CN114894870B - CuNC/graphene paper-based electrode for sensitively detecting phthalein sulfonamides, and preparation method and application thereof - Google Patents
CuNC/graphene paper-based electrode for sensitively detecting phthalein sulfonamides, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- GSLUMIUEZQSUQS-UHFFFAOYSA-N ac1ne2r4 Chemical compound [Cu+2].[N-]1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)[N-]3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 GSLUMIUEZQSUQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229940124530 sulfonamide Drugs 0.000 title claims abstract description 7
- 150000003456 sulfonamides Chemical class 0.000 title abstract description 4
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 CuNC modified graphene Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 235000013305 food Nutrition 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002390 adhesive tape Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
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- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
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- 238000000835 electrochemical detection Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 229960002989 glutamic acid Drugs 0.000 claims description 3
- 238000010147 laser engraving Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000011896 sensitive detection Methods 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 5
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- 238000011895 specific detection Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
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- 238000009360 aquaculture Methods 0.000 description 1
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- 239000012490 blank solution Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 210000000777 hematopoietic system Anatomy 0.000 description 1
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
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Abstract
The invention relates to the field of electrochemical sensors, and particularly discloses a CuNC/graphene paper-based electrode for sensitively detecting phthalein sulfonamides, a preparation method and application thereof, wherein the modified electrode is a CuNC modified graphene paper-based electrode with high electrochemical activity. The invention adopts a graphene paper-based electrode modified by a high electrochemical activity CuNC material as a modified electrode for the first time, and provides a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide, and a preparation method and application thereof; the modified electrode prepared by the method has higher selectivity and sensitivity to the phthalosulfonamide, the linear range is 1-70 mu M, and the detection limit is 0.26 mu M; compared with other detection methods, the modified electrode has the advantages of small volume, low cost, rapidness, good stability and suitability for field detection.
Description
Technical Field
The invention relates to the field of electroanalytical chemistry and electrochemical sensors, in particular to a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide, and a preparation method and application thereof.
Background
The thalenesulfonamide is a sulfonamide, has the advantages of broad-spectrum antibacterial activity, stable property, low price, convenient use and the like, is widely applied to the fields of animal feed, aquaculture and the like, and is extremely easy to cause residues in animal bodies when being used excessively. If animal-derived food with exceeding residue of sulfanilamide medicines is taken for a long time, various toxic effects such as urinary system damage, hematopoietic system dysfunction, allergy, cancer and the like can be directly or indirectly generated on human body. Common methods for measuring the phthalosulfonamide include GC-MS, GC, LC-MS, HPLC, SFC and the like, but the methods are relatively complicated in operation, expensive in instrument, difficult to miniaturize and complex in sample pretreatment.
The electrochemical analysis method has the characteristics of rapidness, high efficiency, sensitivity, simplicity, convenience, strong anti-interference capability, environmental friendliness and the like. It is necessary to study a new method for sensitive detection of phthalosulfonamide.
The CuNC composite material has large specific surface area, can enhance the enrichment amount of the thalenesulfonamide in an electrochemical detection medium, improve the measurement sensitivity, and can also effectively accelerate the electron transfer and improve the electrochemical response signal.
Therefore, the method for realizing the sensitive detection of the phthalosulfamide by using the CuNC/graphene paper-based electrode as a sensing interface is a problem worthy of research.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide, and a preparation method and application thereof; the method established by the invention can effectively reduce the interference of complex matrix components, and is successfully applied to the measurement of the thalenesulfonamide in various animal-derived foods, and the detection limit of the thalenesulfonamide is 0.26 mu M.
The purpose of the invention is realized in the following way:
the preparation method of the CuNC/graphene paper-based electrode for sensitively detecting the phthalosulfamide comprises the following steps of:
step 1, synthesizing CuNC:
1.160 g of 1,3, 5-benzene tricarboxylic acid is dissolved in the mixed solution of 450 mL water and 50 mL ethanol to obtain solution 1; copper acetate monohydrate 2.092 g and 0.771 g of L-glutamic acid are dissolved in 500: 500 mL water to obtain solution 2; solution 1 was added to solution 2 and stirred at room temperature for 2 h, the precipitate was collected after filtration, washed well with water and dried under vacuum at 40 ℃; mixing 10. 10 mg of the product with 1.00 g dicyandiamide in a mortar, and grinding 1 h to obtain a uniform precursor; placing the precursor into a tube furnace, and calcining 3h in an argon atmosphere at a speed of 3 ℃/min to 800 ℃; after the product is cooled to room temperature, the product is placed in 5 wt percent hydrochloric acid solution for soaking 4 h to remove metal residues, thus obtaining a product CuNC;
step 2, preparation of graphene:
2.5, g graphite powder is weighed and dispersed in 500 mL of N-methylpyrrolidone solution, ultrasonic treatment is carried out for 6 h, standing is carried out for 2 days, and the upper layer graphene solution is collected for standby; uniformly mixing 10 mL graphene and 300 mL water for preparing a graphene paper-based electrode;
step 3, a graphene paper-based electrode preparation method comprises the following steps:
respectively soaking a polyvinylidene fluoride PVDF filter membrane in ethanol and water for 1 h, attaching a PVC adhesive tape template obtained by laser engraving on the surface of the polyvinylidene fluoride PVDF filter membrane, placing the PVC adhesive tape template on a filter device, adding the graphene solution obtained in the step 2 into a filter cup, and continuously adding a mixed solution of ethanol and water into the filter cup after the graphene solution is filtered so as to remove redundant N-methylpyrrolidone; after the filtration is finished, the graphene paper-based electrode is dried in vacuum for 3 hours at the temperature of 30 ℃; cutting the three electrode areas from the electrode array on the PVDF film for electrochemical testing;
step 4, preparing a CuNC/graphene paper-based electrode:
dispersing CuNC in water to prepare a dispersion liquid of 0.5 mg/mL, taking 3 mu L of the dispersion liquid, dripping the dispersion liquid in a working electrode area, and drying a paper electrode in a drying oven at 50 ℃ to obtain a CuNC/graphene paper-based electrode;
a three-electrode system with a CuNC/graphene paper-based electrode as a working electrode is adopted for subsequent electrochemical detection, and the method is particularly applied to detection of the thalenesulfonamide in animal-derived foods;
the specific detection conditions and means are as follows:
HAc-NaAc buffer solution with pH of 3.8 is used as a supporting electrolyte for measuring the phthalosulfamide; when DPV is measured, the enrichment potential is 0.5V, the enrichment time is 20 min, the potential range is 0.5-1.1V, the amplitude is 50 mV, the pulse width is 0.2 s, and the pulse period is 0.5 s; taking a CuNC/graphene paper-based electrode as a working electrode, placing a three-electrode system in an HAc-NaAc buffer solution with the pH of 3.8, setting the enrichment time to be 20 min and the enrichment potential to be 0.5V, and recording DPV curves of 28 mu M of phthalosulfamide on the graphene paper-based electrode and the CuNC/graphene paper-based electrode; collecting DPV curves of the phthalocyanine sulfonamides with different concentrations on a CuNC/graphene paper-based electrode; taking several animal-derived foods as examples to examine the practical application value of the CuNC/graphene paper-based electrode, and detecting and analyzing the thalenesulfonamide in the animal-derived food samples.
Has the positive beneficial effects that: the invention adopts a graphene paper-based electrode modified by a high electrochemical activity CuNC material as a modified electrode for the first time, and provides a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide, and a preparation method and application thereof; the modified electrode prepared by the method has higher selectivity and sensitivity to the phthalosulfonamide, the linear range is 1-70 mu M, and the detection limit is 0.26 mu M; compared with other detection methods, the modified electrode has the advantages of small volume, low cost, rapidness, good stability and suitability for field detection.
Drawings
FIG. 1 is a photograph of a graphene paper-based electrode;
FIG. 2 is a schematic diagram of a graphene paper-based electrode;
FIG. 3 is an SEM image of PVDF filter (A) and graphene paper-based electrode (B);
FIG. 4 is an SEM image of CuNC;
FIG. 5 is a graph of DPV curves of 28. Mu.M of phthalocyanine-sulfonic acid amide on a graphene paper-based electrode (a) and a CuNC/graphene paper-based electrode (b) in a pH 3.8 HAc-NaAc solution, curve c being the DPV behavior of the CuNC/graphene paper-based electrode in a blank solution;
FIG. 6 shows DPV curves of various concentrations of thalenesulfonamide in pH 3.8 HAc-NaAc solution on CuNC/graphene paper-based electrode, interpolated fromI p And (3) withcIs a linear relationship of (c).
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments.
Examples
The preparation method of the CuNC/graphene paper-based electrode for sensitively detecting the phthalosulfamide comprises the following steps of:
step 1, synthesizing CuNC:
1.160 g of 1,3, 5-benzene tricarboxylic acid is dissolved in the mixed solution of 450 mL water and 50 mL ethanol to obtain solution 1; copper acetate monohydrate 2.092 g and 0.771 g of L-glutamic acid are dissolved in 500: 500 mL water to obtain solution 2; solution 1 was added to solution 2 and stirred at room temperature for 2 h, and the precipitate was collected after filtration, washed well with water and dried under vacuum at 40 ℃. 10 mg of the product was mixed with 1.00 g dicyandiamide in a mortar and milled 1 h to give a homogeneous precursor. Placing the precursor into a tube furnace, and calcining 3h in an argon atmosphere at a speed of 3 ℃/min to 800 ℃; after the product cooled to room temperature, it was immersed in 5 wt% hydrochloric acid solution for 4: 4 h to remove metal residues to obtain a product CuNC as shown in FIG. 4.
Step 2, preparation of graphene:
2.5 g g graphite powder is weighed and dispersed in 500 mL of N-methylpyrrolidone solution, ultrasonic treatment is carried out for 6 h, the mixture is kept stand for 2 days, and the upper layer graphene solution is collected for standby. Uniformly mixing 10 mL graphene and 300 mL water for preparing a graphene paper-based electrode;
step 3, a graphene paper-based electrode preparation method comprises the following steps:
respectively soaking the polyvinylidene fluoride PVDF filter membrane in ethanol and water for 1 h to obtain a PVDF filter membrane with the surface morphology shown in figure 3A; and then, attaching a PVC adhesive tape template obtained through laser engraving on the surface of the PVC adhesive tape template, placing the PVC adhesive tape template on a filtering device, adding the graphene solution obtained in the step 2 into a filter bowl, and continuously adding a mixed solution of ethanol and water into the filter bowl after the graphene solution is filtered so as to remove redundant N-methylpyrrolidone. After the filtration is finished, the graphene paper-based electrode is dried in vacuum at 30 ℃ for 3h, so that the graphene paper-based electrode shown in figure 1 is obtained; cutting the three electrode areas from the electrode array on the PVDF film respectively to obtain electrodes shown in figure 2, wherein the surface morphology of the electrodes is shown in figure 3B;
step 4, preparing a CuNC/graphene paper-based electrode:
dispersing CuNC in water to prepare a dispersion liquid of 0.5 mg/mL, taking 3 mu L of the dispersion liquid, dripping the dispersion liquid in a working electrode area, and drying a paper electrode in a drying oven at 50 ℃ to obtain a CuNC/graphene paper-based electrode;
a three-electrode system with a CuNC/graphene paper-based electrode as a working electrode is adopted for subsequent electrochemical detection, and the method is particularly applied to detection of the thalenesulfonamide in animal-derived foods;
the specific detection conditions and means are as follows:
HAc-NaAc buffer solution with pH of 3.8 is used as a supporting electrolyte for determining the phthalenesulfonamide. When DPV is measured, the enrichment potential is 0.5-V, the enrichment time is 20 min, the potential range is 0.5-1.1V, the amplitude is 50 mV, the pulse width is 0.2-s, and the pulse period is 0.5-s. Taking a CuNC/graphene paper-based electrode as a working electrode, placing a three-electrode system in HAc-NaAc buffer solution with pH of 3.8, setting enrichment time to be 20 min and enrichment potential to be 0.5 and V, and recording DPV curves of 28 mu M of phthalosulfamide on the graphene paper-based electrode and the CuNC/graphene paper-based electrode (shown in figure 5); collecting DPV curves (shown in figure 6) of the phthalocyanine-sulfonic acid acetamides with different concentrations on the CuNC/graphene paper-based electrode; taking several animal-derived foods as examples to examine the practical application value of the CuNC/graphene paper-based electrode, and detecting and analyzing the thalenesulfonamide in the animal-derived food samples.
Practical application: taking several animal-derived food samples as examples to examine the application value of the CuNC/graphene paper-based electrode. The CuNC/graphene paper-based electrode is used for detecting an actual sample, and the concentration of the phthalein sulfoamide contained in the sample is calculated by an experiment and a labeled recovery method, so that the labeled recovery experiment result of the phthalein sulfoamide in the animal-derived food is measured as shown in the following table 1:
TABLE 1
Each sample was measured 10 times in parallel, with RSD below 3.5%, indicating that the CuNC/graphene paper-based electrode stability was good.
The invention adopts a graphene paper-based electrode modified by a high electrochemical activity CuNC material as a modified electrode for the first time, and provides a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide, and a preparation method and application thereof; the modified electrode prepared by the method has higher selectivity and sensitivity to the phthalosulfonamide, the linear range is 1-70 mu M, and the detection limit is 0.26 mu M; compared with other detection methods, the modified electrode has the advantages of small volume, low cost, rapidness, good stability and suitability for field detection.
The foregoing description of the preferred embodiments of the invention is presented only to illustrate and explain the invention and is not intended to be limiting. Modifications and equivalents may be made to the arrangement shown in the above-described embodiments without departing from the spirit and principles of the invention, and any such modifications or equivalents are intended to be covered by this disclosure.
Claims (2)
1. The application of a CuNC/graphene paper-based electrode for sensitively detecting phthalosulfamide is characterized in that: the electrode is a graphene paper-based electrode modified by a CuNC compound; the preparation method of the CuNC compound modified graphene paper-based electrode is characterized by comprising the following specific steps of:
step 1, synthesizing CuNC:
1.160 g of 1,3, 5-benzene tricarboxylic acid is dissolved in the mixed solution of 450 mL water and 50 mL ethanol to obtain solution 1; copper acetate monohydrate 2.092 g and 0.771 g of L-glutamic acid are dissolved in 500: 500 mL water to obtain solution 2; solution 1 was added to solution 2 and stirred at room temperature for 2 h, the precipitate was collected after filtration, washed well with water and dried under vacuum at 40 ℃; mixing the 10 mg product with 1.00 g dicyandiamide in a mortar, and grinding 1 h to obtain a uniform precursor;
placing the precursor into a tube furnace, and calcining 3h at a rate of 3 ℃ per minute to 800 ℃ in an argon atmosphere; after the product is cooled to room temperature, the product is placed in 5 wt percent hydrochloric acid solution for soaking 4 h to remove metal residues, thus obtaining a product CuNC;
step 2, preparation of graphene:
2.5, g graphite powder is weighed and dispersed in 500 mL of N-methylpyrrolidone solution, ultrasonic treatment is carried out for 6 h, standing is carried out for 2 days, and the upper layer graphene solution is collected for standby; uniformly mixing 10 mL graphene and 300 mL water for preparing a graphene paper-based electrode;
step 3, a graphene paper-based electrode preparation method comprises the following steps:
respectively soaking a polyvinylidene fluoride PVDF filter membrane in ethanol and water for 1 h, attaching a PVC adhesive tape template obtained by laser engraving on the surface of the polyvinylidene fluoride PVDF filter membrane, placing the PVC adhesive tape template on a filter device, adding the graphene solution obtained in the step 2 into a filter cup, and continuously adding a mixed solution of ethanol and water into the filter cup after the graphene solution is filtered so as to remove redundant N-methylpyrrolidone; after the filtration is finished, the graphene paper-based electrode is dried in vacuum at 30 ℃ for 3h; cutting the three electrode areas from the electrode array on the PVDF film for electrochemical testing;
step 4, preparing a CuNC/graphene paper-based electrode:
dispersing CuNC in water to prepare a dispersion liquid of 0.5 mg/mL, taking 3 mu L of the dispersion liquid, dripping the dispersion liquid in a working electrode area, and putting a paper electrode in a 50 ℃ oven for drying to obtain the CuNC/graphene paper-based electrode;
the three-electrode system with the CuNC/graphene paper-based electrode as a working electrode is adopted for subsequent electrochemical detection, and the method is particularly applied to detection of the thalenesulfonamide in animal-derived foods.
2. The CuNC/graphene paper-based electrode application for the sensitive detection of phthalosulfonamide according to claim 1, characterized in that:
HAc-NaAc buffer solution with pH of 3.8 is used as a supporting electrolyte for measuring the phthalosulfamide; taking a CuNC/graphene paper-based electrode as a working electrode, placing a three-electrode system in an HAc-NaAc buffer solution with the pH of 3.8, setting the enrichment time to be 20 min and the enrichment potential to be 0.5V, and recording DPV curves of 28 mu M of phthalosulfamide on the graphene paper-based electrode and the CuNC/graphene paper-based electrode; collecting DPV curves of the phthalocyanine sulfonamides with different concentrations on a CuNC/graphene paper-based electrode; taking several animal-derived foods as examples to examine the practical application value of the CuNC/graphene paper-based electrode, and detecting and analyzing the thalenesulfonamide in the animal-derived food samples.
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| CN111974435A (en) * | 2020-08-26 | 2020-11-24 | 太原理工大学 | Preparation method and application of high-stability Cu/N-doped carbon nanosheet catalyst |
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