CN109647333B - Microporous-mesoporous carbon and preparation method and application thereof - Google Patents
Microporous-mesoporous carbon and preparation method and application thereof Download PDFInfo
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- CN109647333B CN109647333B CN201811515446.2A CN201811515446A CN109647333B CN 109647333 B CN109647333 B CN 109647333B CN 201811515446 A CN201811515446 A CN 201811515446A CN 109647333 B CN109647333 B CN 109647333B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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Abstract
A microporous-mesoporous carbon, a preparation method and application thereof, belonging to the technical field of carbon nano-material preparation. The preparation method comprises the following steps: putting the citrate into a tubular muffle furnace, activating at high temperature under the protection of nitrogen, carbonizing, and cooling to room temperature; pickling the obtained substance, drying and grinding to obtain mesoporous carbon; mixing the obtained mesoporous carbon with an activating agent, activating at high temperature, carbonizing, and cooling to room temperature; and (3) carrying out acid washing, drying and grinding on the obtained substance to obtain the microporous-mesoporous carbon. The micropore-mesoporous carbon prepared by the method has the advantages of large effective activation area and good activation effect, and the prepared micropore-mesoporous carbon is fixed on the surface of the stainless steel wire in a physical adhesion mode, so that a novel, cheap and efficient solid-phase microextraction probe can be prepared, and the micropore-mesoporous carbon can be used for detecting volatile organic pollutants in a water environment.
Description
Technical Field
The invention belongs to the technical field of carbon nano-material preparation, and particularly relates to microporous-mesoporous carbon and a preparation method and application thereof.
Background
The porous carbon is a carbon material with developed pore structure and stable physical-chemical properties, and is widely applied to environmental purification (atmosphere, water and soil) and novel battery materials. Wherein, the pore structure directly determines the performance of the composite material. The micropores promote the increase of the specific surface area and strengthen the adsorption performance; the mesopores contribute to mass transport and promote the increase in the number of effective micropores. Therefore, the optimization of the pore structure is a research hotspot of the porous carbon material and is also a difficult point to attack.
At present, the preparation method of the porous carbon is mostly based on a one-step template method or an activation method. Plum Shiwei et al (preparation of nitrogen-doped porous carbon sheet by template method and study on lithium storage performance thereof [ J]2018,76(03): 209-214) and preparing the porous carbon by using polyethylene glycol as a carbon source and a bonding agent, melamine as a nitrogen source, magnesium oxide as a template and a pore-forming agent. The specific surface area reaches 370.8 m2·g-1Mainly mesoporous, and has a small number of micropores. Aarthi Pandrirajan et al (OPAC (organic peptide activated carbon) driven from water organic peptide for the Adsorption of chlorinated acrylic acids from water, kinetic modifying and thermal modifying peptides [ J]Bioresource Technology, 2018, 261: 329-341) using orange peel as a carbon precursor, porous carbon was prepared using KOH high temperature activation. The specific surface area reaches 592.4 m2·g-1The method is mainly characterized by micropores and small quantity of mesopores. As can be seen from the above, it is still difficult to prepare a porous carbon material having a large number of mesopores and micropores.
With the discharge of three industrial wastes, a large amount of organic pollutants continuously enter the water environment, and seriously threaten the human health. Therefore, accurate detection of organic pollutants in water environments is very important, especially volatile organic pollutants with high toxicity and long-distance mobility. The solid phase micro-extraction is a new detection technology, integrates sampling, purification, enrichment and sample introduction, is simple and efficient, and develops rapidly in recent years. However, the extraction probe, which is a core component, is expensive and difficult to popularize and use in a large range. Therefore, it is necessary to make cheap solid phase micro-extraction probes and apply the probes to detect volatile organic pollutants in water environment.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides microporous-mesoporous carbon and a preparation method and application thereof, the prepared microporous-mesoporous carbon has large effective activation area and good activation effect, and the prepared microporous-mesoporous carbon is fixed on the surface of a stainless steel wire in a physical adhesion mode, so that a novel, cheap and efficient solid-phase micro-extraction probe can be prepared and used for detecting volatile organic pollutants in a water environment.
The technical scheme is as follows: a preparation method of microporous-mesoporous carbon comprises the following steps:
step one, placing citrate in a tubular muffle furnace, protecting with nitrogen at 50-400 mL/min, heating to 600-1000 ℃ at 2-10 ℃/min, keeping for 1-4 h, and then naturally cooling to room temperature to obtain a black solid product;
taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 10-20 vt% hydrochloric acid or hydrofluoric acid for 30-60 min by using ultrasound, pickling, washing with ultrapure water, and drying to obtain mesoporous carbon;
putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the corundum crucible and the activating agent into a tubular muffle furnace, protecting nitrogen by 50-400 mL/min, heating to 600-1000 ℃ at the speed of 2-10 ℃/min, keeping for 1-4 h, and naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is (1-8): 1;
taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking the carbon in 10-20 vt% hydrochloric acid or hydrofluoric acid for 30-60 min by ultrasonic treatment, pickling, washing with ultrapure water, and drying to obtain the microporous-mesoporous carbon.
Preferably, the preparation method comprises the following steps:
step one, placing citrate in a tubular muffle furnace, protecting by nitrogen at 100 mL/min, heating to 800 ℃ at 3 ℃/min, keeping for 1 h, and then naturally cooling to room temperature to obtain a black solid product;
taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 10 vt% hydrochloric acid or hydrofluoric acid for 40 min, carrying out acid washing for 3 times, washing the black solid product with ultrapure water for 3 times, and drying the black solid product at 120 ℃ to obtain mesoporous carbon;
putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the corundum crucible and the activating agent into a tubular muffle furnace, protecting with 100 mL/min of nitrogen, heating to 800 ℃ at a speed of 3 ℃/min, keeping for 1 h, and then naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is 8: 1;
taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking the carbon in 10 vt% hydrochloric acid or hydrofluoric acid for ultrasonic treatment for 40 min, pickling for 3 times, washing with ultrapure water for 3 times, and drying at 120 ℃ to obtain the microporous-mesoporous carbon.
Preferably, the citrate in the first step includes at least one of calcium citrate, ferric citrate and zinc citrate.
Preferably, the activating agent in the third step comprises KOH, NaOH and NaHCO3And KHCO3At least one of (1).
The micropore-mesopore carbon prepared by the preparation method.
The micropore-mesoporous carbon is applied to the preparation of solid phase micro-extraction probes.
Preferably, the steps for preparing the solid phase micro-extraction probe are as follows: diluting the Xika sealing adhesive by using cyclohexane, wherein the dilution concentration of the Xika sealing adhesive is 0.25 mg/mL; ultrasonically cleaning a stainless steel wire, immersing the stainless steel wire into a Xika sealing compound diluent, and then immersing the stainless steel wire into microporous-mesoporous carbon powder; taking out and drying in a drying oven at 75-95 ℃ for 5-15 min; repeating the steps twice to obtain the solid-phase micro-extraction probe.
Preferably, the prepared solid phase microextraction probe is applied to detecting trace volatile and semi-volatile organic pollutants in water.
Preferably, the organic contaminant is at least one of 1,3, 5-trichlorobenzene, 1,2, 4-trichlorobenzene, 1,2,3, 4-tetrachlorobenzene, 1,2,4, 5-tetrachlorobenzene, pentachlorobenzene and hexachlorobenzene.
Has the advantages that: (1) according to the invention, citrate is used as a mesoporous carbon precursor, and the mesoporous carbon is prepared by utilizing the size of a metal oxide; then activating by potassium salt to prepare microporous-mesoporous carbon; the method is simple and convenient, and the mesoporous carbon is used as a micropore-mesoporous carbon precursor, so that the effective activation sites can be improved, micropores and mesopores can be fused together, and the specific surface area is improved.
(2) The micropore-mesopore carbon prepared by the method has high specific surface area, simultaneously has a large number of micropores and mesopores, is beneficial to enriching organic micropollutants, has the pore diameter distribution range of 0.4-50 nm, and has the specific surface area of 2638 m2(ii) in terms of/g. In comparison with previous studies: aarthi Pandrirajan et al (OPAC (organic peptide activated carbon) driven from water organic peptide for the Adsorption of chlorinated acrylic acids from water, kinetic modifying and thermal modifying peptides [ J]Bioresource Technology, 2018, 261: 329-341) orange peel as a carbon precursor, and KOH high-temperature activation is used for preparing porous carbon with specific surface area of 592.4 m2·g-1The number of mesopores is small, and micropores are mainly used; han et al (The N-bonded activated carbon derived from biomass gas for CO)2 adsorption [J]Industrial Crops and Products, 2019, 128: 290-297) bagasse is used as a carbon precursor, and urea and KOH are jointly activated at high temperature to prepare porous carbon with the specific surface area of 1113 m2·g-1The method is mainly characterized by micropores and small quantity of mesopores. The micropore-mesopore carbon prepared by the invention not only has high specific surface area, but also has a large amount of mesopores and micropores.
(3) The solid-phase micro-extraction probe prepared by the microporous-mesoporous carbon prepared by the invention can efficiently enrich organic micro-pollutants, has the extraction capacity 2.0-52.0 times of that of a commercial carbon-based solid-phase micro-extraction probe, and can be used for trace detection and monitoring of the organic micro-pollutants in a water environment.
Drawings
Fig. 1 is SEM and TEM images of microporous-mesoporous carbon prepared in example 3 of the present invention, in which (a) is an SEM image of microporous-mesoporous carbon prepared in example 3 of the present invention, and (b) is a TEM image of microporous-mesoporous carbon prepared in example 3 of the present invention;
fig. 2 is a graph showing a nitrogen adsorption/desorption curve and a pore size distribution curve of microporous-mesoporous carbon prepared in example 3 of the present invention, in which (a) is a graph showing a nitrogen adsorption/desorption curve of microporous-mesoporous carbon prepared in example 3 of the present invention, and (b) is a graph showing a pore size distribution curve of microporous-mesoporous carbon prepared in example 3 of the present invention;
fig. 3 is an X-ray diffraction pattern, a raman spectrum, an X-ray photoelectron spectrum-total scan, and an X-ray photoelectron spectrum-C1 s of the microporous-mesoporous carbon prepared in example 3 of the present invention, in which (a) is the X-ray diffraction pattern of the microporous-mesoporous carbon prepared in example 3 of the present invention, (b) is the raman spectrum of the microporous-mesoporous carbon prepared in example 3 of the present invention, (C) is the X-ray photoelectron spectrum-total scan of the microporous-mesoporous carbon prepared in example 3 of the present invention, and (d) is the X-ray photoelectron spectrum-C1 s of the microporous-mesoporous carbon prepared in example 3 of the present invention;
FIG. 4 is a diagram showing the comparison of the performance of the solid phase microextraction probe prepared in example 4 of the present invention with commercial CAR/PDMS probe and PDMS probe for detecting and monitoring organic micropollutants, wherein (a) is a diagram showing the final product of the solid phase microextraction probe prepared in example 4 of the present invention, (b) is a diagram showing the SEM diagram showing the solid phase microextraction probe prepared in example 4 of the present invention, and (c) is a diagram showing the solid phase microextraction probe prepared in example 4 of the present invention with commercial CAR/PDMS probe and PDMS probe containing the following organic micropollutants 1,3, 5-trichlorobenzene, 1,2, 4-trichlorobenzene, 1,2,3, 4-tetrachlorobenzene, 1,2,4, 5-tetrachlorobenzene, pentachlorobenzene, carbon dioxide, the comparative graph of the extraction detection and monitoring performance of hexachlorobenzene, (c) 135-TCB is 1,3, 5-trichlorobenzene, 124-TCB is 1,2, 4-trichlorobenzene, 123-TCB is 1,2, 3-trichlorobenzene, 1234-TeCB is 1,2,3, 4-tetrachlorobenzene, 1245-TeCB is 1,2,4, 5-tetrachlorobenzene, PeCB is pentachlorobenzene, and HCB is hexachlorobenzene.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
Step one, placing citrate in a tubular muffle furnace, protecting with 50 mL/min of nitrogen, heating to 600 ℃ at the speed of 2 ℃/min, keeping for 1 h, and then naturally cooling to room temperature to obtain a black solid product;
taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 10 vt% hydrochloric acid for 30 min, repeatedly pickling for 3 times, washing with ultrapure water for 3 times, and drying at 100 ℃ to obtain mesoporous carbon;
putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the corundum crucible and the activating agent into a tubular muffle furnace, protecting with 50 mL/min of nitrogen, heating to 600 ℃ at the speed of 2 ℃/min, keeping for 1 h, and then naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is 1: 1;
taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking the carbon in 10 vt% hydrochloric acid for 30 min, carrying out acid washing for 3 times, washing the carbon by using ultrapure water for 3 times, and drying the carbon at 100 ℃ to obtain the micropore-mesoporous carbon.
Example 2
Step one, placing citrate in a tubular muffle furnace, protecting with 400 mL/min of nitrogen, heating to 1000 ℃ at a speed of 10 ℃/min, keeping for 4 h, and then naturally cooling to room temperature to obtain a black solid product;
taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 20 vt.% hydrofluoric acid for ultrasonic treatment for 60 min, pickling the black solid product for 3 times, washing the black solid product with ultrapure water for 3 times, and drying the black solid product at 120 ℃ to obtain mesoporous carbon;
putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the corundum crucible and the activating agent into a tubular muffle furnace, protecting with nitrogen at 400 mL/min, heating to 1000 ℃ at 10 ℃/min, keeping for 4 hours, and then naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is 8: 1;
taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking and carrying out ultrasonic treatment for 60 min by using 20 vt% hydrofluoric acid, carrying out acid washing for 3 times, washing for 3 times by using ultrapure water, and drying at 120 ℃ to obtain the micropore-mesoporous carbon.
Example 3
Step one, placing citrate in a tubular muffle furnace, protecting by nitrogen at 100 mL/min, heating to 800 ℃ at 3 ℃/min, keeping for 1 h, and then naturally cooling to room temperature to obtain a black solid product;
taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 10 vt% hydrochloric acid or hydrofluoric acid for 40 min, carrying out acid washing for 3 times, washing the black solid product with ultrapure water for 3 times, and drying the black solid product at 120 ℃ to obtain mesoporous carbon;
putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the corundum crucible and the activating agent into a tubular muffle furnace, protecting with 100 mL/min of nitrogen, heating to 800 ℃ at a speed of 3 ℃/min, keeping for 1 h, and then naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is 8: 1;
taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking the carbon in 10 vt% hydrochloric acid for 40 min, carrying out acid washing for 3 times, washing the carbon by using ultrapure water for 3 times, and drying the carbon at 120 ℃ to obtain the micropore-mesoporous carbon.
Referring to fig. 1, an SEM (scanning electron microscope) image and a TEM (transmission electron microscope) image of the prepared microporous-mesoporous carbon show that a large number of macropores are distributed on the surface of the microporous-mesoporous carbon, and the TEM image shows that a large number of mesopores and micropores are distributed on the surface of the microporous-mesoporous carbon and has structural stripes unique to graphene. The nitrogen adsorption and desorption curve and the pore size distribution curve chart of the prepared microporous-mesoporous carbon are shown in figure 2, and the microporous-mesoporous carbon has large specific surface area which can reach 2638.09 m2·g−1The pore volume can reach 1.77 cm3·g−1Consists of micropores and mesopores, and the pore volume of the micropores is 0.78 cm3·g−1The mesoporous volume is 0.99 cm3·g−1. The X-ray diffraction pattern, the Raman spectrogram, the X-ray photoelectron spectrum-full scan pattern and the X-ray photoelectron spectrum-C1 s pattern of the prepared microporous-mesoporous carbon are shown in figure 3, and the microporous-mesoporous carbon has a certain graphene structure, is high in hydrophobicity and is very stable. In comparison with previous studies: aarthi Pandrirajan et al (OPAC (organic peptide activated carbon) driven from water organic peptide for the Adsorption of chlorinated acrylic acids from water, kinetic modifying and thermal modifying peptides [ J]Bioresource Technology, 2018, 261: 329-341) orange peel as a carbon precursor, and KOH high-temperature activation is used for preparing porous carbon with specific surface area of 592.4 m2·g-1The number of mesopores is small, and micropores are mainly used; han et al (The N-bonded activated carbon derived from biomass gas for CO)2 adsorption [J]Industrial Crops and Products, 2019, 128: 290-297) bagasse is used as a carbon precursor, and urea and KOH are jointly activated at high temperature to prepare porous carbon with the specific surface area of 1113 m2·g-1The method is mainly characterized by micropores and small quantity of mesopores. The method provided by the invention not only has high specific surface area, but also has a large number of mesopores and micropores.
Example 4
Based on the microporous-mesoporous carbon prepared in example 3.
In this example, a solid-phase microextraction probe was prepared by using cyclohexane to dilute the seeca sealing compound and binding the microporous-mesoporous carbon to the surface of the stainless steel wire by physical adhesion. The method comprises the following specific steps:
a. diluting 0.25 mg of the Cika sealant in a 2 mL centrifuge bottle with 1 mL of cyclohexane;
b. ultrasonically cleaning a stainless steel wire with the diameter of 127 mu m and the length of 1 cm, then immersing the stainless steel wire into a Xika sealing compound diluent, and then rapidly immersing the stainless steel wire into microporous-mesoporous carbon powder;
c. taking out, and drying at 80 deg.C for 10 min;
d. and (c) repeating the steps b and c twice respectively to obtain the solid-phase microextraction probe.
Example 5
The process of monitoring volatile and semi-volatile organic contaminants in a water body using the solid phase microextraction probe prepared in example 4 is as follows: placing 20 mL of water containing the pollutants in a brown glass bottle, tightly covering a gasket-containing hollow cover of the glass bottle, puncturing the gasket by a solid phase microextraction probe, heating in water bath to 80 ℃, extracting for 20 minutes, quickly taking out, and carrying out thermal desorption at 310 ℃ for 5 min at a sample inlet of a gas chromatograph.
Meanwhile, commercial CAR/PDMS, PDMS probes were used to extract contaminants and compared to the homemade probes of this example. Fig. 4a is a diagram of a finished solid phase microextraction probe prepared in example 4, fig. 4b is a SEM diagram of the solid phase microextraction probe prepared in example 4, and fig. 4c is a diagram of the extraction detection and monitoring performance comparison of the solid phase microextraction probe prepared in example 4 with a commercial CAR/PDMS probe and a PDMS probe for 1,3, 5-trichlorobenzene, 1,2, 4-trichlorobenzene, 1,2, 3-trichlorobenzene, 1,2,4, 5-tetrachlorobenzene, pentachlorobenzene and hexachlorobenzene containing the following organic micropollutants, and it can be seen from the figure that the extraction capacity of the solid phase microextraction probe prepared by the microporous-mesoporous carbon is much higher than that of the commercial solid phase microextraction probe.
Claims (1)
1. The application of the microporous-mesoporous carbon in the preparation of the solid phase micro-extraction probe for detecting the trace volatile and semi-volatile organic pollutants in the water body is characterized in thatThe preparation steps of the microporous-mesoporous carbon are as follows: step one, placing citrate in a tubular muffle furnace, protecting by nitrogen at 100 mL/min, heating to 800 ℃ at 3 ℃/min, keeping for 1 h, and then naturally cooling to room temperature to obtain a black solid product; taking out the black solid product, grinding the black solid product by using a mortar, soaking the black solid product in 10 vt% hydrochloric acid or hydrofluoric acid for 40 min, carrying out acid washing for 3 times, washing the black solid product with ultrapure water for 3 times, and drying the black solid product at 120 ℃ to obtain mesoporous carbon; putting the mesoporous carbon into a corundum crucible, uniformly mixing the mesoporous carbon with an activating agent, putting the mixture into a tubular muffle furnace, protecting with nitrogen at 100 mL/min, heating to 800 ℃ at 3 ℃/min, keeping the temperature for 1 h, and then naturally cooling to room temperature, wherein the mass ratio of the activating agent to the mesoporous carbon is 8:1, and the activating agent is KOH, NaOH or NaHCO3And KHCO3At least one of; taking out the cooled mesoporous carbon, grinding the mesoporous carbon by using a mortar, soaking the mesoporous carbon in 10 vol.% hydrochloric acid for 40 min, carrying out acid washing for 3 times, washing the mesoporous carbon with ultrapure water for 3 times, and drying the mesoporous carbon at 120 ℃ to obtain the micropore-mesoporous carbon; diluting the Xika sealing adhesive by using cyclohexane, wherein the dilution concentration of the Xika sealing adhesive is 0.25 mg/mL; ultrasonically cleaning a stainless steel wire, immersing the stainless steel wire into a Xika sealing compound diluent, and then immersing the stainless steel wire into microporous-mesoporous carbon powder; taking out and drying in a drying oven at 75-95 ℃ for 5-15 min; repeating the steps twice to obtain the solid-phase micro-extraction probe.
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