CN115212856A - 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 trihydroxymethyl aminomethane buffer solution of dopamine hydrochloride, stirring uniformly, adding a dimethyl sulfoxide solution of 1,4-benzenedithiol, reacting at room temperature for 6 to 18h under the conditions of low-speed stirring and light shielding for post-modification, washing an obtained product with water and ethanol alternately, and drying to obtain a 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 abundant surface groups after the surface is modified by dopamine and 1,4-benzenedithiol, can obviously enhance the acting force with an analyte, can be used as a solid phase micro-extraction material for adsorption and extraction of 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 and extraction of organophosphorus, pyrethroid, carbamate or sulfonamide and other pesticide residues, and belongs to the technical field of preparation of novel solid phase extraction materials.
Background
The material is the core of the solid phase micro-extraction technology, and the structural characteristics of the material greatly determine the performance of the solid phase micro-extraction method. The development of novel high-efficiency adsorbent materials is the key to promote the development of solid-phase microextraction technology. Metal organic framework Materials (MOFs) are regular crystalline porous materials formed by self-assembly of metal ions or metal clusters and organic complexes through strong coordination. MOFs with different topological structures, pore diameters and morphologies can be synthesized by regulating and controlling the categories of metal ions and organic ligands, the molar ratio of the metal to the ligands, the type of a solvent, the reaction time, the temperature and other parameters. Based on the advantages of diversity and designability of MOFs, the MOFs become an ideal platform for synthesizing novel adsorbent materials.
The currently reported MOFs exceed tens of thousands, and various series MOFs such as IRMOFs, ZIFs, MILs, PCNs and the like are used for adsorption and 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 the like. Therefore, in order to promote the application of MOFs materials in solid-phase extraction, the development of a proper method has important significance for modifying MOFs.
Disclosure of Invention
The invention aims to provide a preparation method of a surface polymer functionalized spherical MOFs material;
the invention also aims to apply the prepared material to the adsorption and extraction of organophosphorus, pyrethroid, carbamate or sulfonamide and other pesticide residues.
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, uniformly dispersing, transferring into a high-pressure reaction kettle, and reacting at the reaction temperature of 120 to 180 ℃ for 8 to 24h; and (3) alternately centrifuging, washing and drying the obtained product by using water and ethanol to obtain the metal organic framework Materials (MOFs).
Wherein the divalent metal nitrate is one or a mixture of nickel nitrate, cobalt nitrate, copper nitrate and zinc nitrate; the mass ratio of the divalent metal nitrate to the trimesic acid is 1 to 1.
The average molecular weight of the polyvinylpyrrolidone is 50000 to 70000; the mass ratio of the divalent metal nitrate to the polyvinylpyrrolidone is 1 to 2-1.
The water/alcohol/N, N-dimethylformamide mixed system comprises the following components in percentage by volume: 10 to 35 percent of water, 20 to 50 percent of ethanol and 30 to 80 percent of N, N-dimethylformamide; the concentration of the divalent metal nitrate in a water/ethanol/N, N-dimethylformamide mixed system is 5-20 g/L.
(2) Adding a proper amount of the prepared MOFs into a trihydroxymethyl aminomethane buffer solution of dopamine hydrochloride, uniformly stirring, adding a proper amount of a dimethyl sulfoxide solution of 1,4-benzenedithiol, reacting at room temperature for 6-18h under the conditions of low-speed stirring and shading for post-modification; and washing the obtained product with water and ethanol alternately, and drying to obtain powdery solid, namely the spherical MOFs with the surface subjected to composite copolymerization modification.
Wherein the mass ratio of the MOFs to the dopamine hydrochloride is 2 to 1; the mass ratio of the MOFs to the 1,4-benzenedithiol is 1 to 15. The pH value of the tris buffer solution is 8.5; the rotating speed of the low-speed stirring is 50 to 200 r/min. The concentration of dopamine hydrochloride in the tris buffer solution is 1 to 5 mg/mL; the concentration of the 1,4-benzenedithiol in the dimethyl sulfoxide solution is 3 to 6 mg/mL.
2. Characterization of surface Polymer functionalized spherical MOFs adsorbents
FIG. 1 shows the results of Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) characterization of the MOF prepared in example 3 of the present invention and the surface polymer functionalized spherical MOF, respectively. Wherein 1a is an SEM image before modification of the Ni/Co-MOF-2, the Ni/Co-MOF-2 can be seen to have a unique spherical shape, the size is about 2 mu m, and a partially crushed sphere can be seen to also have a hollow structure and an obvious hollow structure; b and c are SEM and Transmission Electron Microscope (TEM) images of pBDT @ PDA-Ni/Co-MOF-2 obtained after modification respectively, further confirm the hollow spherical morphology, and simultaneously show that the surface of the modified product has a polymer coating obtained by composite copolymerization; d is an electron diffraction pattern of a selected area of the Ni/Co-MOF-2 before modification, and spots and annular apertures can be seen to indicate that the material is in a regularly assembled polycrystalline structure; e is pBDT @ PDA-Ni/Co-MOF-2 element mapping representation, and shows the successful modification of the material.
FIG. 2 is an X-ray diffraction XRD and infrared FTIR characterization chart of Ni/Co-MOF-2 and modified pBDT @ PDA-Ni/Co-MOF-2 materials prepared in example 3 of the present invention, respectively. As can be seen from FIG. 2a, the Ni/Co-MOF has distinct diffraction peaks at 9.15, 12.60, 16.11, 25.38, 28.50, 32.25, 36.82 and 42.18. The modified pBDT @ PDA-Ni/Co-MOF crystal diffraction peak is not changed, the peak shape is good but the peak intensity is slightly reduced; FIG. 2b is an 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 Respectively belonging to the association O-H, the organic ligand carboxylic acid C = O, the stretching vibration peak of C-O, 1633.8 cm -1 And 1579.9cm -1 From stretching vibration of the benzene ring skeleton. In addition, the modified pBDT @ PDA-Ni/Co-MOF-2 was modified at 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 graph of nitrogen adsorption desorption (BET) 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 figure, the Ni/Co-MOF-2 belongs to a type IV nitrogen gas adsorption curve, and the specific surface area is 199.5 m 2 (iv)/g, total pore volume of 0.45 cm 2 (ii) in terms of/g. The modified pBDT @ PDA-Ni/Co-MOF-2 presents a III-type nitrogen adsorption curve, and the measured specific surface area is 61.3 m 2 (iv)/g, total pore volume of 0.30 cm 2 In terms of/g, phase ratioIn the meantime, a certain degree of degradation occurs.
FIG. 4 is an X-ray photoelectron spectroscopy XPS chart of pBDT @ PDA-Ni/Co-MOF-2 prepared in example 3 of the present invention. As can be seen from the figure, peaks at 164,284, 399, 531, 781, 855 eV are respectively assigned to S2p, C1S, N1S, O1S, co2p and Ni2p, and the characteristic element composition corresponds to the element mapping characterization, which indicates that the material is composed of the above characteristic elements.
3. Application of surface polymer functionalized spherical MOFs adsorbent
The surface polymer functionalized spherical MOFs material pBDT @ PDA-Ni/Co-MOF-2 prepared in the embodiment 3 of the invention is taken as an example, and the adsorption and extraction of sulfonamides in a multi-solute mixed mode are evaluated for the surface polymer functionalized spherical MOFs material.
1. Evaluation of adsorption Properties
In real life, more than one sulfonamide pollutant is detected, and the multi-solute adsorption test can evaluate the actual adsorption performance better. 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 specific steps:
isothermal adsorption experiments of pBDT @ PDA-Ni/Co-MOF-2 on seven sulfanilamide mixed targets were performed within an initial concentration range of 1 to 100mg/L. When the concentration of single sulfanilamide substance in the mixed standard solution is 1,2.5,5, 10, 20, 25, 50, 75, 100mg/L respectively, the isothermal adsorption curves of pBDT @ PDA-Ni/Co-MOF-2 to seven sulfanilamide substances are shown in figure 5a, and the maximum adsorption capacities of sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxazole, sulfisoxazole and sulfadimethoxine are 14.64, 11.96, 11.15, 10.33, 11.94, 13.35 and 9.79 mg/g respectively. Isothermal line experimental results were fitted with Langmuir and Freundlich isothermal models, the relevant parameters are shown in Table 1, and n values of seven sulfonamides in Freundlich are all greater than 2, indicating that pBDT @ PDA-Ni/Co-MOF-2 is easily adsorbed to sulfonamides. Theoretical maximum saturated adsorption Q obtained by Langmuir model m Similar to the experimental result, the total adsorption capacity is 86.98 mg/g, which shows that the material prepared in the multi-solute mixed adsorption mode conforms to a Langmuir model and belongs to monolayer adsorption.
The adsorption kinetics experiment of pBDT @ PDA-Ni/Co-MOF-2 on the sulfonamide mixed standard is carried out in the sulfonamide mixed standard solution (the concentration of each sulfonamide substance is 50 mg/mL). As shown in fig. 5b, which is a curve of the sulfanilamide adsorption amount Qt with time, it can be seen that seven sulfanilamide species are rapidly adsorbed in the initial time, gradually saturated in about 15 min and reach the adsorption equilibrium. The prepared material has good adsorption speed.
2. Evaluation of extraction Performance
The extraction performance of pBDT @ PDA-Ni/Co-MOF-2 is evaluated by the method detection limit, the quantitative limit, the correlation coefficient, the enrichment recovery rate, the precision in the day and other parameter indexes. The results are shown in Table 2, the correlation coefficients of sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxazole and sulfadimethoxine in the linear concentration range are 0.9998,0.9999,0.9995,0.9993,0.9998,0.9997,0.9995, the detection limit of the method is between 0.4 and 0.5 mug/L, and the quantification limit is 1.0 to 1.4 mug/L. The enrichment factor (EF value) of pBDT @ PDA-Ni/Co-MOF-2 to sulfanilamide substances under different concentrations is between 19.3 and 23.6, the recovery rate is between 77.3 and 92.6, the Relative Standard Deviation (RSD) in the day is within the range of 0.83 to 4.79 percent, and the range of the RSDs in the day for more than 5 continuous days is 2.64 to 9.55 percent.
3. Evaluation of reusability
The used pBDT @ PDA-Ni/Co-MOF-2 is recovered and activated, washed twice by methanol, deionized water and methanol in sequence, and the adsorption performance of the activated product is evaluated again after vacuum drying. As a result, as shown in FIG. 6, pBDT @ PDA-Ni/Co-MOF-2 showed a certain decrease in the recovery of sulfanilamide after three times of repeated use, which may be caused by failure to completely desorb sulfanilamide in frequent use. But the recovery rate of about 75 percent is still maintained when the catalyst 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 micro-extraction material for adsorption extraction of trace pesticide residues in a complex system, and particularly used as an adsorbent for needle cylinder type solid phase micro-extraction for extraction of pesticide residue samples in a water sample; pesticide residues include, but are not limited to, organophosphates, pyrethroids, carbamates, or sulfonamides. The adsorption extraction process is as follows:
adding the preparation material into a water sample (the concentration is 2-200 mu g/L) containing low-concentration pesticide residue, 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 mu m organic filter membrane after adsorption balance, and filtering to remove residual adsorption liquid; and (3) absorbing the eluent into the needle cylinder, carrying out ultrasonic desorption for 3 to 10 minutes, filtering the eluent into a sample bottle, drying the nitrogen, and carrying out constant volume on the eluent for analysis. The eluent can be one or more of ethanol, acetonitrile, methanol and acetone; the solid-phase micro-extraction in the needle cylinder is based on the interception of a filter membrane with the diameter of 0.22 mu m on the material, 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, the surface of the metal organic framework adsorbent is modified by dopamine and 1,4-benzenedithiol to form abundant surface groups, the acting force with an analyte can be obviously enhanced, the metal organic framework adsorbent has excellent adsorption and extraction performances, has a good enrichment and recovery effect on pesticide residues and a certain reusability when being used as a novel solid phase extracting agent, can be used as a solid phase micro-extraction material for adsorption and extraction of trace pesticide residues in a complex system, and has a wide application prospect.
The prepared surface polymer functionalized spherical MOFs uses the dopamine and 1,4-benzenedithiol to be modified into a compound modifier, the surface functional groups of the prepared material can be regulated and controlled by changing the proportion of the dopamine and the 1,4-benzenedithiol, and a high-efficiency adsorbing material can be prepared according to the structural characteristics of a target analyte; meanwhile, the regular spherical shape and the micron-sized size can be perfectly combined with the needle cylinder solid phase micro-extraction 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) pBDT @ PDA-Ni/Co-MOF-2 field emission Transmission Electron Microscopy (TEM) image; (d) A selected area electron diffraction (SEAD) map of the pre-modification Ni/Co-MOF; (e) pBDT @ PDA-Ni/Co-MOF-2 element map.
FIG. 2 is an (a) X-ray diffraction (XRD) pattern of Ni/Co-MOF-2 and pBDT @ PDA-Ni/Co-MOF-2; (b) infrared spectroscopy (FTIR) profile.
FIG. 3 is a graph of the nitrogen adsorption desorption (BET) of Ni/Co-MOF-2 and pBDT @ PDA-Ni/Co-MOF-2.
FIG. 4 is an x-ray photoelectron spectroscopy (XPS) graph of pBDT @ PDA-Ni/Co-MOF-2.
FIG. 5 is (a) adsorption isotherm of pBDT @ PDA-Ni/Co-MOF-2; (b) adsorption kinetics.
FIG. 6 is a graph showing the recovery rate of sulfonamides from pBDT @ PDA-Ni/Co-MOF-2 as a solid phase extractant.
Detailed Description
The preparation and application of the surface polymer functionalized spherical MOFs of the present invention are further described by the following specific examples.
Example 1
0.436 g of nickel nitrate and 0.158g of trimesic acid were dissolved in 60 mL in a volume ratio of 1:1:1 water/ethanol/N, N-dimethylformamide, 3g polyvinylpyrrolidone was added and stirred for 30 minutes until the solution was clear. And (3) placing the solution in a high-pressure reaction kettle to react for 12 hours at 120 ℃, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain the spherical MOFs material, namely Ni-MOF, with the yield of more than 80%. Adding 150mg of Ni-MOF into 20mL of buffer solution of dopamine with the concentration of 2mg/mL, stirring uniformly, adding a dimethylsulfoxide solution of 1,4-benzenedithiol with the concentration of 10 mm L4 mg/mL, reacting for 10 hours under the conditions of light shielding and low-speed stirring, alternately washing a product with water and ethanol, and drying to obtain the modified MOF, namely pBDT @ PDA-Ni-MOF.
Adding 5 mg into 5ml of sulfonamide water sample of 50 μ g/L, shaking for 20 min at constant temperature by using a shaking table, and pouring into a filter device made of a needle cylinder and a 0.22 μm organic filter membrane for filtering after adsorption balance. Ultrasonically eluting the material in the needle cylinder for 3 minutes by using 1.5mL of ethanol, filtering and collecting eluent, drying the eluent by using nitrogen, then fixing the volume to 200 mu L by using the ethanol, and detecting by using HPLC-UV to obtain the enrichment recovery rate of the seven sulfonamides, wherein the enrichment recovery rate is 42.3-63.6 percent, and the recovery rate is poor.
Example 2
0.363g of nickel nitrate, 0.073g of cobalt nitrate and 0.158g of trimesic acid were dissolved in a 60 mL volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 150 ℃ for 12h, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain Ni/Co-MOF-1 with the yield of over 90 percent. Adding 140mg of Ni/Co-MOF-1 into 15 mL2mg/mL of dopamine buffer solution, stirring uniformly, adding 15 mL4 mg/mL of 1,4-benzene dithiol dimethyl sulfoxide solution, reacting under the conditions of light shielding and low-speed stirring for 12h, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-1.
Adding 5 mg into 5ml 50 μ g/L sulfanilamide water sample, shaking at constant temperature for 20 min, and filtering with a filter device composed of a syringe and 0.22 μm organic filter membrane. Ultrasonic desorbing the material in the needle cylinder by using acetone of 1.5mL for 3 minutes, filtering and collecting eluent, drying by nitrogen, then fixing the volume to 200 mu L by using acetone, and detecting by using HPLC-UV to obtain the enrichment recovery rate of the seven sulfonamides, wherein the enrichment recovery rate is 61.6-71.3%, and the recovery rate is good compared with the recovery rate in example 1.
Example 3
0.327 g nickel nitrate, 0.109 g cobalt nitrate and 0.158g trimesic acid were dissolved in a 60 mL volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 160 ℃ for 12h, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain Ni/Co-MOF-2 with the yield of more than 95%. Adding 150mg of Ni/Co-MOF-2 into 15 mL2mg/mL dopamine buffer solution, uniformly stirring, adding 15 mL4 mg/mL 1,4-benzenedithiol dimethyl sulfoxide solution, reacting under the conditions of light shielding and low-speed stirring for 14 h, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-2.
Adding 5 mg into 5ml 50 μ g/L sulfanilamide water sample, shaking at constant temperature for 20 min, and filtering with a filter device composed of a syringe and 0.22 μm organic filter membrane. And ultrasonically desorbing the material in the needle cylinder by using 1.5mL methanol for 5 minutes, filtering and collecting eluent, drying the eluent by using nitrogen, fixing the volume to 200 mu L by using the methanol, and detecting by using HPLC-UV (high performance liquid chromatography-ultraviolet), wherein the recovery rate of the seven sulfonamides is 77.3-92.6 percent, and the result is satisfactory.
Example 4
0.655 g nickel nitrate, 0.112 g cobalt nitrate and 0.332 g trimesic acid are dissolved in a mixed solution of 60 mL water/ethanol/N, N-dimethylformamide at a volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 160 ℃ for 12h, alternately and centrifugally washing the product with water and ethanol for multiple times, and drying to obtain Ni/Co-MOF-3 with the yield of over 90%. Adding 200 mg of Ni/Co-MOF-3 into 15 mL2mg/mL of dopamine buffer solution, uniformly stirring, adding 15 mL4 mg/mL of 1,4-benzene dithiol dimethyl sulfoxide solution, and reacting 14 h under the conditions of light protection and low-speed stirring. The product is washed alternately with water and ethanol and dried to obtain pBDT @ PDA-Ni/Co-MOF-3.
Adding 10 mg into 5ml of sulfonamide water sample of 50 mu g/L, carrying out constant-temperature oscillation adsorption for 15 minutes, pouring the mixture into a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane for filtering, carrying out ultrasonic desorption on the material in the needle cylinder for 5 minutes by using 2 mL methanol, filtering and collecting eluent, carrying out blow-drying by using nitrogen, carrying out constant volume to 200 mu L by using methanol, and carrying out HPLC-UV analysis to obtain the recovery rate of the seven sulfonamides, wherein the recovery rate is 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. And (3) placing the solution in a high-pressure reaction kettle to react at 170 ℃ for 12h, alternately and centrifugally washing the product with water and ethanol for multiple times, and drying to obtain Ni/Co-MOF-4 with the yield of over 90%. Adding 200 mg of Ni/Co-MOF-4 into 15 mL buffer solution with the concentration of 2mg/mL dopamine, uniformly stirring, adding 15 mL4 mg/mL of 1,4-benzenedithiol dimethyl sulfoxide solution, reacting for 12 hours under the conditions of light protection and low-speed stirring, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-4.
Adding 5 mg into 5ml 50 μ g/L sulfanilamide water sample, shaking at constant temperature for 20 min, and filtering with a filter device composed of a syringe and 0.22 μm organic filter membrane. And ultrasonically desorbing the trapped material in the needle cylinder by using acetonitrile of 1.5mL for 5 minutes, filtering and collecting eluent, drying by using nitrogen, then fixing the volume to 200 mu L by using the acetonitrile, and analyzing by using HPLC-UV to obtain the recovery rate of the seven sulfonamides, wherein the recovery rate is 63.2-73.5 percent and is equivalent to that of the sulfonamide in example 2.
Example 6
0.327 g nickel nitrate, 0.109 g cobalt nitrate and 0.158g trimesic acid were dissolved in a 60 mL volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 160 ℃ for 12h, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain Ni/Co-MOF-2 with the yield of more than 95%. Adding 150mg of Ni/Co-MOF-2 into 15 mL2mg/mL dopamine buffer solution, stirring uniformly, adding 15 mL4 mg/mL 1,4-benzenedithiol dimethyl sulfoxide solution, reacting under the conditions of light shielding and low-speed stirring for 14 h, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-2 (same as example 3).
5 mg is added into 5ml 50 mug/L water sample containing organic phosphorus, and is vibrated and absorbed for 20 minutes at constant temperature, and is poured into a filtering device made of a needle cylinder and a 0.22 mug organic filter membrane for filtering. The material in the needle cylinder is subjected to ultrasonic desorption for 5 minutes by using 1.5mL methanol, eluent is filtered and collected, nitrogen is dried and the volume is determined to be 200 mu L by using methanol, HPLC-UV detection is carried out, the recovery rate of four organophosphorus (phorate, demeton, methamidophos and parathion) is 82.3 to 94.3 percent, and the result is satisfactory.
Example 7
0.327 g nickel nitrate, 0.109 g cobalt nitrate and 0.158g trimesic acid were dissolved in a 60 mL volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 160 ℃ for 12h, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain Ni/Co-MOF-2 with the yield of more than 95%. Adding 150mg of Ni/Co-MOF-2 into 15 mL2mg/mL of dopamine buffer solution, stirring uniformly, adding 15 mL4 mg/mL of 1,4-benzenedithiol dimethyl sulfoxide solution, reacting 14 h under the conditions of light shielding and low-speed stirring, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-2 (same as example 3).
Adding 5 mg into 5ml 50 μ g/L of pyrethroids water sample, vibrating at constant temperature for 20 min, and filtering with a filter device composed of a syringe and 0.22 μm organic filter membrane. Ultrasonic desorbing the material in the needle cylinder by using methanol of 1.5mL for 5 minutes, filtering and collecting eluent, drying the eluent by using nitrogen, fixing the volume to 200 mu L by using acetonitrile, and detecting by using HPLC-UV to obtain the five types of pyrethroids (cypermethrin, fenpropathrin, deltamethrin, fenvalerate and bifenthrin) with the recovery rate of 80.2-94.7 percent, wherein the result is satisfactory.
Example 8
0.327 g nickel nitrate, 0.109 g cobalt nitrate and 0.158g trimesic acid were dissolved in a 60 mL volume ratio of 1. And (3) placing the solution in a high-pressure reaction kettle to react at 160 ℃ for 12h, alternately centrifuging and washing the product for multiple times by using water and ethanol, and drying to obtain Ni/Co-MOF-2 with the yield of more than 95%. Adding 150mg of Ni/Co-MOF-2 into 15 mL2mg/mL of dopamine buffer solution, stirring uniformly, adding 15 mL4 mg/mL of 1,4-benzenedithiol dimethyl sulfoxide solution, reacting 14 h under the conditions of light shielding and low-speed stirring, alternately washing a product with water and ethanol, and drying to obtain pBDT @ PDA-Ni/Co-MOF-2 (same as example 3).
Adding 5 mg into 5ml of 50 μ g/L carbamate water sample, adsorbing for 20 min under constant temperature shaking, and filtering with a filter device composed of a syringe and 0.22 μm organic filter membrane. The material in the needle cylinder is subjected to ultrasonic desorption for 5 minutes by using 1.5mL methanol, eluent is filtered and collected, nitrogen is dried and the volume is determined to be 200 mu L by using acetone, HPLC-UV detection is carried out, the recovery rate of three carbamates (N-methyl carbamate, N-dimethyl carbamate and oxime carbamate) is between 74.2 and 89.2 percent, and the result is satisfactory.
Claims (10)
1. A preparation method of a 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 to 180 ℃ for 8 to 24h, alternately centrifuging and washing the obtained product with water and ethanol, and drying to obtain the metal organic framework material MOFs;
(2) Adding the MOFs into a trihydroxymethyl aminomethane buffer solution of dopamine hydrochloride, uniformly stirring, adding a dimethyl sulfoxide solution of 1,4-benzenedithiol, reacting at room temperature for 6-18h under the conditions of low-speed stirring and light shielding for post-modification, alternately washing an obtained product with water and ethanol, and drying to obtain a powdery solid, namely the spherical MOFs with the surface subjected to composite copolymerization modification.
2. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: in the step (1), the divalent metal nitrate is one or a mixture of nickel nitrate, cobalt nitrate, copper nitrate and zinc nitrate; the mass ratio of the divalent metal nitrate to the trimesic acid is 1 to 1.
3. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: in the step (1), the average molecular weight of the polyvinylpyrrolidone is 50000 to 70000; the mass ratio of the divalent metal nitrate to the polyvinylpyrrolidone is 1 to 2 to 1.
4. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: in the step (1), the volume percentage of each component of the water/ethanol/N, N-dimethylformamide mixed system is as follows: 10 to 35 percent of water, 20 to 50 percent of ethanol and 30 to 80 percent of N, N-dimethylformamide; the concentration of the divalent metal nitrate in a water/ethanol/N, N-dimethylformamide mixed system is 5 to 20 g/L.
5. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the MOFs to the dopamine hydrochloride is 2 to 1; the mass ratio of the MOFs to the 1,4-benzenedithiol is 1 to 15.
6. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: 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 to 200 r/min.
7. The method for preparing the surface polymer functionalized spherical metal-organic framework material according to claim 1, wherein the method comprises the following steps: the surface polymer functionalized MOFs have spherical or hollow spherical shapes, and the particle size is 1~2 mu m.
8. The application of the surface polymer functionalized spherical metal-organic framework material prepared by the method of claim 1 in pesticide residue adsorption and extraction.
9. The application of the surface polymer functionalized spherical metal organic framework material in pesticide residue adsorption and extraction, which is characterized in that: the adsorption extraction is a syringe type solid phase micro-extraction, and the extraction process is as follows: adding the prepared metal organic framework material into a pesticide residue water sample, and performing shaking adsorption for 15 to 40 minutes by using a shaking table at room temperature; transferring to a filtering device made of a needle cylinder and a 0.22 mu m organic filter membrane after adsorption balance, and filtering to remove residual adsorption liquid; absorbing the eluent into the needle cylinder, performing ultrasonic desorption for 3 to 10 minutes, filtering the eluent into a sample bottle, drying nitrogen, performing constant volume with the eluent, and analyzing; the eluent is one or more of ethanol, acetonitrile, methanol and acetone; the concentration of the pesticide residue water sample is 2 to 200 mu g/L.
10. The application of the surface polymer functionalized spherical metal organic framework material in pesticide residue adsorption and extraction, which is characterized in that: the pesticide residues comprise organic phosphorus, pyrethroid, carbamate or sulfonamide.
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