CN112322287B - Temperature sensing material and preparation method and application thereof - Google Patents
Temperature sensing material and preparation method and application thereof Download PDFInfo
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- CN112322287B CN112322287B CN202011106862.4A CN202011106862A CN112322287B CN 112322287 B CN112322287 B CN 112322287B CN 202011106862 A CN202011106862 A CN 202011106862A CN 112322287 B CN112322287 B CN 112322287B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
Abstract
The invention relates to a temperature sensing material and a preparation method and application thereof, wherein the temperature sensing material comprises a hollow silicon dioxide nanosphere, and CsPbCl is encapsulated in the hollow silicon dioxide nanosphere x Br 3‑x Wherein x is more than 0 and less than 3, and the outside of the hollow silicon dioxide nanosphere is wrapped by K 2 SiF 6 :Mn 4+ And a composite layer formed of an ethylene-vinyl acetate copolymer. The preparation method of the temperature sensing material comprises the following steps: obtaining hollow silicon dioxide nanospheres, and preparing CsPbCl x Br 3‑x@ SiO 2 And with K 2 SiF 6 :Mn 4+ And mixing with ethylene-vinyl acetate copolymer to form the composite wrapping layer. The temperature sensing material provided by the invention has a fluorescent characteristic, can realize rapid detection of temperature, is rapid in method and high in sensitivity, and is easy to popularize and use.
Description
Technical Field
The invention relates to the technical field of temperature sensing, in particular to a temperature sensing material and a preparation method and application thereof.
Background
In daily production and life, various physical and chemical processes are accompanied by temperature changes and closely related to temperature, and the temperature is one of important physical quantities for determining the existence form of a substance. The effective measurement of temperature also plays an important role in many fields such as medical treatment, industry, agriculture and scientific research. However, effective temperature measurement and rapid temperature sensing are still important scientific subjects requiring long-term research, and especially the temperature distribution and precision monitoring of the temperature fields inside the object, inside the reaction system and curved surface are difficult. At present, a relatively large number of methods and instruments are used for measuring temperature, mainly including traditional packaged liquid thermometers, thermocouple type temperature sensors, optical sensors, and the like. The conventional sensors have certain disadvantages, are difficult to apply under severe environmental conditions, and require a high heat exchange rate to satisfy a rapid heat balance, so that the accuracy of temperature measurement is also affected to a certain extent.
The temperature sensor with the fluorescence characteristic has the characteristics of quick response, non-contact measurement, high temperature sensing sensitivity and the like which are not possessed by a plurality of traditional temperature sensors, so that the temperature sensor has wide application potential in the aspects of living cell imaging, aerodynamic research, food outer packaging materials and the like. Most of fluorescent molecules and materials have the characteristic of temperature response, and the Boltzmann distribution and the energy level structure of the materials have influence on the temperature, and the change of the temperature also has great influence on the fluorescence intensity, the service life and the spectral characteristic peak of the materials, so that the temperature sensor with a single unit has great influence on biological tissues and penetrability, and the application of the sensor in the field of biological analysis is greatly limited. Therefore, the development of a novel composite fluorescent material for rapid temperature sensing and the establishment of an efficient and accurate temperature detection system have important significance for the effective and rapid detection of temperature in multiple fields.
The Chinese invention patent application CN 110887811A discloses a perovskite-based composite material for a laser humidity sensor, wherein the composite material comprises a micron-sized hydrophobic molecular sieve and perovskite nano particles loaded on the surface of the hydrophobic molecular sieve, and the micron-sized hydrophobic molecular sieve has a scattering effect. However, materials based on rapid temperature sensing are difficult to develop, such as CsPbBr x Cl 3-x The series of materials are unstable in water phase and air conditions, and collapse is easy to occur, so that the fluorescence stability is reduced, the sensing performance is unstable and the like.
Disclosure of Invention
The invention aims to overcome the problems of poor stability and unstable temperature sensing characteristic of the existing fluorescent material,a temperature sensing material is provided. By mixing CsPbBr x Cl 3-x The PNCs are encapsulated in the hollow silicon dioxide nanospheres, so that the stability and the applicable range of the PNCs can be effectively improved, and the PNCs are combined with K 2 SiF 6 :Mn 4+ After the ethylene-vinyl acetate copolymer is formed into a film, the stability of the film can be further improved, and the characteristic of rapid temperature sensing is realized, so that the effects of high sensitivity and rapid sensing analysis on temperature can be achieved.
The invention also provides a preparation method of the temperature sensing material, which comprises the steps of obtaining the hollow silicon dioxide nanospheres, and obtaining CsPbCl by using the obtained hollow silicon dioxide nanospheres to encapsulate the precursor solution x Br 3-x@ SiO 2 (ii) a And K 2 SiF 6 :Mn 4+ And ethylene-vinyl acetate copolymer to form a composite coating.
The invention also provides application of the temperature sensing material for temperature sensing analysis.
Finally, the invention also protects the film made of the temperature sensing material or the film prepared by the preparation method of the temperature sensing material to obtain the temperature sensor, which has the advantage of rapid temperature sensing, does not need to contact an observed object, and can rapidly analyze the temperature by utilizing the linear correlation characteristic of the fluorescence characteristic.
The specific scheme is as follows:
the temperature sensing material comprises a hollow silica nanosphere, wherein CsPbCl is encapsulated in the hollow silica nanosphere x Br 3-x Wherein x is more than 0 and less than 3, and the outside of the hollow silicon dioxide nanosphere is wrapped by K 2 SiF 6 :Mn 4+ And a composite layer formed of an ethylene-vinyl acetate copolymer.
Further, the inner diameter of the hollow silicon dioxide nanosphere is 20-35nm, and CsPbCl is encapsulated in the hollow silicon dioxide nanosphere x Br 3-x Wherein x =1-2;
optionally, in the composite layer coated outside the hollow silica nanospheres, K 2 SiF 6 :Mn 4+ And BThe mass ratio of the alkene-vinyl acetate copolymer is 0.01-5:5-100 parts of;
optionally, the temperature sensing material has fluorescent properties and can be excited by light in the wavelength range of 450-520nm and emit fluorescent light.
The invention also provides a preparation method of the temperature sensing material, which comprises the following steps:
step 1: obtaining hollow silica nanospheres;
and 2, step: weighing CsBr and PbCl according to stoichiometric ratio 2 With PbBr 2 Adding the precursor solution into a second solvent to form a precursor solution, adding the hollow silica nanospheres obtained in the step (1), uniformly infiltrating the precursor solution with the hollow silica nanospheres, performing ultrasonic treatment, and performing vacuum drying to obtain CsPbCl x Br 3-x@ SiO 2 ；
And step 3: dissolving ethylene-vinyl acetate copolymer in a third solvent, adding K 2 SiF 6 :Mn 4+ And CsPbCl obtained in step 2 x Br 3-x@ SiO 2 And drying after ultrasonic treatment to obtain the temperature sensing material.
Further, in step 1, the preparation method of the hollow silica nanosphere comprises: uniformly mixing a surfactant, water and hydrochloric acid, adding a first solvent, and stirring to obtain an emulsion; adding tetraethoxysilane into the emulsion, adding dimethyl dimethoxysilane after the reaction is finished, evaporating the first solvent and water after the reaction is finished, re-dispersing the obtained solid by using a mixed solution of absolute ethyl alcohol and hydrochloric acid, carrying out reflux treatment, centrifuging after the reflux is finished, washing the solid by using absolute ethyl alcohol, and drying to obtain the hollow silicon dioxide nanospheres.
Further, the first solvent is 1,3,5-trimethylbenzene, the surfactant is pluronic F108, and the adding amount ratio of the substances is that: water: hydrochloric acid: 1,3,5-trimethylbenzene: tetraethoxysilane amount: dimethyldimethoxysilane =0.2-1g:10-30mL:0.01-5mL:0.01-1.5g:0.01-2g:0.01-1.0g, and the volume ratio of the absolute ethyl alcohol to the hydrochloric acid in the mixed solution of the absolute ethyl alcohol and the hydrochloric acid is 10/1-50/0.5.
Further, in the step 2, csBr and PbCl 2 With PbBr 2 The stoichiometric ratio is 1 (0-2) to 1-2 when weighing;
optionally, in the step 2, the second solvent is dimethyl sulfoxide, the time of ultrasonic treatment is 3-10min,
optionally, in the step 2, the temperature of vacuum drying is 130-160 ℃, and the time is 0.5-2h.
Further, in the step 3, the third solvent is toluene;
optionally, in the step 3, the adding ratio of each substance is CsPbCl x Br 3-x @SiO 2 ：K 2 SiF 6 :M n4+ : ethylene-vinyl acetate copolymer =0.01-10:0.01-5:5-100 parts of;
optionally, in the step 3, the concentration of the solution formed by dissolving the ethylene-vinyl acetate copolymer into the third solvent is 50-200mg/mL.
The invention also protects the application of the temperature sensing material for temperature sensing analysis.
Further, the temperature sensing material is made into a film for temperature sensing, the excitation wavelength is fixed, and an external electric heating temperature controller is adopted to control the temperature; performing fluorescence temperature-changing spectrometry at a specific temperature, and performing spectrum collection after the preset value of the temperature of the sample bin reaches the specific temperature and preserving the temperature for 2-10 min; and drawing a relation curve of the fluorescence characteristic and the temperature, so that temperature data can be obtained according to the detected fluorescence characteristic.
The invention also discloses a temperature sensor which comprises a film made of the temperature sensing material or a film prepared by adopting the preparation method of the temperature sensing material, wherein the film has the fluorescence characteristic and can be excited by light with the wavelength range of 450-520nm and emit fluorescence, and the temperature sensor obtains temperature data according to the detection condition of the fluorescence.
Has the advantages that:
the temperature sensing material provided by the invention is packaged CsPbCl in hollow silicon dioxide nanospheres x Br 3-x Precursor solution, csPbCl x Br 3-x Is wrapped inside the hollow silicon dioxide nanospheres, and can effectively improve CsPbCl x Br 3-x Stability of the material and fluorescence properties.
Then, csPbCl x Br 3-x @SiO 2 And K 2 SiF 6 :Mn 4+ And the ethylene-vinyl acetate copolymer is mixed to form a composite wrapping layer, so that the sensitivity characteristic and the applicable range of the material capable of sensing the temperature can be further increased, and the rapid sensing detection of the temperature can be realized.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1a is a transmission electron microscope image of hollow silica nanospheres provided in one embodiment of the present invention;
FIG. 1b shows CsPbCl according to an embodiment of the present invention 1.2 Br 1.8 @SiO 2 Transmission electron microscopy images of;
FIG. 1c shows CsPbCl according to an embodiment of the present invention 1.2 B r1.8 @SiO 2 A scanning transmission electron microscope image of the surface of the/KSF/EVA film;
FIG. 2 shows CsPbCl as a material according to an embodiment of the present invention 1.2 Br 1.8 @SiO 2 XRD characterization pattern of (a);
FIG. 3 shows CsPbCl as a material according to an embodiment of the present invention 1.2 Br 1.8 @SiO 2 The fluorescence spectrum and the ultraviolet-visible absorption spectrum of (a);
FIG. 4a is a CsPbBr provided in accordance with an embodiment of the present invention 3 @SiO 2 The fluorescence temperature-changing spectrum of the EVA film;
FIG. 4b shows CsPbBr according to an embodiment of the present invention 3 @SiO 2 The fluorescence temperature-changing spectrum of the EVA film;
FIG. 4c shows CsPbClBr according to one embodiment of the present invention 2 @SiO 2 The fluorescence temperature-changing spectrum of the EVA film;
FIG. 4d shows CsPbClBr according to one embodiment of the present invention 2 @SiO 2 Fluorescence temperature-variable spectrum of the/KSF/EVA film;
FIG. 4e shows CsPbCl in accordance with one embodiment of the present invention 1.2 Br 1.8 @SiO 2 The fluorescence temperature-changing spectrum of the EVA film;
FIG. 4f is a CsPbCl diagram provided by one embodiment of the present invention 1.2 Br 1.8 @SiO 2 Fluorescence temperature-variable spectrum of the/KSF/EVA film;
FIG. 5 is CsPbCl provided by one embodiment of the present invention 1.2 Br 1.8 @SiO 2 A fluorescence variable temperature (33-45 ℃) spectrogram of the/KSF/EVA film;
FIG. 6 is CsPbCl provided by one embodiment of the present invention 1.2 Br 1.8 @SiO 2 A relation curve graph of the fluorescence intensity ratio of the/KSF/EVA film at 469nm and 632nm and the temperature;
FIG. 7a is one of the graphs comparing the sensitivity of the fluorescence intensity of the thin film to the temperature response;
FIG. 7b is a graph showing a comparison of the sensitivity of the fluorescence intensity of the thin film to the temperature response;
FIG. 7c is a third graph comparing the sensitivity of the fluorescence intensity of the thin film to the temperature response;
FIG. 7d is a graph comparing the sensitivity of the fluorescence intensity ratio of the films to temperature response;
FIG. 8 is CsPbCl 1.2 Br 1.8 @SiO 2 Temperature resolution capability test chart of the/KSF/EVA film.
Detailed Description
The definitions of some of the terms used in the present invention are given below, and other non-mentioned terms have definitions and meanings known in the art:
in the invention, the hollow silicon dioxide nanospheres can be made by self or can be commercialized products. The inner diameter of the hollow silica nanosphere is 20-35nm, preferably 25-30nm. The preparation method of the hollow silica nanosphere is preferably as follows: uniformly mixing a surfactant, water and hydrochloric acid, adding a first solvent, preferably 1,3,5-trimethylbenzene, and stirring to obtain an emulsion; adding tetraethoxysilane into the emulsion, performing hydrolysis reaction on the tetraethoxysilane, adding dimethyl dimethoxysilane after the reaction is finished, evaporating the first solvent and water to dryness after the reaction is finished, re-dispersing the obtained solid by using a mixed solution of absolute ethyl alcohol and hydrochloric acid, performing reflux treatment, centrifuging after the reflux is finished, washing the solid by using the absolute ethyl alcohol, and drying to obtain the hollow silicon dioxide nanospheres. Preferably, the surfactant is Pluronic F108, and the addition ratio of the substances is that: water: hydrochloric acid: 1,3,5-trimethylbenzene: tetraethoxysilane amount: dimethyldimethoxysilane =0.2-1g:10-30mL:0.01-5mL:0.01-1.5g:0.01-2g:0.01-1.0g, preferably 0.3-0.8g:12-28mL:0.1-4mL:0.1-1.0g:0.1-1.6g:0.1-0.8g, more preferably 0.4-0.6g:15-25mL:1-3mL:0.3-0.7g:1-1.4g:0.2-0.6g, wherein the volume ratio of the absolute ethyl alcohol to the hydrochloric acid in the mixed solution of the absolute ethyl alcohol and the hydrochloric acid is 10/1-50/0.5. The hydrochloric acid referred to above is commercially available as 12mol/L concentrated hydrochloric acid.
In the invention, csPbCl is encapsulated inside the hollow silicon dioxide nanosphere x Br 3-x 0 < x < 3 in the material, preferably x =1-2, e.g. x =1.2,1.5,1.8, etc. CsPbCl x Br 3-x Is prepared from CsBr and PbCl 2 With PbBr 2 Mixing, adding the mixture into a second solvent to form a precursor solution, adding hollow silica nanospheres into the precursor solution, uniformly infiltrating the precursor solution into the hollow silica nanospheres, and performing ultrasonic treatment to form CsPbCl in the hollow silica nanospheres x Br 3-x . Specifically, csBr and PbCl 2 With PbBr 2 After the mixture is added into a second solvent to form a precursor solution, the precursor solution enters a silicon sphere hollow structure, quantum dots are formed inside the silicon spheres, and the quantum dots form a quantum confinement effect in nanopores of the silicon spheres. The ultrasonic treatment in the invention is to mix the CsBr and the PbCl uniformly 2 With PbBr 2 And mixing, adding the mixture into a second solvent to form a precursor solution, and feeding the precursor solution into the silicon spheres. The quantum confinement effect means that when the size of the particle reaches the nanometer level, the electronic energy level near the Fermi level is split into discrete energy levels from a continuous state, and the quantum dots form the quantum confinement effect in a nanopore of the silicon sphere, so that the CsPbCl is formed x Br 3-x And a fixed crystal form is formed in the pore canal fixed by the silicon spheres, so that the effect of stabilizing the perovskite nanocrystalline is achieved. Preferably, the second solvent is dimethyl sulfoxide.
CsBr and PbCl 2 With PbBr 2 The stoichiometric ratio is 1 (0.1-2) to (1-2), preferably 1 (0.2-1.8) to (1.2-1.8).
In the invention, the ethylene-vinyl acetate copolymer, called EVA for short, is a general high molecular polymer, and the ethylene-vinyl acetate copolymer is dissolved in a third solvent so as to be convenient for being mixed with K 2 SiF 6 :Mn 4+ Forming a mixed solution. Preferably, the third solvent is toluene, EVA and K 2 SiF 6 :Mn 4+ The addition ratio of each substance is CsPbCl x Br 3-x @SiO 2 ：K 2 SiF 6 :M n4+ : ethylene-vinyl acetate copolymer =0.01-10:0.01-5:5 to 100, preferably 0.1 to 8:0.1-4:10-80, more preferably 1-6:1-3:30 to 50, and the film forming effect is better.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
Hollow SiO 2 Synthesis of nanospheres:
1.0g of surfactant (Pluronic F108) was weighed into a clean beaker, 25mL of ultrapure water and 5.0mL concentrated HCl were added in sequence, and magnetic stirring (850 rpm) was carried out at room temperature until Pluronic F108 was completely dissolved. Then, 1.0g of 1,3, 5-Trimethylbenzene (TMB) was added, and a polyethylene wrap was covered, and stirring was continued at room temperature for 5 hours to form a uniform emulsion. Followed by dropwise addition of 1.0g of tetraethoxysilane with stirring(TEOS), reacted for 6h, followed by dropwise addition of 0.4g dimethyldimethoxysilane (DMDMS) followed by 48h. After completion of the reaction the solvent was evaporated to dryness at 80 ℃ and the solid residue was redispersed with absolute ethanol-hydrochloric acid (25/0.5, v/v) and refluxed at 80 ℃ for 6h twice. Centrifugation was performed at the end of reflux (10 000rpm,10 min), and the whole was washed with absolute ethanol 3 times to remove Pluronic F108 and hydrochloric acid. The white precipitate is dried for 8 hours in vacuum at 70 ℃ to obtain hollow SiO 2 Nanospheres.
Example 2
CsPbCl x Br 3-x @SiO 2 The preparation of (1):
30mg of the hollow SiO prepared in example 1 are weighed out 2 The nanospheres were placed in a clean petri dish and 100. Mu.L 0.1mol/L CsPbCl was added dropwise x Br 3-x Precursor solution (CsBr, pbCl) 2 With PbBr 2 Dissolving in dimethyl sulfoxide according to stoichiometric ratio, x is more than 0 and less than 3), stirring by glass plate to obtain SiO 2 Nanosphere CsPbCl x Br 3-x Uniformly soaking the precursor solution, performing ultrasonic treatment for 5min, and pressing soaked SiO with filter paper 2 The nanospheres blotted off excess solvent and then dried in a vacuum oven at 150 ℃ for 1h.
Example 3
Preparing a temperature sensing film:
weighing 2.0mgCsPbCl x Br 3-x @SiO 2 ,8.0mg K 2 SiF 6 :Mn 4+ (KSF) in 0.5mL ethylene-vinyl acetate copolymer EVA solution (200 mg/mL toluene solution), shaking with ultrasound, and applying 200. Mu.L of the mixed solution to 1 × 1cm 2 And (3) placing the quartz plate at room temperature to volatilize the toluene, and stripping the dried membrane from the quartz plate for later use.
Example 4
Measurement of fluorescence temperature-changing spectrum: the fluorescence spectrum was measured using Hitachi-7100 with an excitation wavelength of 440nm and the temperature of the sample was controlled by an external electrothermal temperature controller (Shanghai Tian Mei scientific instrument, model TCB1402C, accurate to 0.1 ℃). When the fluorescence temperature-changing spectrum is tested, the collection of the spectrum is started after the temperature of the sample bin reaches a preset value and is kept for 2-10min, preferably 5min, at the moment, the temperature of the sample bin is stable, the corresponding spectrum is accurate, and the test reproducibility is good.
And drawing a relation curve of the fluorescence characteristic and the temperature according to the acquired data, so that temperature data can be obtained according to the detected fluorescence characteristic.
Example 5
To observe SiO 2 And CsPbCl grown by confinement x Br 3-x And the change of the shape and structure of the material in the film forming process, namely the hollow silica nanospheres respectively synthesized in the embodiment 1, the embodiment 2 and the embodiment 3 and the CsPbCl subjected to limited-area growth x Br 3-x And the appearance of the formed film are respectively characterized.
As can be seen from FIG. 1a, siO 2 The nanosphere has a hollow nanostructure, and CsPbCl is grown in a limited domain x Br 3-x Post (FIG. 1 b), csPbCl x Br 3-x The material is obviously filled in the hollow structure, and the particle size of the whole material is not obviously changed. While FIG. 1c is in the formation of CsPbCl 1.2 Br 1.8 @SiO 2 After the/KSF/EVA film, the material has complete structural characteristics and complete film structure, so that the material can be used for sensing temperature research.
For characterization in CsPbCl x Br 3-x @SiO 2 The change of the CsPbCl crystal before and after the formation is carried out, XRD characterization is carried out on the material, as shown in figure 2, the CsPbCl crystal structure can be deduced from the crystal structure in figure 2 x Br 3-x The structure being embedded in SiO 2 In the nano-sphere, the CsPbCl is shown to be successfully treated by the quantum confinement effect x Br 3-x And the nano-spheres are encapsulated in the hollow silicon dioxide nano-spheres. The material in fig. 2 was prepared by the method in example 2.
Example 6
To investigate the optimal sensing performance of the reagent of the invention, csPbCl was used as a material x Br 3-x @SiO 2 The fluorescence spectrum and the ultraviolet-visible absorption spectrum of (2) were examined. As shown in fig. 3, different ratios of Cl and Br will have different fluorescence and uv absorption spectral behavior. Abs-CsPbClBr in FIG. 3 3 Is CsPbClBr 3 Absorption Spectrum, PL-CsPbClBr 3 Denotes CsPbClBr 3 Fluorescence spectrum of (2).
Example 7
In order to investigate the temperature sensing performance between different films under the condition of Cl and Br with different proportions, the material CsPbBr is added 3 @SiO 2 EVA film (a), csPbBr 3 @SiO 2 (ii) a/KSF/EVA film (b), csPbClBr 2 @SiO 2 EVA film (c) CsPbClBr 2 @SiO 2 (ii) a/KSF/EVA film (d), csPbCl 1.2 Br 1.8 @SiO 2 EVA film (e) and CsPbCl 1.2 Br 1.8 @SiO 2 The fluorescence temperature swing spectra of the/KSF/EVA films (f) were compared. Wherein the preparation of the film is described in example 3, in particular, csPbBr 3 @SiO 2 CsPbBr in/EVA film 3 @SiO 2 The mass ratio of the EVA to the CsPbBr is 1 3 @SiO 2 CsPbBr mass ratio in/KSF/EVA film 3 @SiO 2 ：K 2 SiF 6 :M n4+ ：EVA＝1:4，CsPbClBr 2 @SiO 2 Mass ratio CsPbClBr in/EVA film 2 @SiO 2 ：EVA＝1:4，CsPbClBr 2 @SiO 2 CsPbClBr mass ratio in/KSF/EVA film 2 @SiO 2 ：K 2 SiF 6 :M n4+ ：EVA＝1:4，CsPbCl 1.2 Br 1.8 @SiO 2 Mass ratio CsPbCl in EVA film 1.2 Br 1.8 ：EVA＝1:4，CsPbCl 1.2 Br 1.8 @SiO 2 CsPbCl mass ratio in/KSF/EVA film 1.2 Br 1.8 ：K 2 SiF 6 :M n4+ ：EVA＝1:4。
As shown in FIGS. 4 a-4 f, cl and Br have different temperature response sensitivities to temperature under different ratio conditions, where CsPbCl 1.2 Br 1.8 @SiO 2 the/KSF/EVA film shows better temperature sensing characteristics. In fig. 4a, according to the direction indicated by the arrow, the spectral curves are detected at 70 ℃, 60 ℃, 50 ℃, 40 ℃ and 30 ℃ from bottom to top, that is, the arrangement order of the spectral curves is consistent with the arrangement order of the right-side temperatures, the spectral curve at the highest position corresponds to the highest temperature, and fig. 4b-4f are analogized in sequence.
Example 8
To investigateThe application performance of the composite membrane material synthesized by the method of the invention to CsPbCl 1.2 Br 1.8 @SiO 2 The temperature of the/KSF/EVA film is examined from 33.0 ℃ to 45 ℃, and CsPbCl 1.2 Br 1.8 @SiO 2 CsPbCl mass ratio in/KSF/EVA film 1.2 Br 1.8 ：K 2 SiF 6 :M n4+ : EVA =1:4. As shown in FIG. 5, the present invention can have a better sensing effect on temperature, and the peak intensities are different at different temperatures. In fig. 5, according to the direction indicated by the arrow, the spectral curves are detected at 45.0 ℃, 43.0 ℃, 41.0 ℃, 39.0 ℃, 37.0 ℃, 35.0 ℃ and 33.0 ℃ from bottom to top, that is, the arrangement order of the spectral curves is consistent with the arrangement order of the right-side temperatures, and the spectral curve at the highest point corresponds to the temperature at the highest point. Meanwhile, csPbCl is adopted 1.2 Br 1.8 @SiO 2 The temperature sensing film made of/KSF/EVA has a better linear relation between temperature and spectral intensity, see FIG. 6, wherein I469 represents the fluorescence intensity of the material at 469nm, I632 represents the fluorescence intensity of the material at 632nm, and T represents temperature, and CsPbCl can be seen 1.2 Br 1.8 @SiO 2 The fluorescence intensity ratio of the/KSF/EVA film at 469nm and 632nm has good linear relation with the temperature, and the coefficient R 2 And (4) =0.989, which is close to 1, shows that the fitting degree of the regression straight line to the data is better.
Example 9
This example shows the sensitivity comparison of different membrane materials to temperature response, using the following test method: the fluorescence spectrum is tested by using Hitachi-7100, the excitation wavelength is 440nm, and the temperature of a sample is controlled by an external electrothermal temperature controller. When the fluorescence temperature-changing spectrum is tested, the spectrum is collected after the temperature of the sample bin reaches a preset value and is kept for 5 min. The test results are shown in FIGS. 7 a-7 d, from which CsPbCl can be seen 1.2 Br 1.8 @SiO 2 the/KSF/EVA film has better temperature sensing characteristic and sensitivity.
Example 10
This example shows CsPbCl 1.2 Br 1.8 @SiO 2 The method for testing the temperature resolution capability of the/KSF/EVA film comprises the following steps: fluorescent lightThe spectrum is tested by using Hitachi-7100, the excitation wavelength is 440nm, and the temperature of a sample is controlled by an external electrothermal temperature controller. When the fluorescence temperature-variable spectrum is tested, the spectrum is collected after the temperature of the sample bin reaches a preset value and is kept for 5 min. The test results are shown in FIG. 8, and it can be seen from FIG. 8 that CsPbCl is present 1.2 Br 1.8 @SiO 2 the/KSF/EVA film can have better resolution capability for different temperatures such as 37 ℃, 39 ℃, 40 ℃, 40.5 ℃ and 40.8 ℃.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A temperature sensing material, characterized by: the temperature sensing material comprises a hollow silicon dioxide nanosphere, wherein CsPbCl is encapsulated in the hollow silicon dioxide nanosphere x Br 3-x Wherein x is more than 0 and less than 3, and the outside of the hollow silicon dioxide nanosphere is wrapped by K 2 SiF 6 : Mn 4+ And a composite layer formed of an ethylene-vinyl acetate copolymer.
2. The temperature sensing material of claim 1, wherein: the inner diameter of the hollow silicon dioxide nanosphere is 20-35nm, and the inside of the hollow silicon dioxide nanosphere is encapsulated with CsPbCl x Br 3-x Wherein x =1-2.
3. The temperature sensing material of claim 2, wherein: in the composite layer coated outside the hollow silicon dioxide nanosphere, K is 2 SiF 6 : Mn 4+ And the mass ratio of the ethylene-vinyl acetate copolymer is 0.01-5: 5-100.
4. The temperature sensing material of claim 2, wherein: the temperature sensing material has fluorescence characteristics, and can be excited by light in the wavelength range of 450-520nm and emit fluorescence.
5. A method for preparing a temperature sensing material according to any one of claims 1 to 4, wherein: the method comprises the following steps:
step 1: obtaining hollow silica nanospheres;
step 2: weighing CsBr and PbCl according to stoichiometric ratio 2 With PbBr 2 Adding the precursor solution into a second solvent to form a precursor solution, adding the hollow silica nanospheres obtained in the step (1), uniformly infiltrating the precursor solution with the hollow silica nanospheres, performing ultrasonic treatment, and performing vacuum drying to obtain CsPbCl x Br 3-x @SiO 2 ；
And step 3: dissolving ethylene-vinyl acetate copolymer in a third solvent, adding K 2 SiF 6 : Mn 4+ And CsPbCl obtained in step 2 x Br 3-x @SiO 2 And drying after ultrasonic treatment to obtain the temperature sensing material.
6. The method for producing a temperature sensing material according to claim 5, wherein: in the step 1, the preparation method of the hollow silica nanosphere comprises the following steps: uniformly mixing a surfactant, water and hydrochloric acid, adding a first solvent, and stirring to obtain an emulsion; adding tetraethoxysilane into the emulsion, adding dimethyl dimethoxysilane after the reaction is finished, evaporating the first solvent and water after the reaction is finished, re-dispersing the obtained solid by using a mixed solution of absolute ethyl alcohol and hydrochloric acid, carrying out reflux treatment, centrifuging after the reflux is finished, washing the solid by using absolute ethyl alcohol, and drying to obtain the hollow silicon dioxide nanospheres.
7. The method for producing a temperature sensing material according to claim 6, characterized in that: the first solvent is 1,3,5-trimethylbenzene, the surfactant is Pluronic F108, and the addition proportion of the substances is that: water: hydrochloric acid: 1,3,5-trimethylbenzene: tetraethoxysilane amount: dimethyldimethoxysilane =0.2-1g:10-30mL:0.01-5mL:0.01-1.5g:0.01-2g:0.01-1.0g, and the volume ratio of the absolute ethyl alcohol and the hydrochloric acid in the mixed solution of the absolute ethyl alcohol and the hydrochloric acid is 10/1-50/0.5.
8. The method for producing a temperature sensing material according to claim 5, wherein: in the step 2, csBr and PbCl 2 With PbBr 2 The stoichiometric ratio is 1 (0.1-2) to 1-2 when weighing.
9. The method for producing a temperature sensing material according to claim 8, characterized in that: in the step 2, the second solvent is dimethyl sulfoxide, and the ultrasonic treatment time is 3-10min.
10. The method for producing a temperature sensing material according to claim 8, characterized in that: in the step 2, the temperature of vacuum drying is 130-160 ℃, and the time is 0.5-2h.
11. Use of a temperature sensing material according to any of claims 1 to 4, wherein: the method is used for temperature sensing analysis.
12. Use of a temperature sensing material according to claim 11, wherein: the method comprises the following steps: making the temperature sensing material into a film, carrying out temperature sensing, fixing the excitation wavelength, and controlling the temperature by adopting an external electric heating temperature controller; performing fluorescence temperature-changing spectrometry at a specific temperature, and performing spectrum collection after the preset value of the temperature of the sample bin reaches the specific temperature and preserving the temperature for 2-10 min; and drawing a relation curve of the fluorescence characteristic and the temperature, so that temperature data can be obtained according to the detected fluorescence characteristic.
13. A temperature sensor comprising a film made of the temperature sensing material according to any one of claims 1 to 4, or a film made of the temperature sensing material obtained by the method for producing the temperature sensing material according to any one of claims 5 to 10, wherein: the film has fluorescence characteristics, can be excited by light in the wavelength range of 450-520nm and emits fluorescence, and the temperature sensor obtains temperature data according to the detection condition of the fluorescence.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108319077A (en) * | 2018-02-08 | 2018-07-24 | 深圳市华星光电技术有限公司 | Quantum dot enhances film and preparation method thereof, quantum dot backlight module and display device |
| CN108840571A (en) * | 2018-07-03 | 2018-11-20 | 中国科学院福建物质结构研究所 | A kind of twin crystal phase glass ceramics and preparation method thereof for fluorescence temperature probe |
| CN110079313A (en) * | 2019-04-10 | 2019-08-02 | 济南大学 | A kind of large scale, spherical shape CsPbBr3/SiO2The preparation method of illuminator |
| CN110887811A (en) * | 2019-12-03 | 2020-03-17 | 南方科技大学 | Perovskite-based composite material for laser humidity sensor, and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108319077A (en) * | 2018-02-08 | 2018-07-24 | 深圳市华星光电技术有限公司 | Quantum dot enhances film and preparation method thereof, quantum dot backlight module and display device |
| CN108840571A (en) * | 2018-07-03 | 2018-11-20 | 中国科学院福建物质结构研究所 | A kind of twin crystal phase glass ceramics and preparation method thereof for fluorescence temperature probe |
| CN110079313A (en) * | 2019-04-10 | 2019-08-02 | 济南大学 | A kind of large scale, spherical shape CsPbBr3/SiO2The preparation method of illuminator |
| CN110887811A (en) * | 2019-12-03 | 2020-03-17 | 南方科技大学 | Perovskite-based composite material for laser humidity sensor, and preparation method and application thereof |
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