CN115212856B - Preparation and application of surface polymer functionalized spherical metal organic framework material - Google Patents
Preparation and application of surface polymer functionalized spherical metal organic framework material Download PDFInfo
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Abstract
The invention discloses a preparation method of a surface polymer functionalized spherical metal organic framework material, which comprises the steps of adding MOFs into a tris (hydroxymethyl) aminomethane buffer solution of dopamine hydrochloride, uniformly stirring, adding a dimethyl sulfoxide solution of 1, 4-benzenedithiol, reacting for 6-18 h at room temperature under the conditions of low-speed stirring and light shielding to carry out post-modification, alternately washing the obtained product with water and ethanol, and drying to obtain powdery solid, namely the surface polymer functionalized spherical MOFs. The metal organic framework adsorbent prepared by the invention has a unique spherical/hollow structure, has rich surface groups after being modified by dopamine and 1, 4-benzene dithiol, can obviously enhance acting force with analytes, can be used as a solid-phase microextraction material for adsorbing and extracting trace pesticide residues in a complex system, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a surface polymer functionalized spherical MOFs material, which is mainly used for adsorption extraction of pesticide residues such as organic phosphorus, quasi-deinsectization polyester, carbamate or sulfonamide and the like, and belongs to the technical field of preparation of novel solid phase extraction materials.
Background
The material is the core of the solid-phase microextraction technology, and the structural characteristics of the material greatly determine the performance of the solid-phase microextraction method. Development of novel efficient adsorbent materials is a key to the development of solid-phase microextraction technology. Metal organic framework Materials (MOFs) are regularly crystalline porous materials that are self-assembled from metal ions or metal clusters and organic complexes by strong complexation. MOFs with different topological structures, pore diameters and morphologies can be synthesized by regulating and controlling parameters such as the types of metal ions and organic ligands, the molar ratio of metal to ligand, the type of solvent, the reaction time and the temperature. Based on the advantages of diversity and designability of MOFs structure, the MOFs structure becomes an ideal platform for synthesizing novel adsorbent materials.
Over ten thousand MOFs are reported, and various series of MOFs such as IRMOFs, ZIFs, MILs, PCNs are used for adsorption extraction of organic pollutants, so that satisfactory results are obtained. However, researchers have also found that many single-phase MOFs have problems of low adsorption capacity, low adsorption selectivity and poor stability due to single surface sites, and the problems can be effectively improved by appropriate surface modification and other measures. Therefore, in order to promote the application of MOFs materials in solid-phase extraction, development of a proper method for modifying MOFs is of great importance.
Disclosure of Invention
The invention aims to provide a preparation method of a spherical MOFs material functionalized by a surface polymer;
the invention also aims to apply the prepared material to the adsorption extraction of pesticide residues such as organic phosphorus, quasi-pyrethroid, carbamate or sulfonamide and the like.
1. Preparation of surface polymer functionalized spherical MOFs adsorbent
The preparation method of the surface polymer functionalized spherical MOFs material comprises the following steps:
(1) Dispersing divalent metal nitrate and trimesic acid in a water/ethanol/N, N-dimethylformamide mixed system according to a certain mass ratio; adding polyvinylpyrrolidone as a dispersing agent into the solution, dispersing uniformly, transferring into a high-pressure reaction kettle, and reacting for 8-24 hours at the reaction temperature of 120-180 ℃; and (3) washing the obtained product by using water and ethanol alternately and centrifugally, and drying to obtain the metal organic framework Material (MOFs).
Wherein the divalent metal nitrate is one or two of nickel nitrate, cobalt nitrate, copper nitrate and zinc nitrate; the mass ratio of the divalent metal nitrate to the trimesic acid is 1:1-6:1.
The average molecular weight of the polyvinylpyrrolidone is 50000-70000; the mass ratio of the divalent metal nitrate to the polyvinylpyrrolidone is 1:2-1:12.
The water/alcohol/N, N-dimethylformamide mixed system comprises the following components in percentage by volume: 10-35% of water, 20-50% of ethanol and 30-80% of N, N-dimethylformamide; the concentration of the divalent metal nitrate in the water/ethanol/N, N-dimethylformamide mixed system is 5-20 g/L.
(2) Adding a proper amount of MOFs into a tris buffer solution of dopamine hydrochloride, uniformly stirring, adding a proper amount of dimethyl sulfoxide solution of 1, 4-benzenedithiol, and carrying out room temperature reaction for 6-18 h under the conditions of low-speed stirring and light shielding for post-modification; the obtained product is alternately washed by water and ethanol and dried, and the obtained powdery solid is the spherical MOFs with the surface compositely copolymerized and modified.
Wherein the mass ratio of MOFs to dopamine hydrochloride is 2:1-10:1; the mass ratio of MOFs to 1, 4-benzene dithiol is 1:1-15:1. The pH value of the tris buffer solution is 8.5; the rotating speed of the low-speed stirring is 50-200 r/min. The concentration of dopamine hydrochloride in the tris buffer solution is 1-5 mg/mL; the concentration of the 1, 4-benzene dithiol in the dimethyl sulfoxide solution is 3-6 mg/mL.
2. Characterization of surface Polymer functionalized spherical MOFs adsorbents
FIG. 1 shows the results of Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) characterization of the MOFs prepared in example 3 of the present invention and the surface polymer functionalized sphere MOFs, respectively. Wherein 1a is an SEM image before modification of Ni/Co-MOF-2, which can be seen to have unique spherical morphology, the size is about 2 mu m, and the partially broken sphere can be seen to have a hollow structure and an obvious hollow structure; b and c are SEM and Transmission Electron Microscope (TEM) images of the modified pBDT@PDA-Ni/Co-MOF-2 respectively, and further confirm the hollow spherical morphology of the modified pBDT@PDA-Ni/Co-MOF-2, and simultaneously indicate that a polymer coating obtained by composite copolymerization exists on the surface of the modified pBDT@PDA-Ni/Co-MOF-2; d is a selected area electron diffraction diagram of Ni/Co-MOF-2 before modification, and light spots and annular diaphragms can be seen, so that the material is in a polycrystalline structure assembled regularly; e is the pBDT@PDA-Ni/Co-MOF-2 element mapping characterization, which shows the successful modification of the material.
FIG. 2 is an X-ray diffraction XRD and infrared FTIR characterization of the Ni/Co-MOF-2 and modified pBDT@PDA-Ni/Co-MOF-2 materials, respectively, prepared in example 3 of the present invention. As can be seen from FIG. 2a, the Ni/Co-MOFs had distinct diffraction peaks at 9.15, 12.60, 16.11, 25.38, 28.50, 32.25, 36.82 and 42.18. The diffraction peak of the modified pBDT@PDA-Ni/Co-MOF crystal is not changed, and the peak type is good but the peak intensity is slightly reduced; FIG. 2b is a FTIR spectrum of Ni/Co-MOF-2 and modified pBDT@PDA-Ni/Co-MOF-2, 3435 cm -1 ，1715.8 cm -1 And 1375.4 cm -1 The absorption peaks of (a) are respectively assigned to the telescopic vibration peaks of the associated O-H and the organic ligand carboxylic acid C=O and C-O, 1633.8 cm -1 And 1579.9cm -1 From the stretching vibration of the benzene ring framework. In addition, modified pBDT@PDA-Ni/Co-MOF-2, 3604.8 cm -1 ，532cm -1 Characteristic peaks of N-H and S-S disulfide bonds of the composite polymer were also observed, indicating successful preparation of the material.
FIG. 3 is a nitrogen adsorption desorption (BET) chart of Ni/Co-MOF-2 and modified pBDT@PDA-Ni/Co-MOF-2 prepared in example 3 of the present invention. As can be seen from the graph, ni/Co-MOF-2 belongs to the IV type nitrogen adsorption curve, and the specific surface area is 199.5 m 2 Per gram, a total pore volume of 0.45. 0.45 cm 2 And/g. The modified pBDT@PDA-Ni/Co-MOF-2 shows a III type nitrogen adsorption curve, and the specific surface area is 61.3 m 2 Per g, a total pore volume of 0.30 cm 2 In contrast, a certain degree of drop in g occurs.
FIG. 4 is an XPS chart of the X-ray photoelectron spectroscopy of pBDT@PDA-Ni/Co-MOF-2 prepared in example 3 of the present invention. As can be seen from the figures, peaks at 164,284, 399, 531, 781, 855 and eV are respectively assigned to S2p, C1S, N1S, O1S, co2p, ni2p, and characteristic element compositions correspond to the element mapping characterizations, indicating that the material is composed of the above characteristic elements.
3. Application of surface polymer functionalized spherical MOFs adsorbent
The adsorption extraction of the sulfanilamide drugs by the surface polymer functionalized spherical MOFs material prepared in the embodiment 3 of the invention is evaluated in a multi-solute mixing mode by taking the surface polymer functionalized spherical MOFs material pBDT@PDA-Ni/Co-MOF-2 as an example.
1. Evaluation of adsorption Performance
In actual life, the detection of sulfonamide pollutants is usually more than one, and the multi-solute adsorption test can evaluate the actual adsorption performance. In order to verify the adsorption performance of the prepared material, a series of multi-solute adsorption performance tests are carried out. The method comprises the following steps:
isothermal adsorption experiments of seven sulfanilamide mixed targets by pBDT@PDA-Ni/Co-MOF-2 are carried out within the initial concentration range of 1-100 mg/L. When the concentration of the single sulfanilamide substances in the mixed standard solution is 1,2.5,5, 10, 20, 25, 50, 75 and 100mg/L, the isothermal adsorption curves of the pBDT@PDA-Ni/Co-MOF-2 to seven sulfanilamide substances are shown in FIG. 5a, and the maximum adsorption capacities of sulfadiazine, sulfathiazole, sulfamethyl pyrimidine, sulfadimethyl pyrimidine, sulfamethoxazole, sulfaisooxazole and sulfadimethoxine are 14.64, 11.96, 11.15, 10.33, 11.94, 13.35 and 9.79 mg/g respectively. The isothermal line experiment results were fitted by using Langmuir and Freundlich isothermal models, and the relevant parameters are shown in Table 1, and the n values of seven sulfonamides in Freundlich are all greater than 2, which indicates that pBDT@PDA-Ni/Co-MOF-2 is easy to adsorb to the sulfonamides. Theoretical maximum saturated adsorption quantity Q obtained by Langmuir model m The total adsorption capacity is 86.98 mg/g, which is similar to the experimental result, and shows that the material prepared in the multi-solute mixed adsorption mode accords with the Langmuir model and belongs to monolayer adsorption.
Adsorption kinetics experiments of pBDT@PDA-Ni/Co-MOF-2 on the sulfa Co-mixer were performed in a sulfa Co-mixer solution (the concentration of the individual sulfa substances was 50 mg/mL). As shown in FIG. 5b, which shows the relationship curve of the adsorption amount Qt of sulfanilamide with time, seven sulfanilamide is rapidly adsorbed in the initial time, and gradually saturated and reaches the adsorption equilibrium within about 15 min. Indicating that the prepared material has good adsorption speed.
2. Evaluation of extraction Performance
The method comprises the steps of treating low-concentration sulfanilamide in a water sample by using a sitting solid phase microextraction adsorbent through pBDT@PDA-Ni/Co-MOF-2, and evaluating the extraction performance of pBDT@PDA-Ni/Co-MOF-2 by using parameter indexes such as method detection limit, quantitative limit, correlation coefficient, enrichment recovery rate, daytime and daily precision. As shown in Table 2, in the linear concentration range, the correlation coefficients of sulfadiazine, sulfathiazole, sulfamethidine, sulfadimidine, sulfamethoxazole, sulfaisoxazole and sulfadimidine are 0.9998,0.9999,0.9995,0.9993,0.9998,0.9997,0.9995 respectively, the detection limit of the method is 0.4-0.5 mug/L, and the quantitative limit is 1.0-1.4 mug/L. The enrichment factor (EF value) of pBDT@PDA-Ni/Co-MOF-2 on sulfonamide substances at different concentrations is 19.3-23.6, the recovery rate is 77.3-92.6, the daily Relative Standard Deviation (RSD) is 0.83-4.79%, and the daily RSDs range over 5 continuous days is 2.64-9.55%.
3. Reusable property evaluation
The used pBDT@PDA-Ni/Co-MOF-2 is recovered and activated, and is washed twice respectively in the sequence of methanol, deionized water and methanol, and the adsorption performance is evaluated again after vacuum drying. As shown in FIG. 6, pBDT@PDA-Ni/Co-MOF-2 showed some decrease in recovery of sulfanilamide after three repeated uses, which may be caused by failure to completely desorb sulfanilamide during frequent use. But the recovery rate of about 75% is still maintained when the water-soluble polymer is recycled for five times. Indicating that the prepared material has certain reusability.
The performance evaluation shows that the surface polymer functionalized spherical metal organic framework material can be used as a solid-phase microextraction material for the adsorption extraction of trace pesticide residues in a complex system, and particularly used as an adsorbent for the needle cylinder type solid-phase microextraction for the extraction of pesticide residue samples in water samples; pesticide residues include, but are not limited to, organic phosphorus species, pyrethroid species, carbamate species, or sulfonamide species. The adsorption extraction process is as follows:
adding the preparation material into a water sample containing low-concentration pesticide residues (the concentration is 2-200 mu g/L), and oscillating and adsorbing for 15-40 minutes at room temperature by using a shaking table; transferring to a filtering device made of a needle cylinder and a 0.22 μm organic filter membrane after adsorption equilibrium, and filtering to remove adsorption residual liquid; sucking the eluent into the needle cylinder, performing ultrasonic desorption for 3-10 minutes, filtering the eluent into a sample bottle, and performing constant volume by using the eluent for nitrogen blow-drying for analysis. The eluent can be one or more of ethanol, acetonitrile, methanol and acetone; the syringe solid-phase microextraction is based on the interception of the material by a 0.22 mu m filter membrane, so that the separation of the material from the adsorption residual liquid and the eluent is completed by filtration without a centrifugal process.
In conclusion, the metal organic framework adsorbent prepared by the invention has a unique spherical/hollow structure, has rich surface groups after being modified by dopamine and 1, 4-benzene dithiol, can remarkably enhance acting force with analytes, has excellent adsorption and extraction performance, has good enrichment and recovery effects on pesticide residues as a novel solid phase extractant, has certain reusable performance, can be used as a solid phase microextraction material for adsorption and extraction of trace pesticide residues in a complex system, and has wide application prospect.
The surface polymer functionalized spherical MOFs prepared by the invention are modified into a composite modifier by using the baamine and the 1, 4-benzenedithiol, the surface functional groups of the prepared material can be regulated and controlled by changing the proportion of the baamine and the 1, 4-benzenedithiol, and the high-efficiency adsorption material can be prepared according to the structural characteristics of target analytes; meanwhile, the regular spherical morphology and micron-sized dimension can be perfectly combined with the syringe solid-phase microextraction technology established in the invention, and the adsorption and extraction of target analysis can be realized without a centrifugal process. In addition, the method provided by the invention has the advantages of simple reaction process, high reaction yield and good stability, and is suitable for popularization and application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of (a) Ni/Co-MOF and (b) pBDT@PDA-Ni/Co-MOF-2 obtained after modification; (c) A pBDT@PDA-Ni/Co-MOF-2 field emission Transmission Electron Microscope (TEM) image; (d) A selective electron diffraction (SEAD) pattern of Ni/Co-MOF prior to modification; (e) pBDT@PDA-Ni/Co-MOF-2 element map.
FIG. 2 is (a) an X-ray diffraction (XRD) pattern of Ni/Co-MOF-2 and pBDT@PDA-Ni/Co-MOF-2; (b) infrared spectroscopy (FTIR) plot.
FIG. 3 is a graph of nitrogen adsorption and desorption (BET) of Ni/Co-MOF-2 and pBDT@PDA-Ni/Co-MOF-2.
FIG. 4 is an x-ray photoelectron spectroscopy (XPS) of pBDT@PDA-Ni/Co-MOF-2.
FIG. 5 is (a) adsorption isotherms of pBDT@PDA-Ni/Co-MOF-2; (b) adsorption kinetics.
FIG. 6 is a graph of the repeated recovery of sulfonamide by pBDT@PDA-Ni/Co-MOF-2 as a solid phase extractant.
Detailed Description
The preparation and use of the surface polymer functionalized spherical MOFs of the present invention are further illustrated by the following examples.
Example 1
Nickel nitrate 0.436 g and trimesic acid 0.158g were dissolved in 60 mL volume ratio 1:1:1 water/ethanol/N, N-dimethylformamide, 3g of polyvinylpyrrolidone was added and stirred for 30 minutes until the solution was clear. And (3) placing the solution into a high-pressure reaction kettle to react for 12 hours at 120 ℃, alternately centrifuging and washing the product with water and ethanol for multiple times, and drying to obtain the spherical MOFs material, namely the Ni-MOF, wherein the yield is more than 80%. 150mgNi-MOF is added into 20mL of 2mg/mL dopamine buffer solution, 10mL of 4 mg/mL dimethyl sulfoxide solution of 1, 4-benzenedithiol is added after stirring uniformly, reaction is carried out for 10h under the conditions of light shielding and low-speed stirring, the product is alternately washed by water and ethanol, and the modified MOF is obtained after drying, namely pBDT@PDA-Ni-MOF.
Adding 5ml of mg materials into 5 mu g/L sulfonamide water sample, oscillating at constant temperature by using a shaking table for adsorption for 20 minutes, and pouring into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering after adsorption balance. The materials in the needle cylinder are eluted by 1.5mL of ethanol for 3 minutes, the eluent is filtered and collected, the volume of the eluent is fixed to 200 mu L by ethanol after nitrogen is dried, and the enrichment recovery rate of seven sulfonamides is 42.3-63.6 percent by HPLC-UV detection, so that the recovery rate is poor.
Example 2
0.363g of nickel nitrate, 0.073g of cobalt nitrate and 0.158g of trimesic acid are dissolved in a 60: 60 mL volume ratio of water/ethanol/N, N-dimethylformamide mixed solution, 2g of polyvinylpyrrolidone is added and stirred for 20 minutes until the solution is transparent. The solution is placed in a high-pressure reaction kettle to react at 150 ℃ for 12h, the product is washed by water and ethanol alternately and centrifugally for many times, and the Ni/Co-MOF-1 is obtained after drying, and the yield is more than 90%. 140mg of Ni/Co-MOF-1 is added into 15 mL of dopamine buffer solution, after stirring evenly, 15 mL of 4 mg/mL of 1, 4-benzene dithiol dimethyl sulfoxide solution is added, under the condition of light shielding and low-speed stirring, 12h is reacted, the product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-1 is obtained after drying.
Adding 5ml of mg materials into 5ml of sulfanilamide water sample with the concentration of 50 mu g/L, vibrating at constant temperature for adsorption for 20 minutes, and pouring into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering. The material in the needle cylinder is desorbed by acetone with the concentration of 1.5-mL for 3 minutes, the eluent is filtered and collected, the volume of the eluent is fixed to 200 mu L by acetone after nitrogen is dried, and the enrichment recovery rate of seven sulfonamides is 61.6-71.3% by HPLC-UV detection, so that the recovery rate is good compared with the embodiment 1.
Example 3
Nickel nitrate 0.327 and g, cobalt nitrate 0.109 and g and trimesic acid 0.158 and g were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed solution, and 2g polyvinylpyrrolidone was added and stirred for 20 minutes until the solution was clear. The solution is placed in a high-pressure reaction kettle to react at 160 ℃ for 12h, the product is washed by water and ethanol alternately and centrifugally for many times, and the Ni/Co-MOF-2 is obtained after drying, and the yield is over 95 percent. 150mg of Ni/Co-MOF-2 is added into 15 mL of 2mg/mL of dopamine buffer solution, after being stirred uniformly, 15 mL of 4 mg/mL of 1, 4-benzene dithiol dimethyl sulfoxide solution is added, the reaction is carried out under the conditions of light shielding and low-speed stirring for 14 h, the product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-2 is obtained after drying.
Adding 5ml of mg materials into 5ml of sulfanilamide water sample with the concentration of 50 mu g/L, vibrating at constant temperature for adsorption for 20 minutes, and pouring into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering. The material in the needle cylinder is desorbed by methanol ultrasonic for 5 minutes with the concentration of 1.5mL, the eluent is filtered and collected, the nitrogen is blown dry, the methanol is used for constant volume to 200 mu L, the HPLC-UV is used for detection, the recovery rate of seven sulfonamides is 77.3-92.6%, and the result is satisfactory.
Example 4
0.655 g nickel nitrate, 0.112 g cobalt nitrate and 0.332 g trimesic acid were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed solution, 4 g polyvinylpyrrolidone was added, and stirring was carried out for 20 minutes until the solution was clear. The solution is placed in a high-pressure reaction kettle to react at 160 ℃ for 12h, the product is centrifugally washed with water and ethanol alternately for many times, and the Ni/Co-MOF-3 is obtained after drying, and the yield is over 90 percent. 200 mg of Ni/Co-MOF-3 is added into 15 mL of 2mg/mL of dopamine buffer solution, after being stirred uniformly, 15 mL of 4 mg/mL of 1, 4-benzenedithiol dimethyl sulfoxide solution is added, and the reaction is carried out under the conditions of light shielding and low-speed stirring, wherein 14 h is obtained. The product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-3 is obtained after drying.
Adding 10 mg of the materials into a sulfanilamide water sample of 5ml of 50 mu g/L, vibrating and adsorbing for 15 minutes at constant temperature, pouring the mixture into a filtering device made of a syringe and a 0.22 mu m organic filter membrane for filtering, desorbing the materials in the syringe by using 2 mL methanol ultrasound for 5 minutes, filtering and collecting eluent, drying by nitrogen, using methanol to fix the volume to 200 mu L, and analyzing by using HPLC-UV to obtain seven sulfanilamide recovery rates of 67.3-85.3%.
Example 5
0.582 g nickel nitrate, 0.292 g cobalt nitrate and 0.332 g trimesic acid were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed system, 4 g polyvinylpyrrolidone was added, and stirring was carried out for 30 minutes until the solution was transparent. The solution is placed in a high-pressure reaction kettle to react at 170 ℃ for 12h, the product is centrifugally washed with water and ethanol alternately for many times, and the Ni/Co-MOF-4 is obtained after drying, and the yield is over 90 percent. 200 mg of Ni/Co-MOF-4 is added into a buffer solution of which the concentration is 2mg/mL of dopamine, 15 mL of dimethyl sulfoxide solution of 4 mg/mL of 1, 4-benzenedithiol is added after uniform stirring, the reaction is carried out for 12 hours under the conditions of light shielding and low-speed stirring, the product is alternately washed by water and ethanol, and the pBDT@PDA-Ni/Co-MOF-4 is obtained after drying.
Adding 5ml of mg materials into 5ml of sulfanilamide water sample with the concentration of 50 mu g/L, vibrating at constant temperature for adsorption for 20 minutes, and pouring into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering. The trapped material in the syringe is desorbed with acetonitrile of 1.5. 1.5mL for 5 minutes, the eluent is filtered and collected, nitrogen is blown dry, acetonitrile is used for fixing the volume to 200 mu L, and HPLC-UV analysis is used for obtaining the recovery rate of seven sulfonamides to be 63.2-73.5 percent, which is equivalent to that of the embodiment 2.
Example 6
Nickel nitrate 0.327 and g, cobalt nitrate 0.109 and g and trimesic acid 0.158 and g were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed solution, and 2g polyvinylpyrrolidone was added and stirred for 20 minutes until the solution was clear. The solution is placed in a high-pressure reaction kettle to react at 160 ℃ for 12h, the product is washed by water and ethanol alternately and centrifugally for many times, and the Ni/Co-MOF-2 is obtained after drying, and the yield is over 95 percent. 150mg of Ni/Co-MOF-2 is added into 15 mL of 2mg/mL of dopamine buffer solution, after being stirred uniformly, 15 mL of 4 mg/mL of 1, 4-benzenedithiol dimethyl sulfoxide solution is added, the reaction is carried out under the conditions of light shielding and low-speed stirring for 14 h, the product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-2 is obtained after drying (the same as in example 3).
Adding 5ml of mg materials into 5 mu g/L water sample containing organic phosphorus, oscillating at constant temperature for adsorption for 20 min, and filtering with a filter device made of a syringe and 0.22 mu m organic filter membrane. The material in the needle cylinder is desorbed by methanol ultrasonic for 5 minutes of 1.5mL, the eluent is filtered and collected, nitrogen is blown dry, the volume is fixed to 200 mu L by methanol, the HPLC-UV is used for detection, and the recovery rate of four organic phosphorus (methamidophos, methamidophos and parathion) is 82.3-94.3%, so that the result is satisfactory.
Example 7
Nickel nitrate 0.327 and g, cobalt nitrate 0.109 and g and trimesic acid 0.158 and g were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed solution, and 2g polyvinylpyrrolidone was added and stirred for 20 minutes until the solution was clear. The solution is placed in a high-pressure reaction kettle to react at 160 ℃ for 12h, the product is washed by water and ethanol alternately and centrifugally for many times, and the Ni/Co-MOF-2 is obtained after drying, and the yield is over 95 percent. 150mg of Ni/Co-MOF-2 is added into 15 mL of 2mg/mL of dopamine buffer solution, after being stirred uniformly, 15 mL of 4 mg/mL of 1, 4-benzenedithiol dimethyl sulfoxide solution is added, the reaction is carried out under the conditions of light shielding and low-speed stirring for 14 h, the product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-2 is obtained after drying (the same as in example 3).
5 mg the above materials are added into 5ml of a water sample of the quasi-avermectin polyester with the concentration of 50 mu g/L, and the mixture is subjected to constant temperature vibration adsorption for 20 minutes and then poured into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering. The materials in the needle cylinder are desorbed by methanol ultrasonic wave of 1.5mL for 5 minutes, the eluent is filtered and collected, nitrogen is blown dry, acetonitrile is used for constant volume to 200 mu L, HPLC-UV is used for detection, and the recovery rate of five pyrethroid polyesters (cypermethrin, fenpropathrin, deltamethrin, fenvalerate and bifenthrin) is 80.2-94.7%, so that the result is satisfactory.
Example 8
Nickel nitrate 0.327 and g, cobalt nitrate 0.109 and g and trimesic acid 0.158 and g were dissolved in a 60 mL volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide mixed solution, and 2g polyvinylpyrrolidone was added and stirred for 20 minutes until the solution was clear. The solution is placed in a high-pressure reaction kettle to react at 160 ℃ for 12h, the product is washed by water and ethanol alternately and centrifugally for many times, and the Ni/Co-MOF-2 is obtained after drying, and the yield is over 95 percent. 150mg of Ni/Co-MOF-2 is added into 15 mL of 2mg/mL of dopamine buffer solution, after being stirred uniformly, 15 mL of 4 mg/mL of 1, 4-benzenedithiol dimethyl sulfoxide solution is added, the reaction is carried out under the conditions of light shielding and low-speed stirring for 14 h, the product is washed by water and ethanol alternately, and the pBDT@PDA-Ni/Co-MOF-2 is obtained after drying (the same as in example 3).
Adding 5 mg above materials into 5ml of carbamate water sample with concentration of 50 μg/L, oscillating at constant temperature for adsorption for 20 min, and filtering with a filter device made of syringe and 0.22 μm organic filter membrane. The material in the syringe is desorbed by methanol ultrasonic wave of 1.5mL for 5 minutes, the eluent is filtered and collected, nitrogen is blown to dry, acetone is used for fixing volume to 200 mu L, HPLC-UV is used for detection, and the recovery rate of three carbamates (N-methyl carbamate, N-dimethyl carbamate and oxime carbamate) is 74.2-89.2%, so that the result is satisfactory.
Claims (8)
1. The application of the surface polymer functionalized spherical metal-organic framework material in pesticide residue adsorption extraction is provided, and the preparation method of the surface polymer functionalized spherical metal-organic framework material comprises the following steps:
(1) Dispersing divalent metal nitrate and trimesic acid in a water/ethanol/N, N-dimethylformamide mixed system, adding polyvinylpyrrolidone as a dispersing agent, uniformly dispersing, reacting at 120-180 ℃ for 8-24 hours, alternately centrifuging, washing and drying the obtained product by using water and ethanol to obtain a metal organic framework material MOFs; the divalent metal nitrate is nickel nitrate and cobalt nitrate;
(2) Adding MOFs into a tris buffer solution of dopamine hydrochloride, stirring uniformly, adding a dimethyl sulfoxide solution of 1, 4-benzene dithiol, reacting for 6-18 h at room temperature under low-speed stirring and light-shielding conditions, performing post-modification, alternately washing the obtained product with water and ethanol, and drying to obtain powdery solid, namely the surface polymer functionalized spherical metal-organic framework material;
the functional spherical metal organic framework material has a hollow spherical shape, and the particle size is 1-2 mu m.
2. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: in the step (1), the mass ratio of the divalent metal nitrate to the trimesic acid is 1:1-6:1.
3. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: in the step (1), the average molecular weight of polyvinylpyrrolidone is 50000-70000; the mass ratio of the divalent metal nitrate to the polyvinylpyrrolidone is 1:2-1:12.
4. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: in the step (1), the volume percentages of the components of the water/ethanol/N, N-dimethylformamide mixed system are as follows: 10-35% of water, 20-50% of ethanol and 30-80% of N, N-dimethylformamide; the concentration of the divalent metal nitrate in the water/ethanol/N, N-dimethylformamide mixed system is 5-20 g/L.
5. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: in the step (2), the mass ratio of MOFs to dopamine hydrochloride is 2:1-10:1; the mass ratio of MOFs to 1, 4-benzene dithiol is 1:1-15:1.
6. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: in the step (2): the pH value of the tris buffer solution is 8.5; the rotating speed of the low-speed stirring is 50-200 r/min.
7. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: the adsorption extraction is needle cylinder type solid phase microextraction, and the extraction process is as follows: adding the prepared surface polymer functionalized spherical metal organic framework material into a pesticide residue water sample, and oscillating and adsorbing for 15-40 minutes at room temperature by using a shaking table; transferring to a filtering device made of a needle cylinder and a 0.22 μm organic filter membrane after adsorption equilibrium, and filtering to remove adsorption residual liquid; sucking the eluent into the needle cylinder, performing ultrasonic desorption for 3-10 minutes, filtering the eluent into a sample bottle, drying by nitrogen, and performing constant volume by using the eluent for analysis; the eluent is one or more of ethanol, acetonitrile, methanol and acetone; the concentration of the pesticide residue water sample is 2-200 mug/L.
8. The use of the surface polymer functionalized spherical metal organic framework material according to claim 1 in pesticide residue adsorption extraction, which is characterized in that: the pesticide residue comprises organic phosphorus, pyrethroid, carbamate or sulfonamide.
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