CN109470749B - Organic-inorganic hybrid compound based on polyacid, electrochemical sensor, and preparation method and application of electrochemical sensor - Google Patents
Organic-inorganic hybrid compound based on polyacid, electrochemical sensor, and preparation method and application of electrochemical sensor Download PDFInfo
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Abstract
The invention relates to the field of preparation of organic-inorganic composite materials, and particularly discloses a polyacid-based organic-inorganic hybrid compound, and a preparation method and application of an electrochemical sensor. The molecular formula of the organic-inorganic hybrid compound is as follows: (H)2L)3(PMo12O40)2Wherein L is 1, 3-bis (imidazolyl) propane. Provided by the present invention (H)2L)3(PMo12O40)2Compounds and compounds prepared therefrom (H)2L)3(PMo12O40)2The MWCNTs/GCE electrochemical sensor has excellent electrochemical sensing performance, the linear range is 1-20 mu mol/L, the detection limit is 0.05 mu mol/L, the MWCNTs/GCE electrochemical sensor is not interfered by 2-naphthol, hydroquinone, sodium chloride, ferric chloride, copper sulfate and sodium nitrate, and after the MWCNTs/GCE electrochemical sensor is placed for 30 days, the current response value can still reach more than 92 percent of the original current response value, and the MWCNTs/GCE electrochemical sensor has extremely high stability.
Description
Technical Field
The invention relates to the technical field of preparation of organic-inorganic composite materials, in particular to an organic-inorganic hybrid compound based on polyacid, an electrochemical sensor, a preparation method and application thereof.
Background
The inorganic-organic hybrid compound contains both inorganic and organic components, can organically combine the performance advantages of the inorganic compound and the organic compound, improve the defects of the inorganic component and the organic component, and construct a novel hybrid compound with stable and plastic structure. The polyoxometallate becomes an important inorganic component for constructing a novel inorganic-organic hybrid compound due to the structural diversity of the polyoxometallate, and has potential application prospects in various fields such as catalysis, sensors, environmental protection, medicines, photoelectric devices and the like.
Bisphenols (BP) are well known endocrine disrupting compounds, containing two hydroxyphenyl groups, and have more than fifteen analogs; there is a great deal of evidence that bisphenols have adverse effects on human health and the environment. Bisphenol a (bpa) is a very important member of the BP family, and as an important chemical raw material, bisphenol a (bpa) is widely used in the production of epoxy resins and polycarbonate plastics. At present, trace amounts of bisphenol A have been found to be present in baby bottles, plastic beverage bottles, metal packaged foods. BPA can enter an organism to imitate, block, interfere or change the action of the hormone of the organism, so that the endocrine system of the body is disordered, the transmission of the nervous system is blocked, the immune function of the organism is reduced, even the organ malformation and canceration are caused, and the health and the survival of the human body are seriously threatened. Therefore, the method has important practical significance for quickly and accurately detecting the bisphenol A. However, the existing electrochemical sensor for detecting BPA still has the defects of poor selectivity and stability, low sensitivity and the like.
Disclosure of Invention
Aiming at the problems of poor selectivity and stability and low sensitivity of the existing electrochemical sensor for detecting BPA, the invention provides an organic-inorganic hybrid compound based on polyacid, an electrochemical sensor, a preparation method and application thereof.
In order to solve the above technical problems, the embodiment of the present invention provides a technical solution 1:
a polyacid-based organic-inorganic hybrid compound of the formula: (H)2L)3(PMo12O40)2Wherein L is 1, 3-bis (imidazolyl) propane.
In the technical scheme, phosphomolybdic acid and 1, 3-bis (imidazolyl) propane ligand are coordinated to synthesize (H) with three-dimensional supermolecular structure2L)3(PMo12O40)2The organic-inorganic hybrid compound increases the specific surface area of the heteropoly acid, so that the heteropoly acid can be in full contact with reactants when being applied to the sensing field, and the detection sensitivity is improved; and (H)2L)3(PMo12O40)2A large number of gaps exist in the three-dimensional supermolecular structure, and the gaps can be used as transmission channels, so that the electron transfer in the electrochemical reaction process and the diffusion of reactants or reaction products are facilitated; at the same time, (H)2L)3(PMo12O40)2The three-dimensional supermolecular structure also has extremely high stability, the catalytic performance is not obviously reduced after being placed for 30 days, and the application prospect is wide.
(H) produced by the invention in contrast to one-or two-dimensional materials2L)3(PMo12O40)2The three-dimensional supermolecule organic-inorganic compound solves the problem that active substances are easy to agglomerate in the preparation process and the catalytic reaction, so that the catalytic efficiency is seriously reduced.
Preferably, the preparation method of the organic-inorganic hybrid compound comprises the following steps:
step one, respectively weighing 1, 3-bis (imidazolyl) propane and phosphomolybdic acid, and dispersing and dissolving in distilled water to obtain a dispersion liquid;
and step two, adjusting the pH value of the dispersion liquid to 4.0-5.0, heating to 145 ℃ for reaction at 115 ℃ for 125h, cooling, washing and drying to obtain the organic-inorganic hybrid compound.
Preferably, the molar ratio of the 1, 3-bis (imidazolyl) propane to the phosphomolybdic acid is from 0.8 to 1.2: 1.
The preparation method is simple to operate, the product yield is over 85 percent, the product preparation cost is low, and the method can be used for batch industrial production.
The technical scheme 2 provided by the embodiment of the invention is as follows:
a polyacid-based electrochemical sensor: the electrochemical sensor comprises a GCE electrode, a multi-wall carbon nano tube wrapped outside the GCE electrode and the organic-inorganic hybrid compound wrapped outside the multi-wall carbon nano tube.
Due to (H)2L)3(PMo12O40)2The organic-inorganic hybrid compound with a three-dimensional supermolecular structure can organically combine the performance advantages of an inorganic compound and an organic compound, and has excellent electrochemical properties, so the organic-inorganic hybrid compound has wide application prospects in the field of electrochemical sensing.
The multi-wall carbon nano-tube (MWCNTs) has large specific surface area, namely (H)2L)3(PMo12O40)2The compound provides a large number of surface adsorption sites, promotes the transmission rate of electrons on the surface of the electrode, and obviously improves the electrocatalytic activity of the electrochemical sensor through the synergistic effect of the two. And (H)2L)3(PMo12O40)2Has strong electrostatic effect between the compound and the multi-wall carbon nano-tube, and can effectively prevent (H)2L)3(PMo12O40)2The compound falls off, so that the repeatability and stability of the sensor are ensured.
Preferably, the mass ratio of the multi-walled carbon nanotubes to the organic-inorganic compound is 1: 1.3-1.6.
Preferably (H)2L)3(PMo12O40)2The mass ratio of the compound to the multi-walled carbon nanotube can ensure that the prepared electrochemical sensor has the optimal electrochemical catalytic activity.
Preferably, the method for preparing the polyacid-based electrochemical sensor comprises the following steps:
step a, respectively weighing the organic-inorganic hybrid compound and the multi-walled carbon nano tube, and ultrasonically dispersing in distilled water to obtain an organic-inorganic hybrid compound dispersion liquid and a multi-walled carbon nano tube dispersion liquid;
b, dripping the multi-wall carbon nanotube dispersion liquid on the surface of the GCE electrode, and airing to obtain a multi-wall carbon nanotube/GCE electrode;
c, dropwise coating the organic-inorganic hybrid compound dispersion liquid on the surface of the multi-walled carbon nanotube/GCE electrode, and airing to obtain polyacid-based (H)2L)3(PMo12O40)2the/MWCNTs/GCE electrochemical sensor.
The preparation method is that (H)2L)3(PMo12O40)2Directly dripping the compound and multi-wall carbon nano-tube on the surface of a glassy carbon electrode, and airing at room temperature to obtain (H)2L)3(PMo12O40)2The MWCNTs membrane is not cracked and firmly adhered to the surface of an electrode, so that the sensitivity and the stability of the electrochemical sensor are improved.
Preferably, the concentration of the organic-inorganic hybrid compound dispersion liquid and the concentration of the multi-wall carbon nano tube dispersion liquid are both 8-12 mg/mL.
The organic-inorganic hybrid compound dispersion liquid and the multi-walled carbon nanotube dispersion liquid are respectively set to have concentrations of 8-12mg/mL so as to obtain (H)2L)3(PMo12O40)2And the multi-wall carbon nano tubes are more uniformly distributed on the surface of the GCE electrode, so that the sensing performance of the electrode is improved.
The invention also provides application of the organic-inorganic hybrid compound in the field of detection of bisphenol compounds.
The invention also provides application of the polyacid-based electrochemical sensor in the field of detection of bisphenol compounds.
Provided by the present invention (H)2L)3(PMo12O40)2The organic-inorganic hybrid compound has higher affinity to bisphenol A, can realize rapid detection of bisphenol A by preparing the electrochemical sensor from the organic-inorganic hybrid compound, has high sensitivity, low detection limit and simple operation, can be stored for a long time, and can be stably stored for one month.
Drawings
FIG. 1 is (H) in the preparation of example 12L)3(PMo12O40)2Schematic representation of the structural units of the compound;
FIG. 2 is (H) in the preparation of example 12L)3(PMo12O40)2A schematic representation of the three-dimensional structure of a compound;
FIG. 3 is an electrochemical impedance plot of various modified electrodes prepared in example 1;
FIG. 4 is (H) in preparation of example 12L)3(PMo12O40)2Differential Pulse Voltammetry (DPV) curves of the/MWCNTs/GCE electrochemical sensor in bisphenol A solutions with different concentrations;
FIG. 5 is (H) in preparation of example 12L)3(PMo12O40)2A calibration curve of the current response of the/MWCNTs/GCE electrochemical sensor to the bisphenol A concentration;
FIG. 6 is (H) in preparation of example 12L)3(PMo12O40)2A schematic of the DPV current response of the/MWCNTs/GCE electrochemical sensor to the addition of the different interferent bisphenol A;
FIG. 7 is (H) in preparation of example 12L)3(PMo12O40)2Schematic of the current response of the/MWCNTs/GCE electrochemical sensor to BPA at different times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following 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.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
(H2L)3(PMo12O40)2Preparation of the compound:
step one, weighing 0.11g of 1, 3-bis (imidazolyl) propane and 0.018g of phosphomolybdic acid, adding the 1, 3-bis (imidazolyl) propane and the phosphomolybdic acid into 100mL of distilled water, and performing ultrasonic dissolution to obtain dispersion liquid;
step two, adjusting the pH of the dispersion to4.5, placing the mixed solution with the adjusted pH value into a stainless steel reaction kettle transferred to a polytetrafluoroethylene lining, placing the stainless steel reaction kettle into a blast drying oven, reacting for 120 hours at 140 ℃, cooling, washing and drying to obtain (H)2L)3(PMo12O40)2A compound is provided.
(H2L)3(PMo12O40)2Preparation of the/GCE electrochemical sensor:
respectively polishing glassy carbon electrodes on a polishing plate by sequentially adopting 1.0, 0.3 and 0.05 mu m aluminum oxide powder, sequentially ultrasonically cleaning in water, absolute ethyl alcohol and water after each polishing, and drying by using nitrogen for later use;
weighing (H) prepared as described above2L)3(PMo12O40)2Dissolving 0.1g of compound in 10mL of distilled water, and ultrasonically dispersing for 30min to uniformly disperse the compound to obtain (H)2L)3(PMo12O40)2A dispersion liquid; suction with pipette (H)2L)3(PMo12O40)23 mu L of dispersion liquid is dripped on a pretreated glassy carbon electrode and dried to obtain (H)2L)3(PMo12O40)2A/GCE electrochemical sensor (hereinafter abbreviated as POMs/GCE).
Preparing MWCNTs/GCE electrochemical sensor:
respectively polishing glassy carbon electrodes on a polishing plate by sequentially adopting 1.0, 0.3 and 0.05 mu m aluminum oxide powder, sequentially ultrasonically cleaning in water, absolute ethyl alcohol and water after each polishing, and drying by using nitrogen for later use;
weighing 0.1g of MWCNTs, dissolving in 10ml of distilled water, and performing ultrasonic dispersion for 30min to uniformly disperse the MWCNTs to obtain MWCNTs dispersion liquid; sucking 2 mu L of MWCNTs dispersion liquid by using a liquid transfer gun, dripping the MWCNTs dispersion liquid on the pretreated glassy carbon electrode, and airing for later use to serve as the MWCNTs/GCE electrode;
(H2L)3(PMo12O40)2preparation of MWCNTs/GCE electrochemical sensor:
respectively polishing glassy carbon electrodes on a polishing plate by sequentially adopting 1.0, 0.3 and 0.05 mu m aluminum oxide powder, sequentially ultrasonically cleaning in water, absolute ethyl alcohol and water after each polishing, and drying by using nitrogen for later use;
weighing 0.1g of MWCNTs, dissolving in 10ml of distilled water, and performing ultrasonic dispersion for 30min to uniformly disperse the MWCNTs to obtain MWCNTs dispersion liquid; sucking 2 mu L of MWCNTs dispersion liquid by using a liquid transfer gun, dripping the MWCNTs dispersion liquid on the pretreated glassy carbon electrode, and airing for later use to serve as the MWCNTs/GCE electrode;
weighing (H) prepared as described above2L)3(PMo12O40)2Dissolving 0.1g of compound in 10mL of distilled water, and ultrasonically dispersing for 30min to uniformly disperse the compound to obtain (H)2L)3(PMo12O40)2A dispersion liquid; suction with pipette (H)2L)3(PMo12O40)2Dripping 3 μ L of the dispersion solution on MWCNTs/GCE electrode, and air drying to obtain (H)2L)3(PMo12O40)2the/MWCNTs/GCE electrochemical sensor (hereinafter abbreviated as POMs/MWCNTs/GCE).
Prepared in this example (H)2L)3(PMo12O40)2The crystal structure of the compound was determined, and the results are shown in Table 1.
Hydrogen bonding of the compounds of Table 1
The single crystal diffraction shows that the compound is a tricinic crystal system, the space group is P-1, and the unit cell parameters are
alpha＝72.666deg,
beta＝74.908deg,
gamma＝70.945deg，
The compound contains 3 protonated ligands H2L and two non-coordinating Keggin-type heteropolyanions [ PMo ]12O40]3-As shown in FIG. 1, [ PMo ]12O40]3-Has a structure of one { PO4Tetrahedrally wrapped by 12 MoO6The center of the octahedral formed cage. Valence calculations indicate that all P is in the + V oxidation state, Mo is in the + VI oxidation state, and ligand L is protonated to balance the charge across the molecule.
The polyacid anion and the ligand form a three-dimensional supermolecular structure through hydrogen bonds. The polyacid anions are connected through O-H … O hydrogen bonds formed between terminal oxygens, 2 polyacid anions and three surrounding ligands form secondary structural units through N-H … O hydrogen bonds, and finally, N-H … O hydrogen bonds and C-H … O formed between every two adjacent secondary structural units through the terminal oxygens of the polyacid and the N and C of the ligands respectively form a three-dimensional supramolecular structure, as shown in figure 2.
Example 2
(H2L)3(PMo12O40)2Preparation of the compound:
step one, weighing 0.088g of 1, 3-bis (imidazolyl) propane and 0.018g of phosphomolybdic acid, adding the weighed materials into 100mL of distilled water, and performing ultrasonic dissolution to obtain dispersion liquid;
step two, adjusting the pH of the dispersion to 4.0 by NaOH, placing the mixed solution with the adjusted pH into a stainless steel reaction kettle transferred to a polytetrafluoroethylene lining, placing the stainless steel reaction kettle into a blast drying oven, reacting for 125 hours at 135 ℃, cooling, washing and drying to obtain (H)2L)3(PMo12O40)2A compound is provided.
(H2L)3(PMo12O40)2Preparation of MWCNTs/GCE electrochemical sensor:
respectively polishing glassy carbon electrodes on a polishing plate by sequentially adopting 1.0, 0.3 and 0.05 mu m aluminum oxide powder, sequentially ultrasonically cleaning in water, absolute ethyl alcohol and water after each polishing, and drying by using nitrogen for later use;
weighing 0.08g of MWCNTs, dissolving in 10ml of distilled water, and performing ultrasonic dispersion for 30min to uniformly disperse the MWCNTs to obtain MWCNTs dispersion liquid; sucking 2 mu L of MWCNTs dispersion liquid by using a liquid transfer gun, dripping the MWCNTs dispersion liquid on the pretreated glassy carbon electrode, and airing for later use to serve as the MWCNTs/GCE electrode;
weighing (H) prepared as described above2L)3(PMo12O40)2Dissolving 0.12g of compound in 10mL of distilled water, and ultrasonically dispersing for 30min to uniformly disperse the compound to obtain (H)2L)3(PMo12O40)2A dispersion liquid; suction with pipette (H)2L)3(PMo12O40)2And dripping 1 mu L of dispersion liquid on the MWCNTs/GCE electrode, and airing to obtain the POMs/MWCNTs/GCE electrochemical sensor.
Example 3
(H2L)3(PMo12O40)2Preparation of the compound:
step one, weighing 0.132g of 1, 3-bis (imidazolyl) propane and 0.018g of phosphomolybdic acid, adding the 1, 3-bis (imidazolyl) propane and the phosphomolybdic acid into 100mL of distilled water, and performing ultrasonic dissolution to obtain dispersion liquid;
step two, adjusting the pH of the dispersion to 5.0 by NaOH, placing the mixed solution with the adjusted pH into a stainless steel reaction kettle transferred to a polytetrafluoroethylene lining, placing the stainless steel reaction kettle into a blast drying oven, reacting for 115 hours at 145 ℃, cooling, washing and drying to obtain (H)2L)3(PMo12O40)2A compound is provided.
(H2L)3(PMo12O40)2Preparation of MWCNTs/GCE electrochemical sensor:
respectively polishing glassy carbon electrodes on a polishing plate by sequentially adopting 1.0, 0.3 and 0.05 mu m aluminum oxide powder, sequentially ultrasonically cleaning in water, absolute ethyl alcohol and water after each polishing, and drying by using nitrogen for later use;
weighing 0.12g of MWCNTs, dissolving in 10ml of distilled water, and performing ultrasonic dispersion for 30min to uniformly disperse the MWCNTs to obtain MWCNTs dispersion liquid; sucking 2.2 mu L of MWCNTs dispersion liquid by using a liquid transfer gun, dripping the MWCNTs dispersion liquid on a pretreated glassy carbon electrode, and airing for later use to serve as an MWCNTs/GCE electrode;
weighing (H) prepared as described above2L)3(PMo12O40)2Dissolving 0.08g of compound in 10mL of distilled water, and performing ultrasonic dispersion for 30min to uniformly disperse the compound to obtain (H)2L)3(PMo12O40)2A dispersion liquid; suction with pipette (H)2L)3(PMo12O40)2And dripping 2 mu L of dispersion liquid on the MWCNTs/GCE electrode, and airing to obtain the POMs/MWCNTs/GCE electrochemical sensor.
Example 4
The bisphenol a electrochemical sensor prepared in example 1 was used for electrochemical testing:
(1) electrochemical AC impedance testing of differently modified electrodes
The content of 5mM K is respectively measured on the GCE electrode, the MWCNTs/GCE electrode, the POMs/GCE electrode and the POMs/MWCNTs/GCE electrode3[Fe(CN)6]/K4[Fe(CN)6]The experimental results of the alternating current impedance signals in the electrolyte of the probe are shown in FIG. 3, the impedance values of the GCE electrode, the MWCNTs/GCE electrode, the POMs/GCE electrode and the POMs/MWCNTs/GCE electrode are respectively about 40 omega, 57 omega, 960 omega and 92 omega, and the POMs/MWCNTs/GCE electrode has higher electron transmission rate and smaller electron transfer resistance.
(2) Differential pulse voltammetry test of POMs/MWCNTs/GCE electrode on bisphenol A
The POMs/MWCNTs/GCE electrode is used as a working electrode, the reference electrode is an Ag/AgCl electrode, and the auxiliary electrode is a platinum electrode; the base solution is 0.05mol/L potassium ferricyanide PBS solution (pH 7.0), the molecular imprinting sensor is placed in the differential pulse testing base solution, and blank current I is obtained by scanning0Then the POMs/MWCNTs/GCE electrode is placed in bisphenol A solution with certain concentration, and scanning is carried out to obtain current I, and then the response current of the sensor is delta I-I0And (ii) the results of the assay are shown in FIG. 4. The current values were plotted against the concentration of BPA added to give FIG. 5, where Y is 0.711+0.179X, R2Linear equation of 0.992, where Y isThe resulting current response after the addition of BPA, X is the concentration of BPA. The linear range of bisphenol A was determined to be 1-20. mu. mol/L with a detection limit of 0.05. mu. mol/L.
In FIG. 4, the peaks of the pulse voltammetry curves are arranged from bottom to top, and the concentration of bisphenol A represented by each curve is 1, 4, 7, 12, 15 and 20. mu. mol/L.
(3) Selective testing
BPA usually exists in the same system with some biological small molecules and inorganic ions, so that the prepared sensor can not be interfered by the substances in actual detection and has important significance. The interference rejection was studied using differential pulse voltammetry by adding interfering substances to a 0.05M PBS buffer (pH 7.0) with a BPA concentration of 20 μmol/L. The selected interferents are 2-naphthol, hydroquinone, NaCl, FeCl3，CuSO4，NaNO3The concentration of the interfering substance added was 10. mu. mol/L. The experimental result is shown in FIG. 6, the POMs/MWCNTs/GCE modified electrode has no obvious response to other interfering substances except the BPA, and the prepared sensor has good selectivity and anti-interference capability.
(4) Stability test
To investigate the stability of the prepared sensors, the current response of POMs/MWCNTs/GCE modified electrodes to BPA after 1, 5, 10, 20, 30 days of standing in 0.05M PBS (pH 7.0) buffer solution with BPA concentration of 15 μmol/L was determined using DPV. This demonstrates the good long term stability of the prepared sensor, as shown in fig. 7.
(5) Actual sample testing
To further examine the practical application of the modified electrode, two water samples, i.e., purified water (sample 1) and mineral water (sample 2), were taken, and 5. mu. mol/L BPA and 10. mu. mol/LBPA were added thereto, and the results were measured by DPV, as shown in Table 2.
TABLE 2 actual sample test results
The detection results in table 2 show that the recovery rate of the method for detecting bisphenol A by using the electrochemical sensor with the POMs/MWCNTs/GCE modified electrode is 93.0-100.2%, which indicates that the POMs/MWCNTs/GCE sensor prepared by the invention has high detection precision on bisphenol A and accurate and reliable results.
In summary, (H) in the embodiments of the present invention2L)3(PMo12O40)2Compounds and compounds prepared therefrom (H)2L)3(PMo12O40)2The MWCNTs/GCE electrochemical sensor has excellent electrochemical sensing performance, the linear range is 1-20 mu mol/L, the detection limit is 0.05 mu mol/L, the MWCNTs/GCE electrochemical sensor is not interfered by 2-naphthol, hydroquinone, sodium chloride, ferric chloride, copper sulfate and sodium nitrate, and after the MWCNTs/GCE electrochemical sensor is placed for 30 days, the current response value can still reach more than 92 percent of the original current response value, and the MWCNTs/GCE electrochemical sensor has extremely high stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A polyacid-based organic-inorganic hybrid compound having the formula: (H)2L)3(PMo12O40)2Wherein L is 1, 3-bis (imidazolyl) propane;
the preparation method of the organic-inorganic hybrid compound comprises the following steps:
step one, respectively weighing 1, 3-bis (imidazolyl) propane and phosphomolybdic acid, and dispersing and dissolving in distilled water to obtain a dispersion liquid;
and step two, adjusting the pH value of the dispersion liquid to 4.0-5.0, heating to 145 ℃ for reaction at 115 ℃ for 125h, cooling, washing and drying to obtain the organic-inorganic hybrid compound.
2. A polyacid-based organic-inorganic hybrid compound according to claim 1, wherein the molar ratio of 1, 3-bis (imidazolyl) propane to phosphomolybdic acid is from 0.8 to 1.2: 1.
3. A polyacid-based electrochemical sensor comprising a GCE electrode, multi-walled carbon nanotubes wrapped around the GCE electrode, and an organic-inorganic hybrid compound of claim 1 wrapped around the multi-walled carbon nanotubes.
4. The polyacid-based electrochemical sensor of claim 3, wherein the mass ratio of the multi-walled carbon nanotubes to the organic-inorganic compound is from 1:1.3 to 1.6.
5. The method for preparing a polyacid-based electrochemical sensor of claim 3 or 4, comprising the steps of:
step a, respectively weighing the organic-inorganic hybrid compound and the multi-walled carbon nano tube, and ultrasonically dispersing in distilled water to obtain an organic-inorganic hybrid compound dispersion liquid and a multi-walled carbon nano tube dispersion liquid;
b, dripping the multi-wall carbon nanotube dispersion liquid on the surface of the GCE electrode, and airing to obtain a multi-wall carbon nanotube/GCE electrode;
and c, dropwise coating the organic-inorganic hybrid compound dispersion liquid on the surface of the multi-walled carbon nanotube/GCE electrode, and airing to obtain the polyacid-based electrochemical sensor.
6. The method of claim 5, wherein the organic-inorganic hybrid compound dispersion and the multi-walled carbon nanotube dispersion are each present at a concentration of 8-12 mg/mL.
7. Use of an organic-inorganic hybrid compound according to any one of claims 1-2 for the electrochemical detection of bisphenolic compounds.
8. Use of a polyacid-based electrochemical sensor according to any one of claims 3 to 4 for the detection of bisphenols.
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