CN110152627B - Hydroxyl-containing magnetic microporous organic polymer solid phase extraction agent, preparation method and application - Google Patents
Hydroxyl-containing magnetic microporous organic polymer solid phase extraction agent, preparation method and application Download PDFInfo
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Abstract
The invention provides a hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent, a preparation method and application, namely Fe3O4Hy-MOP solid phase extractant or CoFe2O4A Hy-MOP solid phase extractant; the application of the ultraviolet absorbent in extracting water body. The magnetic Hy-MOP solid phase extractant of the invention has simple synthesis method, low cost of required raw materials, higher yield and reusability. The magnetic Hy-MOP solid phase extracting agent has the advantages of large specific surface area, high porosity, stable chemical property, good dispersibility in water and the like. The magnetic Hy-MOP solid phase extracting agent has rapid magnetic separation capability on three ultraviolet absorbers, so that the rapid separation from a liquid phase can be realized by means of the action of an external magnetic field, the inconvenience caused by centrifugation or filtration separation operation can be avoided, and the difficulty and the cost of the operation are greatly reduced. The magnetic Hy-MOP solid phase extracting agent has higher extraction rate to three ultraviolet absorbers.
Description
Technical Field
The invention belongs to the field of wastewater treatment, relates to a solid phase extracting agent, and particularly relates to a hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent, a preparation method and application.
Background
Ultraviolet absorbers are light stabilizers containing a monocyclic or polycyclic aromatic structure and having a high lipophilicity, and thus are widely used in daily necessities, personal care products, and other pharmaceutical products. Due to the non-uniformity of uv absorbers, some absorbers can penetrate the skin barrier, thereby causing adverse effects in the tissue. In recent years, with the use of ultraviolet absorbers in large quantities and improper disposal, environmental and health risk effects have received attention. Relevant researches show that various ultraviolet absorbers exist in urban domestic sewage, and the urban domestic sewage is finally directly or indirectly discharged into a water environment and enters human bodies through a food chain, so that the ecology and the human health are influenced. In most cases, these substances are present in ambient water in low amounts, and therefore require pretreatment of the analyte prior to instrumental measurements for the purpose of isolating the enriched target.
In a plurality of sample pretreatment technologies, ultrasonic-assisted magnetic solid phase extraction is used as a novel pretreatment technology, and compared with other traditional pretreatment technologies, the method has the advantages of simplicity and convenience in operation, rapidness, small organic solvent usage amount, easiness in recycling materials and the like, so that the method draws wide attention in the aspect of analyzing trace ultraviolet absorbers in the environment. At present, few reports exist about the application of an ultrasonic-assisted magnetic solid-phase extraction method based on a microporous organic polymer to the pretreatment of an ultraviolet absorbent in an environmental water sample. Therefore, it is important to study the method for the pretreatment of the ultraviolet absorber.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent, a preparation method and application, and solve the technical problems of insufficient yield and insufficient recycling performance of the existing solid phase extracting agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent is provided, wherein the hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent is Fe3O4Hy-MOP solid phase extractant or CoFe2O4A Hy-MOP solid phase extractant;
the preparation method of the Hy-MOP comprises the following steps: dissolving bisphenol A in 1, 2-dichloroethane and dimethoxymethane by adopting a Friedel-crafts alkylation method to prepare a mixed solution, uniformly stirring, adding anhydrous ferric trichloride, refluxing and stirring in a nitrogen atmosphere, filtering while hot, repeatedly washing with methanol until filtrate is clear, performing Soxhlet extraction on a product by methanol, performing suction filtration, and drying a filter cake in vacuum to obtain a light brown powdery solid, namely obtaining Hy-MOP;
said Fe3O4The preparation method of the/Hy-MOP solid phase extractant comprises the following steps: FeCl is prepared by chemical coprecipitation3·6H2Aqueous O solution and FeSO4·7H2Adding an O aqueous solution into a Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the mixture to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the mixture for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing a filter cake with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A Hy-MOP solid phase extractant;
the CoFe2O4The preparation method of the/Hy-MOP solid phase extractant comprises the following steps: weighing Hy-MOP and FeCl3·6H2O and CoCl2·6H2Ultrasonically dispersing O into deionized water, and heating and stirring to 85 ℃; adjusting the pH value of the solution to 11, continuously heating and stirring for 5 hours, filtering while the solution is hot, repeatedly washing a filter cake by deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying to obtain CoFe2O4A Hy-MOP solid phase extractant.
The invention also has the following technical characteristics:
said Fe3O4the/Hy-MOP solid phase extractant adopts Fe3O4And @ Hy-MOP solid phase extractant replacement.
Said Fe3O4The preparation method of the @ Hy-MOP solid phase extracting agent comprises the following steps: adopting a chemical coprecipitation method to mix Fe3O4Ultrasonically dispersing nanospheres into water to form a dispersion liquid, then adding the dispersion liquid into Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the dispersion liquid to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the dispersion liquid for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing filter cakes with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A @ Hy-MOP solid phase extractant.
Said Fe3O4The preparation method of the nanosphere comprises the following steps: FeCl is added3·6H2Dissolving O and trisodium citrate in ethylene glycol, stirring at room temperature, and adding anhydrous CH3Continuously stirring COONa to obtain a mixed solution, transferring the obtained mixed solution into a reaction kettle, sealing and reacting; cooling to room temperature, filtering, alternately washing the filter cake with anhydrous ethanol and ultrapure water for several times, and drying to obtain Fe3O4Nanospheres.
Said Fe3O4Preparation of nanospheres of Fe3O4The nanospheres were mixed with Hy-MOP in a mass ratio of 1: 1.
Said Fe3O4In the preparation method of the/Hy-MOP solid phase extractant, FeCl3·6H2O and FeSO4·7H2The molar ratio of O is 2: 1; the FeCl3·6H2O and FeSO4·7H2The mass ratio of the total mass of O to Hy-MOP is 3: 5; the FeCl3·6H2Aqueous O solution and FeSO4·7H2And respectively carrying out ultrasonic treatment on the O aqueous solution for 30min, and then adding the O aqueous solution into the Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment.
The CoFe2O4In the preparation method of the/Hy-MOP solid phase extractant, CoCl2·6H2O、FeCl3·6H2The mass ratio of O to Hy-MOP is 5:12: 9.
The invention also discloses a hydroxyl-containing magnetic microporous organic polymer solid-phase extracting agent which is prepared by the preparation method.
The invention also protects the application of the hydroxyl-containing magnetic microporous organic polymer solid-phase extracting agent prepared by the preparation method in extracting an ultraviolet absorbent in water.
The ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone.
Compared with the prior art, the invention has the following technical effects:
the magnetic Hy-MOP solid phase extractant of the invention has simple synthesis method, low cost of required raw materials, high yield and reusability.
The magnetic Hy-MOP solid phase extracting agent has the advantages of large specific surface area, high porosity, stable chemical property, good dispersibility in water and the like.
(III) the magnetic Hy-MOP solid phase extracting agent has rapid magnetic separation capability on three ultraviolet absorbers, so that the rapid separation from a liquid phase can be realized by means of the action of an external magnetic field, the inconvenience caused by centrifugation or filtration separation operation can be avoided, and the difficulty and the cost of the operation are greatly reduced.
(IV) the magnetic Hy-MOP solid phase extracting agent has higher extraction rate to three ultraviolet absorbers.
Drawings
FIG. 1 shows Hy-MOP and Fe3O4Scanning electron microscope image of Hy-MOP solid phase extractant.
FIG. 2 shows Hy-MOP and Fe3O4A Fourier infrared spectrogram of Hy-MOP, wherein a is the Fourier infrared spectrogram of Hy-MOP, and b is Fe3O4Fourier infrared spectrogram of/Hy-MOP.
FIG. 3 is a diagram showing the relationship between different magnetic Hy-MOP materials and the effect of the different magnetic Hy-MOP materials on the extraction rate of three ultraviolet absorbers.
FIG. 4 is Fe3O4A schematic diagram of the relationship between the extraction rate of the/Hy-MOP magnetic solid-phase extraction agent and three ultraviolet absorbers along with the change of ultrasonic time.
FIG. 5 is Fe3O4A relationship diagram of the extraction rate of the Hy-MOP magnetic solid-phase extraction agent to three ultraviolet absorbers changing along with the repeated use times.
The present invention will be explained in further detail with reference to examples.
Detailed Description
Microporous Organic Polymers (MOPs) are a class of porous materials which are low in cost and easy to prepare, and compared with traditional microporous materials (zeolite and molecular sieve) and metal organic framework Materials (MOFs), the Microporous Organic Polymers (MOPs) have the advantages of low framework density, large specific surface area, good biocompatibility, good chemical stability and thermal stability and the like. In recent years, MOPs have shown great application prospects in the fields of heterogeneous catalysis, separation, gas storage, catalysts, water treatment, and the like, due to their unique advantages. The MOPs materials can selectively separate and enrich target analytes "in size" with molecular dimensions by molecular sieving or micropore packing. The functionalized MOPs have hydrophobic, hydrophilic and magnetic effects, and can effectively improve the separation and enrichment capacity in the pretreatment process.
Based on the advantages of rapid separation and repeated use of the magnetic material, the magnetic Hy-MOP material is synthesized by combining the advantages of large specific surface area, high porosity, stable structure, simple preparation process and low cost of the Hy-MOP material, is used for pretreatment of complex samples, and has wide application value.
Hy-MOP refers to a hydroxyl-containing microporous organic polymer.
The magnetic Hy-MOP solid phase extractant refers to a hydroxyl-containing magnetic microporous organic polymer solid phase extractant.
Fe3O4the/Hy-MOP solid phase extractant refers to Fe3O4Producing the magnetic hydroxyl-containing magnetic microporous organic polymer solid phase extractant.
Fe3O4The @ Hy-MOP solid phase extractant refers to Fe3O4The nanospheres produce a magnetic hydroxyl-containing magnetic microporous organic polymer solid phase extractant.
CoFe2O4the/Hy-MOP solid phase extractant refers to CoFe2O4Producing the magnetic hydroxyl-containing magnetic microporous organic polymer solid phase extractant.
Triclocarban, 3,4, 4' -trichlorodiphenylurea, Triclocarban, TCC for short.
Triclosan, 5-chloro-2- (2, 4-dichlorophenoxy) phenol, Triclosan, abbreviation: TCS.
2, 4-dihydroxybenzophenone, abbreviation: and (5) UV-0.
The apparatus and materials used in the present invention:
high performance liquid chromatography Waters 600 (Waters corporation, usa);
ESG60-4 electronic balance (shenyang dragons electronic weighing instrument ltd);
DL-4 centrifuge (manufactured by Shanghai' an pavilion scientific instruments factory);
SB4200DTD ultrasonic cleaning machine (Ningbo Xinzhi Biotech Co., Ltd.);
DZ-2BC vacuum drying cabinet (Tester instruments, Inc. of Tianjin);
MH-205 adjustable electric heating jacket (Beijing Kogao Yongxing instruments Co., Ltd.).
Triclocarban, triclosan, and 2, 4-dihydroxybenzophenone (Shanghai Michelin biochemistry, Inc.);
bisphenol a (chengdong chemical reagent plant);
1, 2-dichloroethane and anhydrous ferric chloride (Shanghai Merlin Biochemical Co., Ltd.);
dimethoxymethane (shanghai alatin reagent ltd);
methanol (analytically pure, affluent fine chemical company, Tianjin);
ammonia (chemical Limited, Sichuan Ringong);
ferric chloride hexahydrate, ferrous sulfate heptahydrate (sienna chemical reagent plant);
glacial acetic acid, sodium chloride, absolute ethyl alcohol (analytically pure, shinny and meticulous chemical research institute in Tianjin);
methanol, acetonitrile (chromatographically pure, semer fei reagent ltd);
the experimental water was ultrapure water.
In the invention, the method for measuring the high performance liquid chromatography comprises the following steps: 1mL of the resolved supernatant was aspirated, filtered through a 0.22 μm filter, and subjected to HPLC analysis. Detection wavelength: 254 nm; column temperature: 30 ℃; sample introduction volume: 10 μ L. Wherein the detector is: waters (600) 2996-diode array detector; a chromatographic column: XTerrrp18C18Column 5 μm (3.9X 150 mmcolumn); mobile phase: acetonitrile (a), 0.1% glacial acetic acid (B). Gradient elution conditions: 0-5min, 60% A; 5-8min, 60% A-65% A; 8-12min, 65% A-80% A; 12-15min, 80% A-60% of A; 60% A for 5 min.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of Hy-MOP, which comprises the following steps: dissolving bisphenol A in 1, 2-dichloroethane and dimethoxymethane by adopting a Friedel-crafts alkylation method to prepare a mixed solution, uniformly stirring, adding anhydrous ferric trichloride, refluxing and stirring in a nitrogen atmosphere, filtering while hot, repeatedly washing with methanol until filtrate is clear, performing Soxhlet extraction on a product by methanol, performing suction filtration, and drying a filter cake in vacuum to obtain light brown powdery solid, namely obtaining Hy-MOP.
A specific example of the Hy-MOP preparation method of this example is: accurately weighing 2.282g of bisphenol A (BPA) by adopting a Friedel-crafts alkylation method, dissolving the bisphenol A (BPA) in 40mL of 1, 2-Dichloroethane (DCE) and 3.628mL of dimethoxymethane to prepare a mixed solution, uniformly stirring, then adding 4.873g of anhydrous ferric trichloride, refluxing and stirring for 15h at 70-80 ℃ in a nitrogen atmosphere, filtering while hot, repeatedly washing with methanol until the filtrate is clear, soxhlet extracting the product for 18h with methanol, carrying out suction filtration, and carrying out vacuum drying on a filter cake at 60 ℃ to obtain a light brown powdery solid, namely obtaining Hy-MOP.
Example 2:
this example shows Fe3O4The preparation method of the nanosphere comprises the following steps: FeCl is added3·6H2Dissolving O and trisodium citrate in ethylene glycol, stirring at room temperature, and adding anhydrous CH3Continuously stirring COONa to obtain a mixed solution, transferring the obtained mixed solution into a reaction kettle, sealing and reacting; cooling to room temperature, filtering, alternately washing the filter cake with anhydrous ethanol and ultrapure water for several times, and drying to obtain Fe3O4Nanospheres.
Fe of the present example3O4A specific example of a method for preparing nanospheres is: will be provided with0.325gFeCl3·6H2O and 0.20g trisodium citrate are dissolved in 20mL ethylene glycol, stirred for 1h at room temperature, and then added with 1.20gAnhydrous CH3COONa is continuously stirred for 30min to obtain a mixed solution, and then the obtained mixed solution is transferred to a 50mL reaction kettle, sealed and reacted at 200 ℃ for 12 h. Cooling to room temperature, vacuum-filtering, alternately washing the filter cake with anhydrous ethanol and ultrapure water for several times, and vacuum-drying at 60 deg.C for 12 hr to obtain Fe3O4Nanospheres.
Example 3:
this example provides a method for preparing a hydroxyl-containing magnetic microporous organic polymer solid phase extractant, wherein the hydroxyl-containing magnetic microporous organic polymer solid phase extractant is Fe3O4A Hy-MOP solid phase extractant;
Fe3O4the preparation method of the Hy-MOP solid phase extractant comprises the following steps of; FeCl is prepared by chemical coprecipitation3·6H2Aqueous O solution and FeSO4·7H2Adding an O aqueous solution into a Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the mixture to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the mixture for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing a filter cake with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A Hy-MOP extractant;
wherein Hy-MOP is Hy-MOP prepared by the preparation method of example 1.
Wherein FeCl3·6H2O and FeSO4·7H2The molar ratio of O is 2: 1; the FeCl3·6H2O and FeSO4·7H2The mass ratio of the total mass of O to Hy-MOP is 3: 5; the FeCl3·6H2Aqueous O solution and FeSO4·7H2And respectively carrying out ultrasonic treatment on the O aqueous solution for 30min, and then adding the O aqueous solution into the Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment.
A specific example of the preparation method of this embodiment is: dispersing 0.5gHy-MOP in deionized water, and FeCl3·6H2O and FeSO4·7H2O is mixed according to the molar ratio of 2:1 and is respectively subjected to ultrasonic treatment for 30 min. Then the mixture is poured into a 250mL three-neck flask and stirred and mixed uniformly, and heated and stirred to 60 ℃ under the protection of nitrogen. Thereafter, NH was dropwise added to the reaction solution3·H2And O, adjusting the pH value to 9-10. Stirring at constant temperature for 2h, filtering while hot, repeatedly washing filter cake with deionized water and anhydrous ethanol until filtrate is neutral, vacuum drying filter cake at 60 deg.C for 6h to obtain Fe3O4A Hy-MOP solid phase extractant.
FIG. 1 is a scanning electron microscope photograph of Hy-MOP prepared in example 1, and FIG. 1 is a photograph of B in example 33O4Scanning electron microscope picture of/Hy-MOP solid phase extractant, and Fe prepared in the example can be seen from FIG. 13O4the/Hy-MOP solid phase extractant is spherical particles with uniform size, uniform distribution, micropores and rough surfaces.
The spectrum a in FIG. 2 is a Fourier infrared spectrum of Hy-MOP obtained in example 1, and it can be seen from the spectrum a in FIG. 2 that the polymer material is 3446cm-1The absorption peak is caused by the stretching vibration of the hydroxyl O-H bond in the structure of reactant bisphenol A; at 1635cm-1The absorption peak is generated by the stretching vibration of-C-bond on the benzene ring; at 1437cm-1The absorption peak is attributed to-CH3The deformation vibration of the middle C-H bond; and at 2365cm-1The absorption peak is attributed to CO in the air2May be caused by CO in the air during the reaction2Caused by the entry of (c). The b spectrum in FIG. 2 is Fe prepared in example 3 of example 33O4Fourier infrared spectrum of/Hy-MOP solid phase extractant, as can be seen from b spectrum in the graph, Fe3O4In the case of the/Hy-MOP solid phase extractant, except at 592cm-1A new absorption peak appears, and the rest absorption peaks are consistent with the a map in figure 2, which shows that Fe3O4Successfully loaded on the surface of the polymer.
The hydroxyl-containing magnetic microporous organic polymer solid-phase extractant prepared by the preparation method of the embodiment is applied to extraction of ultraviolet absorbers in water.
The ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone.
Example 4:
this example provides a method for preparing a microporous magnetic organic polymer solid phase extractant containing hydroxyl, wherein the microporous magnetic organic polymer solid phase extractant containing hydroxyl is CoFe2O4A Hy-MOP solid phase extractant;
the CoFe2O4The preparation method of the/Hy-MOP solid phase extractant comprises the following steps: weighing Hy-MOP and FeCl3·6H2O and CoCl2·6H2Ultrasonically dispersing O into deionized water, and heating and stirring to 85 ℃; adjusting the pH value of the solution to 11, continuously heating and stirring for 5 hours, filtering while the solution is hot, repeatedly washing a filter cake by deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying to obtain CoFe2O4A Hy-MOP solid phase extractant.
Wherein Hy-MOP is Hy-MOP prepared by the preparation method of example 1.
Wherein, CoCl2·6H2O、FeCl3·6H2The mass ratio of O to Hy-MOP is 5:12: 9.
A specific example of the preparation method of this embodiment is: 0.45g of Hy-MOP and 0.600g of FeCl3·6H2O and 0.2500g CoCl2·6H2Dispersing O in 200mL deionized water, performing ultrasonic treatment for 2 hours, uniformly mixing and loading the mixture into a 500mL three-neck flask, and heating and stirring the mixture to 85 ℃. Subsequently, ammonia was added dropwise to the solution to adjust the pH to 11.0. Stirring at constant temperature for 5h, cooling to room temperature, vacuum-filtering, washing the filter cake with deionized water and anhydrous ethanol respectively until the solution is neutral, vacuum-drying at 60 deg.C for 24h to obtain CoFe2O4A Hy-MOP solid phase extractant.
The hydroxyl-containing magnetic microporous organic polymer solid-phase extractant prepared by the preparation method of the embodiment is applied to extraction of ultraviolet absorbers in water.
The ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone.
Example 5:
this example provides a method for preparing a hydroxyl-containing magnetic microporous organic polymer solid phase extractantFe3O4A @ Hy-MOP solid phase extractant;
Fe3O4the preparation method of the @ Hy-MOP solid phase extracting agent comprises the following steps: adopting a chemical coprecipitation method to mix Fe3O4Ultrasonically dispersing nanospheres into water to form a dispersion liquid, then adding the dispersion liquid into Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the dispersion liquid to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the dispersion liquid for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing filter cakes with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A @ Hy-MOP solid phase extractant.
Wherein Hy-MOP is Hy-MOP prepared by the preparation method of example 1.
Wherein, Fe3O4The nanospheres were Fe prepared using the preparation method of example 23O4Nanospheres.
Wherein, Fe3O4The nanospheres were mixed with Hy-MOP in a mass ratio of 1: 1.
A specific example of the production method of this example is substantially the same as in example 3. .
The hydroxyl-containing magnetic microporous organic polymer solid-phase extractant prepared by the preparation method of the embodiment is applied to extraction of ultraviolet absorbers in water.
The ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone.
Example 6:
the embodiment provides an application of a hydroxyl-containing magnetic microporous organic polymer solid-phase extracting agent for extracting an ultraviolet absorbent in a water body. The ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone.
The hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent adopted in the embodiment is the hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent prepared in the embodiments 3,4 and 5, namely Fe3O4/Hy-MOP、CoFe2O4Hy-MOP and Fe3O4@Hy-MOP。
The extraction performance applied in this example was tested, and the specific method for the extraction performance test was:
the method comprises the following steps: 0.01g of magnetic Hy-MOP solid phase extractant (Fe) was weighed out separately3O4/Hy-MOP、CoFe2O4Hy-MOP and Fe3O4@ Hy-MOP) and 0.01g NaCI in a 12mL glass cuvette, 10mL of three aqueous ultraviolet absorber solutions at a concentration of 100. mu.g/L were added. Performing ultrasonic treatment at room temperature for 10min, separating magnetic material loaded with target molecules with magnet, adding 1mL acetonitrile solution, performing ultrasonic treatment for 10min, separating the desorbed magnetic material with magnet, filtering the desorbed supernatant with 0.22 μm filter membrane, measuring the concentrations of three ultraviolet absorbers in the supernatant by high performance liquid chromatography, and calculating the extraction rate. The extraction capacity of each prepared magnetic solid phase extraction agent on three ultraviolet absorbers is compared, as shown in FIG. 3. Experiments prove that Fe3O4The Hy-MOP solid phase extractant has the best extraction effect on three ultraviolet absorbers in water. This is because of Fe3O4The saturation value of the magnetization of the/Hy-MOP material is higher than that of the other two magnetic materials.
The second method comprises the following steps: 0.01g of Fe is taken3O4Adding 10mL of three ultraviolet absorbent aqueous solutions with the concentration of 100 mu g/L into a 12mL cuvette by using a/Hy-MOP solid phase extracting agent and 0.01g of NaCI, and investigating the influence of the ultrasonic time on the ultraviolet absorption extraction rate of three samples. As shown in FIG. 4, Fe of the present invention3O4The extraction rate of the Hy-MOP solid phase extraction agent to the three ultraviolet absorbers is increased rapidly along with the extension of the ultrasonic time (3-10min), and the extraction rate of the three analytes is maximized at 10 min. Further increasing the ultrasonic time (10-20min), the extraction rate gradually decreases. This is because when the sonication time is too short, the contact time of the analyte with the extractant is insufficient, resulting in a low extraction rate. When the sonication time is too long, a portion of the analyte may be desorbed from the extractant. Therefore, for efficient and rapid extraction, 10min is selected as the optimum extraction time for extracting the three ultraviolet absorbers.
Method three, using different resolving agents will affect the elution effect:
separating the extractant loaded with three ultraviolet absorbers by magnet, adding 1mL of resolving agent (absolute ethyl alcohol, methanol and acetonitrile), performing ultrasonic treatment for 10min, separating the supernatant by magnet into a cuvette, passing through a 0.22 μm organic filter membrane (nylon), and performing sample detection. The results show that the extraction rates of acetonitrile as a resolving agent to three ultraviolet absorbers are respectively as follows: 86%, 94%, 91%.
Method IV, Fe3O4The reuse rate of Hy-MOP solid phase extractant:
fe to be used3O4the/Hy-MOP solid phase extractant is alternately washed by absolute ethyl alcohol and deionized water for 3 times, dried and reused, and respectively tests Fe3O4The extraction rate of the/Hy-MOP solid phase extractant for three ultraviolet absorbers after 8 times of use is shown in FIG. 5. The results show that the extraction rate of ultraviolet light in the third step begins to decrease after the material is repeatedly used for 5 times. This shows that the hydroxyl-containing magnetic MOP solid phase extractant as an extractant has good reproducibility and can be recycled.
Claims (7)
1. The application of the hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent in extracting an ultraviolet absorbent in water is provided, wherein the ultraviolet absorbent is triclocarban, triclosan or 2, 4-dihydroxy benzophenone;
the hydroxyl-containing magnetic microporous organic polymer solid phase extracting agent is Fe3O4Hy-MOP solid phase extractant or CoFe2O4A Hy-MOP solid phase extractant;
the preparation method of the Hy-MOP comprises the following steps: dissolving bisphenol A in 1, 2-dichloroethane and dimethoxymethane by adopting a Friedel-crafts alkylation method to prepare a mixed solution, uniformly stirring, adding anhydrous ferric trichloride, refluxing and stirring in a nitrogen atmosphere, filtering while hot, repeatedly washing with methanol until filtrate is clear, performing Soxhlet extraction on a product by methanol, performing suction filtration, and drying a filter cake in vacuum to obtain a light brown powdery solid, namely obtaining Hy-MOP;
said Fe3O4The preparation method of the/Hy-MOP solid phase extractant comprises the following steps: by chemical coprecipitation method, FeCl3∙6H2Aqueous O solution and FeSO4∙7H2Adding an O aqueous solution into a Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the mixture to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the mixture for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing a filter cake with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A Hy-MOP solid phase extractant;
the CoFe2O4The preparation method of the/Hy-MOP solid phase extractant comprises the following steps: weighing Hy-MOP and FeCl3∙6H2O and CoCl2·6H2Ultrasonically dispersing O into deionized water, and heating and stirring to 85 ℃; adjusting the pH value of the solution to 11, continuously heating and stirring for 5 hours, filtering while the solution is hot, repeatedly washing a filter cake by deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying to obtain CoFe2O4A Hy-MOP solid phase extractant.
2. The use according to claim 1, wherein said Fe is3O4the/Hy-MOP solid phase extractant adopts Fe3O4And @ Hy-MOP solid phase extractant replacement.
3. Use according to claim 2, wherein said Fe is3O4The preparation method of the @ Hy-MOP solid phase extracting agent comprises the following steps: adopting a chemical coprecipitation method to mix Fe3O4Ultrasonically dispersing nanospheres into water to form a dispersion liquid, then adding the dispersion liquid into Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment, heating and stirring the dispersion liquid to 60-70 ℃ in a nitrogen atmosphere, adjusting the pH value to 9-10, continuously stirring and heating the dispersion liquid for 1.5-2 h, filtering the mixture while the mixture is hot, repeatedly washing filter cakes with deionized water and absolute ethyl alcohol until the filtrate is neutral, and drying the filtrate to obtain Fe3O4A @ Hy-MOP solid phase extractant.
4. Use according to claim 3, wherein said Fe3O4The preparation method of the nanosphere comprises the following steps: FeCl is added3∙6H2Dissolving O and trisodium citrate in ethylene glycol, and mixingStirring at room temperature, and adding anhydrous CH3Continuously stirring COONa to obtain a mixed solution, transferring the obtained mixed solution into a reaction kettle, sealing and reacting; cooling to room temperature, filtering, alternately washing the filter cake with anhydrous ethanol and ultrapure water for several times, and drying to obtain Fe3O4Nanospheres.
5. Use according to claim 3, wherein said Fe3O4In the preparation method of the @ Hy-MOP solid phase extracting agent, Fe3O4The nanospheres were mixed with Hy-MOP in a mass ratio of 1: 1.
6. The use according to claim 1, wherein said Fe is3O4In the preparation method of the/Hy-MOP solid phase extractant, FeCl3∙6H2O and FeSO4∙7H2The molar ratio of O is 2: 1; the FeCl3∙6H2O and FeSO4∙7H2The mass ratio of the total mass of O to Hy-MOP is 3: 5; the FeCl3∙6H2Aqueous O solution and FeSO4∙7H2And respectively carrying out ultrasonic treatment on the O aqueous solution for 30min, and then adding the O aqueous solution into the Hy-MOP aqueous solution subjected to ultrasonic dispersion treatment.
7. The use of claim 6, wherein the CoFe2O4In the preparation method of the/Hy-MOP solid phase extractant, CoCl2·6H2O、FeCl3·6H2The mass ratio of O to Hy-MOP is 5:12: 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879842A (en) * | 2016-06-22 | 2016-08-24 | 郑州大学 | Magnetic PAFs solid-phase extracting agent and preparation method and application thereof |
| CN105949359A (en) * | 2016-05-18 | 2016-09-21 | 中南大学 | Method for regulating and controlling transmittance of chrysotile nano-fiber films by gap filling |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949359A (en) * | 2016-05-18 | 2016-09-21 | 中南大学 | Method for regulating and controlling transmittance of chrysotile nano-fiber films by gap filling |
| CN105879842A (en) * | 2016-06-22 | 2016-08-24 | 郑州大学 | Magnetic PAFs solid-phase extracting agent and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Fe3O4磁性纳米材料的制备、粒径调控及表征;王宝玲等;《西部皮革》;20190325;第1页 * |
| Impact of Water Coadsorption for Carbon Dioxide Capture in Microporous Polymer Sorbents;Robert Dawson et al.;《J. Am. Chem. Soc.》;20120612;第10741-10744页 * |
| 新型多孔有机框架衍生的磁性吸附剂在一些农药残留测定中的应用;教彩娜;《万方学位论文》;20180530;全文 * |
| 纳米CoFe2O4颗粒制备及性能研究;国秋菊等;《中国粉体技术》;20070418;第16-19页 * |
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