A rutin electrochemical sensing electrode material based on an Au-ZrO2 material and a preparation method and sensor thereof

Abstract

The application provides a rutin electrochemical sensing electrode material based on an Au-ZrO2 material and a preparation method and a sensor thereof, and belongs to the technical field of electrochemical detection.The electrode material comprises the following steps: S1, mixing and stirring zirconium chloride, urea, ethylene glycol and anhydrous ethanol to obtain a mixed solution;S2, reacting the mixed solution in a reaction kettle to obtain a reaction material;S3, sequentially performing centrifugal separation, washing, drying, calcining and grinding on the reaction material to obtain zirconia; and S4, mixing and stirring the zirconia, sodium dodecyl benzene sulfonate, sodium borohydride, a chloroauric acid solution and anhydrous ethanol, and then performing a reaction to obtain the rutin electrochemical sensing electrode material based on the Au-ZrO2 material.The application firstly uses a semiconductor material ZrO2 nanostructure to add Au nanoparticles to perform internal band gap regulation research for the detection of rutin substances, and the sensing performance is good, the linear range is wide, the detection limit is low, and the sensitivity is high.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical detection technology, and specifically relates to a rutin electrochemical sensing electrode material based on Au-ZrO2 material, its preparation method, and a sensor. Background Technology

[0002] Rutin is a pure natural plant extract widely found in fruits and vegetables such as jujubes, apricots, apples, rue leaves, tobacco leaves, orange peel, tomatoes, and buckwheat flowers. It possesses natural antioxidant properties. 1. It can be used as an edible antioxidant and nutritional enhancer. 2. It has anti-inflammatory effects, reducing inflammation caused by mustard oil in animal eyes or skin, and has antiviral properties. 3. It helps maintain vascular resistance, reduces permeability, and decreases fragility. It can be used to prevent and treat diseases such as cerebral hemorrhage, hypertension, retinal hemorrhage, purpura, and acute hemorrhagic nephritis.

[0003] Existing reports indicate that UV-Vis spectrophotometry, capillary electrophoresis, and high-performance liquid chromatography (HPLC) have all been used for rutin detection. While these methods are widely accepted, they are hampered by complex pretreatment requirements, lack of essential specificity, time-consuming nature, and high cost, preventing simultaneous detection and real-time monitoring. The components in actual fruits and vegetables are complex, and chromatographic methods suffer from low sensitivity, long detection cycles, and poor selectivity. Spectrophotometry, while simple to operate, is labor-intensive, has relatively low sensitivity, and its accuracy needs improvement. Capillary electrophoresis requires fewer samples, but the detection process is time-consuming and labor-intensive, and its reproducibility needs improvement. Electrochemical sensing technology has seen widespread application and rapid development this year, with ample technical support. However, its application in rutin detection is currently limited.

[0004] Electrochemical methods offer advantages such as high sensitivity, fast reaction speed, real-time monitoring, portability, and ease of operation. In particular, the portable equipment allows for on-site testing. In recent years, with the implementation of the national health development strategy and increased public awareness of health, food safety, and environmental science, the simultaneous and real-time detection and monitoring of rutin using electrochemical sensing technology in industrial production has become increasingly important.

[0005] Therefore, to detect the rutin content in fruits and vegetables and provide technical support for the development of the fruit and vegetable industry, it is urgent to develop an efficient, convenient, and low-cost detection method for rutin, a flavonoid. Summary of the Invention

[0006] In view of this, the purpose of this invention is to provide a rutin electrochemical sensing electrode material based on Au-ZrO2 material, its preparation method, and a sensor. This invention is the first to use the addition of Au nanoparticles to the semiconductor material ZrO2 nanostructure to study the regulation of its internal band gap for the detection of rutin. It has good sensing performance, wide linear range, low detection limit, and high sensitivity.

[0007] To achieve the above object, the present application provides the following technical solutions.

[0008] In a first aspect, a rutin electrochemical sensing electrode material based on Au-ZrO2 material and a preparation method thereof are provided, which comprises the following steps:

[0009] S1. Zirconium chloride, urea, ethylene glycol and anhydrous ethanol are mixed and stirred to obtain a mixed solution;

[0010] S2. The mixed solution is reacted in a reaction kettle to obtain a reaction material;

[0011] S3. The reaction material is sequentially subjected to centrifugal separation, washing, drying, calcination and grinding to obtain zirconia;

[0012] S4. The zirconia, sodium dodecyl benzene sulfonate, sodium borohydride, chloroauric acid solution and anhydrous ethanol are mixed and stirred, and then reacted to obtain a rutin electrochemical sensing electrode material based on Au-ZrO2 material.

[0013] In the present application, ZrO2 can provide more reactive sites due to its special nanostructure and stable structure, and can make Au nanoparticles better composite therein. Gold nanoparticles have good conductivity and large active area, etc., so they can meet the electrochemical detection of rutin.

[0014] Preferably, the mass-volume ratio of zirconium chloride, urea, ethylene glycol and anhydrous ethanol in S1 is 0.23-0.35g: 0.1-0.2g: 30-50ml: 30-50ml.

[0015] Preferably, the reaction temperature in S2 is 170-190℃, and the reaction time is 10-16h.

[0016] Preferably, the drying temperature in S3 is 110-130℃, and the time is 10-16h.

[0017] Preferably, the calcination time in S3 is 450-550℃, and the time is 1-3h.

[0018] Preferably, the volume-mass ratio of zirconia, sodium dodecyl benzene sulfonate, sodium borohydride, chloroauric acid solution and anhydrous ethanol in S4 is 0.1-0.2g: 0.2-0.3g: 0.02-0.04g: 2.5-4ml: 60-80ml.

[0019] Preferably, the reaction temperature in S4 is 110-130℃, and the time is 3-5h.

[0020] In a second aspect, the application provides a rutin electrochemical sensing electrode material based on Au-ZrO2 material, which is prepared by the method described above.

[0021] In a third aspect, the application provides a preparation method of a rutin electrochemical sensor based on Au-ZrO2 material, which comprises the following steps

[0022] Polishing the GCE electrode;

[0023] And testing the polished GCE in a solution of 5 mM K3[Fe(CN)6], 5 mM K4[Fe(CN)6] and 0.1 M KCl by cyclic voltammetry, wherein the scanning rate is 100 mV, the potential region is -0.2-0.6 V, and the electrode polishing is completed when the potential difference between the oxidation peak and the reduction peak is less than 100 mV.

[0024] Mixing the rutin electrochemical sensing electrode material described above, ethanol, ultrapure water and 0.5% naphthol to obtain a dispersion liquid by ultrasonic dispersion;

[0025] Titration of the dispersion liquid to the surface of the polished GCE electrode, and natural air drying to obtain a sensor for high-performance detection of luteolin.

[0026] As a preferred, the mass-volume ratio of the rutin electrochemical sensing electrode material, ethanol, ultrapure water and 5% naphthol is 1 mg:300 uL:700 uL:10 uL;

[0027] The dosage of the dispersion liquid is 5 uL / cm 2 .

[0028] Beneficial technical effects:

[0029] The application first uses a semiconductor material ZrO2 nanostructure to join Au nanoparticles to regulate the internal band gap for the detection of rutin substances. Meanwhile, the Au@ZrO2 material modified electrode successfully prepared has good detection effect for rutin, the electrode material preparation process is simple, the raw materials are easy to obtain, the preparation method is simple and reliable, the prepared sensing electrode has good sensing performance, wide linear range, low detection limit and high sensitivity. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 XRD pattern of the sensing material obtained in Example 1 and Comparative Example 1;

[0031] Figure 2 SEM image of the sensing material obtained in Example 1 and Comparative Example 1;

[0032] Figure 3 CV curve of the sensor prepared from the sensing material of Example 1 for detecting luteolin;

[0033] Figure 4 Performance detection chart of the sensor prepared by the sensing material of Example 1 for detecting luteolin. DETAILED DESCRIPTION

[0034] The various illustrative embodiments of the present application will now be described in detail in various examples, which should be considered illustrative of the principles of the application, but not in limitation of the same. It is to be understood that the terminology used herein is for the purpose of describing the particular embodiments only and is not intended to be limiting.

[0035] Further, for numerical ranges that are expressly recited herein, it is to be understood that every intervening value between the upper and lower limits of the range is also specifically contemplated. In addition, each smaller range that falls within the interval of any other intervening value in the specific elucidated range is also specifically contemplated. The upper and lower limits of these smaller ranges can independently be included or excluded in the range.

[0036] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict, the present specification will control.

[0037] Various modifications and changes can be made to the specific embodiments of the present application described herein without departing from the scope or spirit of the application. Other embodiments of the application will be apparent to those of ordinary skill in the art from the description and examples presented herein. The description and examples are illustrative of the application and are not intended to limit the scope of the application.

[0038] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", and the like are open-ended terms that are intended to mean including, but not limited to.

[0039] As used herein, the terms "room temperature", "ambient temperature" refer to 25 ± 2 °C, unless otherwise specified.

[0040] The raw materials and instruments used in the following examples of the present application are commercially available, unless otherwise specified.

[0041] Example 1

[0042] This example provides a rutin electrochemical sensing material based on Au-ZrO2 material, and the preparation steps are as follows:

[0043] S1. 0.23 g of zirconium chloride, 0.1 g of urea, 30 ml of ethylene glycol and 30 ml of anhydrous ethanol were mixed and stirred, and placed in a magnetic stirrer for strong stirring to completely dissolve to obtain a mixture;

[0044] S2. The mixture was transferred to a 100 mL stainless steel autoclave coated with polytetrafluoroethylene, and reacted at a temperature of 180°C for 12 hours to obtain a reaction material;

[0045] S3. The reaction material was naturally cooled to obtain a gray-white product, then centrifuged and washed with distilled water and ethanol for 5 times, and finally dried at 120°C for 12h; then the product was calcined by a tube furnace at 500°C for 2 hours, and after grinding, zirconium oxide was obtained;

[0046] S4. 0.1 g of zirconium oxide, 0.2 g of sodium dodecyl benzene sulfonate, 0.02 g of sodium borohydride, 2.5 ml of chloroauric acid solution and 60 ml of anhydrous ethanol were mixed and stirred in a glass beaker, and placed in a magnetic stirrer at room temperature for stirring at a suitable speed to completely dissolve; then the mixture was placed in an oven at 120°C for 4h to obtain a rutin electrochemical sensing material based on Au-ZrO2 material.

[0047] Example 2

[0048] The present embodiment provides a rutin electrochemical sensing material based on Au-ZrO2 material, and the preparation steps are:

[0049] S1. 0.28 g of zirconium chloride, 0.15 g of urea, 40 ml of ethylene glycol and 40 ml of anhydrous ethanol were mixed and stirred, and placed in a magnetic stirrer for strong stirring to completely dissolve to obtain a mixture;

[0050] S2. The mixture was transferred to a 100 mL stainless steel autoclave coated with polytetrafluoroethylene, and reacted at a temperature of 170°C for 16 hours to obtain a reaction material;

[0051] S3. The reaction material was naturally cooled to obtain a gray-white product, then centrifuged and washed with distilled water and ethanol for 5 times, and finally dried at 110°C for 10h; then the product was calcined by a tube furnace at 450°C for 2 hours, and after grinding, zirconium oxide was obtained;

[0052] S4. 0.15 g of zirconium oxide, 0.3 g of sodium dodecyl benzene sulfonate, 0.03 g of sodium borohydride, 3 ml of chloroauric acid solution and 70 ml of anhydrous ethanol were mixed and stirred in a glass beaker, and placed in a magnetic stirrer at room temperature for stirring at a suitable speed to completely dissolve; then the mixture was placed in an oven at 110°C for 5h to obtain a rutin electrochemical sensing material based on Au-ZrO2 material.

[0053] Example 3

[0054] This embodiment provides a rutin electrochemical sensing material based on Au-ZrO2 material, and the preparation steps are as follows:

[0055] S1. Mix 0.35g zirconium chloride, 0.2g urea, 50ml ethylene glycol and 50ml anhydrous ethanol, and stir vigorously with a magnetic stirrer until completely dissolved to obtain a mixture.

[0056] S2. Transfer the mixture to a 150mL stainless steel autoclave coated with polytetrafluoroethylene, and react at 190°C for 12 hours to obtain the reaction mixture;

[0057] S3. The reactants were cooled naturally to obtain a grayish-white product. Then, the product was centrifuged, washed five times with distilled water and ethanol, and finally dried at 130°C for 16 hours. The product was then calcined in a tube furnace at 550°C for 2 hours and ground to obtain zirconium oxide.

[0058] S4. Mix 0.1g zirconium oxide, 0.3g sodium dodecylbenzenesulfonate, 0.04g sodium borohydride, 4ml chloroauric acid solution and 80ml anhydrous ethanol in a glass beaker and stir at a suitable speed with a magnetic stirrer at room temperature until completely dissolved; then place the mixture in an oven at 130℃ for 5h to obtain rutin electrochemical sensing material based on Au-ZrO2 material.

[0059] Experimental Example 1

[0060] XRD pattern analysis:

[0061] like Figure 1 As shown, the peaks of the synthesized ZrO2 at 29.2°, 33.8°, 48.8°, 58.0°, 61.0°, and 72.4° can be attributed to the (101), (200), (220), (211), (222), and (400) crystal plane peaks, which are consistent with the crystal structure of nano ZrO2 (corresponding card PDF#89-6976). The characteristic crystal planes of gold appear in the Au@ZrO2 composite material, and the (101) peak of ZrO2 shows a slight right shift, indicating a strong interaction between Au and ZrO2 in the composite material.

[0062] Experiment Example 2

[0063] Structural characterization:

[0064] like Figure 2The Zr02material is shown to be composed of aggregates of nanoparticles (a) These aggregates are composed of a majority of nanoparticles with sizes ranging from 10 nm to 60 nm. The scanning electron microscopy and transmission electron microscopy of the Au@Zr02composite material are shown in Figures b and c, respectively. It is very prominent that the Au nanoparticles are effectively grown on the spherical Zr02nanostructures. It shows a good uniformity of the particles dispersion (b). The average size of the Au nanoparticles is about 2.35 nm (c). The Zr02nanostructures are obviously changed in structure. This structural change can be attributed to the addition of the Au nanoparticles, which changes the original growth trend of the crystal during the growth process. And this change in the way of crystal growth can theoretically provide more active sites for the detection of catalytic reactions. And the addition of Au nanoparticles itself plays a promoting role in the catalytic process, because Au nanoparticles themselves have good electrical conductivity and catalytic function. Both of them enhance the electrochemical catalytic effect.

[0065] Experimental Example 3

[0066] Performance test of sensing material for detecting rutin

[0067] 1. Preparation of sensing material for high performance detection of rutin

[0068] Electrode polishing:

[0069] The GCE electrode was polished with 0.3 μιη and 0.05 μιη Al203powder to remove the oxide layer on the surface of the electrode, and the polished GCE was tested in a solution of 5 mM K3[Fe(CN)6], 5 mM K4[Fe(CN)6] and 0.1 M KCl by cyclic voltammetry, wherein the scan rate was 100 mV, the potential region was -0.2-0.6 V, and the electrode polishing was completed when the potential difference between the oxidation peak and the reduction peak was less than 100 mV.

[0070] Sensing material and polished electrode composite:

[0071] 1 mg of Au@Zr02obtained in Example 1 was mixed with 400 μΐ^of ethanol, 600 μΐ^of ultrapure water and 10 μΐ^of naphthol (5%), and then ultrasonically treated. Subsequently, 5 μΐ^of the resulting solution was carefully applied to the surface of the original electrode by dispersion titration and allowed to naturally air dry, to obtain a rutin electrochemical sensor based on the Au-Zr02material.

[0072] Meanwhile, a GCE sensor without any modification and a Zr02 / GCE sensor were prepared.

[0073] Electrochemical sensing technology detection: The differential pulse voltammetry (DPV) was used to study the response electrochemical signal of rutin on different electrodes. No obvious DPV response was observed on the bare GCE surface at 100 nM rutin, indicating that the oxidation of rutin on the bare GCE surface was very small or had no catalytic effect. In contrast, the response signal measured on the ZrO2 / GCE was 0.99 μA. A stronger response signal of 4.89 μA was detected on the Au@ZrO2 / GCE, which had a higher rutin response signal. When the potential was scanned from 0 V to 0.8 V at 100 mV / s, rutin was oxidized to a ketone with a similar structure.

[0074] Relationship between electrode response and pH: The DPV oxidation peak current of Au@ZrO2 / GCE was studied in the presence of BR buffer with pH increasing from 2 to 6.5. The DPV oxidation potential shifted from 0 V to 0.8 V. In the BR solution with pH 3, the DPV rutin peak current of Au@ZrO2 was the highest, reaching 20.82 μA. In general, the oxidation of rutin on the electrode surface is mainly a deprotonation process, which is affected by two key factors. High hydrogen ion concentration can inhibit the reaction by increasing the hydrogen ion concentration of the reaction product, while reducing hydrogen ions can enhance the oxidation reaction, but can also reduce the catalytic performance of the electrode. When these opposite factors are balanced, the reaction rate on the electrode surface reaches a peak, producing the largest DPV signal, and the peak current of DPV reaches a maximum at pH 3.

[0075] Actual fruit and vegetable detection:

[0076] The differential pulse voltammetry was used to determine the diluted juice of Kuqia small white apricot by 2000 times;

[0077] The differential pulse voltammetry was also used to determine the diluted juice of Kuqia small white apricot by 2000 times.

[0078] After 5 rounds of testing, the average concentration of rutin in small white apricot juice and small tomato juice was 1.83 and 3.28 nM, respectively, using Au@ZrO2 / GCE as the working electrode.

[0079] In order to improve the reliability of the detection, the standard addition method was used to determine the recovery rate of the electrode in the solution for identifying rutin. After adding rutin at concentrations of 100 nM, 200 nM and 300 nM, the detection recovery rate was always close to 100% (99.78-100.5% in small white apricot juice and 99.79-101.2% in small tomato juice), and the relative standard deviation of each subsequent measurement after addition remained low (1.1%-3.2%).

[0080] 2. Linear relationship detection

[0081] AsFigure 3 As shown in a, the cyclic voltammetry (CV) curve of the Au@ZrO2 / GCE electrode prepared by the application for detecting 100 nM rutin (dissolved in BR buffer, pH: 3) presents regular changes in the redox signal with the increase of the scanning rate, the redox peak intensity gradually increases, the oxidation peak potential moves to the right, and the reduction peak potential moves to the left. The peak voltage and the logarithm of the scanning rate present a linear relationship (b), and thus the charge transfer coefficient is calculated as 0.57, the charge transfer number is 2.3, and it can be obtained that the redox process of rutin on the Au@ZrO2 / GCE is a two-electron and two-proton process. Figure 3

[0082] 3. Sensitivity, detection limit

[0083] As shown in a, the cyclic voltammetry (CV) curve of the Au@ZrO2 / GCE electrode prepared by the application for detecting 100 nM rutin (dissolved in BR buffer, pH: 3) presents regular changes in the redox signal with the increase of the scanning rate, the redox peak intensity gradually increases, the oxidation peak potential moves to the right, and the reduction peak potential moves to the left. The peak voltage and the logarithm of the scanning rate present a linear relationship (b), and thus the charge transfer coefficient is calculated as 0.57, the charge transfer number is 2.3, and it can be obtained that the redox process of rutin on the Au@ZrO2 / GCE is a two-electron and two-proton process. Figure 4 As shown in a, the cyclic voltammetry (CV) curve of the Au@ZrO2 / GCE electrode prepared by the application for detecting 100 nM rutin (dissolved in BR buffer, pH: 3) presents regular changes in the redox signal with the increase of the scanning rate, the redox peak intensity gradually increases, the oxidation peak potential moves to the right, and the reduction peak potential moves to the left. The peak voltage and the logarithm of the scanning rate present a linear relationship (b), and thus the charge transfer coefficient is calculated as 0.57, the charge transfer number is 2.3, and it can be obtained that the redox process of rutin on the Au@ZrO2 / GCE is a two-electron and two-proton process. Figure 4 As shown in a, the cyclic voltammetry (CV) curve of the Au@ZrO2 / GCE electrode prepared by the application for detecting 100 nM rutin (dissolved in BR buffer, pH: 3) presents regular changes in the redox signal with the increase of the scanning rate, the redox peak intensity gradually increases, the oxidation peak potential moves to the right, and the reduction peak potential moves to the left. The peak voltage and the logarithm of the scanning rate present a linear relationship (b), and thus the charge transfer coefficient is calculated as 0.57, the charge transfer number is 2.3, and it can be obtained that the redox process of rutin on the Au@ZrO2 / GCE is a two-electron and two-proton process.

[0084] The above only describes the preferred embodiments of the application, and it should be noted that those of ordinary skill in the art can make several improvements and refinements without departing from the principles of the application, and these improvements and refinements should also be considered within the protection scope of the application.​

Claims

1. A rutin electrochemical sensing electrode material based on Au-Zr02 material, its preparation method, characterized in that, It comprises the following steps: S1. Zirconium chloride, urea, ethylene glycol, anhydrous ethanol are mixed and stirred to obtain a mixed solution; S2. The mixed solution is reacted in a reaction kettle to obtain a reaction material; S3. The reaction material is sequentially subjected to centrifugal separation, washing, drying, calcination and grinding to obtain zirconia; S4. The zirconia, sodium dodecyl benzene sulfonate, sodium borohydride, chloroauric acid solution and anhydrous ethanol are mixed and stirred, and then reacted to obtain a rutin electrochemical sensing electrode material based on Au-ZrO2 material; The volume mass ratio of zirconia, sodium dodecyl benzene sulfonate, sodium borohydride, chloroauric acid solution and anhydrous ethanol in S4 is 0.1-0.2g:0.2-0.3g:0.02-0.04g:2.5-4ml:60-80ml; The reaction temperature in S4 is 110-130℃, and the time is 3-5h.

2. The production method according to claim 1, characterized by, The mass volume ratio of zirconium chloride, urea, ethylene glycol and anhydrous ethanol in S1 is 0.23-0.35g:0.1-0.2g:30-50ml:30-50ml.

3. The preparation method according to claim 1, characterized in that, The reaction temperature in S2 is 170-190℃, and the reaction time is 10-16h.

4. The method of claim 1, wherein, The calcination time in S3 is 450-550℃, and the time is 1-3h.

5. A rutin electrochemical sensing electrode material based on Au-Zr02 material, characterized in that, Prepared by the method of any one of claims 1-4.

6. A method for preparing a rutin electrochemical sensor based on Au-Zr02 material, characterized by, It comprises the following steps The GCE electrode is polished; The rutin electrochemical sensing electrode material of claim 1, ethanol, ultrapure water and 0.5% naphthol are mixed and ultrasonically dispersed to obtain a dispersion liquid; The dispersion liquid is titrated to the surface of the polished GCE electrode, and naturally air-dried to obtain a sensor for high-performance detection of luteolin.

7. The preparation method according to claim 6, characterized in that, The mass volume ratio of the rutin electrochemical sensing electrode material, ethanol, ultrapure water and 5% naphthol is 1mg:300uL:700uL:10uL; The amount of the dispersion liquid is 5 uL / cm 2 .

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