofloxacin and the like.
At present, the production of fluoroquinolone antibiotics in China is large. The antibiotics are used in great quantities in rural and coastal aquaculture areas. However, the nature of such drugs is not known to most farmers or farmers, which results in the eventual release of fluoroquinolone antibiotics in large quantities into the soil and surrounding aqueous environment. When the content of antibiotics in the environment reaches the upper limit, the antibiotics have great influence on the functions of soil and aquatic organisms, and the more serious consequence is that nonpathogenic bacteria in the environment generate drug resistance and then are mutated into pathogenic bacteria with high drug resistance, thereby causing great threat to human health. Generally, sparfloxacin is relatively difficult to degrade in the natural state (particularly in water), and how to better remove the residual sparfloxacin in the environment (e.g., in water) becomes a scientific problem.
The photocatalysis technology is a novel nontoxic and cheap catalytic oxidation technology and has unique advantages in the aspect of treating pollutants in the environment. The photocatalysis technology is a process that a photocatalyst generates active free radicals under the irradiation of sunlight and generates a series of chemical reactions with reactants, and the photocatalysis technology can promote the interaction between active substances and pollutants in the environment through electric energy or chemical energy converted from solar energy in nature, has the effects of oxidizing and degrading toxic substances, and is rapidly developed due to the unique advantages of environmental protection and low cost.
The molecular imprinting technology is a new technology for synthesizing a material with characteristics of specificity, good affinity and the like by adding a functional monomer, a carrier, a cross-linking agent, an initiator and the like on the basis of a molecular template. The molecular imprinting technology refers to a technology for preparing a polymer capable of specifically recognizing a template molecule by polymerizing a certain template molecule and a monomer having a proper functional group in different ways. The molecularly imprinted polymer synthesized by the technology has high selectivity and specificity recognition capability on template molecules, and has the advantages of acid resistance, alkali resistance, strong stability and the like in a complex environment, so that the molecularly imprinted material has outstanding application value and good development prospect.
Disclosure of Invention
An object of the present invention is to provide a photocatalyst having high stability and capable of selectively and effectively degrading sparfloxacin, in order to solve the above technical problems.
Another object of the present invention is to provide a method for preparing the above photocatalyst.
It is yet another object of the present invention to provide a method for degrading sparfloxacin.
In order to achieve the above object, the present invention provides a polypyrrole/cadmium sulfide imprinted composite photocatalyst, which includes a crystalline cadmium sulfide photocatalyst as a support and a polypyrrole imprinted layer formed on the surface of the support, wherein the polypyrrole imprinted layer has a cavity formed by sparfloxacin as a template molecule.
The invention also provides a preparation method of the polypyrrole/cadmium sulfide imprinted composite photocatalyst, which comprises the following steps:
dissolving 0.02g of sparfloxacin in 15m L of dimethyl sulfoxide, adding 1m L of pyrrole to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 15min, stirring for 5h, dropwise adding 0.15g of cadmium sulfide photocatalyst, 0.15g N, N' -methylene-bisacrylamide, 0.011g of ammonium persulfate and 7.0 mu L of tetramethyl ethylenediamine into the mixed solution, and introducing N2Excluding air at 45 ℃ and N2Polymerizing for 12h under the atmosphere, and mixing the obtained product by using a volume ratio of 8: 2, rinsing and carrying out ultrasonic treatment for 5min to remove the sparfloxacin, thus obtaining the polypyrrole/cadmium sulfide imprinted composite photocatalyst.
Preferably, the cadmium sulfide photocatalyst is synthesized by a solvothermal method.
More preferably, the synthesis steps of the cadmium sulfide photocatalyst are as follows: 6.41 g of Cd (NO) are weighed3)2·4H2O and 4.74g thiourea, 55 ml ethylenediamine was injected, heated at 180 ℃ for 72 hours, rapidly quenched to room temperature after solvothermal reaction, and the resulting yellow precipitate was centrifuged and then concentrated in a volume ratio of 8: 2, rinsing for 3 times, and drying at 60 ℃ to obtain the cadmium sulfide photocatalyst.
The invention also provides application of the polypyrrole/cadmium sulfide imprinted composite photocatalyst in degradation of sparfloxacin.
The invention also provides a method for degrading sparfloxacin, which comprises the following steps: and (3) contacting the polypyrrole/cadmium sulfide imprinted composite photocatalyst with sparfloxacin, and irradiating by using ultraviolet light.
The present invention uses Cd (NO)3)2·4H2O and thiourea are used as raw materials to synthesize the CdS photocatalyst, and the synthesized CdS photocatalyst has a strong photocatalytic degradation function on sparfloxacin. The invention further successfully prepares the polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) by taking the synthesized CdS photocatalyst as a carrier through a surface imprinting method, and the polypyrrole/CdS imprinted composite photocatalyst can selectively and effectively degrade sparfloxacin. Therefore, the polypyrrole/cadmium sulfide imprinted composite photocatalyst which is novel, strong in stability and good in effect of selectively degrading sparfloxacin is prepared by the molecular imprinting technology.
Drawings
FIG. 1 is a graph of the ultraviolet absorption spectrum of a standard concentration sparfloxacin solution.
Figure 2 is a standard operating curve of sparfloxacin.
FIG. 3 is the absorption spectrum of sparfloxacin in the reaction solution of the blank experiment.
FIG. 4 is a graph of the change of the absorption spectrum of sparfloxacin after adding CdS photocatalyst.
Fig. 5 is a graph of the degradation efficiency of sparfloxacin under different experimental conditions.
FIG. 6 is a degradation curve diagram of polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) and polypyrrole/CdS non-imprinted composite photocatalyst (NIP-PPy/CdS) for respectively degrading sparfloxacin and moxifloxacin solutions.
FIG. 7 is a graph comparing degradation efficiency curves of the polypyrrole/CdS imprinted composite photocatalyst for degrading sparfloxacin and moxifloxacin.
FIG. 8 is an XRD spectrum of MIP, NIP, CdS photocatalysts.
FIG. 9 is an infrared spectrum of MIP and CdS photocatalysts.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative of the present invention only, and are not intended to limit the scope of the present invention.
Example 1: preparation of cadmium sulfide photocatalyst
Synthesizing the cadmium sulfide photocatalyst by a solvothermal method.
6.41 g of Cd (NO) are weighed3)2·4H2O and 4.74g of thiourea were charged into a dry Teflon-lined autoclave having a capacity of 100m L, and then 55m L of ethylenediamine was injected thereto, the autoclave was sealed and heated at 180 ℃ for 72 hours, rapidly quenched to room temperature after the solvent thermal reaction, and the resulting yellow precipitate was centrifuged, rinsed 3 times with a mixed solution of ethanol/distilled water at a volume ratio of 8: 2, and finally dried in a vacuum oven at 60 ℃.
Example 2: preparation of polypyrrole/cadmium sulfide imprinted composite photocatalyst (MIP-PPy/CdS)
Weighing 0.02g of sparfloxacin, dissolving in 15m L of dimethyl sulfoxide, adding 1m L of pyrrole, carrying out ultrasonic treatment on the mixed solution for 15min, stirring for 5h, then dropwise adding 0.15g of cadmium sulfide photocatalyst, 0.15g N, N' -methylene bisacrylamide, 0.011g of ammonium persulfate and 7.0 mu L of tetramethyl ethylenediamine into the mixed solution, and introducing N2Air is excluded. Then, at a temperature of 45 ℃ N2Polymerizing for 12h under the atmosphere. Finally, the product obtained was purified by distillation at a volume ratio of 8: 2, rinsing and carrying out ultrasonic treatment for 5min to remove the sparfloxacin. The product was collected and dried in a vacuum oven at 60 ℃.
Example 3: preparation of polypyrrole/cadmium sulfide non-imprinted composite photocatalyst (NIP-PPy/CdS)
The polypyrrole/cadmium sulfide non-imprinted composite photocatalyst was synthesized according to the experimental procedures of examples 2 and 3 above. Except that other conditions were kept constant during the synthesis, but no sparfloxacin was added.
Experimental example 1: selective degradation performance research of molecularly imprinted polymer
1. Drawing of sparfloxacin standard curve
Accurately weighing 5mg of sparfloxacin powder by using an electronic balance, preparing a 100 mg/L sparfloxacin standard solution by using a 0.01% hydrochloric acid solution, adding a 100 mg/L sparfloxacin solution of 0m L, 0.5m L0, 1.0m L1, 2.0m L2 and 3.0m L into a 25m L volumetric flask, diluting the solution by using the hydrochloric acid solution to scale lines to prepare a series of sparfloxacin solutions of 0 mg/L, 2 mg/L, 4 mg/L, 8 mg/L and 12 mg/L, measuring the absorbance of the solution by using a UV-vis spectrophotometer, and drawing a standard curve.
The absorbance of the formulated 0-12 mg/L sparfloxacin solution was measured using an Shimadzu UV-2700 ultraviolet-visible spectrophotometer, Japan and a standard working curve for sparfloxacin was prepared.
The specific operation process is as follows:
after the instrument was turned on, the instrument and computer were connected and preheated for several minutes, the baseline was scanned in the range of 250-400nm using a 1cm cuvette with 0.01% hydrochloric acid solution as a blank.
The outer cuvette was removed and after pouring off the 0.01% hydrochloric acid solution, the absorption spectra of a series of sparfloxacin solutions at 0 mg/L, 2 mg/L, 4 mg/L, 8 mg/L, 12 mg/L were measured in order of concentration from low to high, noting that the cuvette was rinsed with the solution to be measured before each measurement of another solution.
And (4) selecting an absorbance value at the maximum absorption wavelength, and drawing a standard curve graph by taking the absorbance as an ordinate and the concentration of the sparfloxacin solution as an abscissa.
As shown in FIG. 1, the maximum absorption peak position of sparfloxacin is at 298 nm. The absorbance and concentration were fitted linearly, the result is shown in FIG. 2, and the linear regression equation isy＝0.03505x+0.00235，R20.9997, indicating that the sparfloxacin solution is in good linear relationship in the range of 0-12 mg/L.
2. Experiment for degrading sparfloxacin
Weighing 0.05g of CdS photocatalyst, adding the CdS photocatalyst into a photocatalytic reactor, adding 50m of L20 mg/L of sparfloxacin solution, introducing condensed water to control the temperature of a reaction system to be about 27 ℃, then, turning on an ultraviolet lamp power supply, irradiating the sparfloxacin solution added with the photocatalyst by visible strong light, taking samples every 10 minutes, centrifuging, and measuring the concentration C of sparfloxacin in supernate.
The degradation efficiency of sparfloxacin (Dr.) was calculated by the following formula. Wherein, C0And C is the initial concentration of sparfloxacin and the residual concentration in the solution, respectively.
A blank experiment is carried out according to the experimental steps, except that no photocatalyst is added, 50m of L20 mg/L of sparfloxacin water solution is directly added into a photocatalytic reactor, the temperature of a reaction system is controlled to be about 27 ℃ by introducing condensed water, then, an ultraviolet lamp power supply is turned on, the sparfloxacin solution is irradiated by visible strong light, a sample is taken every 10 minutes, and the absorption spectrum of the sparfloxacin in the sample liquid after the reaction is measured.
The photodegradation reaction solution obtained after the blank group experiment was measured for the absorption spectrum of sparfloxacin by the same method as described above, and the absorption spectrum was drawn by Origin as shown in fig. 3. As can be seen from fig. 3: the sparfloxacin solution without the photocatalyst is irradiated by strong light for 60min, and the content of the sparfloxacin in the solution is hardly reduced. After the content of the sparfloxacin in the solution is calculated according to the standard curve, the degradation rate of the sparfloxacin is calculated as follows: 2.6 percent. This can be said: the sparfloxacin has good stability in the solution, and is not easy to degrade in a natural state.
After the CdS photocatalyst is added, the change diagram of the ultraviolet absorption spectrum of the sparfloxacin solution after being irradiated by strong visible light for 0, 10, 20, 30, 40, 50 and 60min is shown in figure 4. As can be seen from FIG. 4, the absorption spectrum of sparfloxacin is greatly changed, and after 10min of illumination, the maximum absorption peak disappears, and the absorption value decreases with the increase of time. Calculating the concentration of the sparfloxacin in the solution after reaction at different times through a standard curve, substituting the concentration into a formula to calculate the degradation efficiency, and showing the result: after the CdS photocatalyst is added, the degradation rate of the sparfloxacin reaches 82.7% when the sparfloxacin solution is irradiated for 10min, and the degradation rate of the sparfloxacin reaches 93.3% when the sparfloxacin solution is irradiated for 60 min. The prepared CdS photocatalyst can be used for well photocatalytic degradation of sparfloxacin.
The degradation efficiency curve of sparfloxacin under different experimental conditions is shown in fig. 5. In the blank experiment group, the concentration of the sparfloxacin solution hardly changes within 30min of strong light irradiation, and the absorbance value of the sparfloxacin solution after 20min of light irradiation at the wavelength of 298nm is slightly higher than that of the original solution due to manual misoperation or instrument measurement errors during measurement. This in turn resulted in a calculated degradation efficiency of-0.3%, which was within the error range, so the efficiency taught here was treated approximately as 0.
3. Experiment of Material Selective degradation
And (2) degrading the sparfloxacin solution and the moxifloxacin solution by respectively using a polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) and a polypyrrole/CdS non-imprinted composite photocatalyst (NIP-PPy/CdS) according to the proportion of 1mg of photocatalyst to 1m L of antibiotic solution and 2.3.2 experimental steps.
Degradation curves of polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) and polypyrrole/CdS non-imprinted composite photocatalyst (NIP-PPy/CdS) for respectively degrading sparfloxacin and moxifloxacin solutions are shown in FIG. 6.
The degradation efficiency of polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) for photodegrading sparfloxacin for 60min is as high as 94.6%, and the degradation rate of polypyrrole/CdS non-imprinted composite photocatalyst (NIP-PPy/CdS) for sparfloxacin is reduced to 88.2%. However, when the polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) degrades moxifloxacin solution with a structure very similar to that of sparfloxacin, the degradation curve of the polypyrrole/CdS imprinted composite photocatalyst is greatly different from that of the sparfloxacin. At 10min, the degradation efficiency of the polypyrrole/CdS imprinted composite photocatalyst on the sparfloxacin reaches 79.6%, while the degradation efficiency on the moxifloxacin is only 46.5%. After 60min, the degradation rates of MIP-PPy/CdS on sparfloxacin and moxifloxacin are respectively 94.6% and 87.4%, and a comparison graph is shown in figure 7. Compared with MIP-PPy/CdS and NIP-PPy/CdS, the degradation rate of moxifloxacin is higher than that of sparfloxacin, and the degradation efficiency reaches 96.5% after 60min of illumination.
Experimental example 2: structural characterization of materials
1. Characterization of XRD
The CdS photocatalyst, MIP-PPy/CdS and NIP-PPy/CdS are dried in advance, a proper amount of three samples are taken to prepare samples respectively, then an X-ray diffractometer is used for representing the samples, and experimental data are analyzed so as to determine the crystal structures of different samples.
The XRD spectrogram of MIP-PPy/CdS photocatalyst, NIP-PPy/CdS photocatalyst and CdS photocatalyst is shown in figure 8. The characteristic peaks of the three samples can be matched with CdS standard map card PDF #80-0006 of a hexagonal crystal phase, and diffraction peaks with 2 theta of 25.1 degrees, 26.7 degrees, 28.5 degrees, 36.8 degrees, 44.0 degrees, 48.1 degrees, 52.0 degrees and 66.9 degrees in the figure correspond to crystal faces of (100), (002), (101), (102), (110), (103), (112) and (203). This is a good indication that no change in the crystalline structure of the synthesized product has occurred. And corresponding diffraction peak intensities of MIP-PPy/CdS and NIP-PPy/CdS are obviously changed, which is probably caused by coating the functional monomer on the surface of the CdS photocatalyst.
XRD analysis results show that: polypyrrole/CdS imprinted composite photocatalysts (MIP-PPy/CdS) and polypyrrole/CdS non-imprinted composite photocatalysts (NIP-PPy/CdS) have been successfully synthesized.
2. FT-IR characterization of CdS and MIP
Drying potassium bromide, CdS photocatalyst and polypyrrole/CdS imprinted composite photocatalyst (MIP-PPy/CdS) in advance, tabletting, and adding sodium chloride at 4000-400cm-1Fourier infrared converter used in rangeAnd scanning the prepared pressed sheet to obtain an infrared spectrogram of the CdS photocatalyst and the polypyrrole/CdS imprinted composite photocatalyst. The infrared spectra were analyzed to determine if MIP-PPy/CdS were successfully produced.
The infrared spectrums of the CdS photocatalyst and the polypyrrole/CdS imprinting composite photocatalyst (MIP-PPy/CdS) are shown in FIG. 9. 1627cm-1、1385cm-1、1120cm-1、618cm-1The four characteristic absorption peaks are contained by MIP-PPy/CdS and CdS photocatalysts. Is located at 1528cm-1And 1448cm-1The peaks of (a) are due to symmetric and antisymmetric pyrrole ring stretching modes, respectively; 1291cm-1The absorption peak corresponds to the in-plane vibration of polypyrrole ring ═ C-H; located at 1195cm-1The peak at (A) is related to the C-N stretching vibration; it was also observed that the out-of-plane vibration peak for ═ C-H was at 952cm-1To (3).
Therefore, the imprinting layer exists on the surface of the polypyrrole/CdS imprinting composite photocatalyst.
Claims (6)
1. The polypyrrole/cadmium sulfide imprinted composite photocatalyst comprises a crystalline cadmium sulfide photocatalyst serving as a carrier and a polypyrrole imprinted layer formed on the surface of the carrier, wherein a cavity formed by using sparfloxacin as a template molecule is formed in the polypyrrole imprinted layer.
2. The preparation method of the polypyrrole/cadmium sulfide imprinted composite photocatalyst according to claim 1, comprising the following steps:
dissolving 0.02g of sparfloxacin in 15m L of dimethyl sulfoxide, adding 1m L of pyrrole to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 15min, stirring for 5h, dropwise adding 0.15g of cadmium sulfide photocatalyst, 0.15g N, N' -methylene-bisacrylamide, 0.011g of ammonium persulfate and 7.0 mu L of tetramethyl ethylenediamine into the mixed solution, and introducing N2Excluding air at 45 ℃ and N2Polymerizing for 12h under the atmosphere, and mixing the obtained product by using a volume ratio of 8: 2, rinsing and carrying out ultrasonic treatment for 5min to remove the sparfloxacin, thus obtaining the polypyrrole/cadmium sulfide imprinted composite photocatalyst.
3. The method of claim 2, wherein the cadmium sulfide photocatalyst is synthesized by a solvothermal method.
4. The method of claim 2, wherein the cadmium sulfide photocatalyst is synthesized by the steps of: 6.41 g of Cd (NO) are weighed3)2·4H2O and 4.74g thiourea, 55 ml ethylenediamine was injected, heated at 180 ℃ for 72 hours, rapidly quenched to room temperature after solvothermal reaction, and the resulting yellow precipitate was centrifuged and then concentrated in a volume ratio of 8: 2, rinsing for 3 times, and drying at 60 ℃ to obtain the cadmium sulfide photocatalyst.
5. Use of the polypyrrole/cadmium sulfide imprinted composite photocatalyst according to claim 1 for degrading sparfloxacin.
6. A method for degrading sparfloxacin, characterized by comprising the steps of: contacting the polypyrrole/cadmium sulfide imprinting composite photocatalyst of claim 1 with sparfloxacin, and irradiating with ultraviolet light.
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