CN109358142B - Manufacturing method of carbon nanofiber/carbon fiber solid phase micro-extraction device - Google Patents
Manufacturing method of carbon nanofiber/carbon fiber solid phase micro-extraction device Download PDFInfo
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Abstract
The invention discloses a manufacturing method of a carbon nanofiber/carbon fiber solid phase micro-extraction device. The invention prepares carbon nanofiber/carbon fiber and provides a chromatographic analysis method for extracting micro-enrichment real-time detection of phytohormone. According to the invention, the carbon nanofiber is modified on the carbon fiber to form a spatial three-dimensional structure, so that the active sites are effectively increased, the enrichment rate is further improved, and the problem that real-time detection is difficult to realize due to low concentration of the phytohormone is solved. The carbon nanofiber/carbon fiber solid phase microextraction device manufactured by the invention comprises a carbon nanofiber/carbon fiber microextraction column, wherein the microextraction column is arranged in a solid phase microextraction device with a longitudinal extension spring at the front end, the carbon nanofiber/carbon fiber microextraction column is prepared from the carbon nanofiber/carbon fiber solid phase microextraction material, one end of the carbon nanofiber/carbon fiber is fixed by PAN, so that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, and the tip needle shape is arranged in a PTFE tube.
Description
The application is a divisional application with the application date of 2016, 8 and 17, the application number of 201610681314.1, and the name of 'preparation method and device for carbon nanofiber/carbon fiber solid-phase microextraction coating', and is filed by Yanbian university.
Technical Field
The invention relates to a carbon nanofiber/carbon fiber solid-phase microextraction material and a preparation method thereof, and a manufacturing method and a device of a carbon nanofiber/carbon fiber solid-phase microextraction device.
Background
The plant hormone is a series of trace organic micromolecular compounds synthesized in the plant body, is sensitive to high temperature, strong light and oxygen, can initiate physiological reaction under extremely low content, and has very complex and various physiological effects. Considering that plant hormones play a crucial role in regulating each physiological process of plants, how to accurately and rapidly analyze the content of the plant hormones in each organ and the cell level thereof becomes a topic of times, especially in-situ living body analysis. The extraction solvent of phytohormones mostly adopts 80% cold methanol (MeOH), and some people adopt methanol/water/formic acid, acetone/water/acetic acid, acetonitrile and the like. During the extraction process, the determination of the phytohormone content is subject to artefacts due to hydrolysis, changes in the enzymatic activity and chemical derivatization. The phytohormone extracting and purifying process includes liquid-liquid extraction, solid-phase extraction, matrix dispersion solid-phase extraction, dispersion liquid-liquid micro extraction, etc. The existing sample extraction and purification mode mainly has the problems of large reagent dosage, incomplete purification and complicated steps of the traditional column; different types of samples and different types of hormones require different types of columns, and automation and simultaneous analysis of multiple types and hormones cannot be realized. The solid phase micro-extraction technology integrates sampling, extraction, separation and concentration, is easy to be connected with GC and LC, reduces the pollution of the original sample and the partial loss of the analyte, and provides a new idea for detecting the phytohormone in real time. However, the technology is applied to plant sample analysis, and has the defects that the extraction fiber head is easy to be polluted, the coating is easy to fall off, the price is expensive, the enrichment rate is low, the low-concentration hormone is difficult to detect, and the like. The carbon fiber is widely applied to the research of adsorbing organic pollutants, but the carbon fiber has small specific surface area and low extraction efficiency, and the online full analysis of trace phytohormone is difficult to realize. Therefore, attention has been directed to the preparation of new coating materials or the development of new extraction models.
Disclosure of Invention
The invention prepares carbon nanofiber/carbon fiber and provides a chromatographic analysis method for extracting micro-enrichment real-time detection of phytohormone. The carbon nanofiber is modified on the carbon fiber to form a spatial three-dimensional structure, so that active sites are effectively increased, the enrichment rate is further improved, and the problem that real-time detection is difficult to realize due to low concentration is solved.
The invention provides a preparation method of a carbon nanofiber/carbon fiber solid-phase microextraction material, which comprises the following steps:
(1) removing slurry of carbon fibers: removing the sizing agent on the surface of the carbon fiber, then drying in an oven at 35-50 ℃ for 15-30min, and then storing in a dryer;
(2) the de-slurried pure Carbon Fibers (CFs) were removed from the dryer and rinsed with methanol and water to remove surface impurities. Then drying in an oven at 35-50 deg.C for 15-30 min;
(3) acid treatment of the carbon fiber surface: and (3) carrying out acid treatment on the dried carbon fiber by using a nitric acid/sulfuric acid solution with the volume ratio of 1:3 at normal temperature and pressure for 12-15h to enable the surface of the carbon fiber to be rich in carboxyl. Acidifying carbon fibers (CFs-H), repeatedly leaching with ultrapure water until the surface is neutral, and drying in an oven;
(4) deposition of catalyst on the surface of carbon fibers: the acidified carbon fiber is dipped in the prepared catalyst solution (normal)Ethyl silicate: surfactant (P123, Pluronic P123, EO)20PO70EO20,Mav＝5800)：H2O: ethanol: hydrochloric acid: nickel nitrate 1:0.0103:9.36:21.4:0.04:0.47) for 48 h;
(5) brushing the carbon fiber impregnated with the catalyst, then carrying out suction filtration, leaching the carbon fiber with the catalyst, and then carrying out suction filtration. Repeatedly operating until the catalyst solution is uniformly attached to the surface of the carbon fiber;
(6) calcining the carbon fiber obtained in the step (5) in a furnace at the temperature of 420-470 ℃ for 20-60 min;
(7) preparing carbon nanofiber/carbon fiber (CNFs/CFs composite fiber) by a chemical vapor deposition method: placing the carbon fiber with the catalyst uniformly coated on the CFs-H surface in a furnace, introducing 150-300cc/min inert gas (nitrogen, argon or helium) at a heating rate of 2-20 ℃/min, heating to 500-700 ℃, and then introducing 10-50 cc/min H2Reducing the catalyst for 20-40min, introducing a carbon source acetylene for 20-40min (10-60 cc/min), and closing H after the chemical vapor deposition reaction is finished2And acetylene, heating to 900 ℃ of 700-2Gas is used for 30-120 min, surface oxidation treatment is carried out, and CO is closed2And (5) cooling the gas to room temperature.
The invention also provides the carbon nanofiber/carbon fiber solid-phase microextraction material prepared by the preparation method.
The invention also provides a manufacturing method of the carbon nanofiber/carbon fiber solid phase micro-extraction device, which comprises the following steps:
(1) firstly, a bundle of carbon nano fiber/carbon fiber modified by 5-7cm in length is taken, and is rinsed by methanol and ultrapure water in sequence. Wetting the carbon nanofibers/carbon fibers with ultrapure water to enable the carbon nanofibers/carbon fibers to be gathered into a cluster. Then taking a PTFE tube (the inner diameter is 0.6-0.75mm) with the diameter of 4.5-5.5cm, wherein the cleaning process is the same as that of the carbon nano fiber/carbon fiber;
(2) fixing one end of the carbon nanofiber/carbon fiber by Polyacrylonitrile (PAN) to ensure that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, so that the carbon nanofiber/carbon fiber can be more easily arranged in a Polytetrafluoroethylene (PTFE) tube, and then slowly arranging the carbon fiber in the PTFE tube;
(3) placing the prepared carbon nanofiber/carbon fiber micro-extraction column into a test tube filled with methanol, acetonitrile or ultrapure water for storage, preventing the carbon nanofiber/carbon fiber micro-extraction column from contacting air and adsorbing impurities in the air, refrigerating the test tube for storage, and taking out the test tube when needed;
(4) the commercialized solid phase micro-extraction device is improved, a longitudinal extension spring is welded at the front end of the commercialized solid phase micro-extraction device, and one section of the spring is in a needle shape, so that the spring is ensured to enter a plant sample more easily;
(5) the prepared carbon nano fiber/carbon fiber micro-extraction column is equivalent to an extraction head and is arranged in an improved solid phase micro-extraction device with a longitudinal spring. The prepared solid phase micro-extraction device is shown in figure 4;
(6) during the experiment, the carbon nanofiber/carbon fiber micro-extraction column is taken out of the solvent and put into an improved commercial solid phase micro-extraction device.
The carbon nanofiber/carbon fiber solid phase microextraction device comprises a carbon nanofiber/carbon fiber microextraction column, wherein the microextraction column is arranged in a solid phase microextraction device with a longitudinal extension spring at the front end, the carbon nanofiber/carbon fiber microextraction column is prepared from the carbon nanofiber/carbon fiber solid phase microextraction material, one end of the carbon nanofiber/carbon fiber is fixed by PAN, one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, and the tip needle shape is arranged in a PTFE tube.
The invention also provides a carbon nanofiber/carbon fiber solid phase micro-extraction method, which comprises the following steps:
(1) and taking the carbon nanofiber/carbon fiber micro-extraction column prepared from the carbon nanofiber/carbon fiber solid-phase micro-extraction material out of the solvent, and leaching the surface with methanol and ultrapure water in sequence to remove impurities adsorbed on the surface.
(2) And (3) placing the cleaned carbon nano fiber/carbon fiber micro-extraction column into a mixed standard solution water solution containing phytohormone for static adsorption for 1-30 min.
(3) Placing the carbon nanofiber/carbon fiber micro-extraction column after adsorbing for 1-30min into an inner insertion tube containing methanol solvent, performing ultrasonic desorption for 1-10min, and performing LC-MS/MS analysis on 5-15 μ L.
Compared with the prior art, the preparation method of the carbon nanofiber/carbon fiber solid-phase microextraction material and the manufacturing method of the carbon nanofiber/carbon fiber solid-phase microextraction device have the following outstanding beneficial effects:
1. the carbon nanofiber is modified on the carbon fiber to form a spatial three-dimensional structure, so that active sites are effectively increased, the enrichment rate is further improved, and the problem that real-time detection is difficult to realize due to low concentration is solved.
2. The method can quickly and accurately analyze the plant hormone, the whole process can be completed within 4 minutes, and the quick analysis of the plant hormone is realized.
3. The invention has important guiding significance for researching the mutual relation among various hormones, knowing the mechanism of regulating the plant environment by the hormones, determining the level content of the plant hormones in each organ and cell of the plant, regulating the quality of crops, increasing the yield, carrying out genetic breeding and the like.
Drawings
FIG. 1 is a scanning electron micrograph of carbon fiber (left), carbon nanofiber/carbon fiber (right);
FIG. 2 is a transmission electron micrograph of carbon nanofibers/carbon fibers;
FIG. 3 is an X-ray photoelectron spectrum of O1s and C1s for carbon fiber (left) and carbon nanofiber/carbon fiber (right);
FIG. 4 is a schematic view of a solid phase micro-extraction apparatus;
FIG. 5 is the effect of adsorption time on extraction efficiency;
FIG. 6 is the effect of desorption time on extraction efficiency;
figure 7 is a comparison of different material extraction performance.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a carbon nanofiber/carbon fiber solid-phase microextraction material, which comprises the following steps:
(1) removing slurry of carbon fibers: removing the sizing agent on the surface of the carbon fiber, then drying in an oven at 35-50 ℃ for 15-30min, and then storing in a dryer;
(2) the de-slurried pure Carbon Fibers (CFs) were removed from the dryer and rinsed with methanol and water to remove surface impurities. Then drying in an oven at 35-50 deg.C for 15-30 min;
(3) acid treatment of the carbon fiber surface: and (3) carrying out acid treatment on the dried carbon fiber by using a nitric acid/sulfuric acid solution with the volume ratio of 1:3 at normal temperature and pressure for 12-15h to enable the surface of the carbon fiber to be rich in carboxyl. Acidifying carbon fibers (CFs-H), repeatedly leaching with ultrapure water until the surface is neutral, and drying in an oven;
(4) deposition of catalyst on the surface of carbon fibers: the acidified carbon fibres were immersed in a prepared catalyst solution (tetraethoxysilane: surfactant (P123, Pluronic P123, EO)20PO70EO20,Mav＝5800)：H2O: ethanol: hydrochloric acid: nickel nitrate 1:0.0103:9.36:21.4:0.04:0.47) for 48 h;
(5) brushing the carbon fiber impregnated with the catalyst, then carrying out suction filtration, leaching the carbon fiber with the catalyst, and then carrying out suction filtration. Repeatedly operating until the catalyst solution is uniformly attached to the surface of the carbon fiber;
(6) calcining the carbon fiber obtained in the step (5) in a furnace at the temperature of 420-470 ℃ for 20-60 min;
(7) preparing carbon nanofiber/carbon fiber (CNFs/CFs composite fiber) by a chemical vapor deposition method: placing the carbon fiber with the catalyst uniformly coated on the CFs-H surface in a furnace, introducing 150-300cc/min inert gas (nitrogen, argon or helium) at a heating rate of 2-20 ℃/min, heating to 500-700 ℃, and then introducing 10-50 cc/min H2Reducing the catalyst for 20-40min, introducing a carbon source acetylene for 20-40min (10-60 cc/min), and closing H after the chemical vapor deposition reaction is finished2And acetylene, heating to 900 ℃ of 700-2Gas is used for 30-120 min, surface oxidation treatment is carried out, and CO is closed2Gas, cooling toAnd (4) room temperature.
The invention provides a preparation method of a carbon nanofiber/carbon fiber solid-phase microextraction material, which comprises the following steps:
(1) removing slurry of carbon fibers: removing the sizing agent on the surface of the carbon fiber, then drying in an oven at 40 ℃ for 20min, and then storing in a dryer;
(2) the de-slurried pure Carbon Fibers (CFs) were removed from the dryer and rinsed with methanol and water to remove surface impurities. Then drying in an oven at 40 ℃ for 20 min;
(3) acid treatment of the carbon fiber surface: and (3) carrying out acid treatment on the dried carbon fiber for 12 hours at normal temperature and normal pressure by using a nitric acid/sulfuric acid solution with the volume ratio of 1:3 to ensure that the surface of the carbon fiber is rich in carboxyl. Acidifying carbon fibers (CFs-H), repeatedly leaching with ultrapure water until the surface is neutral, and drying in an oven;
(4) deposition of catalyst on the surface of carbon fibers: the acidified carbon fibres were immersed in a prepared catalyst solution (tetraethoxysilane: surfactant (P123, Pluronic P123, EO)20PO70EO20,Mav＝5800)：H2O: ethanol: hydrochloric acid: nickel nitrate 1:0.0103:9.36:21.4:0.04:0.47) for 48 h;
(5) brushing the carbon fiber impregnated with the catalyst, then carrying out suction filtration, leaching the carbon fiber with the catalyst, and then carrying out suction filtration. Repeatedly operating until the catalyst solution is uniformly attached to the surface of the carbon fiber;
(6) calcining the carbon fiber obtained in the step (5) in a furnace at 450 ℃ for 30 min;
(7) preparing carbon nanofiber/carbon fiber (CNFs/CFs composite fiber) by a chemical vapor deposition method: placing the carbon fiber with the catalyst uniformly coated on the surface of the CFs-H in a furnace, introducing inert gas (nitrogen, argon or helium) with the flow rate of 200cc/min at the heating rate of 10 ℃/min, heating to 600 ℃, and then introducing H with the flow rate of 30cc/min2Reducing the catalyst for 30min, introducing acetylene as a carbon source for 30min (20cc/min), and closing H after the chemical vapor deposition reaction is finished2And acetylene, heating to 800 deg.C, introducing 150cc/min CO2Gas for 60min, surface oxidation treatment, and CO shutoff2Gas, cooling toAnd (4) room temperature.
The invention also provides the carbon nanofiber/carbon fiber solid-phase microextraction material prepared by the preparation method.
The invention also provides a manufacturing method of the carbon nanofiber/carbon fiber solid phase micro-extraction device, which comprises the following steps:
(1) firstly, a bundle of carbon nano fiber/carbon fiber modified by 5-7cm in length is taken, and is rinsed by methanol and ultrapure water in sequence. Wetting the carbon nanofibers/carbon fibers with ultrapure water to enable the carbon nanofibers/carbon fibers to be gathered into a cluster. Then a PTFE tube (the inner diameter is 0.6-0.75mm) with the diameter of 4.5-5.5cm is taken, and the cleaning process is the same as that of the carbon nano fiber/carbon fiber. The PTFE tube is selected in the experiment mainly because PTFE is easy to cut and easy to manufacture;
(2) fixing one end of the carbon nanofiber/carbon fiber by Polyacrylonitrile (PAN) to ensure that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, so that the carbon nanofiber/carbon fiber is easier to be loaded into a Polytetrafluoroethylene (PTFE) tube, and then slowly loading the carbon fiber into the PTFE tube, wherein the integrity of the carbon nanofiber/carbon fiber is ensured in the whole process;
(3) placing the prepared carbon nanofiber/carbon fiber micro-extraction column into a test tube filled with methanol for storage, preventing the carbon nanofiber/carbon fiber micro-extraction column from contacting air and adsorbing impurities in the air, refrigerating the test tube for storage, and taking out the test tube when needed;
(4) the commercialized solid phase micro-extraction device is improved, a longitudinal extension spring is welded at the front end of the commercialized solid phase micro-extraction device, and one section of the spring is in a needle shape, so that the spring is ensured to enter a plant sample more easily;
(5) the prepared carbon nano fiber/carbon fiber micro-extraction column is equivalent to an extraction head and is arranged in an improved solid phase micro-extraction device with a longitudinal spring. The prepared solid phase micro-extraction device is shown in figure 4;
(6) during the experiment, the carbon nanofiber/carbon fiber micro-extraction column is taken out of the solvent and put into an improved commercial solid phase micro-extraction device.
The invention also provides a manufacturing method of the carbon nanofiber/carbon fiber solid phase micro-extraction device, which comprises the following steps:
(1) firstly, a bundle of carbon nano fiber/carbon fiber modified by 6cm in length is taken, and is sequentially leached by methanol and ultrapure water. Wetting the carbon nanofibers/carbon fibers with ultrapure water to enable the carbon nanofibers/carbon fibers to be gathered into a cluster. Then, a 4.5cm PTFE tube (inner diameter: 0.75mm) was taken, and the cleaning process was the same as that for the carbon nanofibers/carbon fibers. The PTFE tube is selected in the experiment mainly because PTFE is easy to cut and easy to manufacture;
(2) fixing one end of the carbon nanofiber/carbon fiber by using PAN (polyacrylonitrile), so that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, the carbon nanofiber/carbon fiber is ensured to be more easily arranged in a PTFE (polytetrafluoroethylene) tube, then the carbon fiber is slowly arranged in the PTFE tube, and the integrity of the carbon nanofiber/carbon fiber is ensured in the whole process;
(3) placing the prepared carbon nanofiber/carbon fiber micro-extraction column into a test tube filled with methanol for storage, preventing the carbon nanofiber/carbon fiber micro-extraction column from contacting air, preventing the carbon nanofiber/carbon fiber micro-extraction column from adsorbing impurities in the air, refrigerating the test tube for storage, and taking out the test tube when needed;
(4) the commercialized solid phase micro-extraction device is improved, a longitudinal extension spring is welded at the front end of the commercialized solid phase micro-extraction device, and one section of the spring is in a needle shape, so that the spring is ensured to enter a plant sample more easily; the spring has a protection effect on the carbon nano fiber/carbon fiber, so that mechanical damage in the extraction process is avoided, and the interference of macromolecular compounds is also avoided. Meanwhile, the expansion amplitude of the spring ensures the sufficient diffusion space of the carbon nano fiber/carbon fiber, increases the sample amount, improves the sensitivity and is beneficial to quantitative analysis;
(5) the prepared carbon nano fiber/carbon fiber micro-extraction column is equivalent to an extraction head and is arranged in an improved solid phase micro-extraction device with a longitudinal spring. The prepared solid phase micro-extraction device is shown in figure 4;
(6) during the experiment, the carbon nanofiber/carbon fiber micro-extraction column is taken out of the solvent and put into an improved commercial solid phase micro-extraction device.
The invention also provides a carbon nanofiber/carbon fiber solid phase microextraction device which comprises a carbon nanofiber/carbon fiber microextraction column, wherein the microextraction column is arranged in a solid phase microextraction device with a longitudinal extension spring at the front end, the carbon nanofiber/carbon fiber microextraction column is prepared from the carbon nanofiber/carbon fiber solid phase microextraction material, one end of the carbon nanofiber/carbon fiber is fixed by PAN, so that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, and the tip needle shape is arranged in a PTFE tube.
The invention also provides a carbon nanofiber/carbon fiber solid phase micro-extraction method, which comprises the following steps:
(1) and taking the carbon nanofiber/carbon fiber micro-extraction column prepared from the carbon nanofiber/carbon fiber solid-phase micro-extraction material out of the solvent, and leaching the surface by using methanol and ultrapure water in sequence to remove impurities adsorbed on the surface.
(2) And (3) placing the cleaned carbon nano fiber/carbon fiber micro-extraction column into a mixed standard solution water solution containing phytohormone for static adsorption for 1-30 min.
(3) Placing the carbon nanofiber/carbon fiber micro-extraction column after adsorbing for 1-30min into an inner insertion tube containing methanol solvent, performing ultrasonic desorption for 1-10min, and performing LC-MS/MS analysis on 5-15 μ L.
The invention also provides a carbon nanofiber/carbon fiber solid phase micro-extraction method, which comprises the following steps:
(1) and taking the carbon nanofiber/carbon fiber micro-extraction column prepared from the carbon nanofiber/carbon fiber solid-phase micro-extraction material out of the solvent, and leaching the surface by using methanol and ultrapure water in sequence to remove impurities adsorbed on the surface.
(2) And (3) placing the cleaned carbon nano fiber/carbon fiber micro-extraction column into a mixed standard solution water solution containing phytohormone for standing and adsorbing for 3 min.
(3) And putting the carbon nanofiber/carbon fiber micro-extraction column after 3min of adsorption into an inner insertion tube containing a methanol solvent, performing ultrasonic desorption for 1min, and performing LC-MS/MS analysis on 10 mu L of the carbon nanofiber/carbon fiber micro-extraction column.
Fig. 1 is a scanning electron microscope image representing carbon fibers and carbon nanofibers/carbon fibers, and a photograph is obtained by observing the physical state of the surface of the carbon fibers using a scanning electron microscope at magnification of 5000 times and 10000 times. As can be seen from the SEM image, the diameters of the carbon fiber monofilaments are all about 8 μm, and the surfaces of the carbon fibers are provided with grooves along the axial direction of the fibers and have different widths and depths. The carbon nano-fiber grows on the surface of the carbon fiber uniformly.
Fig. 2 is a transmission electron microscope image characterizing carbon nanofibers/carbon fibers, and we observe the surface morphology of the carbon nanofibers by transmission electron microscope. The carbon nanofibers grow uniformly at a certain angle along the axis of the carbon fibers.
Fig. 3 is an X-ray photoelectron spectrum of carbon fibers and carbon nanofibers/carbon fibers, which is used for qualitatively and quantitatively analyzing surface elements and existing forms of the material, and further evaluating the surface chemical state of the material prepared by the method.
The XPS characterization of CFs and CNF/CFs in FIG. 3, Table 1, shows that both the C and O elements are present on the surfaces of CFs and CNF/CFs, but the carbon content of the CNF/CFs surface is higher than that of the CFs surface.
TABLE 1 analysis of surface elements of carbon fibers and carbon nanofibers/carbon fibers
Adsorption time optimization
Solid Phase Microextraction (SPME) is a balanced extraction technology, and sample extraction is a time limiting step in the SPME process, so that the selection of a better extraction time is a key step in the SPME method development process. The choice of adsorption time is a compromise between sensitivity and reproducibility and the length of the analytical method. The sensitivity of the equilibrium extraction is highest, but the time is much longer than the pre-equilibrium time. Both the balancing and pre-balancing require precise and excellent time repeatability, but for the latter time is of greater importance. The excellent control time is of utmost importance in the pre-equilibration, and therefore the present application mentions the influence of the adsorption time on the extraction efficiency.
Taking the carbon nanofiber/carbon fiber micro-extraction column out of the solvent, and leaching the surface by using methanol and ultrapure water in sequence to remove impurities adsorbed on the surface; placing the cleaned carbon nanofiber/carbon fiber micro-extraction column into a mixed standard solution water solution containing phytohormone for static adsorption (1min,3min,5min,15min,20min,30 min); then placing the carbon nanofiber/carbon fiber micro-extraction column into an inner insertion tube containing a methanol solvent, performing ultrasonic desorption for 10min, performing constant volume of 200 mu L, taking 10 mu L to perform LC-MS/MS analysis, and performing adsorption for three times in parallel. FIG. 5 shows the effect of adsorption time on extraction efficiency, after 3min, the recovery rates of the three phytohormones were substantially stable, all above 70%, and the Relative Standard Deviation (RSD) was less than 10%. After 3min, pre-equilibrium extraction had been reached, and 3min was chosen as adsorption time.
Desorption time optimization
Off-line desorption requires several considerations, the amount of solvent being as small as possible if sensitivity is to be improved, but sufficient to completely submerge the fiber coating. However, larger solvent volumes can result in more efficient desorption, minimizing or eliminating residuals. Typically, off-line desorption processes are performed using the minimum amount of desorption solvent that can cover the entire coating length. Cantu et al selects 70 μ L of mobile phase as desorption solvent, and carries out desorption time test in 5-30min, and finds that 20min is enough for target substance desorption, and no residue is found after blank detection; hu et al, who adopts ultrasonic treatment, selects methanol as a desorption solvent, and finds that complete desorption is realized in 3min, with the volume of the desorption solvent being 100 μ L; musteata et al successfully desorbed benzodiazepines in plastic insert tubes with only 20. mu.L acetonitrile-water-acetic acid
A class of substance; these examples illustrate that: the smaller the desorption solvent volume, the higher the sensitivity, but the longer the desorption time. The use of large volumes of desorption solvent can reduce the sensitivity of some processes, but can significantly shorten the time to complete desorption.
Taking the carbon nanofiber/carbon fiber micro-extraction column out of the solvent, and leaching the surface by using methanol and ultrapure water in sequence to remove impurities adsorbed on the surface; placing the cleaned carbon nanofiber/carbon fiber micro-extraction column into a mixed standard solution water solution containing phytohormone, standing and adsorbing for 3 min; then placing the carbon nanofiber/carbon fiber micro-extraction column into an inner insertion tube containing a methanol solvent, ultrasonically desorbing (1min,3min,5min,10min), fixing the volume to 200 mu L, taking 10 mu L to perform LC-MS/MS analysis, and paralleling each desorption time for three times. FIG. 6 shows the effect of desorption time on extraction efficiency, after 1min, the recovery rates of the three phytohormones were substantially stable, all over 70%, and the Relative Standard Deviation (RSD) was less than 8%. Ultrasonic desorption is selected for 1min, the desorption solvent is methanol, and the volume of the desorption solvent is 200 mu L as desorption conditions.
Comparison of materials
In order to further evaluate the extraction effect and sensitivity of the method, the developed carbon nano fiber/carbon fiber (CNFs/CFs) solid phase micro-extraction new coating, common glass fiber (SFs) and Carbon Fiber (CFs) and mesoporous silica coating carbon fiber (SiO) are used for coating2CFs) and carbon nanofiber/glass fiber (CNFs/SFs), the results are shown in fig. 7. The glass fiber has the weakest extraction capability, and the carbon nano fiber/carbon fiber has the strongest extraction capability (glass fiber (SFs) < Carbon Fiber (CFs) < mesoporous silica coating carbon fiber (SiO))2CFs) < carbon nanofibers/glass fibers (CNFs/SFs) < carbon nanofibers/carbon fibers (CNFs/CFs)); the carbon nanofiber/carbon fiber solid phase microextraction new coating has better reproducibility, and the Relative Standard Deviation (RSD) is less than 4%. The extraction performance is obviously improved by modifying the carbon nanofiber coating (CNFs/SFs) on the glass fiber, but the dispersibility of the glass fiber is not good as that of the carbon fiber, so that the contact area of the carbon nanofiber is reduced, and the recovery rate is lower than that of the carbon nanofiber/carbon fiber. The carbon nanofiber is modified on the carbon fiber to form a spatial three-dimensional structure, so that active sites are effectively increased, the enrichment rate is further improved, and the problem that real-time detection is difficult to realize due to low concentration is solved.
Claims (4)
1. The manufacturing method of the carbon nanofiber/carbon fiber solid phase micro-extraction device comprises the following steps:
(1) firstly, taking a bundle of carbon nanofiber/carbon fiber modified by 5-7cm in length, and leaching the bundle of carbon nanofiber/carbon fiber with methanol and ultrapure water in sequence; wetting the carbon nanofibers/carbon fibers with ultrapure water to enable the carbon nanofibers/carbon fibers to be gathered into a cluster; then taking a polytetrafluoroethylene tube with the length of 4.5-5.5cm, wherein the cleaning process is the same as that of the carbon nanofiber/carbon fiber;
(2) fixing one end of the carbon nanofiber/carbon fiber by polyacrylonitrile, so that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, ensuring that the carbon nanofiber/carbon fiber is easier to be loaded into a polytetrafluoroethylene tube, and then slowly loading the carbon fiber into the polytetrafluoroethylene tube, wherein the integrity of the carbon nanofiber/carbon fiber is ensured in the whole process;
(3) placing the prepared carbon nanofiber/carbon fiber micro-extraction column into a test tube filled with methanol for storage, preventing the carbon nanofiber/carbon fiber micro-extraction column from contacting air and adsorbing impurities in the air, refrigerating the test tube for storage, and taking out the test tube when needed;
(4) the commercialized solid phase micro-extraction device is improved, a longitudinal extension spring is welded at the front end of the commercialized solid phase micro-extraction device, and one section of the spring is in a needle shape, so that the spring is ensured to enter a plant sample more easily;
(5) the prepared carbon nano fiber/carbon fiber micro-extraction column is equivalent to an extraction head and is arranged in an improved solid phase micro-extraction device with a longitudinal spring; preparing a solid phase micro-extraction device;
(6) taking out the carbon nanofiber/carbon fiber micro-extraction column from the solvent, and putting the carbon nanofiber/carbon fiber micro-extraction column into an improved commercial solid phase micro-extraction device;
the preparation method of the carbon nanofiber/carbon fiber comprises the following steps:
(1) removing slurry of carbon fibers: removing the sizing agent on the surface of the carbon fiber, then drying in an oven at 35-50 ℃ for 15-30min, and then storing in a dryer;
(2) taking out the pure carbon fiber after pulp removal from the dryer, leaching with methanol and water to remove surface impurities, and then drying in an oven at 35-50 ℃ for 15-30 min;
(3) acid treatment of the carbon fiber surface: treating the dried carbon fiber with nitric acid/sulfuric acid solution with a volume ratio of 1:3 at normal temperature and pressure for 12-15h to ensure that the surface of the carbon fiber is rich in carboxyl, acidifying the carbon fiber, repeatedly leaching with ultrapure water until the surface is neutral, and then drying in an oven;
(4) deposition of catalyst on the surface of carbon fibers: will be provided withSoaking the acidified carbon fibers in a prepared catalyst solution for 48 hours, wherein the catalyst solution consists of tetraethoxysilane, a surfactant, water, ethanol, hydrochloric acid and nickel nitrate; the mass ratio of the ethyl orthosilicate to the surfactant to the water to the ethanol to the hydrochloric acid to the nickel nitrate is 1:0.0103:9.36:21.4:0.04: 0.47; the surfactant is EO20PO70EO20(ii) a The EO20PO70EO20Mav ═ 5800 g/moL;
(5) brushing the carbon fiber impregnated with the catalyst, then carrying out suction filtration, leaching the carbon fiber with the catalyst, carrying out suction filtration again, and repeatedly operating until the catalyst solution is uniformly adhered to the surface of the carbon fiber;
(6) calcining the carbon fiber obtained in the step (5) in a furnace at the temperature of 420-470 ℃ for 20-60 min;
(7) preparing carbon nano fiber/carbon fiber by chemical vapor deposition: uniformly coating a catalyst on the surface of acidified carbon fibers, placing the acidified carbon fibers in a furnace, introducing 150-300cc/min inert gas at a heating rate of 2-20 ℃/min, then heating to 500-700 ℃, introducing 10-50 cc/min hydrogen, maintaining the reduction catalyst for 20-40min, introducing 10-60 cc/min carbon source acetylene for 20-40min, closing the hydrogen and the acetylene after the chemical vapor deposition reaction is finished, heating to 700-900 ℃, introducing 100-200 cc/min carbon dioxide for 30-120 min, performing surface oxidation treatment, and finally closing CO2Cooling the gas to room temperature; the inert gas is nitrogen, argon or helium.
2. The method according to claim 1, wherein the polytetrafluoroethylene tube in step (1) has a radius of 0.6 to 0.75 mm.
3. The manufacturing method of the carbon nanofiber/carbon fiber solid phase micro-extraction device comprises the following steps:
(1) firstly, taking a bundle of carbon nano fiber/carbon fiber modified by 6cm in length, and leaching the bundle of carbon nano fiber/carbon fiber with methanol and ultrapure water in sequence; wetting the carbon nanofibers/carbon fibers with ultrapure water to enable the carbon nanofibers/carbon fibers to be gathered into a cluster; then taking a polytetrafluoroethylene tube with the length of 4.5cm, wherein the cleaning process is the same as the process for cleaning the carbon nano fiber/carbon fiber;
(2) fixing one end of the carbon nanofiber/carbon fiber by polyacrylonitrile, so that one end of the carbon nanofiber/carbon fiber is dispersed and polymerized into a tip needle shape, ensuring that the carbon nanofiber/carbon fiber is easier to be loaded into a polytetrafluoroethylene tube, and then slowly loading the carbon fiber into the polytetrafluoroethylene tube, wherein the integrity of the carbon nanofiber/carbon fiber is ensured in the whole process;
(3) placing the prepared carbon nanofiber/carbon fiber micro-extraction column into a test tube filled with methanol for storage, preventing the carbon nanofiber/carbon fiber micro-extraction column from contacting air and adsorbing impurities in the air, refrigerating the test tube for storage, and taking out the test tube when needed;
(4) the commercialized solid phase micro-extraction device is improved, a longitudinal extension spring is welded at the front end of the commercialized solid phase micro-extraction device, and one section of the spring is in a needle shape, so that the spring is ensured to enter a plant sample more easily; the spring has a protection effect on the carbon nano fiber/carbon fiber, so that not only is mechanical damage in the extraction process avoided, but also the interference of macromolecular compounds is avoided; meanwhile, the expansion amplitude of the spring ensures the sufficient diffusion space of the carbon nano fiber/carbon fiber, increases the sample amount, improves the sensitivity and is beneficial to quantitative analysis;
(5) the prepared carbon nano fiber/carbon fiber micro-extraction column is equivalent to an extraction head and is arranged in an improved solid phase micro-extraction device with a longitudinal spring; preparing a solid phase micro-extraction device;
(6) taking out the carbon nanofiber/carbon fiber micro-extraction column from the solvent, and putting the carbon nanofiber/carbon fiber micro-extraction column into an improved commercial solid phase micro-extraction device;
the preparation method of the carbon nanofiber/carbon fiber comprises the following steps:
(1) removing slurry of carbon fibers: removing the sizing agent on the surface of the carbon fiber, then drying in an oven at 35-50 ℃ for 15-30min, and then storing in a dryer;
(2) taking out the pure carbon fiber after pulp removal from the dryer, leaching with methanol and water to remove surface impurities, and then drying in an oven at 35-50 ℃ for 15-30 min;
(3) acid treatment of the carbon fiber surface: treating the dried carbon fiber with nitric acid/sulfuric acid solution with a volume ratio of 1:3 at normal temperature and pressure for 12-15h to ensure that the surface of the carbon fiber is rich in carboxyl, acidifying the carbon fiber, repeatedly leaching with ultrapure water until the surface is neutral, and then drying in an oven;
(4) deposition of catalyst on the surface of carbon fibers: soaking the acidified carbon fibers in a prepared catalyst solution for 48 hours, wherein the catalyst solution consists of tetraethoxysilane, a surfactant, water, ethanol, hydrochloric acid and nickel nitrate; the mass ratio of the ethyl orthosilicate to the surfactant to the water to the ethanol to the hydrochloric acid to the nickel nitrate is 1:0.0103:9.36:21.4:0.04: 0.47; the surfactant is EO20PO70EO20(ii) a The EO20PO70EO20Mav ═ 5800 g/moL;
(5) brushing the carbon fiber impregnated with the catalyst, then carrying out suction filtration, leaching the carbon fiber with the catalyst, carrying out suction filtration again, and repeatedly operating until the catalyst solution is uniformly adhered to the surface of the carbon fiber;
(6) calcining the carbon fiber obtained in the step (5) in a furnace at the temperature of 420-470 ℃ for 20-60 min;
(7) preparing carbon nano fiber/carbon fiber by chemical vapor deposition: uniformly coating a catalyst on the surface of acidified carbon fibers, placing the acidified carbon fibers in a furnace, introducing 150-300cc/min inert gas at a heating rate of 2-20 ℃/min, then heating to 500-700 ℃, introducing 10-50 cc/min hydrogen, maintaining the reduction catalyst for 20-40min, introducing 10-60 cc/min carbon source acetylene for 20-40min, closing the hydrogen and the acetylene after the chemical vapor deposition reaction is finished, heating to 700-900 ℃, introducing 100-200 cc/min carbon dioxide for 30-120 min, performing surface oxidation treatment, and finally closing CO2Cooling the gas to room temperature; the inert gas is nitrogen, argon or helium.
4. The production method according to claim 3, wherein the polytetrafluoroethylene tube in said step (1) has an inner diameter of 0.75 mm.
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