阅读说明：本技术 一种基于钙钛矿量子点的防伪皮革及其制备方法 (Perovskite quantum dot-based anti-counterfeiting leather and preparation method thereof ) 是由 高党鸽 张莹 吕斌 马建中 郭旭 于 2020-12-16 设计创作，主要内容包括：本发明涉及一种基于钙钛矿量子点的防伪皮革及其制备方法。市场上皮革制品的鉴别,没有统一、客观的判断标准,使得防伪皮革的开发具有重要意义。本发明首先以溴化铯和溴化铋,或碳酸铯和氯化亚锡为原料制备全无机铋基或锡基钙钛矿量子点；然后采用真空抽滤法使具有纳米尺度的钙钛矿量子点渗透进入皮革内部,借助钙钛矿量子点的发光特性,得到在紫外光照射下显示特定颜色的防伪皮革。本发明涉及的防伪皮革的制备方法简单易行,成本低廉,制备过程对环境友好无害。(The invention relates to anti-counterfeiting leather based on perovskite quantum dots and a preparation method thereof. The identification of leather products in the market has no unified and objective judgment standard, so that the development of anti-counterfeiting leather has important significance. Firstly, cesium bromide and bismuth bromide or cesium carbonate and stannous chloride are used as raw materials to prepare all-inorganic bismuth-based or tin-based perovskite quantum dots; and then, the perovskite quantum dots with the nano-scale are permeated into the leather by adopting a vacuum filtration method, and the anti-counterfeiting leather which shows a specific color under the irradiation of ultraviolet light is obtained by virtue of the light-emitting characteristics of the perovskite quantum dots. The preparation method of the anti-counterfeiting leather is simple and easy to implement, low in cost and environment-friendly and harmless in the preparation process.)

1. A preparation method of anti-counterfeiting leather based on perovskite quantum dots is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

mixing 0.0100-0.0500g CsBr and 0.0200-0.0600g BiBr₃Dissolving 10-40uL oleylamine in 1-5mL of dimethyl sulfoxide, and stirring at 60-90 ℃ to obtain a first mixed solution;

slowly dripping 0.2-0.6mL of the first mixed solution into a mixed solution of 3-6mL of ethanol and 0.2-0.6mL of oleic acid within 20-30min to obtain a second mixed solution;

centrifuging the second mixed solution at 6000-10000rpm for 5-10min, and discarding large-particle precipitates to obtain Cs₃Bi₂Br₉A quantum dot solution;

step two: CsSnCl₃Preparation of quantum dot solution:

mixing 0.0500-0.1000g Cs₂CO₃Placing 4-10mL of octadecene and 0.2-1.0mL of oleic acid in a three-neck flask, and drying in a vacuum oven at 40-70 ℃ for 2-5 h; then in N₂Heating to 110-150 ℃ in atmosphere to enable Cs to be in₂CO₃Completely dissolving to obtain a first mixed solution;

placing 4-10mL of octadecene and 0.0100-0.0500g of stannous chloride into a three-neck flask, and drying in a vacuum oven at 40-70 ℃ for 2-5 h; then in N₂Heating to 110-150 ℃ in the atmosphere to completely dissolve stannous chloride to obtain a second mixed solution;

heating the second mixed solution to 150-180 ℃, sequentially injecting 0.2-0.6mL of oleic acid and 0.3-0.7mL of oleylamine, finally injecting 0.3-0.8mL of the first mixed solution, stirring for 2-10s, and placing in an ice water bath to obtain CsSnCl₃A quantum dot solution;

step three: preparing anti-counterfeiting leather:

flatly paving 1-20g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.7-0.9 MPa;

1-5mL of the Cs₃Bi₂Br₉Quantum dot solution or CsSnCl₃Quantum dot solution for 1-15minDripping the mixture on the wet white leather; and drying the white wet leather at 20-40 ℃ for 5-15h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

2. The preparation method of the anti-counterfeiting leather based on the perovskite quantum dots as claimed in claim 1, which is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

mixing 0.0500g CsBr, 0.0400g BiBr₃And 30uL oleylamine were dissolved in 4mL of dimethyl sulfoxide, and stirred at 80 ℃ to obtain a first mixed solution;

slowly dripping 0.5mL of the first mixed solution into a mixed solution of 3mL of ethanol and 0.5mL of oleic acid within 20min to obtain a second mixed solution;

centrifuging the second mixed solution at 7000rpm for 10min to remove large-particle precipitate to obtain Cs₃Bi₂Br₉A quantum dot solution;

step two: preparing anti-counterfeiting leather:

flatly paving 10g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.7 MPa;

3mL of the Cs₃Bi₂Br₉The quantum dot solution is dripped onto the wet white leather within 10 min; and drying the white wet leather at 30 ℃ for 8h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

3. The preparation method of the anti-counterfeiting leather based on the perovskite quantum dots as claimed in claim 1, which is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: CsSnCl₃Preparation of quantum dot solution:

mixing 0.0500g of Cs₂CO₃Placing 5mL of octadecene and 0.5mL of oleic acid in a three-neck flask, and drying in a vacuum oven at 60 ℃ for 5 hours; then in N₂Heating to 120 deg.C in atmosphere to make Cs₂CO₃Completely dissolving to obtain a first mixed solution;

placing 5mL of octadecene and 0.0500g of stannous chloride into a three-neck flask, and drying for 4h in a vacuum oven at 60 ℃; then in N₂Heating to 120 ℃ in the atmosphere to completely dissolve stannous chloride to obtain a second mixed solution;

heating the second mixed solution to 150 ℃, sequentially injecting 0.5mL of oleic acid and 0.5mL of oleylamine, finally injecting 0.4mL of the first mixed solution, stirring for 5s, and placing in an ice-water bath to obtain CsSnCl₃A quantum dot solution;

step two: preparing anti-counterfeiting leather:

flatly paving 5g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.8 MPa;

3mL of the CsSnCl₃The quantum dot solution is dripped onto the wet white leather within 10 min; and drying the white wet leather at 35 ℃ for 10h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

4. The method for preparing the anti-counterfeiting leather based on the perovskite quantum dots as claimed in any one of claims 1 to 3, wherein the anti-counterfeiting leather based on the perovskite quantum dots is prepared.

Technical Field

The invention belongs to the technical field of preparation of anti-counterfeiting leather, and particularly relates to anti-counterfeiting leather based on perovskite quantum dots and a preparation method thereof.

Background

The identification of leather products in the market mainly depends on the subjective experience of buyers, and the identification needs abundant experience of the people who need to identify the leather products by touching, seeing and smelling, and the like, and objective judgment standards cannot be provided, particularly some valuable leather products are extremely easy to counterfeit by lawbreakers. Therefore, the development of the anti-counterfeiting leather has important significance.

Perovskite quantum dots are a photoluminescence material emerging in recent years, and can emit fluorescence under ultraviolet irradiation. Compared with the traditional luminescent material, the luminescent material has longer service life and higher color purity. Among them, bismuth-based and tin-based perovskite quantum dots are widely used in the fields of solar cells, photocatalysis, light emitting diodes, etc. due to the advantages of low toxicity, high photoluminescence quantum yield, etc. However, reports of application of bismuth-based and tin-based perovskite quantum dots in the anti-counterfeiting field are not yet seen.

The size of the perovskite quantum dot is in a nanometer level, and the perovskite quantum dot can well penetrate into a porous structure in the collagen fiber; meanwhile, carboxyl in the collagen fiber can play a role in sealing the quantum dots; therefore, the quantum dots can stably exist in the collagen fibers, and the anti-counterfeiting leather showing a specific color under the irradiation of ultraviolet light is obtained.

Disclosure of Invention

The invention aims to provide perovskite quantum dot-based anti-counterfeiting leather and a preparation method thereof, so that leather with good anti-counterfeiting performance is obtained, and the problem of counterfeiting and faking of leather products is solved.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of anti-counterfeiting leather based on perovskite quantum dots specifically comprises the following steps:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

mixing 0.0100-0.0500g CsBr and 0.0200-0.0600g BiBr₃Dissolving 10-40uL oleylamine in 1-5mL of dimethyl sulfoxide, and stirring at 60-90 ℃ to obtain a first mixed solution;

slowly dripping 0.2-0.6mL of the first mixed solution into a mixed solution of 3-6mL of ethanol and 0.2-0.6mL of oleic acid within 20-30min to obtain a second mixed solution;

centrifuging the second mixed solution at 6000-10000rpm for 5-10min, and discarding large-particle precipitates to obtain Cs₃Bi₂Br₉A quantum dot solution;

step two: CsSnCl₃Preparation of quantum dot solution:

mixing 0.0500-0.1000g Cs₂CO₃Placing 4-10mL of octadecene and 0.2-1.0mL of oleic acid in a three-neck flask, and drying in a vacuum oven at 40-70 ℃ for 2-5 h; then in N₂Heating to 110-150 ℃ in atmosphere to enable Cs to be in₂CO₃Completely dissolving to obtain a first mixed solution;

placing 4-10mL of octadecene and 0.0100-0.0500g of stannous chloride into a three-neck flask, and drying in a vacuum oven at 40-70 ℃ for 2-5 h; then in N₂Heating to 110-150 ℃ in the atmosphere to completely dissolve stannous chloride to obtain a second mixed solution;

heating the second mixed solution to 150-180 ℃, sequentially injecting 0.2-0.6mL of oleic acid and 0.3-0.7mL of oleylamine, finally injecting 0.3-0.8mL of the first mixed solution, stirring for 2-10s, and placing in an ice water bath to obtain CsSnCl₃A quantum dot solution;

step three: preparing anti-counterfeiting leather:

flatly paving 1-20g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.7-0.9 MPa;

1-5mL of the Cs₃Bi₂Br₉Quantum dot solution or CsSnCl₃The quantum dot solution is dripped onto the wet white leather within 1-15 min; and drying the white wet leather at 20-40 ℃ for 5-15h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

The specific technical scheme 1 comprises the following steps:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

mixing 0.0500g CsBr, 0.0400g BiBr₃And 30uL oleylamine were dissolved in 4mL of dimethyl sulfoxide, and stirred at 80 ℃ to obtain a first mixed solution;

slowly dripping 0.5mL of the first mixed solution into a mixed solution of 3mL of ethanol and 0.5mL of oleic acid within 20min to obtain a second mixed solution;

centrifuging the second mixed solution at 7000rpm for 10min to remove large-particle precipitate to obtain Cs₃Bi₂Br₉A quantum dot solution;

step two: preparing anti-counterfeiting leather:

flatly paving 10g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.7 MPa;

3mL of the Cs₃Bi₂Br₉The quantum dot solution is dripped onto the wet white leather within 10 min; and drying the white wet leather at 30 ℃ for 8h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

The specific technical scheme 2 comprises the following steps:

the method comprises the following steps: CsSnCl₃Preparation of quantum dot solution:

mixing 0.0500g of Cs₂CO₃Placing 5mL of octadecene and 0.5mL of oleic acid in a three-neck flask, and drying in a vacuum oven at 60 ℃ for 5 hours; then in N₂Heating to 120 deg.C in atmosphere to make Cs₂CO₃Completely dissolving to obtain a first mixed solution;

placing 5mL of octadecene and 0.0500g of stannous chloride into a three-neck flask, and drying for 4h in a vacuum oven at 60 ℃; then in N₂Heating to 120 ℃ in the atmosphere to completely dissolve stannous chloride to obtain a second mixed solution;

heating the second mixed solution to 150 ℃, sequentially injecting 0.5mL of oleic acid and 0.5mL of oleylamine, finally injecting 0.4mL of the first mixed solution, stirring for 5s, and placing in an ice-water bath to obtain CsSnCl₃A quantum dot solution;

step two: preparing anti-counterfeiting leather:

flatly paving 5g of white wet leather on a filter membrane of a vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, and emphasizing the pressure of the vacuum pump to 0.8 MPa;

3mL of the CsSnCl₃The quantum dot solution is dripped onto the wet white leather within 10 min; and drying the white wet leather at 35 ℃ for 10h to obtain the anti-counterfeiting leather showing yellow under the irradiation of ultraviolet light.

Compared with the prior art, the invention has the following beneficial effects:

1) the leather collagen fiber has a porous structure, and the perovskite quantum dots are nano-sized and can well permeate into the leather;

2) carboxyl in the collagen can play a role in sealing the perovskite quantum dots, so that the stability of the perovskite quantum dots in the collagen fibers is improved;

3) the preparation method of the anti-counterfeiting leather is simple and easy to implement, has low cost, and is environment-friendly and harmless in the preparation process;

4) the anti-counterfeiting leather prepared by the invention can display yellow luminescence under the irradiation of an ultraviolet lamp, and the anti-counterfeiting method is simple and easy to realize.

Detailed Description

The present invention will be described in detail with reference to specific examples. These embodiments are provided to illustrate the present invention, and any techniques realized based on the above-described contents of the present invention are within the scope of the present invention. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.

Example 1:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

0.0100g CsBr and 0.0200g BiBr₃And 10uL oleylamine were dissolved in 1mL of dimethyl sulfoxide, and stirred at 60 ℃ to obtain a first mixed solution;

slowly dripping 0.2mL of the first mixed solution into a mixed solution of 3mL of ethanol and 0.2mL of oleic acid within 20min to obtain a second mixed solution;

centrifuging the second mixed solution at 6000rpm for 5min to remove large-particle precipitate,obtained Cs₃Bi₂Br₉A quantum dot solution.

Step two: preparing anti-counterfeiting leather:

flatly paving 2g of white wet leather on a filter membrane of a vacuum filtration bottle, assembling the vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, turning on a switch of the vacuum pump, and enhancing the pressure to 0.7 MPa;

sucking 1mL of Cs prepared in the first step by using a syringe injector₃Bi₂Br₉The quantum dot solution is slowly dripped onto the white wet skin within 20 min;

drying the white wet leather at 25 ℃ for 8h, and placing under an ultraviolet lamp with the wavelength of 350nm for irradiation to obtain the yellow anti-counterfeiting leather.

Example 2:

the method comprises the following steps: CsSnCl₃Preparation of quantum dot solution:

0.1000g of Cs₂CO₃Placing 10mL of octadecene and 1.0mL of oleic acid in a three-neck flask, and drying in a vacuum oven at 50 ℃ for 3 h; then in N₂Heating to 150 deg.C in atmosphere to make Cs₂CO₃Completely dissolving to obtain a first mixed solution;

placing 10mL of octadecene and 0.0500g of stannous chloride into a three-neck flask, and drying in a vacuum oven at 60 ℃ for 2 h; then in N₂Heating to 150 ℃ in the atmosphere to completely dissolve stannous chloride to obtain a second mixed solution;

heating the second mixed solution to 180 ℃, sequentially injecting 0.6mL of oleic acid and 0.7mL of oleylamine, finally injecting 0.8mL of the first mixed solution, stirring for 10s, and placing in an ice-water bath to obtain CsSnCl₃A quantum dot solution.

Step two: preparing anti-counterfeiting leather:

flatly paving 5g of white wet leather on a filter membrane of a vacuum filtration bottle, assembling the vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, turning on a switch of the vacuum pump, and enhancing the pressure to 0.9 MPa;

sucking 3mL of CsSnCl obtained in the first step by using a needle syringe₃Adding quantum dot solution dropwise into the wet white skin within 15minThe above step (1);

drying the white wet leather at 30 ℃ for 8h, and placing under an ultraviolet lamp with the wavelength of 280nm for irradiation to obtain the yellow anti-counterfeiting leather.

Example 3:

the method comprises the following steps: cs₃Bi₂Br₉Preparation of quantum dot solution:

mixing 0.0400g CsBr and 0.0500g BiBr₃Dissolving 20uL oleylamine in 3mL of dimethyl sulfoxide, and stirring at 70 ℃ to obtain a first mixed solution;

slowly dripping 0.5mL of the first mixed solution into a mixed solution of 5mL of ethanol and 0.4mL of oleic acid within 30min to obtain a second mixed solution;

centrifuging the second mixed solution at 8000rpm for 5min, and discarding large-particle precipitate to obtain Cs₃Bi₂Br₉A quantum dot solution.

Step two: preparing anti-counterfeiting leather:

flatly paving 10g of white wet leather on a filter membrane of a vacuum filtration bottle, assembling the vacuum filtration bottle, connecting the vacuum filtration bottle with a vacuum pump, turning on a switch of the vacuum pump, and enhancing the pressure to 0.8 MPa;

sucking 2mL of Cs prepared in the first step by using a needle syringe₃Bi₂Br₉The quantum dot solution is dripped onto the wet white leather within 10 min;

drying the white wet leather at 25 ℃ for 10h, and placing under an ultraviolet lamp with the wavelength of 320nm for irradiation to obtain the yellow anti-counterfeiting leather.

The above examples are only for further detailed description of the summary of the present invention, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the above examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the technical knowledge and common means in the field, and all changes and alterations are included in the scope of the invention.