Quantum dot material based on viologen, and gel patch, preparation method and application thereof

Abstract

The application discloses a viologen-based quantum dot material and a gel patch based on the same, a preparation method and application thereof, and belongs to the field of quantum dot materials.The viologen-based quantum dot material fuses the characteristics of black phosphorus quantum dots and viologen groups, exhibits excellent optical and electrical properties, the introduction of the viologen groups not only regulates the fluorescence emission characteristics of the material, widens the absorption spectrum range of the material, but also improves the absorption efficiency of light of specific wavelengths, and effectively optimizes the carrier mobility; the gel patch based on the material has advantages such as flexibility, conformability and processability, and provides the possibility for application in the fields of biomedicine, wearable devices, intelligent sensing and the like; as a sensor, the gel patch can detect parameters such as temperature and rays in the environment, and has a wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the field of quantum dot materials and relates to a viologen-based quantum dot material and a gel patch thereof, a preparation method and an application thereof. Background Art

[0002] Traditional radiation sensors and temperature sensors utilize discrete designs, each relying on independent detection elements. This discrete design not only limits device miniaturization and integration but also increases system complexity and cost. In high-radiation environments, such as those in the nuclear industry, aerospace, and medical diagnostics, most traditional sensors struggle to maintain stable performance or may even fail completely due to limitations in their material properties and operating principles, significantly limiting their potential applications. Furthermore, the accuracy of radiation detectors is susceptible to changes in ambient temperature, further reducing their reliability.

[0003] To address these issues, scientists have been exploring new functional materials and sensor technologies. In recent years, black phosphorus quantum dots, a new type of non-metallic semiconductor nanomaterial, have attracted widespread attention due to their excellent electronic and optical properties, including tunable band gaps, high carrier mobility, and significant in-plane anisotropy. Black phosphorus quantum dots not only exhibit thickness-dependent photoluminescence, emitting fluorescence in a variety of colors, but also have a broad absorption band, spanning the ultraviolet to near-infrared region. These properties give them great application prospects in the field of optical sensing. However, single black phosphorus quantum dot materials still have certain limitations in specific application scenarios, such as insufficient stability and the need to improve the absorption efficiency of specific wavelengths of light. To further enhance the performance of black phosphorus quantum dot materials, scientists have begun to try to combine them with other functional groups to prepare new composite materials with better performance. As an organic compound with unique optoelectronic properties, whether the viologen group can be introduced into black phosphorus quantum dot materials to improve their performance and whether it can be used in the preparation of radiation detector sensors has not been reported in the literature or patents. Summary of the Invention

[0004] In response to the technical problems of traditional sensors being limited in miniaturization and integration, insufficient stability in high-radiation environments, inability to synchronously and accurately monitor radiation and temperature, and the need to improve sensor performance, the present invention aims to provide a viologen-based quantum dot material and its gel patch, preparation method and application. The viologen-based quantum dot material obtained by introducing viologen groups into black phosphorus quantum dots has excellent optical and electrical properties, overcomes the limitations of single black phosphorus quantum dots, and the gel patch prepared using the material is used in conjunction with a gamma-ray measuring instrument to achieve synchronous and accurate monitoring of radiation and temperature, enhance the stability, sensitivity and response speed of the sensor, and provide strong support for scientific and technological progress and development in related fields.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides a class of viologen-based black phosphorus quantum dot materials, wherein the viologen-based black phosphorus quantum dot materials are obtained by reacting a viologen-based compound after acyl chloride treatment with black phosphorus quantum dots protected by aminopolyethylene glycol;

[0007] The viologen-based compound benzoyl viologen or benzoyl selenium-containing viologen;

[0008] The mass ratio of the viologen-based compound to the black phosphorus quantum dots is 1-2:1, the reaction temperature is 70-90° C., and the reaction time is 10-14 hours.

[0009] The acyl chloride treatment is obtained by placing the viologen compound in excess thionyl chloride and refluxing and concentrating it.

[0010] Furthermore, the viologen-based compound is: Any one of the following, wherein R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridyl-5'-methylene.

[0011] Furthermore, the viologen-based compound is obtained by reacting compound 1 with R-Br at a molar ratio of 1:1-2 at 60-80°C for 1-3 days, filtering and drying, wherein compound 1 is Any one of the foregoing, wherein R in the R—Br is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridine-5'-methylene.

[0012] The black phosphorus quantum dot solvent is N,N'-dimethylacetamide (DMA).

[0013] The concentration of the viologen-based black phosphorus quantum dot material is 2 mg / mL to 3 mg / mL.

[0014] The application of the above-mentioned type of viologen-based black phosphorus quantum dot materials in the preparation of gel patches.

[0015] The present invention provides a method for preparing a gel patch of a viologen-based black phosphorus quantum dot material, comprising: mixing the above-mentioned viologen-based black phosphorus quantum dot material, a monomer, a photoinitiator and a cross-linking agent, and obtaining a gel patch of the viologen-based black phosphorus quantum dot material after a photoinitiated polymerization reaction, wherein the monomer is acrylamide or sulfonic acid acrylamide.

[0016] Furthermore, the monomer is acrylamide.

[0017] The photoinitiator is any one of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenyl ethylphosphonate and 1-hydroxycyclohexylphenyl ketone.

[0018] Furthermore, the photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0019] The cross-linking agent is N,N-methylenebisacrylamide.

[0020] The viologen-based black phosphorus quantum dot material accounts for 5% to 10% of the monomer mass.

[0021] Furthermore, the viologen-based black phosphorus quantum dot material accounts for 10% of the monomer mass.

[0022] The added amount of the cross-linking agent is 2‰ to 3‰ of the monomer mass, and the added amount of the photoinitiator is 0.5‰ to 1‰ of the monomer mass.

[0023] Furthermore, the added amount of the cross-linking agent is 2‰ of the monomer mass, and the added amount of the photoinitiator is 0.5‰ of the monomer mass.

[0024] The conditions for the photo-initiated polymerization reaction are: 350-400 nm ultraviolet light, and a reaction time of 1-2 hours.

[0025] The present invention provides a gel patch of viologen-based black phosphorus quantum dot material obtained by the above-mentioned preparation method.

[0026] The application of the above-mentioned gel patch based on viologen-based black phosphorus quantum dot material in the preparation of intelligent sensors in radiation measuring instruments.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention provides a class of viologen-based black phosphorus quantum dot materials, as a new type of functional material, which shows great application prospects in the field of optical sensing due to its unique optoelectronic properties and tunable luminescence characteristics. Obtained by reacting a chlorinated viologen-based compound with black phosphorus quantum dots, this viologen-based black phosphorus quantum dot material combines the unique properties of black phosphorus quantum dots and viologen groups, and has excellent optical and electrical properties. It can not only efficiently absorb light or heat energy, but also adjust the luminescence wavelength by changing its size and surface modification, providing a basic material for realizing multi-parameter detection and subsequent applications.

[0029] The present invention provides a type of gel patch based on viologen-based black phosphorus quantum dot material, which has the advantages of flexibility, conformability and processability, and provides the possibility for the wide application of viologen-based black phosphorus quantum dot materials in biomedicine, wearable devices, smart sensing and other fields.

[0030] The application provided by the present invention is that the gel patch of the viologen-based black phosphorus quantum dot material is combined with a polymer matrix, which can further enhance the stability, sensitivity and response speed of the sensor, so that the sensor can maintain excellent performance under extreme conditions, such as strong radiation environment; the gel patch based on the viologen-based black phosphorus quantum dot material is used to develop a multifunctional sensor with the functions of detecting radiation and temperature, breaking the limitations of traditional sensors. Through material innovation and structural design, the two key parameters of radiation and temperature are synchronously and accurately monitored; the temperature-responsive color-changing gel is used in combination with a detector to provide the user with a visual temperature reminder, which can not only simplify the structure of the sensing system and improve the overall performance, but also bring revolutionary changes to the fields of radiation protection, environmental monitoring, nuclear facility safety monitoring, etc., and promote the scientific and technological progress and development of related industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a flow chart for the preparation of viologen-based quantum dot materials according to the present invention;

[0032] Figure 2 The present invention is a viologen and selenium-containing viologen-based black phosphorus quantum dot material (c~10 -4 M) UV-visible absorption spectrum;

[0033] Figure 3 Stretching of gels prepared from viologen and selenium-containing viologen-based black phosphorus quantum dot materials;

[0034] Figure 4 Changes in UV-visible absorption spectra of the gel patch at different temperatures;

[0035] Figure 5 Photo of the temperature response of the patch combined with the radiation sensor.

[0036] Figure 6 This is a test chart of the cyclic stability of the selenium-viologen-based black phosphorus quantum dot gel patch at different temperatures in Example 2 of the present invention. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0038] It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects and are not necessarily used to describe a specific order or precedence. It should be understood that the numbers used in this manner are interchangeable where appropriate so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to these processes, methods, products, or apparatuses.

[0039] The present invention is described in further detail below with reference to the accompanying drawings:

[0040] The preparation process of the gel patch of the viologen-based black phosphorus quantum dot material of the present invention is as follows:

[0041] 1. Preparation of Benzoic Acid Viologen and Selenium-Containing Viologen Molecules

[0042] (1) Preparation of benzoyl viologen

[0043]

[0044] Under inert gas protection, compound 1 (1.0 mmol) and alkyl bromide (1.1 mmol) were dissolved in 8 mL of N,N-dimethylformamide (DMF) and reacted at 70°C for 2 days. After filtration, the mixture was washed with DMF and dried to obtain benzoyl viologen 2, where R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridyl-5'-methylene.

[0045] (2) Preparation of benzoyl selenium-containing violet

[0046]

[0047] Under inert gas protection, compound 3 (1.0 mmol) and alkyl bromide (1.1 mmol) were dissolved in DMF and reacted at 70°C for 2 days. After filtration, the mixture was washed with DMF and dried to obtain benzoyl selenium-containing viologen 4, where R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridine-5'-methylene.

[0048] (3) Preparation of benzoylphenyl viologen

[0049]

[0050] Under inert gas, compound 5 (1.0 mmol) and alkyl bromide (1.1 mmol) were dissolved in DMF and reacted at 70°C for 2 days. After filtration, the mixture was washed with DMF and dried to obtain benzoylphenyl viologen 6, where R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridyl-5'-methylene.

[0051] Taking benzoic acid-based selenium-containing viologen (R is 5-methyl-2,2'-bipyridyl-5'-methylene) as an example, its physical properties and structural analysis are as follows:

[0052] Benzoic acid-containing selenium violet 4: aprimrose yellow solid.Yield: 81.1H NMR (DMSO-d6, 400MHz): δ13.23 (s, 1H, COOH), 10.00 (d, J = 19.2 Hz, 2H, PyH), 9.52-9.47 (m, 2H, PyH), 9.43-9.41 (m, 2H, PyH), 8.95 (d, J = 2 Hz, 1H, PyH), 8.56 (s, 1H, PyH), 8.47 (d, J = 8.0 Hz, 1H, PyH), 83.3 3(d,J=8.0Hz,1H,PyH),8.15(dd,J1=8.0Hz,J2=2Hz,1H,PyH),8.04(d,J=8.0Hz,2H,PhH),7.83(d,J =8.0Hz,1H,PyH),7.69(d,J=8.0Hz,2H,PhH),6.18(s,2H,CH2),6.15(s,2H,CH2),2.38(s,3H,CH3),

[0053] 13C NMR(DMSO-d6,150MHz): δ166.84,156.48,151.99,150.41,149.84,146.16,146.11,145.54,145.46,144.03,143.99,140.69, 140.60,138.71,138.18,137.86,134.40,131.89,130.23,129.64,129.32,124.46,120.47,120.35,63.81,61.71,17.89; 19F NMR(DMSO-d6,376MHz): δ-69.16,-71.05; 31P NMR(DMSO-d6,162MHz): δ-144.21;

[0054] HRMS(ESI)m / z:[M-2PF6 - ]calcd for C 30 H 24 N4O2Se 276.0527; found276.0528; Mp (℃): 225-230; UV / vis (in DMF): λmax (ε) = 421nm (6788M -1 cm -1 ).

[0055] 2. Preparation of viologen and selenium-containing viologen-based black phosphorus quantum dot materials based on benzoic acid-based viologen and selenium-containing viologen molecules

[0056] See attached Figure 1 , 5 mg of black phosphorus powder was added to 10 ml of N-methylpyrrolidone (NMP) solution and uniformly dispersed after 1 hour of ultrasonic treatment; subsequently, a 900-watt ultrasonic cell disruptor was used to perform ultrasonic treatment for 6 hours at 60% power and 3 seconds intervals under ice bath conditions to fully peel off the black phosphorus powder; after the ultrasonic treatment, the obtained yellow transparent liquid was centrifuged at 4000 rpm and 7000 rpm for 30 minutes, respectively, and the upper yellow transparent liquid was taken as black phosphorus quantum dots (BPQDs) with NMP as solvent; the yellow transparent liquid was distilled using a rotary evaporator to remove the NMP solvent and washed three times; 1 ml of deionized water was added thereto and nitrogen (concentration of 0.15 mol / L) was introduced to obtain black phosphorus quantum dots (BPODs) with water as solvent.

[0057] 25 mg of NH2-PEG-NH2 was dissolved in 4 mL of water and ultrasonically dissolved; then, 1 mL of BPQDs solution was added to the above mixture; the mixture was ultrasonically crushed for 1 hour under ice bath conditions (power 60%, interval 3 seconds) and stirred in an ice bath for 3 hours (the whole process should be protected from light); the above liquid was added to a regenerated cellulose dialysis bag (molecular weight cutoff value 3500D) and dialyzed with pure water for 15 hours to remove unreacted NH2-PEG-NH2, thereby obtaining amino polyethylene glycol-protected black phosphorus quantum dots BPQDs@PEG; the solvent was vacuum-evacuated and redispersed in 7.5 mL of N,N'-dimethylacetamide (DMA) solution to obtain an amino polyethylene glycol-protected black phosphorus quantum dot solution.

[0058] 10 mg of benzoyl selenium violetogen 4 was refluxed and concentrated in excess thionyl chloride to prepare benzoyl chloride selenium violetogen; the prepared benzoyl chloride selenium violetogen was added to 7.5 mL of aminopolyethylene glycol-protected black phosphorus quantum dot solution, and then reacted at 80°C overnight; after dialysis and washing, selenium violetogen-based black phosphorus quantum dot material (2 mg in 1 mL DMA) was obtained.

[0059] 3. Preparation of gel patches based on viologen and selenium-containing viologen-based black phosphorus quantum dot materials

[0060] The gel patch was prepared by free radical polymerization using acrylamide as the monomer, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO) as the photoinitiator, N,N-methylenebisacrylamide (MBAA) as the crosslinker (0.2% by weight of the monomer), and viologen and selenium-based viologen-based black phosphorus quantum dots as the thermochromic agents (0.1% by weight of the monomer). The above substances were mixed at 70°C, heated and stirred in an argon atmosphere, and the solution was added to a patch mold. The gel patch was then irradiated under a UV lamp (350-400nm, 10W) ​​for 1 hour to prepare the gel patch.

[0061] Example 1

[0062] This embodiment provides a method for preparing viologen and selenium-containing viologen-based black phosphorus quantum dot materials based on benzoic acid-based selenium-containing viologen. The specific preparation process is as follows:

[0063] 10 mg of benzoic acid-based selenium violet was chlorinated (refluxed and concentrated in excess thionyl chloride) to prepare benzoyl chloride-based selenium violet; the prepared benzoyl chloride-based selenium violet was added to 7.5 mL of aminopolyethylene glycol-protected black phosphorus quantum dot solution, stirred evenly and reacted at 80°C overnight; after dialysis 3 times using a regenerated cellulose dialysis bag (34 mm, 3500D), a violet-based black phosphorus quantum dot material (2 mg in 1 mL DMA) was obtained.

[0064] Example 2

[0065] This embodiment provides a gel patch of black phosphorus quantum dot material based on viologen based materials on the basis of embodiment 1. The specific preparation process is as follows:

[0066] The gel patch was prepared by free radical polymerization: 5 g acrylamide was weighed as a monomer, 2.5 mg (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) was used as a photoinitiator, 0.1 g N,N-methylenebisacrylamide (MBAA) was used as a crosslinker, 0.5 g viologen and selenium-containing viologen-based black phosphorus quantum dot material were used as thermochromic agents, mixed at 70 ° C, stirred under argon protection, and the solution was added to the patch mold. It was irradiated under ultraviolet lamp (350-400 nm, 10 W) for 1 hour. The TPO photoinitiator will decompose to produce free radicals, which will initiate the free radical polymerization reaction of acrylamide to form a gel structure. After the reaction is completed, the gel patch is washed and dried to obtain a gel patch based on viologen-based black phosphorus quantum dot material.

[0067] The gel patch prepared in Example 2 was used to paste a 5 cm × 5 cm gel patch on a γ-ray measuring instrument to prepare a multifunctional gel sensor based on viologen-based quantum dots and polymers. The relevant performance tests were carried out. The test results are shown in the attached Figure 1-6 shown.

[0068] The UV / visible absorption spectra of benzoic acid-containing selenium viologen 4 (hereinafter referred to as HOOC-SeRV), amino polyethylene glycol-protected black phosphorus quantum dots (BPQDs@PEG), and selenium viologen-containing black phosphorus quantum dot materials (BPQDs@PEG-SeRV) were investigated using a UV / visible spectrophotometer (Ocean Optics DH-2000-BAL model) with a test wavelength range of 200-800 nm. The specific test results are shown in the attached Figure 2 As shown. Figure 2The data show that there are significant differences in the absorption intensities of the three materials at different wavelengths. The absorption intensity of HOOC-SeRV is relatively low in the entire wavelength range, especially in the visible light region above 400nm. In contrast, the absorption intensity of BPQDs@PEG in the visible light region increases significantly, indicating that the introduction of quantum dots has a positive effect on the light absorption properties of the material. The absorption intensity of BPQDs@PEG-SeRV is the highest among the three, especially in the region above 400nm, further confirming the significant enhancement of the light absorption properties of the material by the introduction of quantum dots. By calculating the molar extinction coefficient, it is found that the molar extinction coefficients of BPQDs@PEG and BPQDs@PEG-SeRV in the visible light region are significantly higher than that of HOOC-SeRV, further verifying the positive effect of the introduction of quantum dots on the light absorption properties of the material. In summary, the introduction of quantum dots significantly enhances the light absorption properties of the material in the visible light region. Higher light absorption performance means higher energy conversion efficiency and better device performance, which is of great significance for the application of optoelectronic devices.

[0069] See attached Figure 3 In Example 2 of the present invention, the cyclic stability of the selenium-violet-based black phosphorus quantum dot gel patch was studied. This experiment carried out cyclic tests under different strains. The device showed repeated resistance changes under different strain cycles, which proved the long-term stability of the ion gel for visualization sensors.

[0070] See attached Figure 4 The UV / visible absorption spectrum of the selenium-containing viologen-based black phosphorus quantum dot gel patch of Example 2 of the present invention at different temperatures shows that in the wavelength range of 500-800nm, the absorption peak increases significantly with increasing temperature. This shows that in this wavelength range, the absorption of light increases with increasing temperature; as the temperature increases, the color of the patch gradually changes to dark blue. When the temperature is higher than 50°C, the absorption peak in the wavelength range of 500-800nm ​​increases significantly, and the color of the patch gradually changes to dark blue. It can be seen that the effect of temperature on the optical properties of the selenium-containing viologen-based black phosphorus quantum dot gel patch of the present invention has a temperature-dependent change in absorption characteristics, which provides an important reference for the application of such materials in optoelectronic devices, temperature sensors and other fields.

[0071] See attached Figure 5-6 A 5 cm × 5 cm selenium-containing viologen-based black phosphorus quantum dot gel patch obtained in Example 2 of the present invention was pasted on a telescopic rod gamma-ray measuring instrument (QZ42-1106T). Before the start of the experiment, the initial color of the gel patch and the initial state of the gamma-ray measuring instrument were recorded. As the temperature increased, the color change of the gel patch was closely observed to observe its color change. When the gel patch turned blue, the gamma-ray measuring instrument was used to detect the radiation amount. The detection results were recorded, and the relationship between the color change of the gel patch and the temperature detection was analyzed.

[0072] Temperature and color change: By analyzing the experimental data, the color change characteristics of the gel patch at different temperatures were determined. Special attention was paid to the color change of the gel patch above 50 degrees Celsius to verify its effectiveness as a temperature warning; the correlation between the color change of the gel patch and the radiation detection results was analyzed to verify whether it can provide a temperature warning while detecting the radiation; the test results of different batches or under different conditions were compared to ensure the stability and consistency of the test results; it was confirmed that the application of the selenium-containing violet-based black phosphorus quantum dot gel patch in Example 2 of the present invention on the gamma-ray measuring instrument has a significant temperature warning effect. The patch can significantly turn blue when the temperature rises to 50 degrees Celsius, providing an intuitive temperature warning for the operator.

[0073] At temperatures below 50°C, the transmittance of the gel patch basically remains between 80% and 100%, with little fluctuation, indicating that in low-temperature environments, the transmittance of the gel patch has high stability and can maintain high transmittance performance; above 50°C, the transmittance of the gel patch decreases significantly and fluctuates greatly, with the lowest being close to 0%, indicating that under high-temperature conditions, the transmittance of the gel patch decreases significantly, indicating that the cyclic stability of the temperature-changing color of the gel patch is very good.

[0074] The above content is only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A type of viologen-based black phosphorus quantum dot material, characterized in that: The viologen-based black phosphorus quantum dot material is obtained by reacting a viologen-based compound after acyl chloride treatment with black phosphorus quantum dots protected by amino polyethylene glycol; The viologen compound is a benzoic acid-based selenium-containing viologen; the structural formula of the benzoic acid-based selenium-containing viologen is , R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridyl-5'-methylene; The mass ratio of the viologen-based compound to the black phosphorus quantum dots is 1-2:1, the reaction temperature is 70° C.-90° C., and the reaction time is 10 h-14 h.

2. The viologen-based black phosphorus quantum dot material according to claim 1, characterized in that: The acyl chloride treatment is obtained by placing the viologen compound in excess thionyl chloride and refluxing and concentrating it.

3. Use of a viologen-based black phosphorus quantum dot material according to any one of claims 1 to 2 in the preparation of a gel patch.

4. A method for preparing a gel patch of viologen-based black phosphorus quantum dot material, characterized in that: include: The viologen-based black phosphorus quantum dot material according to any one of claims 1 to 2, a monomer, a photoinitiator and a cross-linking agent are mixed, and a gel patch of the viologen-based black phosphorus quantum dot material is obtained after a photoinitiated polymerization reaction, wherein the monomer is acrylamide or sulfonic acid acrylamide.

5. The method for preparing a gel patch of viologen-based black phosphorus quantum dot material according to claim 4, characterized in that: The photoinitiator is any one of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenyl ethylphosphonate and 1-hydroxycyclohexylphenyl ketone.

6. The method for preparing a gel patch of viologen-based black phosphorus quantum dot material according to claim 4, characterized in that: The cross-linking agent is N,N-methylenebisacrylamide.

7. The method for preparing a gel patch of viologen-based black phosphorus quantum dot material according to claim 4, characterized in that: The viologen-based black phosphorus quantum dot material accounts for 5% to 10% of the monomer mass; the added amount of the cross-linking agent is 2 to 3‰ of the monomer mass, and the added amount of the photoinitiator is 0.5 to 1‰ of the monomer mass.

8. The method for preparing a gel patch of viologen-based black phosphorus quantum dot material according to claim 4, characterized in that: The conditions for the photo-initiated polymerization reaction are: 350nm-400nm ultraviolet light, and a reaction time of 1h-2h.

9. A gel patch of viologen-based black phosphorus quantum dot material obtained by the preparation method according to any one of claims 4 to 8.

10. Use of the gel patch of viologen-based black phosphorus quantum dot material according to claim 9 in preparing an intelligent sensor for a radiation measuring instrument.

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