CN111077196A

CN111077196A - Processing method of nano material composite and application of nano material composite in bisphenol A detection

Info

Publication number: CN111077196A
Application number: CN201911268525.2A
Authority: CN
Inventors: 李灿鹏
Original assignee: Yunnan University YNU
Current assignee: Yunnan University YNU
Priority date: 2019-12-11
Filing date: 2019-12-11
Publication date: 2020-04-28

Abstract

The invention discloses a processing method of a nano material compound and application thereof in bisphenol A detection, the method firstly synthesizes column [5] arene, and then synthesizes a nano composite material CP5@ RGO by modifying graphene; the PtPd-CP5@ RGO nano composite material is synthesized by introducing a platinum-palladium (PtPd) noble metal alloy. Column [5] arene is used as a supermolecular host, bisphenol A (BPA) is used as a guest molecule, and the host molecule CP5 is combined through pi-pi stacking effect, electrostatic effect and hydrophobic effect. PtPd-CP5@ RGO is used as an electrochemical sensing platform, and a current response signal of a bisphenol A (BPA) oxidation peak is improved by introducing a platinum-palladium (PtPd) noble metal alloy, so that the bisphenol A is detected; the method overcomes the defects of complex sample pretreatment, expensive instrument, low sensitivity and the like in the bisphenol A detection method in the prior art, is simple, convenient, quick and efficient, is suitable for industrial production, and has wide market application prospect.

Description

Processing method of nano material composite and application of nano material composite in bisphenol A detection

Technical Field

The invention relates to the field of electrochemical sensors, in particular to a processing method of a nano material composite and application of the nano material composite in bisphenol A detection.

Background

BPA, bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), an endocrine disrupter with estrogen-like properties that makes infants precocious, so the european union, canada, and the united states have prohibited the use of BPA in baby bottles. In addition, prolonged exposure to BPA can cause various respiratory diseases, heart disease, cancer, and the like. BPA is one of the most widely used industrial compounds in the world, and is an intermediate for producing various high molecular materials such as polysulfone resin, polyphenylene ether resin, polycarbonate, epoxy resin, unsaturated polyester resin, and the like, and thus, a large amount of BPA is often discharged into rivers through the sewage of these chemical plants. In the process of manufacturing plastic products, manufacturers can make products have the characteristics of durability, light weight, strong impact resistance and the like by adding BPA. Therefore, detection of BPA is essential for human health.

Currently, methods for detecting bisphenol a include high performance liquid chromatography, gas chromatography-mass spectrometry, gas chromatography, and chemiluminescence. However, these methods are complicated in sample pretreatment, expensive in instruments, and low in sensitivity.

Disclosure of Invention

The invention aims to provide a processing method of a nano material composite and application of the nano material composite in bisphenol A detection, and solves the problems of complexity, low detection speed and low bisphenol A identification of the existing bisphenol A detection method.

In order to solve the technical problems, the invention adopts the following technical scheme:

a method for processing a nanocomposite, the method comprising: the column [5] arene is modified by graphene, and then PtPd noble metal alloy is introduced to obtain the PtPd-CP5@ RGO nano composite material.

Preferably, the graphene modified column [5] arene is prepared by preparing a mixed solution of the graphene and the column [5] arene, carrying out pre-reaction, and refluxing at the temperature of 80-100 ℃, wherein the precipitate in the product is CP5@ RGO.

Preferably, the mass ratio of the graphene to the column [5] arene is 1:0.5-1.5, the pre-reaction time is 0.5-1h, and NaOH is added into the mixed solution after the pre-reaction to adjust the pH value to 12.

Preferably, CP5@ RGO is mixed with PdCl₂、H₂PtCl₆Polyethylene glycol, sodium citrate and NaBH₄Mixing and reacting to obtain the PtPd-CP5@ RGO nano composite material.

Preferably, wherein CP5@ RGO is reacted with PdCl₂、H₂PtCl₆Sodium citrate and NaBH₄The molar ratio of 1:0.8-1.2:0.8-1.2:0.8-1.2:0.01-0.02, the reaction temperature is 18-25 ℃, and the reaction time is 1-3 h.

Preferably, the preparation process of the column [5] arene comprises the following steps:

the method comprises the following specific steps:

step A: dissolving hydroquinone di (2-hydroxyethyl) ether and triphenylphosphine in anhydrous acetonitrile, cooling, mixing, adding carbon tetrabromide for a first reaction, adding cold water for quenching reaction after the first reaction is finished, and separating white precipitate in a first reaction product to obtain a compound 1;

and B: dissolving a compound 1 and trioxymethylene in 1, 2-dichloroethane, cooling, adding boron trifluoride diethyl etherate to carry out a second reaction, adding water to quench after the second reaction is completed, separating the following structure in the second reaction to obtain a compound 2,

and C: adding ethanol, the compound 2 and trimethylamine ethanol into a reactor, refluxing, performing a third reaction, and separating and purifying the product to obtain the light brown solid column [5] arene.

Preferably, in the first reaction, the mass ratio of hydroquinone bis (2-hydroxyethyl) ether to triphenylphosphine is 0.1-1:1, the mass ratio of hydroquinone bis (2-hydroxyethyl) ether to carbon tetrabromide is 0.1-0.5:1, and the reaction temperature is 18-22 ℃.

Preferably, in the second reaction, the mass ratio of the compound 1 to trioxymethylene is 0.05-0.1:1, the mass ratio of the compound 1 to boron trifluoride diethyl ether is 0.9-1.0:1, and the reaction temperature is 18-22 ℃.

Preferably, in the second reaction, the mass ratio of the compound 2 to the trimethylamine ethanol is 0.1-0.5:1, and the reflux reaction is carried out for 18-36 h.

An application of PtPd-CP5@ RGO nano composite material in bisphenol A detection.

Firstly synthesizing column [5] arene, and then synthesizing a nano composite material CP5@ RGO by modifying graphene; the PtPd-CP5@ RGO nano composite material is synthesized by introducing a platinum-palladium (PtPd) noble metal alloy. Column [5] arene is used as a supermolecular host, bisphenol A (BPA) is used as a guest molecule, and the host molecule CP5 is combined through pi-pi stacking effect, electrostatic effect and hydrophobic effect. Constructing a PtPd-CP5@ RGO electrochemical sensing platform, and quantitatively detecting the bisphenol A according to the linear relation between the current intensity change and the bisphenol A adding concentration.

Compared with the prior art, the invention has the beneficial effects that:

compared with the common composite sensing interface, the composite sensing interface based on the PtPd-CP5@ RGO has higher sensitivity and better stability; the method is carried out at normal temperature and normal pressure, is simple and rapid, has high controllability and has wide application prospect.

Drawings

FIG. 1 is a drawing of Compound 1¹H NMR (A) and¹³C NMR(B)；

FIG. 2 is a drawing of Compound 2¹H NMR (A) and¹³C NMR(B)；

FIG. 3 shows Compound CP5¹H NMR (A) and¹³C NMR(B)；

FIG. 4 is a schematic diagram of an electrochemical sensor constructed based on PtPd-CP5@ RGO nanocomposite for detecting bisphenol A;

FIG. 5 is an infrared spectrum of RGO, CP5 and CP5@ RGO (with RGO, CP5 and CP5@ RGO from top to bottom);

FIG. 6 is an experiment of the binding constant of bisphenol A to column [5] arene;

FIG. 7 is a graph showing the linear relationship between the current intensity of PtPd-CP5@ RGO system and the concentration of bisphenol A;

FIG. 8 is a graph of the electrochemical behavior of BPA on a modified electrode, wherein the top graph is a cyclic voltammogram and the bottom graph is a differential pulse voltammogram;

FIG. 9 is a graph of the effect of BPA on the enrichment time and enrichment potential of modified electrode PtPd-CP5@ RGO/GCE, where graph A is the effect of enrichment time and graph B is the effect of enrichment potential;

FIG. 10 is a graph of the effect of pH and scan rate on the electrochemical behavior of BPA at the modified electrode PtPd-CP5@ RGO/GCE, where graph A is the effect of pH on DPV and graph B is a plot of cyclic voltammetry at different scan rates;

FIG. 11 is a graph of the interference rejection performance of the PtPd-CP5@ RGO sensor for BPA identification.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The chemical reagents and solvents used in the examples of the present application are analytically pure; the stirring mode adopts a magnetic stirrer. The electrochemical determination conditions are all within the potential range of 0.0-1.0V.

The processing method of the nano material composite in the application is as follows:

(1) putting hydroquinone bis (2-hydroxyethyl) ether, triphenylphosphine and anhydrous acetonitrile into a flask in sequence, cooling by using an ice water bath, uniformly stirring, slowly adding carbon tetrabromide, stirring at 18-22 ℃ for reaction, adding cold water into the mixture after the reaction is completed to quench the reaction to obtain white precipitate, filtering and collecting the precipitate, washing for 3-4 times by using a methanol aqueous solution, recrystallizing by using methanol, and drying to obtain a compound 1, wherein the hydroquinone bis (2-hydroxyethyl) ether: the mass ratio of triphenylphosphine is 0.1-1:1, hydroquinone di (2-hydroxyethyl) ether: the mass ratio of carbon tetrabromide is 0.1-0.5: 1; (2) adding a compound 1, trioxymethylene and 1, 2-dichloroethane into a flask, cooling by using an ice water bath, adding boron trifluoride diethyl etherate into the flask, stirring for reacting at 18-22 ℃, adding water for quenching after the reaction is completed, extracting by using dichloromethane, drying an organic phase by using anhydrous sodium sulfate, and removing a solvent by vacuum concentration to obtain a crude product; the crude product was purified by column chromatography to give compound 2, compound 1: the mass ratio of trioxymethylene is 0.05-0.1:1, and the mass ratio of the compound 1: the mass ratio of boron trifluoride diethyl etherate is 0.9-1.0: 1;

(3) adding the compound 2 and trimethylamine ethanol into a flask, carrying out reflux reaction for 18-36h, cooling to 18-22 ℃ after the reaction is finished, carrying out reduced pressure concentration to remove the solvent, dissolving the residual solid in water, filtering to remove insoluble substances, carrying out vacuum rotary evaporation on the obtained filtrate to remove the solvent, washing the residue with ethanol, and carrying out vacuum drying to obtain light brown solid column [5] arene, wherein the compound 2: the mass ratio of the trimethylamine ethanol is 0.1-0.5: 1;

(4) adding graphene and a column [5] arene solution into water, respectively ultrasonically dissolving, placing the mixed solution at 18-22 ℃ for reacting for 0.5-1.5h, adjusting the pH to 12 by NaOH, transferring the solution to a round-bottom flask, heating and refluxing for 3-6h at 80-100 ℃, cooling to room temperature after the reaction is finished, centrifuging to obtain a stable black solution, centrifugally cleaning the precipitate for 3-4 times by deionized water, and preparing CP5@ RGO, wherein the mass ratio of CP5 to RGO can be 1: 1-2.

(5) Adding CP5@ RGO into water, ultrasonically dissolving, and adding PdCl₂，H₂PtCl₆PEG (400), sodium citrate, NaBH₄Stirring for 1-3h at 18-22 ℃. Cooling to 18-22 deg.C after reaction, centrifuging to obtain stable black solution, centrifuging and cleaning precipitate with deionized water for 3-4 times, and freeze drying CP5@ RGO and PdCl₂、H₂PtCl₆Sodium citrate and NaBH₄The molar ratio of 1:0.8-1.2:0.8-1.2:0.8-1.2: 0.01-0.02. .

Example 1:

the preparation method of the electrochemical sensor comprises the following steps:

(1) putting 10g of hydroquinone di (2-hydroxyethyl) ether, 31.5g of triphenylphosphine and 250mL of anhydrous acetonitrile into a round-bottom flask in sequence, cooling the mixture by using an ice water bath, uniformly stirring the mixture, adding 39.8g of carbon tetrabromide, stirring the mixture at room temperature for reaction for 5 hours, adding 200mL of cold water into the mixture after the reaction is completed to quench the reaction to obtain a white precipitate, filtering the white precipitate, collecting the precipitate, washing the precipitate for 3 times by using a methanol aqueous solution with a volume ratio of 3:2, recrystallizing the precipitate by using methanol, drying the dried white crystal, and obtaining 14.5g of compound 1¹H NMR and¹³c NMR is shown in FIG. 1A and FIG. 1B, respectively;

(2) adding 5.06g of compound 1, 0.523g of trioxymethylene and 100mL of 1, 2-dichloroethane into a round-bottom flask, cooling by using an ice-water bath, adding 4.89g of boron trifluoride diethyl ether into the round-bottom flask, stirring at room temperature for reacting for 1h, adding 50mL of water for quenching after the reaction is completed, finally extracting by using dichloromethane, drying an organic phase by using anhydrous sodium sulfate, and concentrating under reduced pressure to remove a solvent to obtain a crude product; the crude product is passed through a silica gel columnPurifying by chromatography, eluting with petroleum ether-ethyl acetate (volume ratio 100:1), collecting eluate, and vacuum freeze drying to obtain compound 2, compound 2¹H NMR and¹³c NMR is shown in FIG. 2A and FIG. 2B, respectively;

(3) adding 100mL of ethanol, 2.0g of compound 2 and 12.8mL of trimethylamine ethanol into a round-bottom flask, refluxing and reacting at 9 ℃ for 24h, cooling to room temperature after the reaction is finished, concentrating under reduced pressure to remove the solvent, dissolving the residual solid in 40mL of water, filtering to remove insoluble substances, performing vacuum rotary evaporation on the obtained filtrate to remove the solvent, washing the residue with ethanol, and performing vacuum drying to obtain a white solid column [5]]Aromatic hydrocarbons 2.0g, CP5¹H NMR and¹³c NMR is shown in FIG. 3A and FIG. 3B, respectively;

(4) respectively adding 10mg of graphene oxide and CP5 into 20mL of water, carrying out ultrasonic dissolution, placing the mixed solution at room temperature for reaction for 1h, adjusting the pH value to 12.0 by using 1.0M NaOH, then transferring the solution to a round-bottom flask, heating and refluxing for 4h at 90 ℃, cooling to room temperature after the reaction is finished, centrifuging the obtained stable black solution, and centrifugally cleaning the precipitate for 3-4 times by using deionized water to obtain CP5@ RGO;

(5) adding 20mg of CP5@ RGO into 5mL of water, dispersing in the water solution by ultrasonic dissolution to obtain black CP5@ RGO dispersion liquid, wherein the ultrasonic time is about 0.5h, and adding 0.5mL of PdCl under stirring at room temperature₂(0.01M)，0.25mLH₂PtCl₆(0.01M), 0.15mL PEG (400),1.5mL sodium citrate (0.01M), 4.5mL NaBH₄(15mM), and stirred at room temperature for 2 h. And finally, centrifugally cleaning with ultrapure water, and freeze-drying to obtain the PtPd-CP5@ RGO electrochemical sensor, wherein the schematic diagram of the electrochemical sensor constructed on the basis of the PtPd-CP5@ RGO nanocomposite for detecting the bisphenol A is shown in FIG. 4.

Example 2:

the preparation method of the chemical sensor comprises the following steps:

(1) putting 10g of hydroquinone bis (2-hydroxyethyl) ether, 31.5g of triphenylphosphine and 250mL of anhydrous acetonitrile into a flask in sequence, cooling the mixture by using an ice water bath, uniformly stirring the mixture, adding 39.8g of carbon tetrabromide, stirring the mixture at room temperature for reaction for 5 hours, adding 200mL of cold water into the mixture after the reaction is completed to quench the reaction to obtain a white precipitate, filtering the white precipitate, collecting the precipitate, washing the white precipitate for 3 times by using a methanol aqueous solution with a volume ratio of 3:2, recrystallizing the white precipitate by using methanol, and drying the methanol aqueous solution to obtain a compound 1;

(2) adding 5.06g of compound 1, 0.523g of trioxymethylene and 100mL of 1, 2-dichloroethane into a round-bottom flask, cooling by using an ice-water bath, adding 4.89g of boron trifluoride diethyl ether into the round-bottom flask, stirring at room temperature for reacting for 1h, adding 50mL of water for quenching after the reaction is completed, finally extracting by using dichloromethane, drying an organic phase by using anhydrous sodium sulfate, and concentrating under reduced pressure to remove a solvent to obtain a crude product; purifying the crude product by silica gel column chromatography, eluting with petroleum ether-ethyl acetate (volume ratio 100:1), collecting eluate, and vacuum freeze drying to obtain compound 2;

(3) adding 100mL of ethanol, 2.0g of compound 2 and 12.8mL of trimethylamine ethanol into a round-bottom flask, refluxing and reacting at 90 ℃ for 24h, cooling to room temperature after the reaction is finished, concentrating under reduced pressure to remove the solvent, dissolving the residual solid in 40mL of water, filtering to remove insoluble substances, performing vacuum rotary evaporation on the obtained filtrate to remove the solvent, washing the residue with ethanol, and performing vacuum drying to obtain a white solid column [5]]Aromatic hydrocarbon 2.4g, FIG. 5 Infrared Spectrum shows that the characteristic peak of CP5 has 3428cm^-1，1612cm^-1，1401cm^-1，1427cm^-1，1209cm^-1. Wherein 3428cm^-1Is a stretching vibration peak of unsaturated C-H on a benzene ring; 1612cm^-1，1457 cm^-1，1401cm^-1Is a vibration absorption peak of a benzene ring framework; 1401cm^-1Is a C-H bending vibration absorption peak;

(4) respectively adding 10mg of graphene oxide and CP5 into 20mL of water, ultrasonically dissolving, placing the mixed solution at room temperature for reaction for 1h, adjusting the pH value to 12.0 by using 1.0M NaOH, then transferring the solution to a round-bottom flask, heating and refluxing at 90 ℃ for 4h, cooling to room temperature after the reaction is finished, centrifuging the obtained stable black solution, centrifugally washing the precipitate for 3-4 times by using deionized water,to obtain CP5@RGOThe preparation and use principle of the electrochemical sensor PtPd-CP5@ RGO is shown in figure 4, and the CP5@ RGO infrared spectrum in figure 5 shows that the characteristic peak of CP5@ RGO is 3428cm^-1，1612cm^-1，1457cm^-1，1401 cm^-1，1209cm^-1；3428cm^-1Is a stretching vibration peak of unsaturated C-H on a benzene ring;1457cm^-1，1401cm^-1is a C-H bending vibration absorption peak; the difference between the two spectra was compared and the data above demonstrates the successful preparation of CP5@ RGO.

Example 3:

experiment of binding constant of bisphenol A to column [5] arene:

to 20 u mol/L CP5 solution continuously adding different concentrations of BPA standard solution, each time adding 10 u L, get a group of fluorescence absorption curves, according to the curve makes the corresponding correlation linear relationship, thereby calculating the CP5 and BPA between the apparent binding constant Ka, as shown in figure 6. The binding constant relationship among the objects lays an experimental foundation for the CP5 to adsorb BPA and increase the conductivity of the material.

Example 4:

the linear relationship between the current intensity of the PtPd-CP5@ RGO system and the concentration of bisphenol A is shown as follows:

BPA with a concentration of 0.00-1000.00. mu. mol/L is prepared with ultrapure water as a stock solution for future use, and the BPA stock solution is added into a 25mL beaker, and the DPV curve is measured. The current of the oxidation peak of BPA increased with the increase of the concentration of BPA, and a linear relationship between the concentration of bisphenol a and the current intensity was obtained, as shown in fig. 7A, in this example, bisphenol a was detected in a concentration range of 0.0 to 5.0 μ M, and its linear equation I (μ a) was 1.107C (μ M) +4.730, as shown in fig. 7B, in a concentration range of 5.0 to 1000.0 μ M, and its linear equation I (μ a) was 0.01672C (μ M) +10.246, as shown in the inset of fig. 7B, with correlation coefficients of 0.996 and 0.994, respectively, and a detection limit of 0.003 μ M.

Example 5:

an electrochemical behavior diagram of BPA on a modified electrode, wherein the diagram A is a cyclic voltammogram, and the diagram B is a differential pulse voltammogram:

the electrochemical response of BPA at the modified electrodes RGO/GCE, CP5@ RGO/GCE, Pt-CP5@ RGO/GCE, Pd-CP5@ RGO/GCE, and PtPd-CP5@ RGO/GCE was characterized by CV. All modified electrodes were each subjected to CV scans in 1.0mM BPA, as shown in the upper panel of fig. 8, and DPV scans in the lower panel of fig. 8.

Example 6:

graph of the effect of BPA on the enrichment time and the enrichment potential of the modified electrode PtPd-CP5@ RGO/GCE, wherein A is the effect of the enrichment time and B is the effect of the enrichment potential:

the conditions for the enrichment time and the enrichment potential of BPA on the modified electrode PtPd-CP5@ RGO/GCE were studied by DPV. PtPd-CP5@ RGO/GCE response to current flow in 1mM BPA at different enrichment times, as shown in FIG. 9A, the response current increased with increasing enrichment time between 0 and 200s, but the current hardly changed after 200 s. This resulted in an optimal enrichment time of 200 s. The enrichment potential of PtPd-CP5@ RGO/GCE was optimized, and it can be seen from FIG. 9B that the current of the oxidation peak reached the maximum value when the enrichment potential was-0.1V, and thus the optimal enrichment time and potential were 200s and-0.1V, respectively.

Example 7:

pH and scan rate impact profiles of BPA on modified electrode PtPd-CP5@ RGO/GCE;

DPV was used to study the effect of pH on the electrochemical behavior of BPA on the modified electrode PtPd-CP5@ RGO/GCE. The buffer solution was prepared as Phosphate Buffered Saline (PBS) with a pH range of 4.0-6.0 (FIG. 10). When the pH was increased from 4.0 to 6.0, the oxidation peak current of BPA increased with increasing pH, whereas when the pH was increased from 6.0 to 8.0, the oxidation peak current decreased instead, the optimum pH being 6.0, taking into account the effects of both current and potential. The effect of scanning rate on detection of BPA was studied. 1mM BPA in PtPd-CP5@ RGO/GCE with different scan rate cyclic voltammetry detection, as shown in figure 10, BPA oxidation peak current increases with the scan rate. Scanning rate 50mVs^-1～400mVs^-1In the range, the linear equation is represented by the square root of the scanning rate versus the non-oxidation peak current of BPA, i.e., Ipa (μ A) ═ 7.46v^1/2(mV s^-1)^1/2-23.107(R²0.9926) this suggests that oxidation of BPA is a typical diffusion-controlled process on PtPd-CP5@ RGO/GCE. Similarly, at a scan rate of 50mVs^-1～400mVs^-1In the range, as shown in fig. 10, a linear plot of the natural logarithm of the scan rate versus the oxidation peak of BPA is obtained, and the linear equation can be expressed as Epa ═ 0.03007ln v +0.551 (R)²＝0.9952)。

Example 8:

the anti-interference performance of the PtPd-CP5@ RGO sensor on BPA identification is as follows:

selecting bisphenol A analogue for interference test, wherein a is BPA of 100 mu M, b-h is o-aminophenol, p-aminophenol, M-aminophenol, phenol, catechol, hydroquinone and resorcinol, and selecting some conventional interferents for interference test, such as i-M is Cl^-、Hg²⁺、Fe³⁺、Zn²⁺And SO₄ ^2-. The interferents were added to BPA solution separately to determine the current intensity, as shown in FIG. 11, and it can be seen from FIG. 11 that these analogs and conventional ions do not interfere with BPA, and PtPd-CP5@ RGO/GCE has higher anti-interference ability to detect BPA.

Example 9:

use of CP5@ RGO sensor:

taking tap water and river water as actual samples, and detecting the content of bisphenol A in the actual samples by adopting a standard addition method; taking tap water and river water which are diluted by 50 times and 500 mu L, respectively adding bisphenol A solutions with the addition standard amounts of 4.0 mu mol/L and 8.0 mu mol/L into tap water and river water samples, preparing to obtain samples to be measured with the addition standard amounts of 4.0 mu mol/L and 8.0 mu mol/L, measuring the current intensity of each sample, carrying out parallel measurement on each sample for 3 times, substituting the fluorescence absorption value of each sample into the linear relation between the bisphenol A and the current intensity obtained in the embodiment 5, calculating the actual measurement concentration of each sample, and further calculating the recovery rate and the standard deviation, and as shown in Table 1, the experimental result shows that the recovery rate is between 97.8% and 102.2%, and the relative standard deviation is between 2.8% and 4.1%, which indicates that the sensor can be used for detecting the content of bisphenol A in tap water and river water, and has great application potential in biomedical and clinical detection.

TABLE 1 Experimental results of bisphenol A recovery in water with standard

Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.

Claims

1. A method for processing a nanocomposite, the method comprising: the column [5] arene is modified by graphene, and then PtPd noble metal alloy is introduced to obtain the PtPd-CP5@ RGO nano composite material.

2. The method of processing a nanocomposite as claimed in claim 1, wherein: the method for modifying the column [5] arene by utilizing the graphene is characterized in that the graphene and the column [5] arene are prepared into a mixed solution for pre-reaction, and then the mixed solution is refluxed at the temperature of 80-100 ℃, and the precipitate in the product is CP5@ RGO.

3. The method of processing a nanocomposite as claimed in claim 2, wherein: the mass ratio of the graphene to the column [5] arene is 1:0.5-1.5, the pre-reaction time is 0.5-1h, and NaOH is added into the mixed solution after the pre-reaction to adjust the pH value to 12.

4. The method of processing a nanocomposite as claimed in claim 1, wherein: mixing CP5@ RGO with PdCl₂、H₂PtCl₆Polyethylene glycol, sodium citrate and NaBH₄Mixing and reacting to obtain the PtPd-CP5@ RGO nano composite material.

5. The method of processing a nanocomposite as claimed in claim 4, wherein: wherein CP5@ RGO and PdCl₂、H₂PtCl₆Sodium citrate and NaBH₄The molar ratio of 1:0.8-1.2:0.8-1.2:0.8-1.2:0.01-0.02, the reaction temperature is 18-25 ℃, and the reaction time is 1-3 h.

6. The method of processing a nanocomposite as claimed in claim 1, wherein: the preparation method of the column [5] arene comprises the following steps:

；

7. The method of processing a nanocomposite as claimed in claim 6, wherein: in the first reaction, the mass ratio of hydroquinone di (2-hydroxyethyl) ether to triphenylphosphine is 0.1-1:1, the mass ratio of hydroquinone di (2-hydroxyethyl) ether to carbon tetrabromide is 0.1-0.5:1, and the reaction temperature is 18-22 ℃.

8. The method of processing a nanocomposite as claimed in claim 6, wherein: in the second reaction, the mass ratio of the compound 1 to the trioxymethylene is 0.05-0.1:1, the mass ratio of the compound 1 to the boron trifluoride diethyl etherate is 0.9-1.0:1, and the reaction temperature is 18-22 ℃.

9. The method of processing a nanocomposite as claimed in claim 6, wherein: in the second reaction, the mass ratio of the compound 2 to the trimethylamine ethanol is 0.1-0.5:1, and the reflux reaction is carried out for 18-36 h.

10. Use of the PtPd-CP5@ RGO nanocomposite of any one of claims 1-9 in the detection of bisphenol a.