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

Abstract

The invention discloses a viologen-based quantum dot material and a gel patch, a preparation method and application thereof, and belongs to the field of quantum dot materials. According to the viologen-based quantum dot material, the characteristics of black phosphorus quantum dots and viologen groups are fused, excellent optical and electrical properties are shown, due to introduction of the viologen groups, the fluorescence emission characteristic of the material is regulated and controlled, the absorption spectrum range of the material is widened, the absorption efficiency of light with a specific wavelength is improved, and the carrier mobility is effectively optimized; the gel patch based on the material has the advantages of flexibility, fitness, machinability and the like, provides possibility for application in the fields of biomedicine, wearable equipment, intelligent sensing and the like, can be used as a sensor for detecting parameters such as temperature and rays in the environment, and has a wide application prospect.

Description

Technical Field

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

[0002] Traditional radiation sensors and temperature sensors use discrete designs, that is, they rely on independent detection elements to work. This discrete design not only limits the miniaturization and integration of equipment, but also increases the complexity and cost of the system. In high-radiation environments, such as the nuclear industry, aerospace, medical diagnosis and other fields, most traditional sensors are often difficult to maintain stable performance due to the limitations of material properties and working principles, and may even fail completely, which greatly limits their application potential. At the same time, the accuracy of radiation detectors is also easily affected by ambient temperature, further reducing their reliability.

[0003] In order to solve these problems, scientists have been exploring new functional materials and sensor technologies. In recent years, black phosphorus quantum dots, as a new type of non-metallic semiconductor nanomaterial, have attracted widespread attention due to its excellent electronic and optical properties such as adjustable band gap, high carrier mobility and significant in-plane anisotropy. Black phosphorus quantum dots not only have thickness-dependent photoluminescence properties and can emit fluorescence in a variety of colors, but also have a wide absorption band spanning the ultraviolet to near-infrared region. These characteristics make them show 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 absorption efficiency of light of specific wavelengths needs to be improved. In order to further improve 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 violet group can be introduced into black phosphorus quantum dot materials to improve its performance and apply it to the preparation of radiation detector sensors has not been reported in literature and patents. Summary of the invention

[0004] In view of the technical problems that traditional sensors are limited in miniaturization and integration, lack stability in high-radiation environments, cannot synchronously and accurately monitor radiation and temperature, and sensor performance needs to be improved, 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 into black phosphorus quantum dots has excellent optical and electrical properties, overcomes the limitations of single black phosphorus quantum dots, and uses the gel patch prepared by the material in combination 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 type of viologen-based black phosphorus quantum dot material, wherein 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 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 an excess of thionyl chloride and refluxing and concentrating it.

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

[0011] Further, 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 above-mentioned type of viologen-based black phosphorus quantum dot material is used 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 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, ethyl 2,4,6-trimethylbenzoylphenylphosphonate 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 crosslinking 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 crosslinking 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 a viologen-based black phosphorus quantum dot material obtained by the above-mentioned preparation method.

[0026] The above-mentioned gel patch based on viologen-based black phosphorus quantum dot material is used 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 type of black phosphorus quantum dot material based on viologen, as a new type of functional material, with its unique photoelectric properties and tunable luminescence characteristics, it has shown great application prospects in the field of optical sensing. Obtained by reacting a viologen compound after chlorination with black phosphorus quantum dots, the viologen-based black phosphorus quantum dot material combines the unique properties of black phosphorus quantum dots and viologen groups, has excellent optical and electrical properties, can not only efficiently absorb light energy or heat energy, but also adjust the luminescence wavelength by changing its size and surface modification, to achieve multi-parameter detection, and provides a basic material for subsequent applications.

[0029] The present invention provides a type of gel patch of viologen-based black phosphorus quantum dot material, which has the advantages of flexibility, fit and processability, and provides the possibility for the wide application of viologen-based black phosphorus quantum dot material in biomedicine, wearable devices, smart sensors 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 still maintain excellent performance under extreme conditions, such as in a strong radiation environment; based on the gel patch of the viologen-based black phosphorus quantum dot material, a multifunctional sensor with the functions of detecting radiation and temperature is developed, which breaks the limitations of traditional sensors and realizes the synchronous and accurate monitoring of the two key parameters of radiation and temperature through material innovation and structural design; the temperature-responsive color-changing gel is used in combination with a detector to provide a visual temperature reminder for the user, 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 of the preparation of viologen-based quantum dot materials according to the present invention;

[0032] Figure 2 The 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 gel patches 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-violet-based black phosphorus quantum dot gel patch at different temperatures according to Example 2 of the present invention. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme 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 described embodiments 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 creative work should fall within the scope of protection of the present invention.

[0038] It should be noted that the terms "first", "second", etc. in the specification 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 sequence. It should be understood that the data used in this way can be interchanged 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" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0039] The present invention is further described in detail below in conjunction with 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 benzoyl 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, wherein R is a C3-C6 alkyl chain or 5-methyl-2,2'-bipyridine-5'-methylene.

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

[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 benzoic acid-based selenium-containing viologen 4, wherein 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 protection, 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'-bipyridine-5'-methylene.

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

[0052] Benzoic acid-containing selenium violet essence 4: aprimrose yellow solid. Yield: 81.1H NMR (DMSO-d6, 400MHz): δ13.23 (s, 1H, COOH), 10.00 (d, J = 19.2Hz, 2H, PyH), 9.52-9.47 (m, 2H, PyH), 9.43-9.41 (m, 2H, PyH), 8.95 (d, J = 2Hz, 1H, PyH), 8.56 (s, 1H, PyH), 8.47 (d, J = 8.0Hz, 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 layer of 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 is 3500D), and dialyzed with pure water for 15 hours to remove unreacted NH2-PEG-NH2, thereby obtaining aminopolyethylene 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 aminopolyethylene glycol-protected black phosphorus quantum dot solution.

[0058] 10 mg of benzoic acid-based selenium violetogen 4 was refluxed and concentrated in excess dichlorothionyl to prepare benzoyl chloride-based selenium violetogen; the prepared benzoyl chloride-based 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 monomer, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) as photoinitiator, N,N-methylenebisacrylamide (MBAA) as crosslinker (2 / 1000 of monomer mass), and viologen and selenium-containing viologen-based black phosphorus quantum dot materials as thermochromic agents (1 / 1000 of monomer mass). The above substances were mixed at 70°C, heated and stirred in an argon atmosphere, and the solution was added to the patch mold, and irradiated under ultraviolet lamp (350-400nm, 10W) ​​for 1h 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 selenium violet was chlorinated (refluxed and concentrated in excess thionyl chloride) to prepare benzoyl chloride selenium violet; the prepared benzoyl chloride 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 dialyzing 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 on the basis of embodiment 1, and 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 taken as a photoinitiator, 0.1 g N,N-methylenebisacrylamide (MBAA) was taken as a crosslinker, 0.5 g viologen and selenium-containing viologen-based black phosphorus quantum dot material were taken as thermochromic agents, mixed at 70°C, stirred under argon protection, and the solution was added to a patch mold. The mixture was irradiated under ultraviolet light (350-400 nm, 10 W) for 1 h. The TPO photoinitiator would decompose to produce free radicals, which would initiate a free radical polymerization reaction of acrylamide to form a gel structure. After the reaction, the gel patch was 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, and relevant performance tests were performed. The test results are shown in the attached Figure 1-6 shown.

[0068] The UV / visible absorption spectra of benzoic acid-based selenium-containing viologen 4 (hereinafter referred to as HOOC-SeRV), amino polyethylene glycol-protected black phosphorus quantum dots (BPQDs@PEG) and selenium-containing viologen-based black phosphorus quantum dots (BPQDs@PEG-SeRV) were investigated using a UV / visible spectrophotometer (Ocean Optics DH-2000-BAL model) with the test wavelength range set to 200-800nm. For specific test results, see the attached Figure 2 As shown. Figure 2The data show that there are significant differences in the absorption intensity 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 performance of the material. The absorption intensity of BPQDs@PEG-SeRV is the highest among the three, especially in the region above 400nm, which further confirms the significant enhancement of the light absorption performance 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 those of HOOC-SeRV, which further verifies the positive effect of the introduction of quantum dots on the light absorption performance of the material. In summary, the introduction of quantum dots significantly enhances the light absorption performance 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 , Example 2 of the present invention shows the cyclic stability of the selenium violet-based black phosphorus quantum dot gel patch. 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 violet-based black phosphorus quantum dot gel patch at different temperatures in Example 2 of the present invention, in the wavelength range of 500-800nm, as the temperature increases, the absorption peak increases significantly. This shows that in this wavelength range, the absorption of light increases with the increase of 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 influence of temperature on the optical properties of the selenium-containing violet-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 5cm×5cm selenium-containing viologen-based black phosphorus quantum dot gel patch obtained in Example 2 of the present invention is pasted on a telescopic rod γ-ray measuring instrument (QZ42-1106T). Before the experiment begins, the initial color of the gel patch and the initial state of the γ-ray measuring instrument are recorded. As the temperature rises, the color change of the gel patch is closely observed to observe its color change. When the gel patch turns blue, the γ-ray measuring instrument is used to detect the radiation amount; the detection results are recorded, and the relationship between the color change of the gel patch and the temperature detection is analyzed.

[0072] Temperature and color change: By analyzing the experimental data, the color change characteristics of the gel patch at different temperatures are determined. Pay special attention to the color change of the gel patch above 50 degrees Celsius to verify its effectiveness as a temperature warning; analyze the correlation between the color change of the gel patch and the radiation detection results to verify whether it can provide a temperature warning while detecting the radiation; compare the test results of different batches or under different conditions to ensure the stability and consistency of the test results; confirm 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 significantly decreases 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 color change of the gel patch is very good.

[0074] The above contents are 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 aminopolyethylene glycol; The viologen compound is benzoyl viologen or benzoyl selenium-containing viologen; The mass ratio of the viologen-based compound to the black phosphorus quantum dots is 1 to 2:1, the reaction temperature is 70° C. to 90° C., and the reaction time is 10 h to 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 an excess of 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 crosslinker 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, ethyl 2,4,6-trimethylbenzoylphenylphosphonate 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 described in any one of claims 4 to 8.

10. Use of the gel patch of viologen-based black phosphorus quantum dot material as claimed in claim 9 in the preparation of intelligent sensors in radiation measuring instruments.

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