CN-116773632-B - Copper-based ternary sulfur semiconductor material and preparation method and application thereof

Abstract

The invention discloses a copper-based ternary sulfur semiconductor material, and a preparation method and application thereof. The preparation method of the material comprises the steps of mixing the CuSn (OH) 6 nano material, thioacetamide, ethylenediamine tetraacetic acid and water for hydrothermal reaction to obtain the Cu 3 SnS 4 nano material. The semiconductor material has excellent photoelectrochemical property, and the photoelectrochemical sensor constructed based on the material has the advantages of high detection accuracy, high response speed, low detection limit and high stability, and can realize the rapid and accurate real-time detection of the content of the microplastic. The preparation method is simple, low in cost and suitable for industrial production.

Inventors

• ZHANG YE
• XIAO ZIZHEN
• ZHANG HAN
• PAN YINLONG
• HAO YABIN

Assignees

• 南华大学
• 深圳万物传感科技有限公司

Dates

Publication Date

20260505

Application Date

20230621

Claims (5)

1. 1. A micro-plastic detection method is characterized in that a photoelectrochemical sensor is adopted for micro-plastic detection, and the construction steps of the photoelectrochemical sensor are as follows: 1) Dispersing Cu 3 SnS 4 nano materials in a dimethylformamide solution containing polyvinylidene fluoride to obtain a mixed solution containing Cu 3 SnS 4 nano materials; 2) Dripping the mixed solution containing Cu 3 SnS 4 nanometer material on the glass surface containing indium tin oxide on the surface, and drying to obtain a working electrode; 3) Sequentially dripping a chitosan solution, a glutaraldehyde solution, a bovine serum albumin solution and a polystyrene microsphere solution onto the working electrode; The Cu 3 SnS 4 nano material is prepared by mixing CuSn (OH) 6 nano material, thioacetamide, ethylenediamine tetraacetic acid and water for hydrothermal reaction, wherein the molar ratio of the CuSn (OH) 6 nano material to the thioacetamide to the ethylenediamine tetraacetic acid is 1:1-8:1-6.
2. 2. The method for detecting microplastic according to claim 1, wherein: The solid-to-liquid ratio of the Cu 3 SnS 4 nanometer material to the dimethylformamide solution containing polyvinylidene fluoride is 1.5-7.5 mg/1 mL; the mass concentration of the chitosan solution is 0.005-0.05 wt%; The mass concentration of the glutaraldehyde solution is 0.1-5 wt%; the mass volume concentration of the bovine serum albumin solution is 10-500 mug/mL; The mass ratio of the polystyrene microsphere solution is 0.5-500 mug/mL; The volume ratio of the chitosan solution to the glutaraldehyde solution to the bovine serum albumin solution to the polystyrene microsphere solution is 1:1-2:1-3:1-5.
3. 3. The method for detecting the microplastic according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 150-200 ℃ for 2-9 hours.
4. 4. The method for detecting the micro-plastic according to claim 1, wherein the CuSn (OH) 6 nano-material is obtained by mixing and reacting tin chloride with alkali and copper chloride in sequence.
5. 5. The method for detecting microplastic according to claim 4, wherein: the molar amount of the alkali is 6-6.5 times of that of the stannic chloride; The molar amount of the copper chloride is 1-1.2 times of that of the tin chloride.

Description

Copper-based ternary sulfur semiconductor material and preparation method and application thereof Technical Field The invention relates to a semiconductor material, in particular to a copper-based ternary chalcogenide semiconductor material, and a preparation method and application thereof, and belongs to the technical fields of semiconductor materials and biosensors. Background Microplastic, which means plastic particles with a diameter of less than 5 mm. In the last decades, microplastic materials have been available for wind transport, marine activity and path flow to the ocean, and also for air floatation, air deposition and irrigation into the soil. Microplastic can even be transferred to higher nutritional levels through the circulation of the food chain, ultimately endangering human health, which has attracted worldwide research attention as a new environmental contaminant. The main methods of the current micro-plastic detection are optical microscope observation method, electron microscope observation method, pyrolysis gas chromatography-mass spectrometry, thermal extraction desorption gas chromatography-mass spectrometry, differential scanning calorimetry and the like. However, the method has the defects of time and labor waste, expensive instrument, low precision, high detection limit and the like. Therefore, development of a new and more advantageous detection method is imperative. Photoelectrochemical biosensing is a novel detection method combining photoelectrochemical analysis technology with biosensing technology. The method integrates the advantages of an optical method and an electrochemical method, and has higher sensitivity, lower background signal, simpler operation and lower cost than the traditional analysis technology. The detection principle is to determine the concentration of the detection object based on the photoelectric conversion characteristics of the photoelectric active material. The photoelectrochemistry biosensing inherits the high sensitivity of the photoelectrochemistry analysis technology and the special biocompatibility among reaction molecules, so that the photoelectrochemistry biosensing has great potential application prospect in the detection of small molecules and biomolecules, and has great significance in improving various analysis performances of the photoelectrochemistry biosensing by combining a high-efficiency signal amplification strategy and realizing high-sensitivity detection. Disclosure of Invention In view of the shortcomings of the prior art, a first object of the present invention is to provide a copper-based ternary chalcogenide semiconductor material. The material has the advantages of narrow band gap, high photosensitivity, good photoconductivity, good thermal stability and low toxicity. The second object of the invention is to provide a preparation method of the copper-based ternary sulfur semiconductor material. The method is simple, low in cost and suitable for industrial production. A third object of the present invention is to provide the use of a copper-based ternary chalcogenide semiconductor material. The photoelectrochemical sensor adopting the copper-based ternary chalcogenide semiconductor material has the characteristics of high detection accuracy, strong sensitivity, wide detection range and the like, and can realize the rapid and accurate real-time detection of the content of the microplastic. In order to achieve the technical aim, the invention provides a preparation method of a copper-based ternary sulfur semiconductor material, which is to mix a CuSn (OH) 6 nano material, thioacetamide, ethylenediamine tetraacetic acid and water for hydrothermal reaction to obtain a Cu 3SnS4 nano material. The Cu 3SnS4 nano material is prepared by taking CuSn (OH) 6 nano material as a precursor, taking thioacetamide as a sulfur source, taking ethylenediamine tetraacetic acid as a metal ion chelating agent, enabling ethylenediamine tetraacetic acid and metal to form a stable water-soluble complex, and carrying out hydrothermal reaction on the raw materials. As a preferable scheme, the molar ratio of the CuSn (OH) 6 nano material to thioacetamide to ethylenediamine tetraacetic acid is 1:1-8:1-6. The usage amount of the three substances can influence the morphology structure and the photoelectric property of the material, and the semiconductor material with excellent performance can be obtained by controlling the usage amount of the three substances in a proper range. When the dosage of CuSn (OH) 6 is too small, the dosage of Cu 3SnS4 obtained by the reaction is small, the resource waste is caused, the cost is increased, when the dosage of thioacetamide is too small or too large, the Cu 3SnS4 cannot be obtained, other substances such as Cu 2SnS3 can be generated, when the dosage of ethylenediamine tetraacetic acid is too small, the reaction for generating Cu 3SnS4 is insufficient, the resource waste is caused, and the cost is increased. As a preferab