CN111701570A - Nitrogen oxide doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on chemical bonding method and application of fiber in detection of aromatic amine - Google Patents
Nitrogen oxide doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on chemical bonding method and application of fiber in detection of aromatic amine Download PDFInfo
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Abstract
The invention belongs to the field of nano material preparation, and particularly relates to a nitrogen oxide doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on a chemical bonding method, a preparation method thereof and application thereof in detection of aromatic amine. The material is based on a nitrogen oxide doped carbon material, and is detected by preparing an SPME fiber coating coated with ONCNTs material and extracting aromatic amine, and then using gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS/MS). The ONCNTs material prepared by the invention has good thermal stability, rich adsorption active sites, strong electronegativity and large specific surface area, the prepared ONCNTs coating fiber has good reproducibility and long service life, and the established method can simultaneously determine a plurality of aromatic amines in a complex matrix.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a nitrogen oxide doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on a chemical bonding method, a preparation method thereof and application thereof in detection of aromatic amine.
Background
Aromatic Amines (AAs) are industrial intermediates that are widely used in pharmaceuticals, pesticides, azo dyes and rubbers. Due to their high solubility in water, aromatic amines are susceptible to environmental pollution through direct industrial discharge or indirect degradation of aromatic amine-based products. After entering human body through respiratory tract, intestinal tract and skin, the aromatic amine with metabolic activity can generate reaction intermediate hydroxylamine, destroy protein and DNA, and cause harm to human respiratory system, nervous system, cardiovascular system and the like. Aromatic amines are often present in water, smoke, textile products and food contact materials, and trace amounts of aromatic amines are still challenging to detect due to their low content and complex matrix.
As a sample pretreatment technique based on the principle of adsorption and desorption of a target substance on a stationary phase, Solid Phase Microextraction (SPME) has been proposed for the first time in 1989, and has attracted much attention because of its advantages of simple operation, easy automation, and easy use with an analytical instrument. The SPME technology has the advantages of small sample demand and no need of organic solvents, is green and cheap, and is widely applied to the fields of food analysis, environmental monitoring, forensic identification and the like. In SPME technology, the selection of fiber coatings plays a key role, and the extraction performance of the fibers on analytes can be greatly improved. The current coating materials for commercialization mainly include polydimethylsiloxane/divinylbenzene (PDMS/DVB), Polyacrylate (PA), Polydimethylsiloxane (PDMS), and other polymers, but most of the commercial coatings are often limited in use due to the problems of high price, poor thermal and chemical stability, and the like. Therefore, the development of cheap, efficient, highly selective and highly stable coatings is the core research content for SPME.
Nitrogen-doped carbon nanotubes have advantages such as large specific surface area and good stability as an adsorbing material, but most carbon-based materials are electropositive, and thus it is difficult to adsorb an electropositive target. The nitrogen-doped carbon nanotube is oxidized, so that the surface of the nitrogen-doped carbon nanotube has a large amount of hydroxyl and carboxyl, has strong negative electricity, has electrostatic interaction with aromatic amine, and has certain selectivity. Therefore, compared with the original material, the nitrogen oxide doped carbon nanotube material has better extraction performance on aromatic amine.
Disclosure of Invention
The invention aims to provide a preparation method and application of ONCNTs coating solid-phase micro-extraction fibers. The material is further oxidized on the basis of nitrogen-doped carbon nanotubes (N-CNTs) to obtain an electronegative carbon nano adsorption material, and stainless steel fibers coated with the ONCNTs are prepared by a chemical bonding method. The ONCNTs-SPME method established by the invention enriches aromatic amine, and then detects the aromatic amine by gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS/MS). The method does not need to use an organic solvent, is green and environment-friendly, needs a small amount of samples, and the prepared ONCNTs have a large number of adsorption active sites, strong electronegativity and a high enrichment effect on aromatic amine.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of nitrogen oxide doped carbon nanotube coating solid phase micro-extraction fiber comprises the following steps:
1) preparation of N-doped carbon materials (N-CNTs)
According to the existing preparation method of the N-CNTs, the steps after improvement are as follows:
(a)2.0 g of dimethylimidazole and 1.7 g of cobalt nitrate hexahydrate were dissolved in 40.0 mL of a mixture of methanol and ethanol (methanol/ethanol ratio 1:1 by volume). Magnetically stirring the solution for 20 s, and standing at room temperature for 20 h;
(b) washing the obtained product with methanol for 5 times, centrifuging and washing at 8000 rpm for 5 min;
(c) drying the obtained solid at 70 ℃ for 24h to obtain a ZIF-67 material;
(d) adding 200.0 mg ZIF-67 to the crucible and placing in a tube furnace at 1 deg.C for min-1Is raised to 700 ℃ and H is passed in2Keeping for 2h, and then gradually reducing to room temperature; finally obtaining black N-CNTs powder.
2) Preparation of ONCNTs material
(a) Suspending 100.0 mg of N-CNTs sample in 200.0 mL of oxidant solution, and stirring at room temperature for 2-8 h;
(b) and cooling the obtained suspension to room temperature, washing the suspension to be neutral by secondary water centrifugation (8000 rpm, 5 min), and drying the suspension at 70 ℃ for 24h to obtain the ONCNTs material.
3) Preparation of ONCNTs coating solid phase micro-extraction fiber
(a) Soaking one end (3 cm) of the stainless steel fiber in 70 deg.C hydrofluoric acid solution for 15min, ultrasonically cleaning with pure water to obtain stainless steel wire with rough surface, and drying;
(b) placing the stainless steel fiber obtained in the step into a solution with the concentration of 2 mg mL-1Regulating the pH value of the solution to 8.5 by using a Tris-HCl solution; the reaction was carried out at room temperature for 24 hours to obtain Polydopamine (PDA) -coated stainless steel fibers;
(c) immersing the stainless steel wire coated with PDA in a silane coupling agent, reacting at room temperature for 12-24 h, mainly reacting with hydroxyl on the surface of the fiber coated with PDA, pulling out the fiber, and immediately putting the fiber into a 70 ℃ oven for 6h to complete a silanization reaction to obtain an amino modified stainless steel fiber;
(d) the amino modified fiber was inserted into a 0.5 wt% aqueous solution of ONCNTs in a water bath at 70 ℃ for 3 hours. Repeating the two operations (c) and (d) for 3 times to obtain the ONCNTs coated solid-phase micro-extraction fiber.
Wherein, the oxidant in the step (a) of the step 2) comprises 35wt% of nitric acid and 10 mol L of nitric acid-1Hydrochloric acid, 30wt% H2O2One or more of them.
The silane coupling reagent in step 3) (c) comprises: one or more of vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltriethoxysilane and 3-aminopropyltriethoxysilane.
The reaction in the step 3) (c) at room temperature for 12-24 h comprises: 12h, 18h and 24 h.
The application comprises the following steps: the ONCNTs coated stainless steel fiber obtained is combined with GC-MS/MS to detect trace aromatic amine.
The invention has the advantages that:
1) the invention uses an environment-friendly, economic and practical method to prepare the ONCNTs material, the material presents electronegativity, provides abundant adsorption active sites, and can quickly enrich aromatic amine.
2) The invention overcomes the problems of unstable heat, low selectivity, short service life and the like existing in the current commercialized coating, and ONCNTs coating fiber prepared by using a chemical bonding method can be recycled, thereby providing possibility for the material to be used for the commercialized production of SPME technology.
3) Under the optimal condition, the ONCNTs material coating fiber has good adsorption on the aromatic amine, and has a lower detection limit (0.1-5.0 ng L) when being used together with a GC-MS/MS method-1) And has good linear correlation coefficient (R)>0.9970）。
Drawings
FIG. 1 is a transmission electron micrograph of ONCNTs material.
FIG. 2 is an X-ray diffraction pattern of ONCNTs material.
FIG. 3 shows the optimization of experimental conditions for detecting aromatic amine by using ONCNTs solid phase micro-extraction fiber and GC-MS/MS (wherein 2,3-DRA is 2, 3-dichloroaniline, 3,4-DRA is 3, 4-dichloroaniline, 1-NA is 1-naphthylamine, 2-NA is 2-naphthylamine, and 4-ABP is 4-aminobiphenyl).
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are not intended to limit the invention, but are intended to facilitate the understanding thereof.
Example 1:
a method for synthesizing ONCNTs material comprises the following steps:
1) preparation of N-CNTs
(a)2.0 g of dimethylimidazole and 1.7 g of cobalt nitrate hexahydrate were dissolved in 40.0 mL of a mixture of methanol and ethanol (methanol/ethanol ratio 1:1 by volume). Magnetically stirring the solution for 20 s, and standing at room temperature for 20 h;
(b) washing the obtained product with methanol for 5 times, centrifuging and washing at 8000 rpm for 5 min;
(c) drying the obtained solid at 70 ℃ for 24h to obtain a ZIF-67 material;
(d) adding 200.0 mg ZIF-67 to the crucible and placing in a tube furnace at 1 deg.C for min-1Is raised to 700 ℃ and H is passed in2Keeping for 2h, and then gradually reducing to room temperature; finally obtaining black N-CNTs powder.
2) Preparation of ONCNTs material
(a) 100.0 mg of N-CNTs sample was suspended in 200.0 mL of 30% H2O2Stirring the solution at room temperature for 8 hours;
(b) and cooling the obtained suspension to room temperature, washing the suspension to be neutral by secondary water centrifugation (8000 rpm, 5 min), and drying the suspension at 70 ℃ for 24h to obtain the ONCNTs material.
3) Preparation of ONCNTs coating solid phase micro-extraction fiber
(a) Soaking one end (3 cm) of the stainless steel fiber in 70 deg.C hydrofluoric acid solution for 15min, ultrasonically cleaning with pure water to obtain stainless steel wire with rough surface, and drying;
b) placing the stainless steel fiber obtained in the step into a solution with the concentration of 2 mg mL-1And adjusting the pH value of the solution to 8.5 by using a Tris-HCl solution. The reaction was carried out at room temperature for 24 hours to obtain PDA coated stainless steel fibers;
(c) immersing the stainless steel wire coated with PDA in a vinyltrimethoxysilane solution, reacting for 12h at room temperature, mainly reacting with hydroxyl on the surface of the fiber coated with PDA, pulling out the fiber, and immediately putting the fiber into a 70 ℃ oven for 6h to complete a silanization reaction to obtain an amino modified stainless steel fiber;
(d) the amino modified fiber was inserted into a 0.5 wt% aqueous solution of ONCNTs in a water bath at 70 ℃ for 3 hours. Repeating the two operations (c) and (d) for 3 times to obtain the ONCNTs coated solid-phase micro-extraction fiber.
Example 2:
1) preparation of N-CNTs
(a)2.0 g of dimethylimidazole and 1.7 g of cobalt nitrate hexahydrate were dissolved in 40.0 mL of a mixture of methanol and ethanol (methanol/ethanol ratio 1:1 by volume). Magnetically stirring the solution for 20 s, and standing at room temperature for 20 h;
(b) washing the obtained product with methanol for 5 times, centrifuging and washing at 8000 rpm for 5 min;
(c) drying the obtained solid at 70 ℃ for 24h to obtain a ZIF-67 material;
(d) adding 200.0 mg ZIF-67 to the crucible and placing in a tube furnace at 1 deg.C for min-1Is raised to 700 ℃ and H is passed in2Keeping for 2h, and then gradually reducing to room temperature; finally obtaining black N-CNTs powder.
2) Preparation of ONCNTs material
(a) 100.0 mg of N-CNTs sample was suspended in 200.0 mL of 10 mol L-1Adding the mixture into HCl solution, and stirring the mixture for 6 hours at room temperature;
(b) and cooling the obtained suspension to room temperature, washing the suspension to be neutral by secondary water centrifugation (8000 rpm, 5 min), and drying the suspension at 70 ℃ for 24h to obtain the ONCNTs material.
3) Preparation of ONCNTs coating solid phase micro-extraction fiber
(a) Soaking one end (3 cm) of the stainless steel fiber in 70 deg.C hydrofluoric acid solution for 15min, ultrasonically cleaning with pure water to obtain stainless steel wire with rough surface, and drying;
b) placing the stainless steel fiber obtained in the step into a solution with the concentration of 2 mg mL-1And adjusting the pH value of the solution to 8.5 by using a Tris-HCl solution. The reaction was carried out at room temperature for 24 hours to obtain PDA coated stainless steel fibers;
(c) immersing the stainless steel wire coated with PDA in a vinyltrimethoxysilane solution, reacting for 12h at room temperature, mainly reacting with hydroxyl on the surface of the fiber coated with PDA, pulling out the fiber, and immediately putting the fiber into a 70 ℃ oven for 6h to complete a silanization reaction to obtain an amino modified stainless steel fiber;
(d) the amino modified fiber was inserted into a 0.5 wt% aqueous solution of ONCNTs in a water bath at 70 ℃ for 3 hours. Repeating the two operations (c) and (d) for 3 times to obtain the ONCNTs coated solid-phase micro-extraction fiber.
Example 3:
1) preparation of N-CNTs
(a)2.0 g of dimethylimidazole and 1.7 g of cobalt nitrate hexahydrate were dissolved in 40.0 mL of a mixture of methanol and ethanol (methanol/ethanol ratio 1:1 by volume). Magnetically stirring the solution for 20 s, and standing at room temperature for 20 h;
(b) washing the obtained product with methanol for 5 times, centrifuging and washing at 8000 rpm for 5 min;
(c) drying the obtained solid at 70 ℃ for 24h to obtain a ZIF-67 material;
(d) adding 200.0 mg ZIF-67 to the crucible and placing in a tube furnace at 1 deg.C for min-1Is raised to 700 ℃ and H is passed in2Keeping for 2h, and then gradually reducing to room temperature; finally obtaining black N-CNTs powder 2) preparation of ONCNTs material
(a) 100.0 mg of N-CNTs sample was suspended in 200.0 mL of 12 mol L-1Adding the mixture into HCl solution, and stirring the mixture for 6 hours at room temperature;
(b) and cooling the obtained suspension to room temperature, washing the suspension to be neutral by secondary water centrifugation (8000 rpm, 5 min), and drying the suspension at 70 ℃ for 24h to obtain the ONCNTs material.
3) Preparation of ONCNTs coating solid phase micro-extraction fiber
(a) Soaking one end (3 cm) of the stainless steel fiber in 70 deg.C hydrofluoric acid solution for 15min, ultrasonically cleaning with pure water to obtain stainless steel wire with rough surface, and drying;
b) placing the stainless steel fiber obtained in the step into a solution with the concentration of 2 mg mL-1And adjusting the pH value of the solution to 8.5 by using a Tris-HCl solution. The reaction was carried out at room temperature for 24 hours to obtain PDA coated stainless steel fibers;
(c) immersing the stainless steel wire coated with PDA in a 3-aminopropyltriethoxysilane solution, reacting for 12h at room temperature, mainly reacting with hydroxyl on the surface of the fiber coated with PDA, pulling out the fiber, and immediately putting the fiber into a 70 ℃ oven for 6h to complete a silanization reaction to obtain an amino modified stainless steel fiber;
(d) the amino modified fiber was inserted into a 0.5 wt% aqueous solution of ONCNTs in a water bath at 70 ℃ for 3 hours. Repeating the two operations (c) and (d) for 3 times to obtain the ONCNTs coated solid-phase micro-extraction fiber.
Examples of the applications
The ONCNTs coating solid phase micro-extraction fiber obtained in the example 1 is combined with GC-MS/MS to be applied to the detection of aromatic amine, and the specific steps are as follows: 20.0. mu.L of the aromatic amine mixed standard solution was added to a 25.0 mL serum bottle to prepare 20.0 mL of the solution to be tested. The prepared fiber was inserted into a serum bottle and placed in a thermostat water bath with a magnetic stirrer for extraction. Subsequently, the fibers were removed from the serum vial and inserted into the GC sample port for thermal desorption. The invention utilizes the SPME fiber pair coated with ONCNTs to extract aromatic amine, and optimizes a series of experimental conditions by combining with GC-MS/MS (gas chromatography-tandem mass spectrometry) (as shown in figure 3). The optimal extraction conditions were found to be: the extraction temperature is 40 ℃; extracting for 30 min; the resolving temperature is 270 ℃; resolution time, 10 min.
Claims (10)
1. The nitrogen oxide-doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on the chemical bonding method is characterized in that nitrogen-doped carbon nanotubes are further oxidized to obtain an electronegative carbon nano-adsorption material, and stainless steel fibers coated with ONCNTs are prepared through the chemical bonding method.
2. The method for preparing the nitrogen oxide doped carbon nanotube coating solid-phase microextraction fiber obtained based on the chemical bonding method as claimed in claim 1, wherein the surface of the nitrogen oxide doped carbon nanotube particle is negatively charged and a large number of carboxyl groups are introduced and coated on the surface of the stainless steel wire by a chemical bonding method; the method specifically comprises the following steps:
step S1 preparation of N-carbon material N-CNTs (carbon nanotubes) doped with N
Step S112.0 g of dimethyl imidazole and 1.7 g of cobalt nitrate hexahydrate are dissolved in 40.0 mL of a mixed solution of methanol and ethanol; magnetically stirring the solution for 20 s, and standing at room temperature for 20 h;
step S12 washing the obtained product with methanol for 5 times, centrifuging and washing at 8000 rpm for 5 min;
drying the solid obtained in the step S13 at 70 ℃ for 24h to obtain a ZIF-67 material;
step S14 adding 200.0 mg of ZIF-67 to a crucible, placing the crucible in a tube furnace, raising the temperature to 700 ℃, and introducing H2Keeping for 2h, and then gradually reducing to room temperature; finally obtaining black N-CNTs powder;
step S2 preparation of nitrogen oxide doped carbon nano tube ONCNTs material
Step S21, suspending 100.0 mg of the N-CNTs sample obtained in the step S1 in 200.0 mL of an oxidant solution, and stirring at room temperature;
cooling the suspension obtained in the step S22 to room temperature, then washing the suspension to be neutral by using secondary water in a centrifugal mode, and drying the suspension for 24 hours at the temperature of 70 ℃ to obtain an ONCNTs material;
step S3 preparation of ONCNTs coating solid phase micro-extraction fiber
Step S31, soaking one end 3cm of the stainless steel fiber in 70 ℃ hydrofluoric acid solution for 15min, then ultrasonically cleaning the stainless steel fiber with pure water to obtain a stainless steel wire with a rough surface, and drying the stainless steel wire for later use;
step S32 placing the stainless steel fiber obtained in the above step in a concentration of 2 mg mL-1Regulating the pH value of the solution to 8.5 by using a Tris-HCl solution; the reaction was carried out at room temperature for 24 hours to obtain polydopamine PDA coated stainless steel fibers;
step S33, immersing the stainless steel wire coated with PDA in a silane coupling agent, reacting for 12-24 h at room temperature, pulling out the fiber, and immediately putting the fiber in a 70 ℃ oven for 6h to complete the silanization reaction to obtain the amino modified stainless steel fiber;
step S34, inserting the amino modified fiber into 0.5 wt% ONCNTs water solution in water bath for reaction;
step S34 repeats the above two operation steps S33 and S343 times to obtain the solid-phase micro-extraction fiber of the ONCNTs coating.
3. The method according to claim 2, wherein the volume ratio of methanol to ethanol in step S11 is 1: 1.
4. The method according to claim 2, wherein the temperature rise rate of the tubular furnace in step S14 is 1 ℃ min-1The rate of (c).
5. The method according to claim 2, wherein the room-temperature stirring time in step S21 is 2 to 8 hours.
6. The method according to claim 2, wherein the oxidizer solution in step S21 includes 35wt% nitric acid, 10 mol L-1Hydrochloric acid, 30wt% H2O2One or more of them.
7. The method according to claim 2, wherein the centrifugation speed of step S22 is 8000 rpm, and the centrifugation time is 5 min.
8. The method according to claim 2, wherein the silane coupling reagent in step S33 comprises: one or more of vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltriethoxysilane and 3-aminopropyltriethoxysilane.
9. The method of claim 2, wherein the reaction conditions in the water bath in step S34 are as follows: the ONCNTs aqueous solution of 0.5 wt% was inserted in a water bath at 70 ℃ for 3 hours.
10. The application of the nitrogen oxide doped carbon nanotube coating solid-phase micro-extraction fiber obtained based on the chemical bonding method in the claim 1 in aromatic amine detection.
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| CN108435138A (en) * | 2018-04-04 | 2018-08-24 | 福州大学 | The solid-phase micro-extracting device prepared using the N that MOFs the is precursor synthesis carbon nanotube coatings adulterated and application |
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| CN109772268A (en) * | 2019-02-15 | 2019-05-21 | 河北大学 | A kind of solid-phase micro-extraction fibre and preparation method thereof |
| CN111135809A (en) * | 2020-02-18 | 2020-05-12 | 福州大学 | Preparation and application of self-assembled functionalized nitrogen-doped carbon nanocage solid-phase microextraction fiber |
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| CN108435138A (en) * | 2018-04-04 | 2018-08-24 | 福州大学 | The solid-phase micro-extracting device prepared using the N that MOFs the is precursor synthesis carbon nanotube coatings adulterated and application |
| CN109364901A (en) * | 2018-12-06 | 2019-02-22 | 福州大学 | The solid-phase micro-extraction coating fiber and application of a kind of carboxylated porous oxidation carbon-nitrogen nano-material and its preparation |
| CN109772268A (en) * | 2019-02-15 | 2019-05-21 | 河北大学 | A kind of solid-phase micro-extraction fibre and preparation method thereof |
| CN111135809A (en) * | 2020-02-18 | 2020-05-12 | 福州大学 | Preparation and application of self-assembled functionalized nitrogen-doped carbon nanocage solid-phase microextraction fiber |
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Application publication date: 20200925 |