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CN-120971527-B - Glass carbon electrode modified by flexibly detecting tertiary butyl hydroquinone, preparation method and application

CN120971527BCN 120971527 BCN120971527 BCN 120971527BCN-120971527-B

Abstract

The invention relates to the technical field of electrochemical analysis and detection, in particular to a modified glassy carbon electrode for sensitively detecting tertiary butyl hydroquinone, a preparation method and application thereof, which have high specific surface area and catalytic activity and good conductivity, and can realize the sensitive detection of tertiary butyl hydroquinone, wherein the modified glassy carbon electrode comprises a glassy carbon electrode and a compound coating, the compound coating is wrapped on the surface of the glassy carbon electrode, and the compound coating consists of graphene oxide and Ti-based MOF derivatives; the preparation method comprises the following steps of (1) MIL-125 (Ti) preparation, (2) TiO 2 /NC preparation, (3) 15% GO@TiO 2 /NC preparation, (4) preparation of 15% GO@TiO 2 /NC composite material dispersion liquid, and (5) preparation of a modified electrode, wherein the application of the modified electrode comprises the following steps of S1, establishing a concentration-electrochemical response signal relation, and S2, measuring the concentration of an object to be measured.

Inventors

  • TANG JING
  • ZHENG SHENGBIAO
  • CUI SHIYU
  • SHU LINGXIU
  • GUO JIAHAO
  • SU XING
  • WANG XUCHUN

Assignees

  • 安徽科技学院

Dates

Publication Date
20260508
Application Date
20250805

Claims (6)

  1. 1. The preparation method of the glassy carbon electrode modified by detecting tertiary butyl hydroquinone is characterized by comprising the following steps of: (1) 2-amino terephthalic acid and terephthalic acid are completely dissolved in N, N-dimethylformamide solution, methanol is added, tetraisopropyl titanate is added into the solution, stirring is carried out until yellow precipitate appears, the solution is sealed in a reaction kettle after ultrasonic treatment, after the reaction kettle is cooled to room temperature, the solution is taken out, and after the solution is washed and centrifuged for three times by DMF and methanol, the solution is put into a vacuum drying oven for drying, and yellow MOF powder is obtained; (2) Preparing TiO 2 /NC, namely completely carbonizing the obtained MIL-125 (Ti) material in a tube furnace under the atmosphere of N 2 to obtain black powder of the TiO 2 /NC composite material; (3) Dissolving a certain amount of single-layer GO into DMF, carrying out ultrasonic treatment, weighing TiO 2 /NC, mixing terephthalic acid with the solution, stirring at room temperature, transferring the solution into a reaction kettle for reaction, taking out the solution after the reaction kettle is cooled to room temperature, washing and centrifuging the solution with DMF and deionized water for three times respectively, and drying the obtained 15% GO@TiO 2 /NC in a vacuum oven to obtain black powder, wherein 15% represents the weight percentage of GO to TiO 2 /NC; (4) 15% GO@TiO 2 /NC dispersion liquid is prepared by dispersing 15% GO@TiO 2 /NC in N, N-dimethylformamide and carrying out ultrasonic treatment on the mixture to obtain 15% GO@TiO 2 /NC dispersion liquid; (5) And (3) preparing a modified electrode, namely dripping the composite material dispersion liquid in the step (4) on the polished and cleaned glassy carbon electrode surface by adopting a dripping method, and drying to obtain the 15% GO@TiO 2 /NC composite modified electrode.
  2. 2. The method for preparing the glassy carbon electrode modified by detecting tertiary butyl hydroquinone according to claim 1, wherein the mixed solution in the step (1) is subjected to ultrasonic treatment for 30 seconds, transferred to a reaction kettle, placed into an oven for reaction at 150 ℃ for 24 hours, centrifuged, and placed into a vacuum drying oven for drying at 100 ℃ for 12 hours.
  3. 3. The method for preparing the glassy carbon electrode modified by detecting tertiary butyl hydroquinone according to claim 1, wherein the MIL-125 (Ti) powder in the step (2) is carbonized at 1000 ℃ for 5 hours under the atmosphere of N 2 .
  4. 4. The method for preparing the glassy carbon electrode modified by detecting tertiary butyl hydroquinone according to claim 1, wherein the dripping amount of the 15% GO@TiO 2 /NC dispersion liquid in the step (5) is 10 mu L.
  5. 5. The application of the glassy carbon electrode modified by detecting tertiary butyl hydroquinone is characterized by comprising the following steps of: S1, establishing a concentration-electrochemical response signal relation, namely preparing standard solutions with a series of concentration gradients, respectively placing a working electrode, an auxiliary electrode and a reference electrode, detecting an electrochemical response signal on the working electrode, and establishing a concentration-electrochemical response signal relation according to the corresponding relation between the electrochemical response signal and the concentration; S2, measuring the concentration of an object to be measured, namely placing a working electrode, an auxiliary electrode and a reference electrode in the solution of the object to be measured, detecting an electrochemical response signal on the working electrode, and calculating to obtain the concentration of the object to be measured according to the relation between the concentration obtained in the S1 and the electrochemical response signal; The working electrode is a 15% GO@TiO 2 /NC compound modified electrode prepared by the preparation method according to any one of claims 1-4, and the solution of the to-be-detected substance in S2 is a tert-butylhydroquinone solution.
  6. 6. The use of a tertiary butyl hydroquinone modified glassy carbon electrode as claimed in claim 5, wherein the method for detecting the electrochemical response signal on the working electrode in S2 is to detect the reduction peak current on the working electrode by cyclic voltammetry.

Description

Glass carbon electrode modified by flexibly detecting tertiary butyl hydroquinone, preparation method and application Technical Field The invention relates to the technical field of electrochemical analysis and detection, in particular to a glassy carbon electrode modified by tert-butylhydroquinone for sensitive detection, a preparation method and application thereof. Background Tertiary butyl hydroquinone is a key synthetic antioxidant in the food industry, can effectively block the oxidation reaction of grease, and remarkably prolongs the shelf life of food. The unique oxidation resistance makes it widely used in oil-containing food such as fried food, instant noodles, etc. However, excessive intake may pose a potential risk to human health. Therefore, the method for detecting tertiary butyl hydroquinone is important for guaranteeing food safety, standardizing food additive use and maintaining consumer health, and provides scientific basis for regulatory departments. The detection of the tertiary butyl hydroquinone of the current food additive mainly depends on traditional methods such as gas chromatography, liquid chromatography, fluorescence analysis and the like, but the technologies generally have the limitations of complicated pretreatment, complex operation and the like. In contrast, electrochemical analysis methods have great potential due to their advantages of rapid response, high precision, good selectivity, etc., but the detection performance of bare electrodes is still significantly insufficient. In recent years, chemical modified electrode technology, especially complex modified electrode, has been widely used in the field of analysis and detection due to its high density of active sites and strong signal response. The research on the application of the dripping modified electrode based on graphene oxide composite Ti-based MOF derivative materials to tertiary butyl hydroquinone detection is not yet reported. Disclosure of Invention In order to solve the technical problems, the invention provides a modified glassy carbon electrode which has high specific surface area and catalytic activity, good conductivity and can realize sensitive determination on tertiary butyl hydroquinone, and a preparation method and application thereof. The invention discloses a sensitive detection tertiary butyl hydroquinone modified glassy carbon electrode, which comprises a glassy carbon electrode and a compound coating, wherein the compound coating is wrapped on the surface of the glassy carbon electrode, and the compound coating is formed by compounding graphene oxide and Ti-based MOF derivatives. The invention discloses a preparation method of a glassy carbon electrode modified by sensitive detection tertiary butyl hydroquinone, which comprises the following steps: (1) MIL-125 (Ti) was prepared from 2-aminoterephthalic acid and terephthalic acid, completely dissolved in N, N-dimethylformamide solution, and methanol was added. Adding tetraisopropyl titanate into the solution, stirring until yellow precipitation appears, and sealing the solution in a reaction kettle after ultrasonic treatment. After the reaction kettle is cooled to room temperature, taking out and centrifuging, washing with DMF and methanol for three times respectively, and then putting into a vacuum drying oven for drying to obtain yellow MOF powder; (2) TiO 2/NC was prepared and the resulting MIL-125 (Ti) was fully carbonized in a tube furnace under an atmosphere of N 2. Obtaining black powder of the TiO 2/NC composite material; (3) 15% GO@TiO 2/NC. A certain amount of monolayer GO was dissolved in DMF and sonicated. TiO 2/NC and terephthalic acid were weighed and mixed with the solution and stirred at room temperature. The solution was then transferred to a reaction vessel for reaction. After the reaction vessel was cooled to room temperature, the solution was removed and centrifuged three times with DMF and deionized water, respectively. Finally, drying the obtained 15% GO@TiO 2/NC in a vacuum oven to obtain black powder; (4) 15% GO@TiO 2/NC dispersion liquid is prepared by dispersing 15% GO@TiO 2/NC in N, N-dimethylformamide and carrying out ultrasonic treatment on the mixture to obtain 15% GO@TiO 2/NC dispersion liquid; (5) And (3) preparing a modified electrode, namely dripping the composite material dispersion liquid in the step (4) on the polished and cleaned glassy carbon electrode surface by adopting a dripping method, and drying to obtain the 15% GO@TiO 2/NC composite modified electrode. Further, 0.5435g (3 mmoL) of 2-amino terephthalic acid and 0.4984g (3 mmoL) of terephthalic acid in step (1) were completely dissolved in 20ml of an N, N-dimethylformamide solution, and 2.2ml of methanol was added. To the solution was added 0.9ml of tetraisopropyl titanate, stirred for 30min until a yellow precipitate appeared, sonicated for 30s and then sealed in a reaction vessel, and reacted at 150 ℃ for 24h. After the reaction vessel was cooled to r