CN111266095B - Solid-phase extraction filler, solid-phase extraction column and preparation method and application thereof - Google Patents
Solid-phase extraction filler, solid-phase extraction column and preparation method and application thereof Download PDFInfo
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Abstract
The diquat molecularly imprinted polymer prepared by the invention can be used as an adsorbent for solid-phase extraction and liquid chromatography, can enrich diquat, has high enrichment efficiency, is suitable for enrichment and purification of trace diquat in water, and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry and drinking water safety detection, and particularly relates to a solid-phase extraction filler, a solid-phase extraction column, and a preparation method and application thereof.
Background
Diquat dibromide is a high-efficiency, low-toxicity and broad-spectrum biocidal herbicide widely used in rubber, mulberry, tea, orchard, sugarcane field and the like. However, with the increasing use of diquat, it has become one of the major contaminants of drinking water. Therefore, the research on enrichment, purification and detection of trace diquat in water has very important practical significance. At present, after the pH value of a solution is adjusted, a proper cation exchange column, an anion exchange column or a C18 column and the like are adopted for processing in different pH values, but the columns used in the existing documents still have the defects of low enrichment efficiency, high cost, poor selectivity and the like, and particularly when solid phase extraction is combined with liquid chromatography-tandem mass spectrometry, the matrix interference of mass spectrometry detection is large due to the poor selectivity, and the matrix effect is serious, so that the accuracy of the detection result is not ideal. Therefore, a simple, practical, efficient and cheap solid-phase extraction column is developed, is used for enriching and purifying trace amount of diquat in water, and has very important practical significance for ensuring the drinking water safety of residents.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a solid-phase extraction filler, a solid-phase extraction column, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a solid phase extraction packing material prepared by the steps of:
1)NH 2 preparation of Fe/Zr/Mn-MOFs materials: mixing a certain weight ratio of Fe (NO) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O and ZrCl 4 Uniformly mixing, dissolving in 0.01mol/L hydrochloric acid solution, adding DMF, adding aminophthalic acid, stirring for dissolving, transferring into a closed reaction container, reacting at 100 deg.C for 24 hr, centrifuging, washing the obtained precipitate with DMF and ethanol, and vacuum drying at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials;
2) Preparation of the filler: 20.0mg NH was added to a 25mL reaction vessel 2 Fe/Zr/Mn-MOFs material, 10.0mL of acetonitrile and 1.0-2.0 mg of diquat template molecules, fully stirring to completely dissolve the diquat, adding 0.40mL of methacrylic acid under the protection of nitrogen, stirring for 1h, adding 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid, reacting for 0.5h at normal temperature, transferring into a 60 ℃ water bath, and reacting for 20h to obtain a polymer material; then crushing the polymer material, placing the crushed polymer material into a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extracting agents, and performing reflux extraction until no diquat in the extract liquor is detected; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer with the particle size of about 10-20 microns.
Further, fe (NO) in step 1) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O and ZrCl 4 The weight ratio of (1).
Further preferably, fe (NO) in said step 1) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O and ZrCl 4 The weight ratio of (1).
Further, the aminobenzene dicarboxylic acid in the step 1) is one of 2-aminoterephthalic acid, 3-aminophthalic acid, 4-aminophthalic acid and 2-amino-6-methyl-terephthalic acid.
More preferably, the amino terephthalic acid in the step 1) is 3-amino terephthalic acid.
Further, in step 1), the amino phthalic acid and Fe (NO) 3 ) 3 ·9H 2 The weight ratio of O is 1-3.
Further preferably, the amino phthalic acid and Fe (NO) in the step 1) 3 ) 3 ·9H 2 The weight ratio of O is 2.
A solid phase extraction column comprises a hollow column, a sieve plate and a filler, wherein the filler is the solid phase extraction filler prepared by the method.
A preparation method of a solid phase extraction column is used for preparing the solid phase extraction column and comprises the following steps:
directly filling the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer into a hollow column, and sealing two ends of the column by a sieve plate to prevent the filler from leaking outside to obtain a solid-phase extraction small column; the top of the column is a sample solution inlet, and the bottom of the column is a sample solution outlet.
Furthermore, the volume of the solid phase extraction column is 1-6 mL, and the filling amount of the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer is 10-60 mg.
Further preferably, the volume of the solid phase extraction column is 3mL, and the filling amount of the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer is 30mg.
Use of a solid phase extraction cartridge for water purification, the solid phase extraction cartridge being prepared by the above-described preparation method.
Further, the application method comprises the following steps: activating and balancing the solid phase extraction column by using 5mL of water and 5mL of methanol, adding 100mL of a water sample containing diquat into the column, controlling the flow rate to be 1.5-2.5 mL/min, then respectively leaching by using methanol, water and a methanol solution containing 0.1-0.5% (V/V) of organic acid/methanol (50/50, V/V), blowing the solid phase extraction column by using nitrogen, eluting by using a methanol solution containing 0.5-5.0% (V/V) of organic acid, collecting eluent, blowing the eluent to be nearly dry by using nitrogen in a water bath at the temperature of 35-45 ℃, redissolving by using methanol and fixing the volume to be 1.0mL, and filtering by using a filter membrane of 0.18-0.22 mu m for later use.
Further, the water sample containing the diquat is water with the diquat concentration ranging from 0.0005 to 2.0 mg/L;
further, the flow rate of the sample water containing the diquat is controlled to be 1.5-2.5 mL/min, which means any flow rate in the range.
More preferably, the flow rate of the sample water containing diquat is 2.0mL/min.
Further, the organic acid is one of formic acid, acetic acid, propionic acid and trifluoroacetic acid;
further preferably, the organic acid is formic acid.
Further, the 0.1 to 0.5% (V/V) organic acid aqueous solution/methanol (50/50, V/V) may be one of 0.1%, 0.2%, 0.3%, 0.4% and 0.5% (V/V) organic acid aqueous solution/methanol (50/50, V/V);
more preferably, the volume ratio of the organic acid in the aqueous solution containing 0.1 to 0.5% (V/V) of the organic acid/methanol (50/50, V/V) in the step 3) may be 0.2% (V/V).
Further, the methanol solution containing 0.5 to 5.0% (V/V) organic acid may be one of methanol solutions containing 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0% (V/V) organic acid;
more preferably, the volume ratio of the organic acid in the methanol solution containing 0.5 to 5.0% (V/V) of the organic acid may be 2.0% (V/V).
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, MOFs materials are used as carriers in the synthesis of the diquat molecular imprinting material for the first time, and compared with the traditional molecular imprinting material, the synthesized diquat molecular imprinting material has the advantages of high mass transfer speed and large specific surface area; the molecular imprinting material can specifically identify diquat and has very high selectivity on a target object.
(2) The Fe/Zr/Mn-MOFs aquacide molecularly imprinted polymer is selected as the adsorption material, and the material has high stability, long service life and strong complex matrix resistance.
(3) According to the invention, fe/Zr/Mn-MOFs diquat molecularly imprinted polymer is used as a filler to prepare the solid-phase extraction column, the obtained solid-phase extraction column has the advantages of large column capacity and high enrichment factor, and the solid-phase extraction column can enrich and purify trace diquat in water.
(4) The preparation method provided by the invention is simple, the cost is low, the experimental operation is simple, the reaction condition is easy to control, and the prepared diquat molecularly imprinted polymer can be used as an adsorbent for combination of solid-phase extraction and liquid chromatography.
(5) The solid phase extraction column prepared by the invention can enrich diquat, has higher enrichment efficiency, is suitable for enriching and purifying trace diquat in water, and has good economic and environmental benefits.
Drawings
FIG. 1 is a SEM image of a scanning electron microscope of a Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer obtained in example 1 of the present invention.
FIG. 2 is a liquid chromatography tandem mass spectrometry (MRM) graph of diquat in a blank water sample (a) and a standard water sample (b) obtained in example 1 of the present invention (the blank water sample refers to a water sample without diquat).
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 1.5g of Mn (NO) 3 ) 2 ·4H 2 O and 1.5g ZrCl 4 Placing the mixture into a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking up, adding 2.0g of 3-amino terephthalic acid, stirring to dissolve, transferring the mixture into a closed reaction kettle, reacting for 24 hours at 100 ℃, performing centrifugal separation to obtain a crude product, washing with 20mL of DMF and 20mL of ethanol respectively for 2 times, and finally performing vacuum drying at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials; to a 25mL stoppered round bottom flask was added 20.0mg NH 2 Fe/Zr/Mn-MOFs material, 4.0mL of acetonitrile and 2.0mg of diquat template molecules, fully stirring to completely dissolve the diquat, then adding 0.40mL of methacrylic acid, stirring for 1h, adding 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid, reacting for 0.5h, introducing nitrogen for 10min, and then carrying out water bath reaction at 60 ℃ for 20h to obtain a polymer material; crushing the polymer material, placing the crushed polymer material in a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extraction solvents, and performing reflux extraction until no diquat in the extraction liquid is detected; vacuum drying at 60 ℃ for 5h to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer (the SEM picture is shown in figure 1), wherein the particle size of the polymer is about 10-20 mu m.
30mg of the diquat molecular imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat water sample with the concentration of 0.05mg/L is injected into a small column at the flow rate of 2.0mL/min, methanol, water and 2.0mL of aqueous solution containing 0.2% (V/V) formic acid/methanol (50/50, V/V) are used for leaching respectively in sequence, the solid phase extraction small column is dried by nitrogen, then 5.0mL of methanol solution containing 2.0% (V/V) formic acid is used for eluting, the eluent is blown to near dryness by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, after being filtered by a 0.22 mu m filter membrane, the determination is carried out by liquid chromatography tandem mass spectrometry, and the MRM picture is shown in figure 2.
The blank water sample has no diquat, and as can be seen from fig. 2 (a), no corresponding MRM peak exists, and the blank value is 0; as can be seen from FIG. 2 (b), by LC-MS/MS analysis, the diquat spiked water sample obtained a good MRM peak without matrix interference.
And the standard recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column passing, and the standard recovery rate of the diquat in the water sample is 97.2%. The solid phase extraction column can be used for enriching the diquat in the purified water, and has higher enrichment efficiency.
Example 2:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 1.0g of Mn (NO) 3 ) 2 ·4H 2 O and 1.0g of ZrCl 4 Placing the mixture into a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking uniformly, adding 2.5g of 3-aminophthalic acid, stirring to dissolve, transferring to a closed reaction kettle, reacting for 24 hours at 100 ℃, obtaining a crude product after centrifugal separation, washing with 20mL of DMF and 20mL of ethanol respectively for 2 times, and finally drying in vacuum at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials; to a 25mL stoppered round bottom flask was added 20.0mg NH 2 Fe/Zr/Mn-MOFs material, 4.0mL of acetonitrile and 1.0mg of diquat template molecule, fully stirring to completely dissolve the diquat, then adding 0.40mL of methacrylic acid, stirring for 1h, adding 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid, reacting for 0.5h, introducing nitrogen for 10min, and then reacting for 20h in a water bath at 60 ℃ to obtain a polymer material; pulverizing the above polymer material, placing in Soxhlet extractor, adding 90mL methanol and 10mL acetic acid as extraction solvent, refluxingExtracting until no diquat is detected in the extract liquor; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer with the particle size of about 10-20 mu m.
30mg of the diquat molecularly imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat water sample with the concentration of 0.02mg/L is injected into a small column at the flow rate of 1.0mL/min, methanol, water and 2.0mL of aqueous solution containing 0.3% (V/V) formic acid/methanol (50/50, V/V) are used for leaching respectively in sequence, the solid phase extraction small column is dried by nitrogen, then 5.0mL of methanol solution containing 3.0% (V/V) formic acid is used for eluting, the eluent is blown to near dryness by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, and after being filtered by a 0.22 mu m filter membrane, the diquat water sample is supplied for liquid chromatography tandem mass spectrometry determination (no diquat water sample is contained before the water sample is added with the standard).
The recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column passing, and the standard recovery rate of the diquat in the water sample is 84.7 percent. The solid phase extraction column can enrich diquat through the standard recovery rate experiment result, and has high enrichment efficiency.
Example 3:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 2.0g of Mn (NO) 3 ) 2 ·4H 2 O and 1.5g ZrCl 4 Placing the mixture into a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking up, adding 1.5g of 3-aminophthalic acid, stirring to dissolve, transferring to a closed reaction kettle, reacting for 24 hours at 100 ℃, obtaining a crude product after centrifugal separation, washing with 20mL of DMF and 20mL of ethanol respectively for 2 times, and finally drying in vacuum at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials; 20.0mg NH was added to a 25mL stoppered round bottom flask 2 Fe/Zr/Mn-MOFs material, 4.0mL acetonitrile and 1.0mg diquat template molecule, fully stirring to completely dissolve the diquat, then adding 0.40mL methacrylic acid, stirring for 1h, adding 0.50mL crosslinking agentReacting tetraethoxysilane serving as an agent with 0.20mL of acetic acid for 0.5h, introducing nitrogen for 10min, and then reacting in a water bath at 60 ℃ for 20h to obtain a polymer material; crushing the polymer material, placing the crushed polymer material into a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extraction solvents, and performing reflux extraction until no diquat is detected in the extraction liquid; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer with the particle size of about 10-20 mu m.
60mg of the diquat molecularly imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat water sample with the concentration of 0.5mg/L is injected into a small column at the flow rate of 2.0mL/min, methanol, water and 2.0mL of aqueous solution containing 0.2% (V/V) formic acid/methanol (50/50, V/V) are used for leaching respectively in sequence, the solid phase extraction small column is dried by nitrogen, then 5.0mL of methanol solution containing 3.0% (V/V) formic acid is used for eluting, the eluent is blown to near dryness by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, and after being filtered by a 0.22 mu m filter membrane, the diquat water sample is supplied for liquid chromatography tandem mass spectrometry determination (no diquat water sample is contained before the water sample is added with the standard).
The recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column chromatography, and the standard recovery rate of the diquat in the water sample is 89.2%. The solid phase extraction column can be used for enriching the diquat in the purified water, and has higher enrichment efficiency.
Example 4:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 2.0g of Mn (NO) 3 ) 2 ·4H 2 O and 1.5g ZrCl 4 Placing the mixture into a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking up, adding 1.5g of 4-aminophthalic acid, stirring to dissolve, transferring to a closed reaction kettle, reacting for 24 hours at 100 ℃, obtaining a crude product after centrifugal separation, washing with 20mL of DMF and 20mL of ethanol respectively for 2 times, and finally drying in vacuum at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials;20.0mg NH was added to a 25mL stoppered round bottom flask 2 Fe/Zr/Mn-MOFs material, 4.0mL of acetonitrile and 2.0mg of diquat template molecules are fully stirred to completely dissolve the diquat, then 0.40mL of methacrylic acid is added, stirring is carried out for 1h, 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid are added for reaction for 0.5h, nitrogen is introduced for 10min, and then water bath reaction at 60 ℃ is carried out for 20h, so as to obtain a polymer material; crushing the polymer material, placing the crushed polymer material into a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extraction solvents, and performing reflux extraction until no diquat is detected in the extraction liquid; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer with the particle size of about 10-20 microns.
60mg of the diquat molecularly imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat labeling water sample with the concentration of 0.5mg/L is injected into a small column at the flow rate of 2.0mL/min, methanol, water and 2.0mL of aqueous solution containing 0.2% (V/V) formic acid/methanol (50/50, V/V) are respectively used for rinsing, nitrogen is used for blowing dry the solid phase extraction small column, then 5.0mL of methanol solution containing 3.0% (V/V) formic acid is used for eluting, the eluent is blown to be nearly dry by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, and after being filtered by a filter membrane of 0.22 mu m, liquid chromatography tandem mass spectrometry is carried out (no diquat is contained before labeling).
The recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column passing, and the standard recovery rate of the diquat in the water sample is 87.2%. The solid phase extraction column can enrich diquat through the standard recovery rate experiment result, and has high enrichment efficiency.
Example 5:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 2.0g of Mn (NO) 3 ) 2 ·4H 2 O and 1.5g of ZrCl 4 Placing in a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking, adding 1.5g of 2-amino terephthalic acid, stirringTransferring the dissolved solution into a closed reaction kettle, reacting for 24 hours at 100 ℃, obtaining a crude product after centrifugal separation, washing the crude product with 20mL of DMF and 20mL of ethanol respectively for 2 times, and finally drying the crude product in vacuum at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs material; 20.0mg NH was added to a 25mL stoppered round bottom flask 2 Fe/Zr/Mn-MOFs material, 4.0mL of acetonitrile and 2.0mg of diquat template molecules are fully stirred to completely dissolve the diquat, then 0.40mL of methacrylic acid is added, stirring is carried out for 1h, 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid are added to react for 0.5h, nitrogen is introduced for 10min, and then water bath reaction at 60 ℃ is carried out for 20h, so as to obtain the polymer material; crushing the polymer material, placing the crushed polymer material in a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extraction solvents, and performing reflux extraction until no diquat in the extraction liquid is detected; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer.
60mg of the diquat molecularly imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat labeling water sample with the concentration of 0.05mg/L is injected into a small column at the flow rate of 2.0mL/min, methanol, water and 2.0mL of aqueous solution containing 0.2% (V/V) formic acid/methanol (50/50, V/V) are respectively used for rinsing, nitrogen is used for blowing dry the solid phase extraction small column, then 5.0mL of methanol solution containing 3.0% (V/V) formic acid is used for eluting, the eluent is blown to be nearly dry by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, and after being filtered by a filter membrane of 0.22 mu m, liquid chromatography tandem mass spectrometry is carried out (no diquat is contained before labeling).
The recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column chromatography, and the standard recovery rate of the diquat in the water sample is 95.8 percent. The solid phase extraction column can be used for enriching the diquat in the purified water, and has higher enrichment efficiency.
Example 6:
1.0g of Fe (NO) 3 ) 3 ·9H 2 O, 1.0g of Mn (NO) 3 ) 2 ·4H 2 O and 0.5g ZrCl 4 Placing the mixture into a 250mL beaker, adding 10mL of 0.01mol/L hydrochloric acid solution, stirring to dissolve, adding 100mL of DMF, shaking up, adding 2.0g of 2-amino terephthalic acid, stirring to dissolve, transferring the mixture into a closed reaction kettle, reacting for 24 hours at 100 ℃, performing centrifugal separation to obtain a crude product, washing with 20mL of DMF and 20mL of ethanol for 2 times respectively, and finally performing vacuum drying at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs material; 20.0mg NH was added to a 25mL stoppered round bottom flask 2 Fe/Zr/Mn-MOFs material, 4.0mL of acetonitrile and 2.0mg of diquat template molecules are fully stirred to completely dissolve the diquat, then 0.40mL of methacrylic acid is added, stirring is carried out for 1h, 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid are added, reaction is carried out for 0.5h, nitrogen is introduced for 10min, and then water bath reaction at 60 ℃ is carried out for 20h, so as to obtain a polymer material; crushing the polymer material, placing the crushed polymer material into a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extraction solvents, and performing reflux extraction until no diquat is detected in the extraction liquid; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer with the particle size of about 10-20 microns.
60mg of the diquat molecularly imprinted polymer is weighed and directly filled into a solid-phase extraction hollow column, sieve plates are added at two ends of the column for sealing, and a small column is activated and balanced by 5mL of water and 5mL of methanol. Then 100mL of diquat water sample with the concentration of 1.0mg/L is injected into a small column at the flow rate of 2.0mL/min, methanol, water and 0.2% (V/V) formic acid aqueous solution/methanol (50/50, V/V) are used for leaching respectively by 2.0mL, the solid phase extraction small column is dried by nitrogen, then 5.0mL of 2.0% (V/V) formic acid-containing methanol solution is used for elution, the eluent is blown to near dryness by nitrogen in water bath at 45 ℃, 1.0mL of methanol is used for redissolving, and after being filtered by a 0.22 mu m filter membrane, the diquat water sample is supplied for liquid chromatography tandem mass spectrometry determination (no diquat water sample is contained before the standard addition).
The recovery rate is expressed by the percentage of the ratio of the content of the diquat in the redissolved solution to the content of the diquat in the standard solution before column chromatography, and the standard recovery rate of the diquat in the water sample is 93.7 percent. The solid phase extraction column can enrich diquat through the standard recovery rate experiment result, and has high enrichment efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the spirit of the present invention, and these modifications and decorations should also be regarded as being within the scope of the present invention.
Claims (8)
1. A solid phase extraction packing, characterized in that it is prepared by the following steps:
1)NH 2 preparation of Fe/Zr/Mn-MOFs Material: mixing a certain weight ratio of Fe (NO) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O and ZrCl 4 Uniformly mixing, dissolving in 0.01mol/L hydrochloric acid solution, adding DMF, adding aminophthalic acid, stirring for dissolving, transferring into a closed reaction container, reacting at 100 deg.C for 24 hr, centrifuging, washing the obtained precipitate with DMF and ethanol, and vacuum drying at room temperature to obtain NH 2 -Fe/Zr/Mn-MOFs materials;
2) Preparing the filler: 20.0mg NH was added to a 25mL reaction vessel 2 Fe/Zr/Mn-MOFs material, 10.0mL of acetonitrile and 1.0-2.0 mg of diquat template molecules, fully stirring to completely dissolve the diquat, adding 0.40mL of methacrylic acid under the protection of nitrogen, stirring for 1h, adding 0.50mL of crosslinking agent tetraethoxysilane and 0.20mL of acetic acid, reacting for 0.5h at normal temperature, transferring into a 60 ℃ water bath, and reacting for 20h to obtain a polymer material; then crushing the polymer material, placing the crushed polymer material into a Soxhlet extractor, adding 90mL of methanol and 10mL of acetic acid as extracting agents, and performing reflux extraction until no diquat is detected in the extract liquor; vacuum drying for 5h at 60 ℃ to obtain the Fe/Zr/Mn-MOFs aquacide molecularly imprinted polymer, namely the solid-phase extraction filler.
2. The solid phase extraction packing material of claim 1, wherein:
fe (NO) in step 1) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O and ZrCl 4 The weight ratio of (1).
3. The solid phase extraction packing material of claim 1, wherein: the amino phthalic acid in the step 1) is one of 2-amino terephthalic acid, 3-amino phthalic acid, 4-amino phthalic acid and 2-amino-6-methyl terephthalic acid.
4. The solid phase extraction packing of claim 1, wherein: in step 1) Aminophthalic acid and Fe (NO) 3 ) 3 ·9H 2 The weight ratio of O is 1-3.
5. A solid phase extraction column, which is characterized by comprising an empty column, a sieve plate and a filler, wherein the filler is the solid phase extraction filler in any one of claims 1 to 4.
6. A method for producing a solid-phase extraction cartridge according to claim 5, comprising the steps of: and directly filling the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer into a hollow column, and sealing two ends of the column by a sieve plate to obtain the solid-phase extraction small column.
7. The method for preparing a solid phase extraction cartridge as claimed in claim 6, wherein: the volume of the solid phase extraction column is 1-6 mL, and the filling amount of the Fe/Zr/Mn-MOFs diquat molecularly imprinted polymer is 10-60 mg.
8. Use of a solid phase extraction cartridge for the pretreatment of a water sample, characterized in that the solid phase extraction cartridge is prepared by the preparation method according to claim 7.
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| CN102500134A (en) * | 2011-09-30 | 2012-06-20 | 宁波大学 | Preparation method and application of molecularly imprinted solid phase extraction small column for separating pyrethroid pesticide |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
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| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
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