CN111707720A - Preparation and application of nano-silver/pyridine functionalized graphene modified electrode - Google Patents
Preparation and application of nano-silver/pyridine functionalized graphene modified electrode Download PDFInfo
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Abstract
A preparation method of a nano-silver/pyridine functionalized graphene modified electrode is characterized by comprising the following steps: the method comprises the steps of synthesizing pyridine functionalized graphene (Py-GO), synthesizing Ag nano particles/pyridine functionalized graphene (AgNPs/Py-RGO) and preparing AgNPs/Py-RGO/GCE, wherein the AgNPs/Py-RGO is synthesized by adding silver nitrate and ethylene diamine tetraacetic acid into Py-GO dispersion liquid to form mixed liquid, carrying out water bath till boiling, slowly adding sodium borohydride, continuously heating, then carrying out centrifugal separation and drying. The Ag loading amount of the AgNPs/Py-RGO/GCE prepared by the invention is high, and the Ag content accounts for 39.62 wt%; the Ag nano particles have uniform particle size, are uniformly distributed on the surface of the graphene, and do not agglomerate; AgNPs/Py-RGO/GCE has excellent detection sensitivity to HQ and CC, and the detection limits are 0.062 mu M and 0.097 mu M respectively; has excellent selectivity and strong anti-interference capability.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to preparation and application of a nano-silver/pyridine functionalized graphene modified electrode.
Background
The dihydroxybenzene is a common chemical raw material, is a dihydroxybenzene isomer, and is widely applied to the fields of preservatives, dyes, stabilizers, antioxidants and the like. However, it causes serious damage to the human body and the environment due to toxicity and low degradability. Among them, Hydroquinone (HQ) causes fatigue, headache and kidney damage, and catechol (CC) causes liver function to be decreased. However, hydroquinone and catechol are dihydroxybenzene isomers, and the structures and the properties of the hydroquinone and the catechol are similar, so that the hydroquinone and the catechol are difficult to detect simultaneously, and interference can be generated during detection.
Conventional analytical methods for the isomers of benzenediol, such as high performance liquid chromatography, gas chromatography/mass spectrometry, spectrophotometry, and simultaneous fluorescence, generally require complicated instruments and specialist operators, resulting in high analytical costs. In contrast, since HQ and CC are all electrochemically active materials, the detection of hydroquinone and catechol using electrochemical techniques is a convenient, fast, economical, and highly sensitive method. Due to the similarity of chemical structures of HQ and CC, the problem of overlapping oxidation peaks exists when electrochemical technology is generally used for detection. Therefore, it is necessary to modify the electrode surface to detect a peak having good separation. The graphene has the advantages that the graphene has large specific surface area, good conductivity and stable chemical properties, and is commonly used for modifying an electrode, and Ag nanoparticles have high conductivity and amplified electrochemical signals, so that the research and development of a sensor are greatly influenced. Therefore, the Glassy Carbon Electrode (GCE) is modified by adopting the composite material prepared by loading Ag nano particles on graphene, and the sensitivity and specificity of the electrode are improved.
However, in the process of preparing the Ag/graphene composite material, Ag nanoparticles are easy to agglomerate, the particle size is not uniform, and graphene is easy to irreversibly agglomerate in the reduction process, so that the loading of Ag nanoparticles is small, the Ag nanoparticles are not uniformly dispersed on the surface of the graphene, the structure of the graphene is damaged, the disorder degree is increased, the electronic conduction capability of the graphene is reduced, the electronic conduction capability of the final composite material is poor, the detection performance of a modified electrode is poor, the adhesive force between the graphene and the electrode is weak, and the modified electrode is easy to fall off in the use process, so that the modified electrode cannot be normally used.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-silver/pyridine functionalized graphene modified electrode.
The invention also aims to provide application of the nano-silver/pyridine functionalized graphene modified electrode.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano-silver/pyridine functionalized graphene modified electrode is characterized by comprising the following steps: the preparation method comprises the steps of synthesizing pyridine functionalized graphene oxide (Py-GO), synthesizing Ag nano particles/pyridine functionalized graphene (AgNPs/Py-RGO) and preparing Ag nano particles/pyridine functionalized graphene modified electrodes (AgNPs/Py-RGO/GCE), wherein the synthesis of the AgNPs/Py-RGO is to add silver nitrate and ethylene diamine tetraacetic acid into a Py-GO dispersion liquid to form a mixed liquid, carry out water bath till boiling, slowly add sodium borohydride, continuously heat, centrifugally separate and dry.
Further, the Py-GO dispersion liquid is prepared by dispersing Py-GO in deionized water and carrying out ultrasonic treatment for 1 hour, wherein the concentration of the dispersion liquid is 1 mg/L.
Further, the mass ratio of Py-GO, silver nitrate and ethylene diamine tetraacetic acid in the mixed solution is 14:85:150, the mass ratio of silver nitrate and sodium borohydride is 0.8-1: 1-1.2, and the mixed solution is continuously heated for 1 hour after the sodium borohydride is added.
In the preparation process, the pyridine group is easy to protonate and cannot exert the effect on Ag+The anchoring effect of (a); ag+Agglomeration and cluster formation can also occur in the process of reduction to nano particles, the size is not controllable, and the graphene surface loading is low and the distribution is not uniform. In the invention, ethylenediamine tetraacetic acid, nitrogen atoms and oxygen atoms thereof and Ag with empty orbitals are added+Coordination enhances the surface charge number and thus increases the electrostatic charge between particlesRepulsive force, inhibiting the aggregation of Ag nano particles; in addition, the pH value of the system is adjusted to a certain extent by the ethylenediamine tetraacetic acid, and H is weakened+And Ag+Competition for N atom in pyridine group reduces protonation degree of N atom, and effectively exerts N atom to Ag+Thereby increasing Ag+The loading amount on the surface of the graphene; when the reducing agent is added, the Ag is adsorbed and fixed+Reducing the Ag atoms to Ag atoms and independently growing the Ag atoms, further preventing the Ag nano particles from agglomerating to form Ag nano particles with uniform particle size and uniformly distributing the Ag nano particles on the surface of the graphene.
Further, the synthesis of the Py-GO is that graphene oxide and pyridine are subjected to ultrasonic treatment for 5-10 min, the reaction is carried out for 40-48 h at the temperature of 60-70 ℃, benzene and acetone are used for washing after the reaction is finished, and the drying is carried out for 12h at the temperature of 60 ℃.
Furthermore, the dosage ratio of the graphene oxide to the pyridine is 1 g: 3-4 mL.
Furthermore, the AgNPs/Py-RGO/GCE is prepared by pretreating a Glassy Carbon Electrode (GCE), dripping 8 mu of aqueous solution of LAgNPs/Py-RGO on the surface of the GCE, and naturally drying, wherein the concentration of the aqueous solution of LAgNPs/Py-RGO is 2 mg/mL.
Most specifically, the preparation method of the nano-silver/pyridine functionalized graphene modified electrode is characterized by comprising the following steps:
(1) Py-GO synthesis
Mixing graphene oxide and pyridine, performing ultrasonic treatment for 5-10 min, reacting at 60-70 ℃ for 40-48 h, washing with benzene and acetone after the reaction is finished, and drying at 60 ℃ for 12h, wherein the dosage ratio of the graphene oxide to the pyridine is 1 g: 3-4 mL;
(2) AgNPs/Py-RGO Synthesis
Dispersing Py-GO in deionized water, performing ultrasonic treatment for 1h to obtain a dispersion liquid with the concentration of 1mg/L, adding silver nitrate and ethylene diamine tetraacetic acid into the Py-GO dispersion liquid to form a mixed liquid, performing water bath till boiling, slowly adding sodium borohydride, continuously heating for 1h, performing centrifugal separation, and drying, wherein the mass ratio of Py-GO to silver nitrate to ethylene diamine tetraacetic acid is 14:85:150, and the mass ratio of silver nitrate to sodium borohydride is 0.8-1: 1-1.2;
(3) preparation of AgNPs/Py-RGO/GCE
And polishing and grinding a glassy carbon electrode (GCE, phi is 3mm) by using alumina powder with the particle size of 0.5 mu m and alumina powder with the particle size of 0.03 mu m respectively, then ultrasonically cleaning the polished glassy carbon electrode by using deionized water, ethanol and the deionized water in sequence, taking 8 mu of LAgNPs/Py-RGO aqueous solution to be dripped on the surface of the GCE, and naturally drying the GCE, wherein the concentration of the AgNPs/Py-RGO aqueous solution is 2 mg/mL.
Graphene oxide is reduced under the action of a reducing agent, and irreversible agglomeration occurs in the reduction process, so that the original carbon structure is damaged. In the invention, a pyridine group is introduced before reduction, so that the oxidation reduction performance of the graphene oxide is adjusted, and the graphene oxide is reacted with Ag+In the synchronous reduction process, the reduction effect of the reducing agent on the graphene oxide is synergistically regulated, the introduction of the pyridine group increases the interlayer distance of the graphene oxide, and the irreversible agglomeration of the graphene is inhibited in the reduction process, so that the graphene forms a large specific surface area, and the improvement and the uniform dispersion of the Ag loading capacity are facilitated. Unshared electron pairs on N atom in group with Ag+Coordination, oxygen-containing functional group on graphene oxide surface to Ag+Adsorption of (A), ethylenediaminetetraacetic acid and Ag+Coordination of (2) to efficiently immobilize Ag+The loading capacity of Ag is improved, the Ag is fixed and independently reduced and grown during reduction, and the Ag is prevented from agglomerating in the reduction process, so that the Ag is uniformly loaded on the surface of the pyridine functionalized graphene in a uniform particle size manner. In the synchronous reduction process, Ag exists due to the existence of pyridine group+The reduction and the specific reducing agent are matched to cooperatively regulate the reduction degree of the graphene oxide, so that the irreversible agglomeration of the graphene is greatly reduced, the carbon structure of the final graphene is stable and not damaged, the increase of the disorder degree is inhibited, and the electronic conductivity of the graphene is improved.
The application of the AgNPs/Py-RGO/GCE is characterized in that: the AgNPs/Py-RGO/GCE is used for detecting hydroquinone and catechol.
Further, the detection is to use 0.2mol/L PBS buffer solution to prepare hydroquinone and catechol into a solution to be detected, the pH value is 5.5, the AgNPs/Py-RGO/GCE is used for voltammetric cyclic scanning, and the potential range is scannedThe enclosure is 0-0.8V, and the scanning speed is 180mVs-1。
The invention has the following technical effects:
the AgNPs/Py-RGO/GCE prepared by the invention has the following technical effects:
(1) the pyridine group increases the surface adhesion of AgNPs/Py-RGO and GCE, is not easy to fall off, and enhances the structural stability of the modified electrode.
(2) The Ag loading in AgNPs/Py-RGO/GCE is high, and the Ag content accounts for 39.62 wt%.
(3) The Ag nano particles have uniform particle size, are uniformly distributed on the surface of the graphene, and do not agglomerate; the catalytic activity and the electronic conduction capability of the modified electrode are greatly improved.
(4) AgNPs/Py-RGO/GCE has excellent detection sensitivity to HQ and CC: HQ is in a linear relation with response current within a concentration range of 0.85-500 mu M, the detection limit is 0.062 mu M, CC is in a linear relation with response current within a concentration range of 0.46-499.66 mu M, and the detection limit is 0.097 mu M; has excellent performance stability: refrigerating at 4 deg.C for four weeks, wherein the response currents of HQ and CC are 95.8% and 96.2% of the measured current before refrigeration respectively; the method has excellent selectivity and strong anti-interference capability; the recovery rates of HQ and CC are respectively 95.4-101.78% and 96.9-103%.
Drawings
FIG. 1: the structure diagram of the pyridine functionalized graphene oxide prepared by the invention.
FIG. 2: and (3) an infrared characterization map of the pyridine functionalized graphene oxide.
FIG. 3: SEM images of GCE (Panel A), GO/GCE (Panel B), Py-GO/GCE (Panel C) and AgNPs/Py-RGO/GCE (Panel D).
FIG. 4: the element distribution map of the AgNPs/Py-RGO composite material prepared by the invention.
FIG. 5: each material modified electrode was at 50mM [ Fe (CN)6]3-/4-CV response curves in solutions containing 0.1 MKCl; a: GCE, b: GO/GCE, c: SGO/GCE, d: AgNPs/Py-RGO/GCE.
FIG. 6: an alternating current impedance diagram of each material modified electrode;
a：GCE、b：GO/GCE、c：SGO/GCE、d：AgNPs/Py-RGO/GCE。
FIG. 7: a CV curve graph of HQ and CC on each material modified electrode at the same time; a: GCE, b: GO/GCE, c: SGO/GCE, d: AgNPs/Py-RGO/GCE.
FIG. 8: DPV profiles of HQ (panel A) and CC (panel B) at different concentrations on AgNPs/Py-RGO/GCE, respectively.
FIG. 9: different concentrations of CC and HQ were simultaneously plotted on a DPV curve on AgNPs/Py-RGO/GCE.
FIG. 10: linear dependence of the peak current on CC (panel a) and HQ (panel B) at different concentrations.
(concentration change a → k in FIGS. 8 and 9: 0.5, 5, 20, 40, 60, 100, 150, 200, 300, 350, 500. mu.M).
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A preparation method of a nano-silver/pyridine functionalized graphene modified electrode comprises the following steps:
(1) Py-GO synthesis
Mixing graphene oxide and pyridine, performing ultrasonic treatment for 7min, reacting at 65 ℃ for 42h, washing with benzene and acetone after the reaction is finished, and drying at 60 ℃ for 12h, wherein the dosage ratio of the graphene oxide to the pyridine is 1 g: 3.5 mL;
(2) AgNPs/Py-RGO Synthesis
Dispersing Py-GO in deionized water, performing ultrasonic treatment for 1h to obtain a dispersion liquid with the concentration of 1mg/L, adding silver nitrate and ethylene diamine tetraacetic acid into the Py-GO dispersion liquid to form a mixed liquid, performing water bath till boiling, slowly adding sodium borohydride, continuously heating for 1h, performing centrifugal separation and drying, wherein the mass ratio of Py-GO to silver nitrate to ethylene diamine tetraacetic acid is 14:85:150, and the mass ratio of silver nitrate to sodium borohydride is 0.9: 1.1;
(3) preparation of AgNPs/Py-RGO/GCE
And polishing and grinding a glassy carbon electrode (GCE, phi is 3mm) by using alumina powder with the particle size of 0.5 mu m and alumina powder with the particle size of 0.03 mu m respectively, then ultrasonically cleaning the polished glassy carbon electrode by using deionized water, ethanol and the deionized water in sequence, taking 8 mu of LAgNPs/Py-RGO aqueous solution to be dripped on the surface of the GCE, and naturally drying the GCE, wherein the concentration of the AgNPs/Py-RGO aqueous solution is 2 mg/mL.
Example 2
A preparation method of a nano-silver/pyridine functionalized graphene modified electrode comprises the following steps:
(1) Py-GO synthesis
Mixing graphene oxide and pyridine, performing ultrasonic treatment for 10min, reacting at 60 ℃ for 40h, washing with benzene and acetone after the reaction is finished, and drying at 60 ℃ for 12h, wherein the dosage ratio of the graphene oxide to the pyridine is 1 g: 3 mL;
(2) AgNPs/Py-RGO Synthesis
Dispersing Py-GO in deionized water, performing ultrasonic treatment for 1h to obtain a dispersion liquid with the concentration of 1mg/L, adding silver nitrate and ethylene diamine tetraacetic acid into the Py-GO dispersion liquid to form a mixed liquid, performing water bath till boiling, slowly adding sodium borohydride, continuously heating for 1h, performing centrifugal separation and drying, wherein the mass ratio of Py-GO to silver nitrate to ethylene diamine tetraacetic acid is 14:85:150, and the mass ratio of silver nitrate to sodium borohydride is 0.8: 1;
(3) preparation of AgNPs/Py-RGO/GCE
And polishing and grinding a glassy carbon electrode (GCE, phi is 3mm) by using alumina powder with the particle size of 0.5 mu m and alumina powder with the particle size of 0.03 mu m respectively, then ultrasonically cleaning the polished glassy carbon electrode by using deionized water, ethanol and the deionized water in sequence, taking 8 mu of LAgNPs/Py-RGO aqueous solution to be dripped on the surface of the GCE, and naturally drying the GCE, wherein the concentration of the AgNPs/Py-RGO aqueous solution is 2 mg/mL.
Example 3
A preparation method of a nano-silver/pyridine functionalized graphene modified electrode comprises the following steps:
(1) Py-GO synthesis
Mixing graphene oxide and pyridine, performing ultrasonic treatment for 5min, reacting at 70 ℃ for 48h, washing with benzene and acetone after the reaction is finished, and drying at 60 ℃ for 12h, wherein the dosage ratio of the graphene oxide to the pyridine is 1 g: 4 mL;
(2) AgNPs/Py-RGO Synthesis
Dispersing Py-GO in deionized water, performing ultrasonic treatment for 1h to obtain a dispersion liquid with the concentration of 1mg/L, adding silver nitrate and ethylene diamine tetraacetic acid into the Py-GO dispersion liquid to form a mixed liquid, performing water bath till boiling, slowly adding sodium borohydride, continuously heating for 1h, performing centrifugal separation and drying, wherein the mass ratio of Py-GO to silver nitrate to ethylene diamine tetraacetic acid is 14:85:150, and the mass ratio of silver nitrate to sodium borohydride is 1: 1.2;
(3) preparation of AgNPs/Py-RGO/GCE
And polishing and grinding a glassy carbon electrode (GCE, phi is 3mm) by using alumina powder with the particle size of 0.5 mu m and alumina powder with the particle size of 0.03 mu m respectively, then ultrasonically cleaning the polished glassy carbon electrode by using deionized water, ethanol and the deionized water in sequence, taking 8 mu of LAgNPs/Py-RGO aqueous solution to be dripped on the surface of the GCE, and naturally drying the GCE, wherein the concentration of the AgNPs/Py-RGO aqueous solution is 2 mg/mL.
The graphene oxide and the pyridine are subjected to an epoxy ring-opening reaction to synthesize the pyridine graphene. From FIG. 2, a and b are the infrared curves of GO and Py-GO respectively, GO has a typical infrared characteristic peak of 1055cm-1、1219cm-1、1735cm-1And 3430cm-1Stretching vibrations of C-O, C-O-C, C ═ O and O-H, respectively; 1632cm in Py-GO infrared curve-1The peak is obviously widened due to the vibration of the C ═ N and C ═ C frameworks in Py-GO, and 1219cm in the GO infrared curve-1The peak is obviously reduced, and the infrared curve of Py-GO is 1108cm-1The peak value is obviously increased, which indicates that C-O-C in Py-GO is converted into C-O, namely the epoxy bond of GO is broken in the synthesis process of Py-GO, thus indicating the successful preparation of Py-GO material.
As shown in fig. 3C, after GO is modified with pyridine, the interplanar spacing of Py-GO is increased, and compared with GO, the pyridine functionalized graphene has a larger specific surface area, which is not only beneficial to the catalytic activity of the graphene, but also provides a larger surface for the subsequent attachment of Ag nanoparticles. As is apparent from fig. 3D, the Ag nanoparticles have uniform particle size, do not agglomerate, and are uniformly attached to the surface of the pyridine-functionalized graphene. As can be seen from the elemental distribution diagram of FIG. 4, the AgNPs/Py-RGO components are uniformly distributed, and the ratio of the components is shown in Table 1.
Table 1: and (5) carrying out statistics on the ratio of the AgNPs/Py-RGO components.
| Element(s) | Wt％ | Wt％Sigma |
| C | 46.85 | 0.18 |
| O | 13.52 | 0.12 |
| Ag | 39.62 | 0.20 |
| Total amount of | 100 |
It can be seen that the percentage of Ag element in the AgNPs/Py-RGO composite material is 39.62wt%, and the Ag element has excellent loading capacity.
GCE, GO/GCE, Py-GO/GCE and AgNPs/Py-RGO/GCE were tested at 50mM [ Fe (CN)6]3-/4-CV response in the solution containing 0.1MKCl, as shown in FIG. 5. Compared with the AgNPs/Py-RGO/GCE in the curve d, the AgNPs/Py-RGO/GCE has the smallest oxidation-reduction peak potential difference and the largest peak current value, which shows that the AgNPs/Py-RGO composite material glassy carbon modified electrode improves the catalytic activity of the sensor and has a faster electron transfer rate. The AC impedance diagram shown in FIG. 6 consists of a semicircle of the high frequency region and a low frequency regionThe straight line of the frequency region is formed, the semi-circle represents the charge transfer resistance, and the semi-circle radius of the AgNPs/Py-RGO/GCE is obviously smaller than that of the other three modified electrodes, which indicates that the AgNPs/Py-RGO/GCE has more excellent electron transfer capability.
FIG. 7 shows a concentration of 1 × 10-4mol L-1And 1 × 10-4mol L-1The CV curve graphs of solutions to be tested prepared by using PBS buffer solution (PH is 5.5) as base solution on GCE, GO/GCE, Py-GO/GCE and AgNPs/Py-RGO/GCE. It can be seen that GCE, GO/GCE, Py-GO/GCE all obtained only one oxidation peak although the peak currents were gradually increased, which may be related to the overlap of the oxidation peaks of hydroquinone and catechol. On the other hand, two separated reduction peaks are respectively displayed on AgNPs/Py-RGO/GCE at the vicinity of 0.1V and 0.25V, and higher redox peak current is displayed, which shows that the conductivity and active sites of the AgNPs/Py-RGO composite material are improved, and the AgNPs/Py-RGO composite material greatly contributes to the redox activity of HQ and CC.
As can be seen from fig. 8, 9 and 10, CC is in the range of 0.46 to 499.66 μ M concentration, the peak current and the concentration have a good linear relationship, and the detection limit is 0.097 μ M (S/N is 3). The linear range of HQ is 0.85-500 μ M with a limit of detection of 0.062 μ M (S/N — 3). When CC and HQ were present simultaneously, the peak current increased with increasing hydroquinone and catechol concentrations, indicating that simultaneous analysis of hydroquinone and catechol was feasible with excellent sensitivity.
In addition to sensitivity, the selectivity, stability and reproducibility of the electrodes are also important indicators in measuring the performance of the sensor. K was added to 0.1mM HQ and 0.1mM CC in PBS at 100 times the concentration+、Ca2+、Cu2+、Mg2+、Na+、Ni2+、Zn2+、CO3 2-Mn 50 times the concentration2+、Fe3+And glucose, urea, etc. at 10 times concentration. In the presence of foreign matters, the response currents of HQ and CC are respectively kept between 93.9 and 103.7 percent and between 95.8 and 102.4 percent when no interference exists, which shows that AgNPs/Py-RGO/GCE has excellent selectivity and interference resistance. In PBS solution containing 0.1mM HQ and 0.1mM CC, a same modifying electrode was used10 consecutive CV measurements were performed and showed Relative Standard Deviations (RSD) of CC and HQ of 2.39% and 3.14%, respectively. The AgNPs/Py-RGO/GCE is shown to have good reproducibility. In addition, when AgNPs/Py-RGO/GCE is placed in the refrigerating chamber at 4 ℃ of the refrigerator for four weeks, the response currents of HQ and CC only slightly change, and are respectively 95.8% and 96.2% of the measured current before refrigeration, so that the AgNPs/Py-RGO/GCE has good stability. In order to examine the recovery of HQ and CC, the present invention performed quantitative analysis of HQ and CC in tap water and lake water using standard addition methods, as shown in table 2.
Table 2: the recovery rate of AgNPs/Py-RGO/GCE is counted.
As can be seen from Table 2, the recovery rates of HQ and CC were 94.4% to 101.78% and 93.9% to 103%, respectively. This shows that AgNPs/Py-RGO/GCE prepared by the invention has practical application potential as a sensor.
Claims (7)
1. A preparation method of a nano-silver/pyridine functionalized graphene modified electrode is characterized by comprising the following steps: the method comprises the steps of synthesizing pyridine functionalized graphene (Py-GO), synthesizing Ag nano particles/pyridine functionalized graphene (AgNPs/Py-RGO) and preparing AgNPs/Py-RGO/GCE, wherein the AgNPs/Py-RGO is synthesized by adding silver nitrate and ethylene diamine tetraacetic acid into Py-GO dispersion liquid to form mixed liquid, carrying out water bath till boiling, slowly adding sodium borohydride, continuously heating, then carrying out centrifugal separation and drying.
2. The preparation method of the nano-silver/pyridine functionalized graphene modified electrode according to claim 1, characterized by comprising the following steps: the mass ratio of Py-GO, silver nitrate and ethylene diamine tetraacetic acid in the mixed solution is 14:85:150, the mass ratio of silver nitrate and sodium borohydride is 0.8-1: 1-1.2, and the mixed solution is continuously heated for 1 hour after the sodium borohydride is added.
3. The preparation method of the nano-silver/pyridine functionalized graphene modified electrode as claimed in claim 1 or 2, wherein the preparation method comprises the following steps: and the synthesis of Py-GO is that graphene oxide and pyridine are subjected to ultrasonic treatment for 5-10 min, the reaction is carried out for 40-48 h at the temperature of 60-70 ℃, benzene and acetone are used for washing after the reaction is finished, and the drying is carried out for 12h at the temperature of 60 ℃.
4. The method for preparing a nano-silver/pyridine functionalized graphene modified electrode according to any one of claims 1 to 3, wherein the method comprises the following steps: the AgNPs/Py-RGO/GCE is prepared by pretreating a Glassy Carbon Electrode (GCE), dripping 8 mu of LAgNPs/Py-RGO aqueous solution on the surface of the GCE, naturally airing, wherein the concentration of the LAgNPs/Py-RGO aqueous solution is 2 mg/mL.
5. A preparation method of a nano-silver/pyridine functionalized graphene modified electrode is characterized by comprising the following steps:
(1) Py-GO synthesis
Mixing graphene oxide and pyridine, performing ultrasonic treatment for 5-10 min, reacting at 60-70 ℃ for 40-48 h, washing with benzene and acetone after the reaction is finished, and drying at 60 ℃ for 12h, wherein the dosage ratio of the graphene oxide to the pyridine is 1 g: 3-4 mL;
(2) AgNPs/Py-RGO Synthesis
Dispersing Py-GO in deionized water, performing ultrasonic treatment for 1h to obtain a dispersion liquid with the concentration of 1mg/L, adding silver nitrate and ethylene diamine tetraacetic acid into the Py-GO dispersion liquid to form a mixed liquid, performing water bath till boiling, slowly adding sodium borohydride, continuously heating for 1h, performing centrifugal separation, and drying, wherein the mass ratio of Py-GO to silver nitrate to ethylene diamine tetraacetic acid is 14:85:150, and the mass ratio of silver nitrate to sodium borohydride is 0.8-1: 1-1.2;
(3) preparation of AgNPs/Py-RGO/GCE
And (2) polishing and grinding a glassy carbon electrode (GCE, phi = 3mm) by using alumina powder with the particle size of 0.5 mu m and 0.03 mu m respectively, then ultrasonically cleaning the polished glassy carbon electrode by using deionized water, ethanol and the deionized water in sequence, taking 8 mu LAgNPs/Py-RGO aqueous solution to be dripped on the surface of the GCE, and naturally drying the GCE, wherein the concentration of the AgNPs/Py-RGO aqueous solution is 2 mg/mL.
6. The application of the nano-silver/pyridine functionalized graphene modified electrode as claimed in any one of claims 1 to 5, wherein: the AgNPs/Py-RGO/GCE is used for detecting hydroquinone and catechol.
7. The application of the nano-silver/pyridine functionalized graphene modified electrode as claimed in claim 6, wherein the nano-silver/pyridine functionalized graphene modified electrode comprises: the detection is to use 0.2mol/L PBS buffer solution to prepare hydroquinone and catechol into a solution to be detected, the pH value is 5.5, the AgNPs/Py-RGO/GCE is used for voltammetric cyclic scanning, the scanning potential range is 0-0.8V, and the scanning speed is 180mVs-1。
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