CN115201292B - CMWNT-Fc-H for detecting bisphenol A 5 PMo 10 V 2 O 40 Preparation of/CHIT composite electrode material - Google Patents
CMWNT-Fc-H for detecting bisphenol A 5 PMo 10 V 2 O 40 Preparation of/CHIT composite electrode material Download PDFInfo
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007772 electrode material Substances 0.000 title claims description 28
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical class O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 22
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The application discloses a CMWNT-Fc-PMo 10 V 2 Preparation and application of a composite material belong to the technical field of composite materials and modified electrodes. The technical proposal is as follows: the preparation method of the composite material comprises 1) dispersing carboxylated multi-wall carbon nanotubes in a mixed solvent of ethanol and water, and performing ultrasonic treatment to form black suspension; 2) Sequentially adding ferrocene and vanadium-substituted phosphomolybdic acid, performing ultrasonic treatment, filtering out precipitate, and drying overnight to obtain the composite material. 3) The negatively charged composite material is fixed on the chitosan matrix through electrostatic adsorption, so that the problem that ferrocene-vanadium-substituted phosphomolybdic acid cannot be stably fixed on the surface of an electrode is solved. The composite material prepared by the application has larger surface area, good conductivity, fast electron transfer rate, lower oxidation potential and excellent oxidation-reduction performance, and shows excellent signal cooperative amplification when being applied to the surface of an electrode by using electrochemical detection of bisphenol A with CHIT.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a CMWNT-Fc-H 5 PMo 10 V 2 O 40 A/CHIT composite electrode material and its application in bisphenol A detection.
Background
Bisphenol A (bpa) is a monomer or additive commonly used in the plastics industry and can cause impaired brain development, sexual differentiation, behavior and immune function. Bisphenol A has two electroactive phenolic hydroxyl groups and is an electrochemically active substance, so that the electrochemical method facilitates the detection of bisphenol A. In recent years, many electrochemically modified electrodes have been developed for the determination of trace amounts of bisphenol a with satisfactory results, but it remains a challenge to explore highly active electrode materials and methods.
Ferrocene (Fc) has been the leading edge of chemical research, giving it many excellent properties due to the strong interaction between the iron center and the cyclopentadienyl ring. More importantly, ferrocene is one of the most potential electroactive compounds for electrochemical sensing due to the fast electron transfer rate and low oxidation potential. Recently, ferrocene was used as an electrochemical medium to detect bisphenol A. However, the fixation on the electrode surface encounters some difficulties due to the low solubility and poor adsorptivity of ferrocene. Polyoxometallates (POMs) are a class of transition metal oxide clusters with a rich structural diversity and excellent redox properties, and have found wide application in electrochemical sensors. Chitosan (CHIT) is a natural cationic biopolymer, and has been widely used in the matrix structure of electrochemical sensors due to its excellent water permeability, non-toxicity, mechanical strength, biocompatibility, adhesion, film forming properties, etc. Based on the advantages of ferrocene, polyoxometallate and chitosan and the respective disadvantages, a ferrocene, polyoxometallate and chitosan composite material for bisphenol A detection needs to be developed.
Disclosure of Invention
The application aims to solve the technical problems that: overcomes the defects of the prior art and provides a CMWNT-Fc-H 5 PMo 10 V 2 O 40 The composite material takes carboxylated multiwall carbon nanotube as a carrier, and the carboxylated multiwall carbon nanotube-ferrocene-vanadium-substituted phosphomolybdic acid composite material is synthesized for the first time through the interaction of ferrocene-vanadium-substituted phosphomolybdic acid, and has larger surface area, good conductivity, fast electron transfer rate, lower oxidation potential and good oxidation-reduction performance, and simultaneously utilizes electrostatic attraction to carry out negatively charged CMWNT-Fc-H 5 PMo 10 V 2 O 40 The ferrocene-vanadium substituted phosphomolybdic acid-chitosan composite electrode material which can be firmly fixed on the surface of the electrode is prepared by fixing the ferrocene-vanadium substituted phosphomolybdic acid-chitosan composite electrode material on a cationic chitosan substrate with film forming capability, and the material has excellent performance in the aspect of electrochemical detection of bisphenol A due to the synergistic effect between components.
The technical scheme of the application is as follows:
in a first aspect, a CMWNT-Fc-H is disclosed 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material comprises the following steps:
1) Carboxylating the multiwall carbon nanotubes, dispersing the carboxylated multiwall carbon nanotubes in a mixed solvent, and performing ultrasonic treatment to form a black suspension;
2) Sequentially adding ferrocene and vanadium-substituted phosphomolybdic acid into the black suspension, performing ultrasonic treatment, filtering out precipitate, and drying the precipitate overnight to obtain a carboxylated multiwall carbon nanotube-ferrocene-vanadium-substituted phosphomolybdic acid composite material CMWNT-Fc-H 5 PMo 10 V 2 O 40 。
3) Negatively charged CMWNT-Fc-H by electrostatic attraction 5 PMo 10 V 2 O 40 Immobilized on a cationic chitosan matrix with film forming capability to prepare ferrocene-vanadium substituted phosphomolybdic acid-chitosan (CMWNT-Fc-H) capable of being firmly fixed on the surface of an electrode 5 PMo 10 V 2 O 40 /CHIT) composite electrode material.
Preferably, carboxylated multiwall carbon nanotubes: ferrocene: the mass ratio of the vanadium-substituted phosphomolybdic acid is 1-2:1-2:1-2.
Preferably, the solvent of step 1) is one or a mixture of two of ethanol or water.
Preferably, the solvent in the step 1) is a mixture of ethanol and water, and the volume ratio of the ethanol to the water is 4:1-3:2. Preferably, the ultrasound time in step 1) is 25-45min.
Preferably, the ultrasound time in step 2) is 5-7 hours and the drying temperature is 55-80 ℃.
Preferably, the carboxylated multiwall carbon nanotubes in step 1) are added in an amount of 60-83 mg, the absolute ethanol is added in an amount of 50-66 mL, the ferrocene is added in step 2) in an amount of 30-150mg, and the vanadium-substituted phosphomolybdic acid is added in an amount of 30-150mg.
In a second aspect, CMWNT-Fc-H is disclosed 5 PMo 10 V 2 O 40 Composite electrode material of CHIT in bisphenol A detectionApplication.
Compared with the prior art, the application has the following beneficial effects:
1. CMWNT-Fc-H prepared by the present application 5 PMo 10 V 2 O 40 The CHIT composite electrode material has larger surface area, good conductivity, fast electron transfer rate, lower oxidation potential and excellent oxidation-reduction performance, and shows excellent performance in electrochemical detection of bisphenol A due to the synergistic effect between components;
2.CMWNT-Fc- H 5 PMo 10 V 2 O 40 the/CHIT composite electrode material combines ferrocene (Fc) with high electron transfer rate, low oxidation potential and vanadium-substituted phosphomolybdic acid (H) 5 PMo 10 V 2 O 40 ) The oxidation property is excellent, the negative charge is extremely high, and the immobilized carrier can be better, and the performance is excellent;
3. the carboxylated multiwall carbon nanotube-ferrocene-vanadium-substituted phosphomolybdic acid compound with negative charges is fixed on a cationic chitosan matrix with film forming capability for the first time by utilizing electrostatic attraction, so that the problem that the ferrocene-vanadium-substituted phosphomolybdic acid cannot be stably fixed on the surface of an electrode is solved.
4.CMWNT-Fc- H 5 PMo 10 V 2 O 40 the/CHIT composite electrode material is applied to the detection of bisphenol A in milk samples, and the recovery rate is higher.
Drawings
Fig. 1 is an SEM image (a) and an elemental mapping image (b) of the composite material prepared in example 1 of the present application.
FIG. 2 is a composite CMWNT-Fc-H prepared in example 1 of the present application 5 PMo 10 V 2 O 40 And H 5 PMo 10 V 2 O 40 PXRD pattern of CMWNT and Fc.
FIG. 3 is a composite CMWNT-Fc-H prepared in example 1 of the present application 5 PMo 10 V 2 O 40 XPS full scan (A) and C1s (B), mo3D (C), fe2P (D), V2P (E) and P2P (F) high resolution spectrograms of the composite material.
FIG. 4 is a schematic diagram of a preferred embodiment of the present applicationCMWNT-Fc-H prepared in example 3 of the present application 5 PMo 10 V 2 O 40 Composite electrode of/CHIT, bare electrode, fc and H 5 PMo 10 V 2 O 40 And CMWNT in 5mM [ Fe (CN) 6 containing 0.1 MKCl] 3-/4- Cyclic voltammogram in solution.
FIG. 5 is a CMWNT-Fc-H prepared in example 3 of the present application 5 PMo 10 V 2 O 40 Composite electrode of/CHIT, bare electrode, fc and H 5 PMo 10 V 2 O 40 And DPV curve of CMWNT in 0.1M PBS (pH 7.0) containing 20 μm bisphenol A.
FIG. 6A is a schematic illustration of CMWNT-Fc-H prepared in example 3 of the present application 5 PMo 10 V 2 O 40 DPV curve of the composite electrode of CHIT under the action of bisphenol A with different concentrations, B is a graph of oxidation peak current and bisphenol A concentration.
FIG. 7 is a graph showing the optimum ratio (A) of example 4 and the acidity value in a solution system of 20. Mu.M bisphenol A in 0.1M PBS (pH 7.0) (B).
Detailed Description
Example 1
This example provides a CMWNT-Fc-H 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material comprises the following steps:
1) Synthesis of carboxylated multiwall carbon nanotubes (CMWNT): 5% MWCNT (300 mg, then MWCNT actually takes 6g of MWCNT) is placed in a beaker, 15 mL 70% HNO is added 3 After 45mL of 98% H was added 2 SO 4 Ultrasonic dispersing for 24h, controlling the ultrasonic temperature at 35-40 ℃, adding distilled water with the amount of 5 times for dilution, centrifuging, washing to be neutral, and drying at 80 ℃ to obtain the carboxylated multiwall carbon nanotube.
2) Vanadium-substituted phosphomolybdic acid (H) 5 PMo 10 V 2 O 40 ) Is synthesized by the following steps: moO 16.59, g and 2.10, g were weighed out separately 3 And V 2 O 5 Dissolved in 250 mL distilled water. Because of MoO 3 And V 2 O 5 Is insoluble in water, and the solution is promoted to orange red. Stirring the solution vigorously, heating and refluxing to 1After 10 min at 20℃the solution turned gradually creamy yellow, followed by slow dropwise addition of 1.33g (slightly excess phosphoric acid; about 10 drops per minute) of 85% phosphoric acid (during actual operation), the solution turned lemon yellow, after the dropwise addition the solution turned yolk and continued to heat and maintain 48. 48 h at this temperature. During this process, the cloudy solution gradually changed to a clear, transparent, clear red solution; standing and precipitating, wherein the upper layer is a haematochrome clear liquid, the lower layer is an unreacted complete orange solid powder, filtering, placing a beaker containing the haematochrome clear liquid on a constant-temperature magnetic stirrer, and slowly evaporating water at a low rotating speed at a reaction temperature of 85 ℃ to obtain an orange solid; finally, the solid is dissolved in a small amount of distilled water, slowly separated out at 0 ℃ and recrystallized for 3 times to obtain the vanadium-substituted phosphomolybdic acid.
3) Dispersing 70mg carboxylated multi-wall carbon nanotubes in a mixed solvent of 60 mL ethanol and water, and performing ultrasonic treatment for 30 minutes to form a uniform black suspension;
4) Sequentially adding 70mg of ferrocene and 70mg of vanadium-substituted phosphomolybdic acid into the black suspension, carrying out ultrasonic treatment for 6 hours, filtering out a precipitate, and drying the precipitate at 60 ℃ overnight to obtain a carboxylated multiwall carbon nanotube-ferrocene-vanadium-substituted phosphomolybdic acid composite material CMWNT-Fc-H 5 PMo 10 V 2 O 40 。
CMWNT-Fc-H was examined using a scanning electron microscope 5 PMo 10 V 2 O 40 The morphology of the composite material is characterized, as shown in fig. 1a, it can be seen from fig. 1a that, unlike the three-dimensional interconnected fibrous network structure of the original carbon nanotubes, rich points are uniformly distributed on the surface of the nanotubes in the composite, and the ferrocene and vanadium-substituted phosphomolybdic acid are fixed on the carboxylated multiwall carbon nanotubes by combining element mapping images.
CMWNT-Fc-H using X-ray powder diffraction 5 PMo 10 V 2 O 40 The composite was further characterized, as shown in fig. 2, and it can be seen from fig. 2 that carboxylated multiwall carbon nanotubes have a strong peak at 26.4 °, which is probably due to the characteristic (002) crystal plane of the carbon-based material. Pure vanadium-substituted phosphomolybdic acid is at 8.9 DEG, 18.6 DEG,The strong diffraction peaks exist at 26.2 degrees, 27.9 degrees and 29.1 degrees, and the ferrocene exists at 15.2 degrees, 17.5 degrees, 18.4 degrees, 18.9 degrees and 20.3 degrees, so that the diffraction peaks are consistent with the results reported in the literature, and all diffraction peaks consist of carboxylated multiwall carbon nanotubes, ferrocene and vanadium-substituted phosphomolybdic acid, thus indicating the successful preparation of the composite material.
CMWNT-Fc-H was determined by XPS 5 PMo 10 V 2 O 40 The elemental composition and chemical state of the composite material, as shown in FIG. 3, from which it can be seen that XPS spectra further reveal the presence of the composite from the elements C, mo, fe, V, P and O. In the C1s spectrum, successful combinations of carboxylated multiwall carbon nanotubes were verified at 284.5,285.4,287.8 and 289.8ev binding energies corresponding to C-C, C-O, c=o, O-c=o, respectively. Mo (Mo) 6 + 3d5/2 and Mo 6 + Typical peaks occur at about 232.8 ev and 235.9 ev for 3d3/2, and 517.3 ev and 524.7 ev for V2p, respectively. The two single peaks at 710.1 and 722.8 ev correspond to Fe2p3/2 and Fe2p1/2, respectively, all of which indicate CMWNT-Fc-H 5 PMo 10 V 2 O 40 The preparation of the composite material was successful.
Example 2
Example 2 CMWNT-Fc-H prepared by using example 5 PMo 10 V 2 O 40 Preparation of multiwall carbon nanotube-ferrocene-vanadium substituted phosphomolybdic acid-chitosan (CMWNT-Fc-H) from composite material 5 PMo 10 V 2 O 40 (CHIT) composite electrode material, the specific preparation method is as follows:
the glassy carbon electrode was polished on a wet polishing cloth with 1.0, 0.3 and 0.05 μm alumina slurries, and then ultrasonically cleaned with double distilled water and ethanol. Simultaneously, 100mg of chitosan was dispersed in 100mL of 1.0% acetic acid solution, and stirred to a uniform paste. Then, 10mg of carboxylated multi-wall carbon nanotube-ferrocene-vanadium substituted phosphomolybdic acid compound is added into 10mL of chitosan solution under the condition of intense stirring for 15-25min, and stirring is continued for 15-25min to form uniform suspension. Then the obtained suspension (5 mu L) was applied to the surface of a polished glassy carbon electrode, and naturally dried to obtain CMWNT-Fc-H 5 PMo 10 V 2 O 40 A CHIT composite electrode.
Example 3
Example 3 was a CMWNT-Fc-H prepared using example 2 5 PMo 10 V 2 O 40 The detection of bisphenol A by the CHIT composite electrode is studied by Differential Pulse Voltammetry (DPV), and the method is concretely as follows:
the electrochemical parameters are as follows: pulse amplitude 50mv, pulse width 40ms, step potential 4mv, sampling width 0.0167, voltage range 0.25-0.95. 0.95 v.
First by [ Fe (CN) 6 ] 3-/4- CMWNT-Fc-H was studied as a probe 5 PMo 10 V 2 O 40 Electron transfer characteristics of the composite electrode of/CHIT at 5.0 mM [ Fe (CN) 6 ] 3- Middle modified bare electrode, fc, H 5 PMo 10 V 2 O 40 CMWNT (bare electrode is commercially available in common structure, fc, H 5 PMo 10 V 2 O 40 And CMWNT and preparation method and-Fc-H 5 PMo 10 V 2 O 40 Identical electrodes) and MWNT-Fc-H 5 PMo 10 V 2 O 40 The cyclic voltammogram of the electrode is shown in FIG. 4, and it can be seen from FIG. 4 that CMWNT-Fc-H 5 PMo 10 V 2 O 40 The maximum current signal and minimum peak-to-peak distance of the/CHIT composite electrode indicate that CMWNT-Fc-H 5 PMo 10 V 2 O 40 the/CHIT composite electrode has the fastest electron transfer capability and the best conductivity. This phenomenon may benefit from the rapid electron transfer of Fc, as well as the large specific surface area and good conductivity of CMWNT.
Example 4
CMWNT-Fc-H prepared by example 1 5 PMo 10 V 2 O 40 Composite electrode material of/CHIT, research system acidity value pair CMWNT-Fc-H 5 PMo 10 V 2 O 40 The electrochemical response of the composite electrode material of/CHIT to bisphenol A is as follows:
the CV curves of bisphenol a were measured using cyclic voltammetry in a 0.1M PBS (pH 7.0) solution containing 20 μm bisphenol a, using composite electrodes of different proportions, and the pH of the PBS was varied to obtain the optimal proportions and acidity values of the system, as shown in figure 7,
experimental results show that in the pH range of 6.0-8.0, from pH 6.0-7.0, the oxidation peak current of bisphenol A gradually increases with increasing pH value and reaches the maximum value at pH value of 7.0, and then the oxidation peak current of bisphenol A becomes smaller with further increasing pH value, so that the pH value of the system is kept at 7.0 in the whole experimental process.
CMWNT-Fc-H was studied by the DPV method in a phosphate buffer solution at 0.1M and pH7.0 5 PMo 10 V 2 O 40 Electrochemical behavior of the sensor on bisphenol A as shown in FIG. 5, FIG. 5 shows bare electrode, fc, H in 0.1M PBS (pH 7.0) containing 20 μm bisphenol A 5 PMo 10 V 2 O 40 CMWNT and CMWNT-Fc-H 5 PMo 10 V 2 O 40 The DPV curve of the electrode was modified. Compared with other electrode materials, CMWNT-Fc-H is adopted 5 PMo 10 V 2 O 40 The sensor obtains maximum current signal, and the peak current is several times higher than other sensors, which indicates that CMWNT-Fc-H 5 PMo 10 V 2 O 40 Structural superiority of/CHIT composite electrode material, fc and H 5 PMo 10 V 2 O 40 Synergistic effects between CMWNT, it is notable that Fc groups also play an important role in facilitating electron conduction by bisphenol a oxidation.
To evaluate CMWNT-Fc-H 5 PMo 10 V 2 O 40 Electrochemical properties of the/CHIT composite electrode material, under optimal conditions, bisphenol A at different concentrations was recorded in CMWNT-Fc-H 5 PMo 10 V 2 O 40 DPV curve on/CHIT composite electrode material, as shown in FIG. 6, FIG. 6A shows CMWNT-Fc-H at 0.1M PBS (pH=7.0) for varying concentrations of bisphenol A 5 PMo 10 V 2 O 40 The current response of the sensor shows that the oxidation peak current increases with the increase of bisphenol A concentration, and the peak current is in the range of 0.06 to 100 μmThe internal linearity was well-linearly dependent on bisphenol a concentration (fig. 6B). By calculation, the lower limit of detection of bisphenol A was 0.035. Mu.M.
In addition, CMWNT-Fc-H prepared in example 3 was examined 5 PMo 10 V 2 O 40 Anti-interference performance of bisphenol A detected by electrochemical detection of CHIT composite electrode, in 0.1M phosphate buffer solution (pH=7.0), 400 mu M Na was contained respectively + 、400 μM K + 、400 μM Ca 2 + 、400 μM Cd 2 + 、400 μM Pb 2 + 、400 μM Al 3+ 、400 μM Cl - 、400 μM NO 3 - 、400 μM SO 4 2- Mu.m, 100. Mu.M hydroquinone, 100. Mu.M bisphenol A, 100. Mu.M para-nitrophenol and 20. Mu.M catechol. The results show that there is little significant change in the peak current of bisphenol A oxidation in the presence of so much potential interfering species, indicating CMWNT-Fc-H 5 PMo 10 V 2 O 40 The composite material has good selectivity for bisphenol A detection.
Comparative examples 1 to 5
Comparative examples 1-5 used other electrochemical sensors in the prior art, niNP/NCN/CS (from J. Alloy Compd. 827 (2020) 154335), tyr-SF-MWCNTs-CoPC (from Chim. Acta 659 (2010) 144-150.), TYR/TiO2/MWCNTs/PDDA (from Talanta 144 (2015) 163-170.), CAS-CB (from electric. 31 (2019) 2162-2170) and RGO-Ag/PLL (from chem.805 (2017) 39-46), respectively.
CMWNT-Fc-H prepared in example 4 of the present application 5 PMo 10 V 2 O 40 Comparison of the performance of the/CHIT composite electrode sensor with other prior art constructions of electrochemical sensors prepared in comparative examples 1-5 bisphenol A was shown in Table 1,
TABLE 1
As can be seen from Table 1, CMWNT-Fc-H 5 PMo 10 V 2 O 40 The base bisphenol A sensor may provide better or substantial detectionThe sensing material has stable structure and good selectivity, and is a good electrochemical platform for detecting bisphenol A.
Example 5
Example 5 CMWNT-Fc-H prepared in example 1 5 PMo 10 V 2 O 40 Examples of applications of the composite material are as follows:
10mL of milk was mixed with 20mL of absolute ethanol, stirred and shaken for 15min, then the mixture was centrifuged, and finally the supernatant was collected and diluted 40-fold with PBS buffer (0.1 m, pH 7.0). Bisphenol A in the actual sample is measured by adopting a standard addition method, under the optimized condition, bisphenol A with known concentration in the diluted milk sample is measured by adopting an electrochemical analysis method, and the recovery rate is between 96.0 and 105.3 percent, which proves that the CMWNT-Fc-H 5 PMo 10 V 2 O 40 The application of the composite material as a sensor in a real sample is reliable.
CMWNT-Fc-H prepared by the present application 5 PMo 10 V 2 O 40 The composite material has larger surface area, good conductivity, fast electron transfer rate, lower oxidation potential and excellent oxidation-reduction performance, and shows excellent performance in electrochemical detection of bisphenol A due to the synergistic effect between components; 2. CMWNT-Fc-H 5 PMo 10 V 2 O 40 The composite material combines ferrocene (Fc) with high electron transfer rate, low oxidation potential and vanadium-substituted phosphomolybdic acid (H5 PMo) 10 V 2 O 40 ) The oxidation property is excellent, the negative charge is extremely high, and the immobilized carrier can be better, and the performance is excellent; CMWNT-Fc-H 5 PMo 10 V 2 O 40 The composite material is applied to the detection of bisphenol A in milk samples, and the recovery rate is higher.
Although the present application has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present application is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present application by those skilled in the art without departing from the spirit and scope of the present application, and it is intended that all such modifications and substitutions be within the scope of the present application/be within the scope of the present application as defined by the appended claims. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (7)
1. CMWNT-Fc-H 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material is characterized by comprising the following steps:
1) Dispersing carboxylated multiwall carbon nanotubes in a solvent, and performing ultrasonic treatment to form a black suspension;
2) Sequentially adding ferrocene and vanadium-substituted phosphomolybdic acid into the black suspension, performing ultrasonic treatment, filtering out precipitate, and drying the precipitate overnight to obtain a carboxylated multiwall carbon nanotube-ferrocene-vanadium-substituted phosphomolybdic acid composite material CMWNT-Fc-H 5 PMo 10 V 2 O 40 ；
3) Negatively charged CMWNT-Fc-H by electrostatic attraction 5 PMo 10 V 2 O 40 Immobilized on a cationic chitosan matrix with film forming capability to prepare ferrocene-vanadium substituted phosphomolybdic acid-chitosan (CMWNT-Fc-H) capable of being firmly fixed on the surface of an electrode 5 PMo 10 V 2 O 40 (CHIT) composite electrode material;
carboxylated multiwall carbon nanotubes: ferrocene: the mass ratio of the vanadium-substituted phosphomolybdic acid is 1-2:1-2:1-2;
synthesis of carboxylated multiwall carbon nanotubes CMWNT: 6g of 5% MWCNT are placed in a beaker and 15 mL of 70% HNO are added 3 45mL of 98% H was added 2 SO 4 Dispersing for 24 hours by ultrasonic, controlling the ultrasonic temperature at 35-40 ℃, adding distilled water with the quantity of 5 times for dilution, centrifuging, washing to be neutral, and drying at 80 ℃ to obtain the carboxylated multiwall carbon nanotube;
vanadium-substituted phosphomolybdic acid H 5 PMo 10 V 2 O 40 Is synthesized by the following steps: moO 16.59, g and 2.10, g were weighed out separately 3 And V 2 O 5 Dissolving in 250 mL distilled water, stirring,heating and refluxing to 120 ℃ for 10 min, gradually changing the solution into cream yellow, then dropwise adding 1.33g of 85% phosphoric acid, changing the solution into lemon yellow, changing the solution into egg yellow after the dropwise adding is finished, continuously heating and keeping 48-h at the temperature, standing and precipitating, wherein the upper layer is a reddish-colored clear liquid, the lower layer is an unreacted complete orange solid powder, filtering, placing a beaker containing the reddish-colored clear liquid on a constant-temperature magnetic stirrer, and evaporating water to dryness at the reaction temperature of 85 ℃ to obtain a reddish-orange solid; finally, dissolving the solid in a small amount of distilled water, separating out at 0 ℃, and recrystallizing for 3 times to obtain the vanadium-substituted phosphomolybdic acid.
2. The CMWNT-Fc-H of claim 1 5 PMo 10 V 2 O 40 The preparation method of the CHIT composite electrode material is characterized in that the solvent in the step 1) is one or a mixture of two of ethanol and water.
3. The CMWNT-Fc-H of claim 1 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material is characterized in that the solvent in the step 1) is a mixture of ethanol and water, and the volume ratio of the ethanol to the water is 4:1-3:2.
4. The CMWNT-Fc-H of claim 1 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material is characterized by comprising the following steps: the ultrasonic time in the step 1) is 25-45min.
5. The CMWNT-Fc-H of claim 1 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material is characterized by comprising the following steps: in the step 2), the ultrasonic time is 5-7h, and the drying temperature is 55-80 ℃.
6. The CMWNT-Fc-H of claim 1 5 PMo 10 V 2 O 40 The preparation method of the/CHIT composite electrode material is characterized by comprising the following steps: the addition amount of the carboxylated multiwall carbon nanotubes in the step 1) is 60-83 mg, 50-66% of ethanol and mL, 30-150mg of ferrocene in step 2), and 30-150mg of vanadium-substituted phosphomolybdic acid.
7. The CMWNT-Fc-H prepared by the method according to any one of claims 1 to 6 5 PMo 10 V 2 O 40 Application of/CHIT composite electrode material in bisphenol A detection.
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