A preparation method of a photoelectrochemical sensor for detecting tetracycline hydrochloride

Abstract

The application belongs to the technical field of detecting tetracycline hydrochloride by photoelectrochemical sensor, and discloses a preparation method of a novel photoelectrochemical sensor material and its application in detecting tetracycline hydrochloride. 2.85 Se 0.15 Nanomaterial is prepared by simple hydrothermal synthesis, and the obtained material is stably attached to ITO conductive glass after centrifugation, washing and drying, so that the photoelectrochemical sensor is obtained. The prepared photoelectrochemical sensor is placed under different concentrations of tetracycline hydrochloride to obtain the corresponding photocurrent change rate curve, and the corresponding results can be obtained through good linear relationship. Meanwhile, the performance difference between different batches of sensors is very low. The photoelectrochemical sensor can be directly used for detecting tetracycline hydrochloride, and has the advantages of low cost, simple preparation, fast response speed, high sensitivity, good repeatability and the like.

Description

Technical Field

[0001] This invention relates to the field of tetracycline hydrochloride detection technology, specifically using Bi2Te 2.85 Se 0.15 Using ITO as the substrate material, a photoelectrochemical sensor for detecting tetracycline hydrochloride is obtained by combining it with an ITO electrode. Background Technology

[0002] Tetracycline hydrochloride, a commonly used antibiotic in daily life, has seen its presence extend beyond its specific applications due to improper wastewater treatment. It is frequently found in soil and lakes, profoundly impacting the environment for human survival and production. Tetracycline hydrochloride accumulated in the human body through various pathways can lead to serious problems such as antibiotic resistance in microbial strains, allergic reactions, or toxic reactions. Because tetracycline hydrochloride is not easily degraded in the natural environment, timely detection of its presence in specific environments is an urgent environmental issue that needs to be addressed.

[0003] For the reasons mentioned above, various detection methods have been developed to determine the concentration of tetracycline hydrochloride, such as high-performance liquid chromatography (HPLC), capillary electrophoresis, chemiluminescence immunoassay, and light scattering. However, these methods all have drawbacks, including complex processes, slow response speed, small detection range, and high cost.

[0004] Photoelectrochemical (PEC) detection methods possess excellent analytical performance, including low background noise and high sensitivity, and are emerging as an effective biosensor detection method. Currently, PEC technology has been used to determine DNA, various proteins, and a wide range of ions. Based on the ternary topological insulator nanomaterial Bi₂Te… 2.85 Se 0.15 Bi₂Te is a thermoelectric material that has attracted much attention due to its advantages such as low pollution, high stability, and low cost, and has been widely used in fields such as photovoltaic cells. Compared with other thermoelectric materials, this material also possesses excellent photoelectric properties, making it applicable to the field of photoelectric sensing. The photoelectrochemical detection method used in this invention has advantages such as simple process, fast response speed, small detection limit, and good stability. Furthermore, it innovatively and for the first time employs the ternary topological insulator nanomaterial Bi₂Te. 2.85 Se 0.15 As a detection receptor, the resulting photoelectrochemical sensor has significant practical value. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] The purpose of this invention is to provide a method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride. The prepared photoelectrochemical sensor has the advantages of high sensitivity, fast response speed and good stability in detecting tetracycline hydrochloride under the excitation of simulated sunlight (xenon lamp).

[0007] (II) Technical Solution

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0009] 1. A method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride, comprising the following steps:

[0010] Bi2Te prepared by hydrothermal method 2.85 Se 0.15 As a photosensitive material, this material has the advantages of simple preparation method, fast photoelectric response speed and good repeatability;

[0011] Tetracycline hydrochloride, the analyte, was directly dissolved in 0.1M phosphate buffer solution (PBS) photoelectrochemical test electrolyte solution to prepare tetracycline hydrochloride electrolyte solutions of different concentrations.

[0012] By Bi2Te 2.85 Se 0.15 Bi2Te was prepared by attaching it to ITO conductive glass. 2.85 Se 0.15 With an ITO electrode, under stable illumination, the photoelectric response signal gradually decreases as the concentration of the analyte tetracycline hydrochloride increases. The decrease intensity has a good linear relationship with the concentration of the analyte, thus achieving sensitive detection of tetracycline hydrochloride.

[0013] This invention also provides an overall fabrication process for the photoelectrochemical sensor described in the above technical solution, as follows:

[0014] Step 1: Place tellurium powder, selenium powder and anhydrous bismuth chloride powder into diethylenetriamine solvent, and stir vigorously with a magnetic stirrer at room temperature for 45 minutes to obtain the material precursor solution;

[0015] Step 2: Transfer the material precursor solution to a 50ml polytetrafluoroethylene liner, place it inside and seal it in an autoclave. Heat the autoclave at a set temperature of 180-200℃ for 24 hours.

[0016] Step 3: After the solution has cooled to room temperature, remove it from the polytetrafluoroethylene liner and centrifuge it at 8000 rpm for 15 minutes. After obtaining a black precipitate, pour off the supernatant and wash it with anhydrous ethanol.

[0017] To further optimize the process, repeat the centrifugation 2-3 times, and wash the product multiple times with deionized water and anhydrous ethanol.

[0018] Further optimized, the final material was thoroughly dried at 60°C for 6–8 hours to obtain Bi2Te. 2.85 Se 0.15 Nanomaterials.

[0019] Step 4: Cut the ITO conductive glass into 2.0×1.0cm pieces. 2 Size. And then, in ethanol, ethanol and deionized water, it was sonicated at 40 kHz for 15 minutes each to remove surface oxides.

[0020] Further optimized, half of its area was covered with copper tape, determining its dimensions to be 1.0 × 1.0 cm. 2 The effective detection area of ​​the size.

[0021] Step 5: Add Bi2Te 2.85 Se 0.15 The powder material is dissolved in a mixed solvent of ethanol and deionized water and sonicated at a frequency of 40 kHz for 60 to 90 minutes. The uniformly dispersed solution is then dropped onto ITO conductive glass.

[0022] Step 6: Dry the conductive glass with the material droplets on it at a set temperature of 40℃ for 4-6 hours, then remove the previously coated copper adhesive strip to obtain Bi2Te. 2.85 Se 0.15 / ITO electrode, ultimately obtaining photoelectrochemical sensor.

[0023] 2. The detection steps of a photoelectrochemical sensor for detecting tetracycline hydrochloride are as follows:

[0024] Step 1: Dissolve dimethyl hydrogen phosphate and methane dihydrogen phosphate separately in deionized water. Mix a certain proportion of the dissolved dimethyl hydrogen phosphate solution with methane dihydrogen phosphate to obtain a pure 0.1M PBS electrolyte solution with pH=7.

[0025] Further optimization involved adding different doses of tetracycline hydrochloride powder to multiple groups of pure 0.1M PBS electrolyte solutions to obtain PBS tetracycline hydrochloride solutions of different concentrations from 1pM to 10μM, which were then used as reagents in the experiment.

[0026] Step 2: Preferably, the specific detection system employs a three-electrode system to detect the concentration of tetracycline hydrochloride in a PBS electrolyte solution under simulated sunlight xenon lamp illumination; the working electrode of the three-electrode system used is the Bi2Te 2.85 Se 0.15 The ITO photoelectrochemical sensor uses a platinum wire electrode as the counter electrode and an Ag / AgCl electrode as the reference electrode.

[0027] Step 3: Preferably, measurements are taken under fixed light intensity conditions.

[0028] Preferably, the simulated solar radiation wavelength is 200nm to 1100nm.

[0029] The photoelectric response performance was measured under pure PBS and 1pM to 10μM tetracycline hydrochloride conditions by changing the PBS electrolyte solution used.

[0030] Step 4: Analyze the experimental results from Step 3, and replace the prepared Bi2Te with the same batch. 2.85 Se 0.15 The experiment in step three was repeated and recorded using the / ITO photoelectrochemical sensor, and the relevant data was finally obtained.

[0031] (III) Beneficial Effects

[0032] This invention proposes a novel method for preparing photoelectrochemical sensors. The photoelectrochemical sensors are prepared by a simple hydrothermal method, which is simple to prepare, produces little pollution, has low cost, and exhibits stable performance.

[0033] This invention proposes a novel photoelectrochemical sensor for the detection of tetracycline hydrochloride, comprising ITO conductive glass and Bi2Te that can be stably modified onto the conductive glass surface without a binder. 2.85 Se 0.15 Detection layer; the Bi2Te 2.85 Se 0.15 The detection layer includes Bi2Te 2.85 Se 0.15 Nanomaterials, Bi2Te 2.85 Se 0.15 The addition of Bi2Te enhances the photoresponse performance of ITO conductive glass. This invention utilizes Bi2Te... 2.85 Se 0.15 The combination of nanomaterials and the conductive surface of ITO conductive glass, Bi2Te 2.85 Se 0.15 The two-dimensional structure of the layer effectively promotes electron-hole transfer efficiency, greatly improving the sensor's sensitivity and detection range, and exhibiting significantly different responses to tetracycline hydrochloride solutions of different concentrations. The intervention of tetracycline hydrochloride directly affects the Bi2Te... 2.85 Se 0.15 The photoelectric properties of the ITO electrode increase with increasing tetracycline hydrochloride concentration, as the Bi2Te electrode is excited by a xenon lamp source. 2.85 Se 0.15 The reduced number of excited electrons generated and transferred to ITO in the Bi2Te layer weakens the original photocurrent, thus achieving the purpose of detecting tetracycline hydrochloride. The corresponding photocurrent generated by the sensor shows a linear decrease. 2.85 Se 0.15The subtle changes in light energy signal caused by layer alteration can be quickly and stably converted into detectable electrical energy signals, thus improving the response speed of photoelectric sensors.

[0034] Experimental data from the embodiments of the present invention show that the three-electrode system of the photoelectrochemical sensor prepared by the present invention has a detection limit of 6 pM for tetracycline hydrochloride, a response time of 0.23 s, a recovery time of 0.53 s, high sensitivity, fast response speed, and excellent stability of the sensor before and after testing.

[0035] Compared with existing methods for detecting tetracycline hydrochloride, this invention has the following advantages:

[0036] (1) This invention is the first to use Bi2Te 2.85 Se 0.15 / ITO, as a detection sensor for tetracycline hydrochloride, has the advantages of simple structure, convenient manufacturing process, and low cost.

[0037] (2) No additional chemical substances selective for tetracycline hydrochloride need to be added in this invention.

[0038] (3) The Bi2Te prepared in this invention 2.85 Se 0.15 ITO exhibits excellent stability and fast response time when used as the working electrode in a three-electrode system.

[0039] (4) The tetracycline hydrochloride photoelectrochemical sensor obtained by the present invention has the characteristics of fast response / recovery, low detection limit, high sensitivity, wide detection range and high repeatability. Attached Figure Description

[0040] Figure 1 This is a structural diagram of the photoelectrochemical sensor of Embodiment 1 of the present invention;

[0041] Figure 2 This is a response / recovery time diagram of the photoelectrochemical sensor obtained in Example 1 of the present invention;

[0042] Figure 3 The figure shown is the It graph of the cyclic stability experiment of the photoelectric sensor obtained in Example 1 of the present invention;

[0043] Figure 4 The images show the photocurrent response of the photoelectric sensor obtained in Example 1 of the present invention under different concentrations of tetracycline hydrochloride and the linear graph showing the rate of change of the response current of the photoelectric sensor obtained in Example 1 of the present invention as a function of the concentration of tetracycline hydrochloride.

[0044] Figure 5 This is a graph showing the performance differences between different finished products from the same batch of photoelectric sensors obtained in Embodiment 1 of the present invention. Detailed Implementation

[0045] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0046] Unless otherwise specified, all experimental materials, reagents, and equipment used in the following examples are commercially available. Unless otherwise specified, the experimental methods used in the following examples are conventional photoelectrochemical experimental methods.

[0047] Example 1:

[0048] This embodiment provides a method for preparing a photoelectrochemical sensor, specifically including the following steps:

[0049] (1)Bi2Te 2.85 Se 0.15 Preparation of nanomaterials: Add 30ml of diethylenetriamine reagent to a clean 50ml beaker, weigh 182mg of tellurium powder, 6mg of selenium powder and 316mg of anhydrous bismuth chloride powder, and add them in sequence. Then add a magnetic swab and place it on a magnetic stirrer. Stir thoroughly at 1200rpm at room temperature of 25℃ for 45 minutes.

[0050] After thorough stirring, transfer the precursor solution from the beaker to a 50ml polytetrafluoroethylene liner, place it in and seal it in an autoclave, set the oven temperature to 200 degrees Celsius, and place the autoclave containing the precursor solution inside for 24 hours.

[0051] After naturally cooling to room temperature, the solution in the polytetrafluoroethylene liner was removed and centrifuged at 8000 rpm for 15 minutes. A black precipitate was obtained, the supernatant was discarded, and the solution was washed with anhydrous ethanol. This centrifugation and washing process was repeated at least twice, followed by washing with deionized water and then anhydrous ethanol sequentially, to obtain impurity-free Bi₂Te. 2.85 Se 0.15 The solution was then dried in anhydrous ethanol at 60°C for 8 hours to obtain dried Bi2Te. 2.85 Se 0.15 Nanomaterials.

[0052] (2) Cleaning of ITO conductive glass: Cut the ITO conductive glass into 2.0×1.0cm pieces. 2 To determine the size, the material was ultrasonically treated in acetone, anhydrous ethanol, and deionized water at a frequency of 40 kHz for 15 minutes each, then washed with ultrapure water, dried, and fixed with copper tape to form an effective material area of ​​1.0 × 1.0 cm2.

[0053] (3) Preparation of 0.1M PBS electrolyte solution: Dissolve 0.1M dimethyl hydrogen phosphate and 0.1M dihydrogen phosphate in 50ml of deionized water respectively. Mix 31ml of dimethyl hydrogen phosphate solution with 19ml of dihydrogen phosphate to obtain 100ml of 0.1M PBS (pH=7).

[0054] Further optimization involved adding different doses of tetracycline hydrochloride powder to multiple 50ml 0.1M PBS solutions to obtain multiple PBS tetracycline hydrochloride solutions of different concentrations from 1pM to 10μM, which were used as reagents in the experiment.

[0055] (4)Bi2Te 2.85 Se 0.15 Preparation of ITO: Take 5 mg of the material obtained in step (1), and sonicate it for 90 minutes to uniformly disperse the material in a mixed solution of 200 μl ethanol and 800 μl deionized water. Drop the resulting solution evenly onto the effective area of ​​the ITO conductive glass. Dry the conductive glass with the material droplets at a set temperature of 40°C for 6 hours to obtain stably attached Bi2Te. 2.85 Se 0.15 / ITO electrode, to obtain the photoelectrochemical sensor prepared in this invention, such as Figure 1 The diagram shows the structure of the obtained photoelectrochemical sensor.

[0056] This invention provides the application of a photoelectrochemical sensor in the detection of tetracycline hydrochloride.

[0057] Furthermore, the applications include:

[0058] (1) Photoelectric response performance test in a three-electrode system: using Bi2Te prepared in Example 1 2.85 Se 0.15 An ITO photoelectric sensor was used as the working electrode, a platinum wire electrode as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A 0.1M PBS buffer solution with pH 7 was used as the electrolyte solution. The three-electrode system was placed in the PBS electrolyte solution, and a 500W xenon lamp was used as the light excitation source. The photoelectric properties of the entire system were collected using a CHI660e electrochemical acquisition workstation.

[0059] Test results show that, under dark conditions, the dark current generated by the electrochemical workstation when a bias voltage of 0.1V is applied is extremely low and can be ignored. After turning on the simulated sunlight xenon lamp source, the photoelectrochemical sensor exhibits a very high photocurrent response instantaneously; its response time and recovery time are shown in [reference needed]. Figure 2The response time was 0.23 s and the recovery time was 0.53 s, indicating that the prepared photoelectrochemical sensor has good photoelectric response performance and fast response / recovery time.

[0060] (2) Different amounts of tetracycline hydrochloride powder were fully dissolved in multiple groups of PBS electrolyte solutions, with the tetracycline hydrochloride concentration increasing from 1 pM to 10 μM. To demonstrate the photoelectric stability of the obtained photoelectrochemical sensor before and after testing, stability tests were conducted on the sensor for up to 1200 s under pure PBS and 2 μM tetracycline hydrochloride conditions, respectively. Figure 3 The current-time results show that the prepared photoelectrochemical sensor has good photoelectric stability before and after testing.

[0061] (3) To compare the photoelectric response of the photoelectrochemical sensor under different concentrations of tetracycline hydrochloride, the photoelectric response current-time plots at various tetracycline hydrochloride concentrations were compared. Figure 4 (a) shows a comparison of photocurrent magnitudes at concentrations ranging from 0 to 10 μM. The photoswitching cycle used was 40 s (20 s of illumination followed by 20 s of darkness). It can be observed that the photocurrent intensity steadily decreases with increasing tetracycline hydrochloride concentration. To more intuitively observe the changes in photocurrent, a plot was created. Figure 4 (b) shows the effect of photoresponse current change rate with concentration. The logarithm of tetracycline hydrochloride concentration is used as the abscissa, and the response current change rate (I0-I) / I is used as the ordinate. I0 is the photocurrent without tetracycline hydrochloride under illumination, and I is the photocurrent at the corresponding tetracycline hydrochloride concentration. Figure 4 The inset in (b) shows the linear fit of the photoelectrochemical sensor in the concentration range of tetracycline hydrochloride from 1 pM to 100 nM. Calculations using data with a signal-to-noise ratio of three times show that the detection limit of the photoelectrochemical sensor is 6 pM, indicating that the sensor has good sensitivity. At the same time, the linearity R² of the fitted curve in this range can reach 0.992, indicating that the photoelectrochemical sensor has a good linear relationship with the rate of change of response current under different concentrations of tetracycline hydrochloride.

[0062] (4) By comparing the performance differences between different batches of the same sensor, the relative standard deviation among the five samples from the same batch was found to be 1.82%. Figure 5 As shown, the influence of different batches of sensors on the detection results is very low. The above demonstrates that the photoelectrochemical sensor prepared in this invention has advantages such as good stability, fast response speed, high sensitivity, wide detection range, and good repeatability, and can meet the detection requirements for tetracycline hydrochloride.

[0063] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0064] 1. A sensor for detecting tetracycline hydrochloride was prepared using photoelectrochemical detection, and a new method for detecting tetracycline hydrochloride was proposed, providing a new approach for water pollution detection.

[0065] 2. The prepared Bi2Te 2.85 Se 0.15 ITO photoelectric sensors are characterized by low manufacturing cost, simple process, high sensitivity, and stable performance.

[0066] 3. First application of ternary topological insulator nanomaterial Bi2Te 2.85 Se 0.15 When applied to photoelectrochemical sensing, it has advantages over other existing detection methods, such as fast response speed, good stability, wide detection range, and low detection limit.

[0067] The following is an explanation of the accompanying drawings for Embodiment 1 of the present invention:

[0068] Figure 1 The diagram shows the structure of the photoelectrochemical sensor: The overall detection process involves constructing a photoelectrochemical detection system, directly illuminating Bi2Te using an external simulated daylight xenon lamp light source. 2.85 Se 0.15 The ITO working electrode generates a photoresponse current. The working electrode, reference electrode, and platinum wire electrode are placed in an electrolytic cell containing an electrolyte solution. The three-electrode system is controlled by an electrochemical workstation and a computer to obtain corresponding data.

[0069] Figure 2 The response / recovery time graph for the photoelectrochemical sensor is shown below: the horizontal axis represents the detection time, and the vertical axis represents the unitless photocurrent response. The first Δt range represents the time it takes for the photocurrent to rise from 10% of its maximum intensity to 90% when the working electrode is photoexcited; the second Δt range represents the time it takes for the photocurrent intensity to recover from 90% to 10% the instant the light source is turned off.

[0070] Figure 3 The It graph shows the cyclic stability of the photoelectrochemical sensor: the horizontal axis represents detection time, and the vertical axis represents photocurrent intensity. The stability of the photoelectrochemical sensor under a xenon lamp was tested for 1200 s before and after the experiment, with a photo-switching cycle of 40 s (20 s on and 20 s off). There was no significant difference in photocurrent changes between the first and last cycles. The upper graph shows the It graph before the experiment in pure PBS electrolyte solution, and the lower graph shows the It graph after the experiment under 2 μM tetracycline hydrochloride conditions.

[0071] Figure 4(a) Photocurrent response of photoelectric sensor under different concentrations of tetracycline hydrochloride: the horizontal axis is the detection time and the vertical axis is the photocurrent intensity. The photocurrent response of each concentration in three periods is compared from 0 to 10 μM tetracycline hydrochloride. Figure 4 (b) is a linear graph of the rate of change of the response current of the photoelectric sensor with the concentration of tetracycline hydrochloride: the horizontal axis is the logarithm of the tetracycline hydrochloride concentration, and the vertical axis is the rate of change of the response current (I0-I) / I, where I0 is the photocurrent without tetracycline hydrochloride under illumination, and I is the photocurrent at the corresponding tetracycline hydrochloride concentration.

[0072] Figure 5 The graph shows the performance differences between different finished products of the same batch of photoelectric sensors obtained in Example 1 of the present invention: the horizontal axis is the photoelectric sensor number, and the vertical axis is the response current change rate (I0-I) / I, where I0 is the photocurrent without tetracycline hydrochloride under illumination, and I is the photocurrent at the corresponding tetracycline hydrochloride concentration.

Claims

1. A method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride, characterized in that, Includes the following steps: (1) Add 30ml of diethylenetriamine reagent to a clean 50ml beaker, weigh 182mg of tellurium powder, 6mg of selenium powder and 316mg of anhydrous bismuth chloride powder, put them into the beaker in sequence, then add a magnetic swab and place it on a magnetic stirrer at 1200rpm at room temperature of 25℃ for 45 minutes. (2) After thorough stirring, move the precursor liquid in step (1) into a 50ml polytetrafluoroethylene liner, place it in and seal it in an autoclave, set the oven temperature to 200 degrees Celsius, and place the autoclave containing the precursor liquid in it for 24 hours. (3) After the autoclave in step (2) has cooled naturally to room temperature, remove the solution from the polytetrafluoroethylene liner and centrifuge it at 8000 rpm for 15 minutes. After obtaining a black precipitate, pour off the supernatant and wash it with anhydrous ethanol and deionized water. Repeat the centrifugation and washing steps more than twice to obtain Bi2Te without impurities. 2.85 Se 0.15 The solution was then dried in anhydrous ethanol at 60°C for 8 hours to obtain dried Bi2Te. 2.85 Se 0.15 Nanomaterials; (4) Cut the ITO conductive glass into 2.0 × 1.0 cm pieces. 2 To determine the size, the sample was sequentially sonicated in acetone, anhydrous ethanol, and deionized water at a frequency of 40 kHz for 15 minutes each. It was then rinsed with ultrapure water, dried, and fixed with copper tape to form a 1.0 × 1.0 cm piece. 2 The effective area of ​​the material of the specified size; (5) Add different doses of tetracycline hydrochloride powder to multiple groups of pure 0.1M PBS electrolyte solutions and dissolve them completely to obtain PBS tetracycline hydrochloride solution, which is used as a reagent in the experiment. (6) Take 5 mg of Bi2Te obtained in step (3) 2.85 Se 0.15 Nanomaterials were uniformly dispersed in a mixed solution of 200 µl ethanol and 800 µl deionized water through 90 minutes of ultrasonication. The resulting solution was then uniformly dropped onto the effective area of ​​ITO conductive glass. The conductive glass with the dropped material was then dried at a set temperature of 40°C for 6 hours to obtain stably adhered Bi₂Te. 2.85 Se 0.15 / ITO electrode.

2. The method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride as described in claim 1, characterized in that, In step (3), the repeated centrifugation and washing involves first washing with anhydrous ethanol, then centrifuging again in anhydrous ethanol, followed by washing with deionized water and repeating this process 2-3 times.

3. The method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride as described in claim 1, characterized in that, In step (3), Bi2Te is synthesized. 2.85 Se 0.15 In solution, the solution appears gray before the reaction and turns dark brown after the reaction is complete.

4. The method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride as described in claim 1, characterized in that, The amount used in step (5) is to obtain tetracycline hydrochloride powder of different concentrations from 1 pM to 10 µM.

5. The method for preparing the photoelectrochemical sensor for detecting tetracycline hydrochloride as described in claim 1, characterized in that, Under the conditions of step (5), the Bi2Te uniformly and stably adhered on the ITO conductive surface obtained in step (6) 2.85 Se 0.15 The nanomaterials do not dissolve or detach in the PBS electrolyte.

6. The method for preparing a photoelectrochemical sensor for detecting tetracycline hydrochloride as described in claim 1, characterized in that, The photoelectrochemical sensor obtained in step (6) exhibits different response phenomena to different concentrations of tetracycline hydrochloride.

7. A photoelectrochemical sensor for detecting tetracycline hydrochloride, characterized in that, The method for preparing the electrochemical sensor is as described in any one of claims 1-6.

8. A photoelectrochemical sensor for detecting tetracycline hydrochloride according to claim 7, characterized in that, The steps for detecting tetracycline hydrochloride are as follows: The steps include coating Bi2Te onto ITO conductive glass. 2.85 Se 0.15 The nanomaterial discrete liquid, after drying, was placed as the working electrode in a three-electrode system of a photoelectrochemical workstation. The other two electrodes were the reference electrode Ag / AgCl electrode and the counter electrode platinum wire electrode. Under simulated natural xenon lamp irradiation, the photoelectric response performance was detected and recorded by adding and changing PBS electrolyte solutions containing different concentrations of tetracycline hydrochloride in the electrolytic cell. The corresponding tetracycline hydrochloride concentration was calculated by fitting the obtained photoelectric response characteristics with the It curve.

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