Water stimulation response luminescent material and preparation method and application thereof

Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to a water stimuli-responsive luminescent material and a preparation method and application thereof.The water stimuli-responsive luminescent material takes water as a stimulating factor, changes optical properties such as color and luminous intensity through heating or humidifying, has high safety, is simple to prepare and has good application prospects. The method has good repeatability, shows high sensitivity, high response speed and stable performance for detecting water molecules, is applied to the field of anti-counterfeiting, and has a remarkable visualization effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a water stimulus responsive luminescent material and a preparation method and application thereof. Background Art

[0002] Among stimuli-responsive luminescent materials, metal halides play an increasingly important role in the development of modern anti-counterfeiting technology due to their excellent optoelectronic characteristics and controllable features. Among the many stimuli, water is a natural resource that is ubiquitous in nature, making it flexible for use in many situations and research. Secondly, compared with other stimuli such as electric current and chemicals, water as a stimulus-response factor has significantly milder properties and higher safety. However, the various organic and inorganic luminescent materials currently available, such as organic dyes, quantum dots, supramolecular and transition metal complexes, and metal halide perovskites, have the following problems:

[0003] (1) Traditional stimuli-responsive luminescent materials have high preparation costs, complex structures, poor performance, and cumbersome processes;

[0004] (2) The inherent properties of ionic compounds determine the impact of water on the optical properties and performance of devices. Generally, the interaction between stimuli-responsive luminescent materials and water can have adverse effects on materials and devices, resulting in reduced stability under operating conditions;

[0005] (3) In traditional anti-counterfeiting technologies, many methods rely on mechanical or chemical methods for anti-counterfeiting. The method of obtaining the stimulus source is cumbersome, requires complex chemical processes, and requires harmful or dangerous chemicals, which is not friendly to the environment.

[0006] (4) Traditional anti-counterfeiting technology has complicated methods for identifying authenticity, high detection limits, low detection accuracy, long response time and poor reusability. Summary of the Invention

[0007] The present invention provides a water stimulus responsive luminescent material and a preparation method and application thereof.

[0008] The technical solutions of the present invention are as follows:

[0009] The present invention provides a water stimulus responsive luminescent material, wherein the luminescent material is (C 10 N2H 15 )2SbCl7·2H2O or (C 10 N2H 15 )2SbCl7.

[0010] (C 10 N2H 15 )2SbCl7·2H2O has a sensitivity of 0.05% for water content detection.

[0011] The (C 10 N2H 15 )2SbCl7·2H2O belongs to the monoclinic crystal system with space group C2 / c;

[0012] The (C 10 N2H 15 )2SbCl7·2H2O, all Sb 3+ They are all coordinated with six chlorine atoms to form a zero-dimensional octahedral structure.

[0013] The (C 10 N2H 15 )2SbCl7, for (C 10 N2H 15 )2SbCl7·2H2O is obtained by drying and losing water.

[0014] The present invention also provides a method for preparing the water stimulus responsive luminescent material, comprising:

[0015] N-phenylpiperazine, antimony trichloride, hydrochloric acid and ethanol were mixed, and the mixture was sonicated at room temperature, heated, washed and dried.

[0016] The molar ratio of N-phenylpiperazine to antimony trichloride is 2:1; the volume ratio of hydrochloric acid to ethanol is 3:2; and the molar to volume ratio of N-phenylpiperazine to hydrochloric acid is 2 mmol:3 mL.

[0017] The ultrasonic time is 10-20 minutes, the heating temperature is 80° C., and the heating time is 4-5 days.

[0018] The present invention also provides an application of the water stimulus responsive luminescent material in anti-counterfeiting materials.

[0019] The anti-counterfeiting material is used to make anti-counterfeiting patterns, QR codes, and Morse codes.

[0020] Beneficial effects

[0021] The stimulus-responsive luminescent material of the present invention uses water as a stimulus and changes its optical properties, such as color and luminescence intensity, by heating or humidifying. It is highly safe, simple to prepare, and has good repeatability. It exhibits high sensitivity to the detection of water molecules, fast response speed, and stable performance. It is applied in the anti-counterfeiting field and has a significant visualization effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 For (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15)X-ray diffraction pattern of 2SbCl7 single crystal.

[0023] Figure 2 The quantum yield test diagram of the single crystal, where (a) is (C 10 N2H 15 )2SbCl7·2H2O single crystal, (b) is (C 10 N2H 15 )2SbCl7 single crystal.

[0024] Figure 3 The fluorescence properties of the single crystal are tested in Figure 1, where (a) is the luminescence under ultraviolet irradiation, (b) is the luminescence spectrum, and (c) is the fluorescence spectrum of the single crystal. 10 N2H 15 )2SbCl7·2H2O decay curve, (d) is (C 10 N2H 15 )2SbCl7 decay curve, (e) is (C 10 N2H 15 )2SbCl7·2H2O color coordinates, (f) is (C 10 N2H 15 )2SbCl7 color coordinates.

[0025] Figure 4 (a) is under ultraviolet irradiation in dry air (C 10 N2H 15 )2SbCl7·2H2O color changes over time; (b) is (C 10 N2H 15 )2SbCl7·2H2O time-dependent photoluminescence spectrum in dry air; (c) is (C 10 N2H 15 )2SbCl7·2H2O exposed to dry and wet reversible conversion of the photoluminescence spectrum intensity; (d) is (C 10 N2H 15 )2SbCl7 photoluminescence spectrum based on time in moist air; (e) is the photoluminescence spectrum of (C 10 N2H 15 )2SbCl7 color changes over time; (f) is a schematic diagram of the mutual conversion of thin films made from single crystal powder by heating or humidification; (g) is the humidity-dependent photoluminescence spectrum; (h) is (C 10 N2H 15 )The emission wavelength of 2SbCl7 changes with humidity.

[0026] Figure 5 For (C 10 N2H 15)2SbCl7·2H2O and (C 10 N2H 15 )2SbCl7 single crystal anti-counterfeiting and information security application diagram, where (a) is a single anti-counterfeiting process; (b) is based on (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 )2SbCl7 single crystal combination as the initial filling material digital information encryption and decryption QR code process diagram; (c) is based on (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 Schematic diagram of the process of encrypting and decrypting Morse code digital information using a )2SbCl7 combination as the initial filling material.

[0027] Figure 6 For the cycle experiment (C 10 N2H 15 )X-ray diffraction pattern of 2SbCl7·2H2O single crystal.

[0028] Figure 7 For different water contents (C 10 N2H 15 )Photoluminescence spectrum of 2SbCl7·2H2O single crystal.

[0029] Figure 8 For different organic solvents (C 10 N2H 15 )X-ray diffraction pattern of 2SbCl7·2H2O single crystal. DETAILED DESCRIPTION

[0030] The following examples are intended to illustrate the present invention rather than to further limit the present invention.

[0031] The present invention provides a water stimulus responsive luminescent material, wherein the luminescent material is (C 10 N2H 15 )2SbCl7·2H2O or (C 10 N2H 15 )2SbCl7.

[0032] Preferably, (C 10 N2H 15 )2SbCl7·2H2O has a sensitivity of 0.05% for water content detection.

[0033] Furthermore, the (C 10 N2H 15)2SbCl7·2H2O belongs to the monoclinic crystal system with space group C2 / c;

[0034] The (C 10 N2H 15 )2SbCl7·2H2O, all Sb 3+ They are all coordinated with six chlorine atoms to form a zero-dimensional octahedral structure.

[0035] In addition, the (C 10 N2H 15 )2SbCl7, for (C 10 N2H 15 )2SbCl7·2H2O is obtained by drying and losing water.

[0036] The present invention also provides a method for preparing the water stimulus responsive luminescent material, comprising:

[0037] N-phenylpiperazine, antimony trichloride, hydrochloric acid and ethanol were mixed, and the mixture was sonicated at room temperature, heated, washed and dried.

[0038] The present invention adopts a solvent volatilization strategy to synthesize single crystals, with simple raw materials and processes and convenient operation.

[0039] Preferably, the molar ratio of N-phenylpiperazine to antimony trichloride is 2:1; the volume ratio of hydrochloric acid to ethanol is 3:2; and the molar to volume ratio of N-phenylpiperazine to hydrochloric acid is 2 mmol:3 mL.

[0040] In addition, the ultrasonic time is 10-20 minutes, the heating temperature is 80° C., and the heating time is 4-5 days.

[0041] The present invention also provides an application of the water stimulus responsive luminescent material prepared by the preparation method in anti-counterfeiting materials.

[0042] Preferably, the water stimulus responsive luminescent material is used to produce anti-counterfeiting patterns, QR codes, and Morse codes.

[0043] The stimulus-responsive luminescent material of the present invention uses water as a stimulus and changes its optical properties, such as color and luminescence intensity, by heating or humidifying. It is highly safe, simple to prepare, and has good repeatability. It exhibits high sensitivity to the detection of water molecules, fast response speed, and stable performance. It is applied in the anti-counterfeiting field and has a significant visualization effect.

[0044] Example 1

[0045] Single crystal (C 10 N2H 15)2SbCl7·2H2O: 2 mmol of N-phenylpiperazine, 1 mmol of antimony trichloride, 3 mL of hydrochloric acid (36%-38% concentrated hydrochloric acid) and 2 mL of ethanol were mixed and transferred to a 25 mL glass vial. The mixture was then ultrasonicated at room temperature for 10 min and then heated at 80°C for 5 days. The product was removed from the solution, washed with ethanol three times and dried in vacuo to obtain (C 10 N2H 15 )2SbCl7·2H2O, save.

[0046] Single crystal (C 10 N2H 15 )2SbCl7 synthesis: (C 10 N2H 15 )2SbCl7·2H2O was heated at 40℃ for half an hour.

[0047] Experimental results

[0048] The single crystal (C 10 N2H 15 )2SbCl7·2H2O, single crystal (C 10 N2H 15 )2SbCl7 was characterized as follows.

[0049] 1. Characterization of crystal structure

[0050] The (C 10 N2H 15 )2SbCl7·2H2O、(C 10 N2H 15 )2SbCl7 was used to characterize the crystal structure, such as Figure 1 In addition, (C 10 N2H 15 )2SbCl7·2H2O single crystal data are shown in Table 1.

[0051] Depend on Figure 1 , Table 1 shows that (C 10 N2H 15 )2SbCl7·2H2O is a monoclinic system with centrosymmetric space group C2 / c. All Sb in these structures 3+ They are all coordinated with six halogen atoms to form a zero-dimensional octahedral structure.

[0052] Table 1 (C 10 N2H 15 )2SbCl7·2H2O single crystal data

[0053]

[0054] a R1=∑||F o |-|F c || / ∑|F o |,wR2={∑w[(F o ) 2 -(F c ) 2 ] 2 / ∑w[(F o ) 2 ] 2} 1 / 2

[0055] 2. Characterization of crystal fluorescence properties

[0056] The (C 10 N2H 15 )2SbCl7·2H2O、(C 10 N2H 15 )2SbCl7 was used to characterize the fluorescence properties of the crystal, such as Figure 2 、 Figure 3 shown.

[0057] Depend on Figure 2 It can be seen that at ambient temperature (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 )2SbCl7 single crystal quantum yield (PLQY) is 2.37% and 19.73% respectively.

[0058] Depend on Figure 3 From (a), we can see that (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 )2SbCl7 single crystal emits red light and yellow light respectively under 365nm ultraviolet light, and can be converted into each other by heating or humidification.

[0059] Depend on Figure 3 From (b), we can see that (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 )2SbCl7 single crystal excitation wavelength (λ ex ) are both 350nm, and emit 645nm (λ em =645nm) red light, 580nm (λ em=580nm). The wavelength difference between yellow light and red light is about 70nm. The naked eye can clearly distinguish the color change, which is sufficient to meet the needs of life and industry.

[0060] Figure 3 (c) and (d) show (C 10 N2H 15 )2SbCl7·2H2O、(C 10 N2H 15 )2SbCl7 decay curves, the lifetimes are 0.21μs and 1.093μs respectively.

[0061] In addition, by Figure 3 From (e) and (f), we can see that (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15 The International Commission on Illumination (CIE) color coordinates of )2SbCl7 are (0.42, 0.49) and (0.55, 0.43) respectively.

[0062] 3. Characterization of crystal fluorescence conversion and humidity detection

[0063] The (C 10 N2H 15 )2SbCl7·2H2O、(C 10 N2H 15 )2SbCl7 for crystal fluorescence conversion and humidity detection characterization, such as Figure 4 shown.

[0064] Figure 4 (a) shows a single crystal (C 10 N2H 15 )2SbCl7·2H2O in a dry environment gradually loses moisture in the single crystal under the irradiation of ultraviolet light for 7 minutes, changing from red to yellow.

[0065] Figure 4 (b) shows a single crystal (C 10 N2H 15 )2SbCl7·2H2O Figure 4 (a) Fluorescence change curve of the single crystal during this process.

[0066] Figure 4 (c) proves that in dry and humid environments, (C 10 N2H 15 )2SbCl7·2H2O and (C 10 N2H 15)2SbCl7 can be repeated more than 15 times, and the fluorescence intensity of the single crystal does not change much, indicating that the single crystal material has good reusability as a new type of water stimulus responsive material.

[0067] In a humid environment, (C 10 N2H 15 The fluorescence curve of 2SbCl7 single crystal changes from yellow to red under 365nm ultraviolet light. Figure 4 As shown in (d), the process photos are as follows Figure 4 As shown in (e).

[0068] The single crystal powder is made into a thin film, which can be transformed into each other under heating (Heat) and humidification (Humid) conditions, such as Figure 4 As shown in (f).

[0069] And under gradient humidity, the single crystal is irradiated by ultraviolet light, and the fluorescence wavelength displayed is as follows Figure 4 In order to understand the relationship between wavelength and humidity in this process, the center wavelength and humidity (RH) are Figure 4 The figure (h) shows that the central wavelength of the single crystal has a linear function relationship with the humidity, and the fitting completion degree is as high as 0.98, indicating that the single crystal has the ability to detect the ambient humidity.

[0070] 4. Application: Characterization of crystals as anti-counterfeiting and encryption and decryption materials

[0071] The (C 10 N2H 15 )2SbCl7·2H2O、(C 10 N2H 15 )2SbCl7 is used in the field of anti-counterfeiting. Figure 5 In (a), the single crystal powder is made into an anti-counterfeiting pattern, and its luminescence is changed by heating or humidification to achieve an anti-counterfeiting effect. The single crystal powder can also be designed into a QR code, such as Figure 5 As shown in (b), when the QR code is yellow, no useful information appears after the mobile phone scans it. After humidification, the mobile phone can scan the required real information. The single crystal powder can also be designed into Morse code, such as Figure 5 As shown in (c), the yellow Morse message is false information used to mislead others, while the red message that appears after humidification is the true message that is intended to be conveyed.

[0072] 5. Repeatability, sensitivity, and stability characterization

[0073] Repeated recycling is a necessary requirement for anti-counterfeiting materials. Figure 4After 15 cycles of experiment in (c), XRD characterization was further performed to prove that the single crystal structure did not change ( Figure 6 ), indicating that the luminescent material of the present invention has good repeatability.

[0074] As a new type of water-stimulated anti-counterfeiting material, the detection range and sensitivity of water content are crucial. Tests have shown that (C 10 N2H 15 )2SbCl7·2H2O single crystal has a high sensitivity to water content detection of 0.05%, and a fast response speed, which helps to make the authenticity identification method more intuitive ( Figure 7 ).

[0075] In order to verify the stability of the single crystal, the (C 10 N2H 15 )2SbCl7·2H2O was immersed in different organic solvents: acetonitrile, tetrahydrofuran, ethyl acetate, toluene, acetone, cyclohexane, and dioxane, and then XRD tests were performed. Figure 8 It can be seen that (C 10 N2H 15 )2SbCl7·2H2O is extremely stable in organic solvents and will not reduce the stability of the crystal structure.

[0076] In summary, the luminescent material of the present invention, as a novel anti-counterfeiting material, uses water as a stimulus, making it flexible for use in a wide range of situations. Compared to chemical reagents and mechanical stress as stimulus sources, it is safer and more reliable. Its high sensitivity, fast response, multiple reuse, and high stability are also significant advantages of this anti-counterfeiting material.

Claims

1. A water stimulus responsive luminescent material, characterized in that: The luminescent material is (C 10 N2H 15 )2SbCl7·2H2O or (C 10 N2H 15 )2SbCl7.

2. The water stimulus responsive luminescent material according to claim 1, characterized in that (C 10 N2H 15 )2SbCl7·2H2O has a sensitivity of 0.05% for water content detection.

3. The water stimulus responsive luminescent material according to claim 1, characterized in that: The (C 10 N2H 15 )2SbCl7·2H2O belongs to the monoclinic crystal system with space group C2 / c; The (C 10 N2H 15 )2SbCl7·2H2O, all Sb 3+ They are all coordinated with six chlorine atoms to form a zero-dimensional octahedral structure.

4. The water stimulus responsive luminescent material according to claim 1, characterized in that The (C 10 N2H 15 )2SbCl7, for (C 10 N2H 15 )2SbCl7·2H2O is obtained by drying and losing water.

5. A method for preparing the water stimulus responsive luminescent material according to claim 1, characterized in that: include: N-phenylpiperazine, antimony trichloride, hydrochloric acid and ethanol were mixed, and the mixture was sonicated at room temperature, heated, washed and dried.

6. The method for preparing a water stimulus responsive luminescent material according to claim 5, wherein: The molar ratio of N-phenylpiperazine to antimony trichloride is 2:1; the volume ratio of hydrochloric acid to ethanol is 3:2; and the molar to volume ratio of N-phenylpiperazine to hydrochloric acid is 2 mmol:3 mL.

7. The method for preparing a water stimulus responsive luminescent material according to claim 5, wherein: The ultrasonic time is 10-20 minutes, the heating temperature is 80° C., and the heating time is 4-5 days.

8. Use of the water stimulus responsive luminescent material according to any one of claims 1 to 4 or the water stimulus responsive luminescent material prepared by the preparation method according to any one of claims 5 to 7 in anti-counterfeiting materials.

9. The use according to claim 8, characterized in that The anti-counterfeiting material is used to make anti-counterfeiting patterns, QR codes, and Morse codes.

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