CN112973186B - Electric enhanced solid phase micro-extraction device based on doped graphene porous polymer - Google Patents
Electric enhanced solid phase micro-extraction device based on doped graphene porous polymer Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- G—PHYSICS
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- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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Abstract
An electrically enhanced solid phase micro-extraction device based on a doped graphene porous polymer belongs to the field of environmental sample pretreatment and separation analysis detection. Comprises an adsorption electrode, a metal wire electrode, a solution bottle, a direct current power supply, a magnetic stirrer and an iron support; the solution bottle is arranged on a magnetic stirrer, the adsorption electrode and the metal wire electrode are fixed on an iron stand and inserted into the solution bottle, and the anode and the cathode of the direct current power supply are respectively connected with the adsorption electrode and the metal wire electrode. The extraction efficiency of the dissociable compound in the water sample is improved by utilizing the electrical enhancement technology, and the electrical enhancement solid-phase microextraction device based on the doped graphene porous polymer is built by combining the advantages of high specific surface area, high mass transfer speed, large adsorption capacity, easiness in modification and the like of the doped graphene porous polymer. The method has the advantages of simple operation, high extraction efficiency, high extraction rate, integration of purification and enrichment, environmental protection and the like, can effectively enrich dissociable compounds in complex samples, and has wide practical application prospect.
Description
Technical Field
The invention belongs to the field of environmental sample pretreatment and separation analysis detection, and particularly relates to an electrically enhanced solid-phase microextraction device based on a doped graphene porous polymer.
Background
Solid-Phase microextraction (SPME) is a Sample Preparation technology integrating purification, extraction and concentration, and has the advantages of simple operation, low organic Solvent consumption and the like (Z.Zhang, M.J.Yang, J.Pawliszyn, Solid-Phase microextraction.A Solvent-Free Alternative for Sample Preparation, anal.chem.66(1994) 844A-853A). With the continuous development of this technology, various solid phase microextraction modes or devices have been proposed (M.Mei, X.J.Huang, D.X.Yuan, Multiple monolithic fiber solid-phase microextraction: a nexitration approach for aqueous samples, J.Chromatogr.A 1345(2014) 29-36; L.Chen, Z.Z.Wang, J.X.Pei, X.J.Huang, high purity capable monomeric-based Multiple in-tip microextraction approach for simple and robust field prediction of peptides and metals in environmental services, analytical chemistry, 92.2251 (2257)). However, the low extraction capacity of conventional SPME due to the low adsorbent usage, especially for dissociable compounds, the long extraction time and low extraction efficiency limit the scope of SPME applications. In order to further improve the enrichment efficiency of the SPME, electric fields with different directions and magnitudes can be applied during adsorption and desorption, so that the extraction efficiency of the SPME on the dissociable compounds is improved, and the extraction time is shortened.
The porous polymer can be synthesized by simple in-situ polymerization reaction, has the advantages of rich raw materials, simple preparation, high mass transfer speed, easy modification and the like, and is widely applied to a plurality of fields of environmental monitoring, drug analysis, life science and the like (M.Vergara-Barberan, E.J.Carrasco-Correa, M.J.Lerma-Garcia, E.F.Simo-Alfonso, J.M.Herreoo-Martinez, Current tress in after-sensitivity-based monoliths in microextraction praces: A review, anal.Chim.acta 1084(2019) 1-20). Because of its many advantages, porous polymers have been used in the field of sample pretreatment as adsorption media (C.K.Su, J.Y.Lin,3D-printed column with porous monolithic packaging for online solid-phase extraction of multiple trace metals in environmental waters, anal.chem.92(2020) 9640-. However, the specific surface area of the porous polymer is small, and the active adsorption sites are few, so that the adsorption capacity is to be improved. Graphene as sp2The two-dimensional carbon nano material in hybrid connection has the advantages of large specific surface area, stable property and the like (E.Er, N.Erk, A novel electrochemical sensing platform based on one-discrete gold nanoparticles modified graphene for the sensitive determination of topotecan, Sensors and Actuators B: Chemical 320(2020) 128320). Based on the reasons, the doped graphene porous polymer electrode is prepared, electric fields with different directions and sizes are applied to the electrode in the adsorption and analysis processes, and the electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer is developed, and can be used for remarkably improving the extraction capacity of a dissociable compound and shortening the extraction time.
Disclosure of Invention
The invention aims to provide an electrically enhanced solid-phase microextraction device based on a doped graphene porous polymer, which has the advantages of simple preparation, high extraction efficiency, large extraction capacity, good repeatability, easiness in operation, environmental friendliness and the like.
The invention comprises an adsorption electrode, a metal wire electrode, a solution bottle, a direct current power supply, a magnetic stirrer and an iron stand; the solution bottle is arranged on a magnetic stirrer, the adsorption electrode and the metal wire electrode are fixed on an iron stand and inserted into the solution bottle, and the anode and the cathode of the direct current power supply are respectively connected with the adsorption electrode and the metal wire electrode.
The voltage of the direct current power supply is 0-30.0V, the current of the direct current power supply is 0-10.0A, and the direct current power supply can be regulated to be constant voltage or constant current.
The magnetic stirrer can regulate and control the rotating speed to be 0-1500 rmp.
The diameter of the metal wire electrode can be 0.2-1.0 mm, and the metal wire can be selected from a stainless steel wire, a copper wire or a platinum wire and the like.
The adsorption electrode and the metal wire electrode are arranged in parallel, and the interval between the adsorption electrode and the metal wire electrode is 0.5-3.0 cm.
The adsorption electrode can be prepared by the following method:
1) mixing a reaction monomer mixture and a pore-foaming agent, doping a certain amount of aminated graphene, uniformly mixing, and performing ultrasonic treatment to obtain a uniform solution;
2) taking a plastic tube or capillary tube with the inner diameter of 1.0-3.0 mm, sealing one end of the plastic tube or capillary tube, fixing a metal wire with the diameter of 0.2-1.0 mm in the middle of the plastic tube or capillary tube, adding the solution obtained in the step 1), controlling the height of the solution to be 1-3 cm, sealing the other end of the plastic tube or capillary tube, and placing the plastic tube or capillary tube in an oven for constant-temperature polymerization reaction;
3) removing the outer plastic tube or capillary tube, soaking in organic solvent until no impurity is detected in the soaking solution, and obtaining the adsorption electrode; before use, the activated carbon can be soaked in ultrapure water for activation treatment.
In the step 1), the reaction monomer mixture comprises, by mass, 20-80% (w/w) of a functional monomer allylmethylimidazolium bis (trifluoromethylsulfonyl) imide, 0.5-3.0% (w/w) of an initiator azobisisobutyronitrile or benzoyl peroxide, and the balance of a crosslinking agent; the crosslinking agent is a mixed crosslinking agent of ethylene glycol dimethacrylate and divinylbenzene, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 0.5-3; the pore-foaming agent adopts dimethyl sulfoxide; the mass ratio of the reaction monomer mixture to the pore-forming agent is 1: 0.5-3.
In the step 2), the temperature of the constant-temperature polymerization reaction can be 60-80 ℃, and the time of the constant-temperature polymerization reaction can be 6-24 hours.
In step 3), the solvent may be selected from methanol, acetonitrile or ethanol; the soaking time can be 1-24 h.
The use method of the electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer is given as follows:
during extraction, vertically immersing an activated graphene-doped porous polymer adsorption electrode and a metal wire electrode in 10-100 mL of sample solution, wherein the rotating speed of a magnetic stirrer is 50-1000 rpm; adjusting a direct current power supply to be in a constant voltage state, wherein the voltage is 0.2-2.0V, connecting the positive electrode and the negative electrode of the direct current power supply to an adsorption electrode and a metal wire electrode respectively, enriching the dissociable compound, and finishing the adsorption process after the dissociative compound is continued for a period of time; then placing the adsorption electrode and the metal wire electrode in 0.4-2.0 mL of desorption solvent; the desorption solvent is a mixed solution of an organic solvent, formic acid and water; wherein the organic solvent is selected from one of methanol, acetonitrile and ethanol; the volume ratio of the organic solvent, the formic acid and the water is 80-100 percent of the organic solvent, 0.0-10.0 percent of the formic acid and the balance of the water; replacing the positive electrode and the negative electrode of the direct current power supply, setting the voltage to be 0.2-2.0V, and continuing for a period of time to complete the desorption process under the stirring of a magnetic stirrer at the rotating speed of 50-1000 rpm; the prepared sample can be used for detection of an analytical instrument.
The invention takes the doped graphene porous polymer material as the extraction medium, and has the advantages of simple preparation, low cost, high extraction efficiency, high extraction rate, easy operation and the like. The doped graphene porous polymer adsorption electrode prepared by utilizing the in-situ polymerization reaction has the advantages of simple preparation, rich raw materials, good permeability, large specific surface area, reusability and the like. The electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer adsorption electrode has wide practical application value.
Drawings
Fig. 1 is a schematic diagram of an adsorption electrode doped with graphene porous polymer in embodiment 2 of the present invention.
Fig. 2 is an infrared spectrum of the graphene-doped porous polymer adsorption electrode in example 2 of the present invention. Wherein, 2981cm-1And 2954cm-1Is methyl and methyleneAbsorption peak of methyl group, 1732cm-1Is carbonyl absorption peak, 1603cm-1And 1456cm-1Is phenyl absorption peak, 1386cm-1The peak is the imidazole group absorption.
Fig. 3 is a scanning electron microscope image of the graphene-doped porous polymer adsorption electrode in example 2 of the present invention.
Fig. 4 is a schematic diagram of an electrically enhanced solid-phase microextraction device based on a doped graphene porous polymer in example 5 of the present invention.
FIG. 5 is a liquid chromatography separation spectrum of a water sample added with 5 kinds of phenoxy carboxylic acids in example 9 of the present invention before extraction, after extraction without power supply and after extraction with power supply of 1.2V. Wherein the peak is 2-nitrophenoxyacetic acid (NPOA), phenoxyacetic acid (POA), 4-chlorophenoxyacetic acid (CPOA), 2,4-D, 4-chloro-2-methylphenoxy acetic acid (MCPA) in sequence.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
The electrically enhanced solid-phase micro-extraction device based on the doped graphene porous polymer comprises an adsorption electrode, a metal wire electrode, a solution bottle, a direct-current power supply, a magnetic stirrer and an iron support; the solution bottle is arranged on a magnetic stirrer, the adsorption electrode and the metal wire electrode are fixed on an iron stand and inserted into the solution bottle, and the anode and the cathode of the direct current power supply are respectively connected with the adsorption electrode and the metal wire electrode.
The voltage of the direct current power supply is 0-30.0V, the current of the direct current power supply is 0-10.0A, and the direct current power supply can be regulated to be constant voltage or constant current.
The magnetic stirrer can regulate and control the rotating speed to be 0-1500 rmp.
The diameter of the metal wire electrode can be 0.2-1.0 mm, and the metal wire can be selected from a stainless steel wire, a copper wire or a platinum wire and the like.
The adsorption electrode and the metal wire electrode are arranged in parallel, and the interval between the adsorption electrode and the metal wire electrode is 0.5-3.0 cm.
The adsorption electrode can be prepared by the following method:
1) preparing a reaction mixed reagent: allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide is used as a functional monomer, ethylene glycol dimethacrylate and divinylbenzene are used as a mixed cross-linking agent, azodiisobutyronitrile or benzoyl peroxide is used as an initiator, dimethyl sulfoxide is used as a pore-foaming agent, and a certain amount of aminated graphene is doped to improve the extraction performance; the reaction monomer mixture comprises 20-80% (w/w) of allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide, 0.5-3.0% (w/w) of azodiisobutyronitrile or benzoyl peroxide as an initiator and the balance of a cross-linking agent, wherein the weight percentage of the ethylene glycol dimethacrylate: the divinylbenzene accounts for 1: 0.5-3; the pore-foaming agent is dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-foaming agent are 1: 0.5-3, and the aminated graphene is added and mixed to form a mixed solution of 0.5-5 mg/0.1 g;
2) polymerization reaction: weighing the reaction substances according to the proportion, performing ultrasonic treatment to obtain a uniform solution, taking a plastic tube or a capillary tube with the inner diameter of 1.0-3.0 mm, sealing one end of the plastic tube or the capillary tube, fixing a 0.2-1.0 mm metal wire in the middle, adding the solution, controlling the height of the polymerization solution to be 1-3 cm, sealing the other end of the polymerization solution, and placing the polymerization solution in a 60-80 ℃ oven for constant-temperature polymerization reaction for 6-24 hours;
3) and (3) post-treatment of the adsorption electrode: removing the outer plastic tube or capillary tube, soaking in methanol or acetonitrile or ethanol until no impurity is detected in the soaking solution; before use, the mixture is soaked in ultrapure water for 1-24 h for activation treatment.
Specific examples are given below.
Example 1:
preparing a graphene-doped porous polymer adsorption electrode:
allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide is used as a functional monomer, ethylene glycol dimethacrylate and divinylbenzene are used as a mixed cross-linking agent, azodiisobutyronitrile or benzoyl peroxide is used as an initiator, dimethyl sulfoxide is used as a pore-foaming agent, and a certain amount of aminated graphene is doped to improve the extraction performance; the composition proportion of the reaction monomer mixing agent is 20 percent (w/w) of allyl methyl imidazolium bis (trifluoromethyl sulfonyl) imide, 0.5 percent (w/w) of azo-bis-isobutyronitrile as an initiator and the balance of a cross-linking agent, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 3; the pore-foaming agent is dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-foaming agent are 1: 3, and the aminated graphene is added and uniformly mixed to form a mixed solution of 0.5mg/0.1 g. Weighing the reaction substances according to the proportion, performing ultrasonic treatment to obtain a uniform solution, taking a capillary tube with the inner diameter of 1.0mm, sealing one end of the capillary tube, fixing a platinum wire with the diameter of 0.2mm in the middle, adding the solution, controlling the height of the polymerization solution to be 1cm, sealing the other end of the capillary tube, and placing the capillary tube in a 60 ℃ oven for constant-temperature polymerization reaction for 24 hours.
The reaction equation of the polymerization reaction of the doped graphene porous polymer adsorption electrode is as follows:
wherein, MA: allylmethylimidazolium bis (trifluoromethylsulfonyl) imide; DVB (digital video broadcasting): divinylbenzene (DVB); EDMA: ethylene glycol dimethacrylate.
And cooling to room temperature, removing the outer capillary wall, and soaking the capillary wall in acetonitrile until no impurity is detected in the soaking solution. Before use, the mixture is soaked in ultrapure water for 1 hour for activation treatment.
Example 2:
preparing a graphene-doped porous polymer adsorption electrode:
allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide is used as a functional monomer, ethylene glycol dimethacrylate and divinylbenzene are used as a mixed cross-linking agent, azodiisobutyronitrile or benzoyl peroxide is used as an initiator, dimethyl sulfoxide is used as a pore-foaming agent, and a certain amount of aminated graphene is doped to improve the extraction performance; the composition proportion of the reaction monomer mixing agent is 55 percent (w/w) of allyl methyl imidazolium bis (trifluoromethyl sulfonyl) imide, 1.0 percent (w/w) of azodiisobutyronitrile as an initiator and the balance of a cross-linking agent, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 0.5; the pore-foaming agent is dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-foaming agent are 1: 0.67, and the aminated graphene is added and mixed uniformly to obtain a mixed solution of 1.5mg/0.1 g. Weighing the reaction substances according to the proportion, performing ultrasonic treatment to obtain a uniform solution, taking a capillary tube with the inner diameter of 2.0mm, sealing one end of the capillary tube, fixing a stainless steel wire with the diameter of 0.5mm in the middle, adding the solution, controlling the height of the polymerization solution to be 2cm, sealing the other end of the capillary tube, and placing the capillary tube in a 70 ℃ oven for constant-temperature polymerization for 12 hours.
After cooling to room temperature, the capillary was removed and the soaked solution was soaked with methanol until no impurities were detected in the soaking solution. Before use, the mixture is soaked in ultrapure water for 6 hours for activation treatment.
Fig. 1 is a physical diagram of the graphene-doped porous polymer adsorption electrode in example 2. Fig. 2 is an infrared spectrum of the graphene-doped porous polymer adsorption electrode in example 2. Fig. 3 is a scanning electron microscope image of the graphene-doped porous polymer adsorption electrode in example 2.
Example 3:
preparing a graphene-doped porous polymer adsorption electrode:
allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide is used as a functional monomer, ethylene glycol dimethacrylate and divinylbenzene are used as a mixed cross-linking agent, azodiisobutyronitrile or benzoyl peroxide is used as an initiator, dimethyl sulfoxide is used as a pore-foaming agent, and a certain amount of aminated graphene is doped to improve the extraction performance; the composition proportion of the reaction monomer mixing agent is 80% (w/w) of allyl methyl imidazolium bis (trifluoromethyl sulfonyl) imide, 3.0% (w/w) of azodiisobutyronitrile as an initiator and the balance of a cross-linking agent, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 1; the pore-foaming agent is dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-foaming agent are 1: 0.5, and the aminated graphene is added and mixed uniformly to obtain a mixed solution of 3.0mg/0.1 g. Weighing the reaction substances according to the proportion, performing ultrasonic treatment to obtain a uniform solution, taking a plastic pipe with the inner diameter of 2.0mm, sealing one end of the plastic pipe, fixing a 0.75mm copper wire in the middle, adding the solution, controlling the height of the polymerization solution to be 2cm, sealing the other end, and placing the plastic pipe in a 70 ℃ oven for constant-temperature polymerization reaction for 6 hours.
Cooling to room temperature, removing the outer plastic tube, and soaking in ethanol until no impurity is detected in the soaking solution. Before use, the mixture is soaked in ultrapure water for 12 hours for activation treatment.
Example 4:
preparing a graphene-doped porous polymer adsorption electrode:
allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide is used as a functional monomer, ethylene glycol dimethacrylate and divinylbenzene are used as a mixed cross-linking agent, azodiisobutyronitrile or benzoyl peroxide is used as an initiator, dimethyl sulfoxide is used as a pore-foaming agent, and a certain amount of aminated graphene is doped to improve the extraction performance; the composition proportion of the reaction monomer mixture is 80 percent (w/w) of allyl methyl imidazolium bis (trifluoromethyl sulfonyl) imide, 2.0 percent (w/w) of benzoyl peroxide as an initiator and the balance of a cross-linking agent according to mass percentage, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 2; the pore-foaming agent is dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-foaming agent are 1: 2, and the aminated graphene is added and uniformly mixed to obtain a mixed solution of 5.0mg/0.1 g. Weighing the reaction substances according to the proportion, performing ultrasonic treatment to obtain a uniform solution, taking a plastic pipe with the inner diameter of 3.0mm, sealing one end of the plastic pipe, fixing a stainless steel wire with the diameter of 1.0mm in the middle, adding the solution, controlling the height of the polymerization solution to be 3cm, sealing the other end of the plastic pipe, and placing the plastic pipe in an oven at 80 ℃ for constant-temperature polymerization for 6 hours.
After cooling to room temperature, the outer plastic tube is removed and soaked in methanol until no impurities are detected in the soaking solution. Before use, the mixture is soaked in ultrapure water for 24 hours for activation treatment.
Example 5:
the application of the electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer comprises the following steps:
50mL of the pretreated water sample was placed in a beaker, and small magnetons were added and placed on a magnetic stirrer. The activated adsorption electrode of example 2 was fixed in parallel with a stainless steel wire with a diameter of 0.5mm at an interval of 0.5cm, and connected to a dc power supply, wherein the positive electrode was connected to the adsorption electrode and the negative electrode was connected to the stainless steel wire. The electrode is fixed by an iron stand and is vertically inserted into a water sample, so that the adsorption electrode is completely immersed in the water sample. At room temperature, the rotation speed of the magnetic stirrer is set to 300rpm, the DC power supply is set to be in a constant voltage state, the voltage is 1.2V, and the adsorption is continued for 25 min. The positive and negative electrodes connected with the adsorption electrode are controlled, the current flow direction is ensured, the aggregation of the dissociable compound towards the adsorption electrode is effectively promoted, and the purpose of rapid enrichment is achieved.
After adsorption, the enriched adsorption electrode is placed in 400 mu L of desorption solvent, and the composition proportion of the desorption solvent is 92 percent (v/v) of acetonitrile, 3 percent (v/v) of formic acid and the balance of ultrapure water according to volume percentage. The rotating speed of the magnetic stirrer is set to 300rpm, the anode and the cathode connected with the direct current power supply are replaced, the current direction is changed, the voltage is 1.2V, and the target object can be effectively desorbed by the adsorption electrode and continuously desorbed for 15 min. The prepared sample can be used for high performance liquid chromatography detection.
Fig. 4 is a schematic diagram of an electrically enhanced solid-phase microextraction device based on a doped graphene porous polymer in example 5. Referring to fig. 4, the apparatus of the present invention includes an adsorption electrode 1, a wire electrode 2, a solution bottle 3, a dc power supply 4, a magnetic stirrer 5, and a stand 6.
Example 6:
the application of the electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer comprises the following steps:
and (3) pretreating the sample, wherein a water sample is filtered through a 0.45-micrometer filter membrane before being used.
100mL of the pretreated water sample was placed in a beaker, and small magnetons were added and placed on a magnetic stirrer. The activated adsorption electrode of example 2 was fixed in parallel with a platinum wire of 1.0mm in diameter at an interval of 3.0cm to form positive and negative electrodes, wherein the positive electrode was connected to the adsorption electrode and the negative electrode was connected to the platinum wire. The electrode is fixed by an iron stand and is vertically inserted into a water sample, so that the adsorption electrode is completely immersed in the water sample. At room temperature, the rotation speed of the magnetic stirrer is set to 800rpm, the DC power supply is set to be in a constant voltage state, the voltage is 1.5V, and the adsorption is continued for 30 min. The positive and negative electrodes connected with the adsorption electrode are controlled, the current flow direction is ensured, the aggregation of the dissociable compound towards the adsorption electrode is effectively promoted, and the purpose of rapid enrichment is achieved.
After adsorption, the enriched adsorption electrode is replaced in 400 mu L of desorption solvent, the composition proportion of the desorption solvent is acetonitrile 90% (v/v), formic acid 5% (v/v) and the rest is ultrapure water according to volume percentage. The rotating speed of the magnetic stirrer is set to be 800rpm, the anode and the cathode connected with the direct current power supply are replaced, the current direction is changed, the voltage is 1.5V, and the target object can be effectively desorbed by the adsorption electrode and continuously desorbed for 20 min. The prepared sample can be used for detection and analysis of high performance liquid chromatography.
Example 7:
the application of the electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer comprises the following steps:
and (3) pretreating the sample, wherein a water sample is filtered through a 0.45-micrometer filter membrane before being used.
100mL of the pretreated water sample was placed in a beaker, and small magnetons were added and placed on a magnetic stirrer. The activated adsorption electrode of example 2 was fixed in parallel with a platinum wire of 1.0mm in diameter at an interval of 3.0cm to form positive and negative electrodes, wherein the positive electrode was connected to the adsorption electrode and the negative electrode was connected to the platinum wire. The electrode is fixed by an iron stand and is vertically inserted into a water sample, so that the adsorption electrode is completely immersed in the water sample. At room temperature, the rotation speed of the magnetic stirrer is set to 800rpm, the DC power supply is set to be in a constant voltage state, the voltage is 1.5V, and the adsorption is continued for 30 min. The positive and negative electrodes connected with the adsorption electrode are controlled, the current flow direction is ensured, the aggregation of the dissociable compound towards the adsorption electrode is effectively promoted, and the purpose of rapid enrichment is achieved.
After the adsorption is finished, the enriched adsorption electrode is replaced in 400 mu L of desorption solvent, and the desorption solvent is pure methanol. The rotating speed of the magnetic stirrer is set to be 800rpm, the anode and the cathode connected with the direct current power supply are replaced, the current direction is changed, the voltage is 1.5V, and the target object can be effectively desorbed by the adsorption electrode and continuously desorbed for 20 min. The prepared sample can be used for detection and analysis of high performance liquid chromatography.
Example 8:
the application of the electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer comprises the following steps:
and (3) pretreating the sample, wherein a water sample is filtered through a 0.45-micrometer filter membrane before being used.
100mL of the pretreated water sample was placed in a beaker, and small magnetons were added and placed on a magnetic stirrer. The activated adsorption electrode of example 2 was fixed in parallel with a platinum wire of 1.0mm in diameter at an interval of 3.0cm to form positive and negative electrodes, wherein the positive electrode was connected to the adsorption electrode and the negative electrode was connected to the platinum wire. The electrode is fixed by an iron stand and is vertically inserted into a water sample, so that the adsorption electrode is completely immersed in the water sample. At room temperature, the rotation speed of the magnetic stirrer is set to 800rpm, the DC power supply is set to be in a constant voltage state, the voltage is 1.5V, and the adsorption is continued for 30 min. The positive and negative electrodes connected with the adsorption electrode are controlled, the current flow direction is ensured, the aggregation of the dissociable compound towards the adsorption electrode is effectively promoted, and the purpose of rapid enrichment is achieved.
After adsorption, the enriched adsorption electrode is replaced in 400 mu L of desorption solvent, wherein the composition proportion of the desorption solvent is 80% (v/v) of ethanol, 10% (v/v) of formic acid and the balance of ultrapure water according to volume percentage. The rotating speed of the magnetic stirrer is set to be 800rpm, the anode and the cathode connected with the direct current power supply are replaced, the current direction is changed, the voltage is 1.5V, and the target object can be effectively desorbed by the adsorption electrode and continuously desorbed for 20 min. The prepared sample can be used for detection and analysis of high performance liquid chromatography.
Example 9:
5 phenoxy carboxylic acid herbicides (phenoxyacetic acid, 2-nitrophenoxyacetic acid, 4-chlorophenoxyacetic acid, 2,4-D and 4-chloro-2-methylphenoxyacetic acid) are prepared, 50mL of aqueous solution with the standard concentration of 200 mu g/L is added, and the treatment is carried out according to the embodiment 5 on the basis of an electrically enhanced solid-phase microextraction device doped with the graphene porous polymer. The prepared sample can be used for detection and analysis of high performance liquid chromatography.
The apparatus used for the chromatographic analysis was Shimadzu high performance liquid chromatograph (Shimadzu, Japan) equipped with a CBM-20A controller, an LC-20AB type binary pump, an SPD-M20A diode array tube detector (DAD), and an SIL-20A autosampler. And (3) chromatographic detection conditions: hypersil ODS-2 column (250 mm. times.4.6 mm i.d., 5 μm particle size); the total flow rate is 1.0 mL/min; the sample injection amount is 20.0 mu L; the mobile phase is a mixed solution (B) of an ultra-pure water solution (A) containing 0.1 percent of phosphoric acid and acetonitrile/methanol (2/3, v/v); the isocratic elution procedure was: 0-32 min, 57% A + 43% B.
FIG. 5 is a liquid chromatographic separation spectrum of a water sample added with 5 kinds of phenoxy carboxylic acids in the example before extraction (a), after non-electrification extraction (b) and after electrification extraction (c).
According to the invention, the extraction efficiency of the dissociable compound in the water sample is improved by utilizing the electrical enhancement technology, and the electrical enhancement solid-phase microextraction device based on the doped graphene porous polymer is built by combining the advantages of high specific surface area, high mass transfer speed, large adsorption capacity, easiness in modification and the like of the doped graphene porous polymer. The device has the advantages of simple operation, high extraction efficiency, high extraction rate, integration of purification and enrichment, environmental protection and the like, and can effectively enrich dissociable compounds in complex samples, so that the electrically enhanced solid phase micro-extraction device based on the doped graphene porous polymer, which is built by the invention, has wide practical application prospect.
Claims (8)
1. The electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer is characterized by comprising an adsorption electrode, a metal wire electrode, a solution bottle, a direct-current power supply, a magnetic stirrer and an iron support; the solution bottle is arranged on a magnetic stirrer, an adsorption electrode and a metal wire electrode are fixed on an iron support and inserted into the solution bottle, and the positive electrode and the negative electrode of a direct current power supply are respectively connected with the adsorption electrode and the metal wire electrode;
the adsorption electrode is prepared by the following method:
1) mixing a reaction monomer mixture and a pore-foaming agent, doping a certain amount of aminated graphene, uniformly mixing, and performing ultrasonic treatment to obtain a uniform solution; the reaction monomer mixture comprises 20-80% (w/w) of functional monomer allyl methyl imidazolium bis (trifluoromethylsulfonyl) imide, 0.5-3.0% (w/w) of initiator azo diisobutyronitrile or benzoyl peroxide and the balance of cross-linking agent according to mass percentage; the crosslinking agent is a mixed crosslinking agent of ethylene glycol dimethacrylate and divinylbenzene, wherein the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1: 0.5-3; the pore-foaming agent adopts dimethyl sulfoxide; according to the mass ratio, the reaction monomer mixture and the pore-forming agent are 1: 0.5-3;
2) taking a plastic tube or capillary tube with the inner diameter of 1.0-3.0 mm, sealing one end of the plastic tube or capillary tube, fixing a metal wire with the diameter of 0.2-1.0 mm in the middle of the plastic tube or capillary tube, adding the solution obtained in the step 1), controlling the height of the solution to be 1-3 cm, sealing the other end of the plastic tube or capillary tube, and placing the plastic tube or capillary tube in an oven for constant-temperature polymerization reaction;
3) removing the outer plastic tube or capillary tube, soaking in organic solvent until no impurity is detected in the soaking solution, and obtaining the adsorption electrode; before use, the activated paper is soaked in ultrapure water for activation treatment.
2. The electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer as claimed in claim 1, wherein the voltage of said DC power supply is 0-30.0V, the current is 0-10.0A, and the voltage and current are both not 0, and can be controlled to be constant voltage or constant current.
3. The electrically enhanced solid phase microextraction device based on doped graphene porous polymer according to claim 1, wherein said magnetic stirrer can regulate and control the rotation speed of 0-1500 rmp.
4. The electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer as claimed in claim 1, wherein the diameter of the metal wire electrode is 0.2-1.0 mm, and the metal wire is selected from stainless steel wire, copper wire or platinum wire.
5. The electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer as claimed in claim 1, wherein the adsorption electrode and the metal wire electrode are placed in parallel with a spacing of 0.5-3.0 cm in between.
6. The electrically enhanced solid-phase microextraction device based on the doped graphene porous polymer according to claim 1, wherein in the step 2), the temperature of the constant-temperature polymerization reaction is 60-80 ℃, and the time of the constant-temperature polymerization reaction is 6-24 h.
7. An electrically enhanced solid phase microextraction device based on doped graphene porous polymer according to claim 1, characterized in that in step 3), said solvent is selected from methanol, acetonitrile or ethanol; the soaking time is 1-24 h.
8. An electrically enhanced solid-phase microextraction device based on doped graphene porous polymer according to claim 1, characterized in that the use method is as follows:
during extraction, vertically immersing an activated graphene-doped porous polymer adsorption electrode and a metal wire electrode in 10-100 mL of sample solution, wherein the rotating speed of a magnetic stirrer is 50-1000 rpm; adjusting a direct current power supply to be in a constant voltage state, wherein the voltage is 0.2-2.0V, connecting the positive electrode and the negative electrode of the direct current power supply to an adsorption electrode and a metal wire electrode respectively, enriching the dissociable compound, and finishing the adsorption process after the dissociative compound is continued for a period of time; then placing the adsorption electrode and the metal wire electrode in 0.4-2.0 mL of desorption solvent; the desorption solvent is a mixed solution of an organic solvent, formic acid and water, and the mixed solution simultaneously contains the organic solvent, the formic acid and the water; wherein the organic solvent is selected from one of methanol, acetonitrile and ethanol; the volume ratio of the organic solvent to the formic acid to the water is 80-100 percent of the organic solvent, 0.0-10.0 percent of the formic acid and the balance of the water; replacing the positive electrode and the negative electrode of the direct current power supply, setting the voltage to be 0.2-2.0V, and continuing for a period of time to complete the desorption process under the stirring of a magnetic stirrer at the rotating speed of 50-1000 rpm; the prepared sample is used for detection by an analytical instrument.
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| CN101563296A (en) * | 2006-12-19 | 2009-10-21 | 通用电气公司 | Supercapacitor desalination device and method of making |
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| CN111533847A (en) * | 2020-06-01 | 2020-08-14 | 中国科学院长春应用化学研究所 | High-strength ionic liquid gel and preparation method thereof |
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| CN101563296A (en) * | 2006-12-19 | 2009-10-21 | 通用电气公司 | Supercapacitor desalination device and method of making |
| WO2012129532A1 (en) * | 2011-03-23 | 2012-09-27 | Andelman Marc D | Polarized electrode for flow-through capacitive deionization |
| CN106904700A (en) * | 2017-03-22 | 2017-06-30 | 厦门大学 | A kind of graphene-based film coated metal as electrode material ion isolation device |
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| CN111533847A (en) * | 2020-06-01 | 2020-08-14 | 中国科学院长春应用化学研究所 | High-strength ionic liquid gel and preparation method thereof |
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