High-efficiency photothermal conversion nano material and preparation method and product thereof

Abstract

The invention discloses a high-efficiency photothermal conversion nano material and a preparation method and a product thereof, four rare earth metal ions are introduced to form a co-doped sodium fluoride matrix nano material NaA (1-x-y) F4: xB / y Bi < 3 + >, A is Yb or Y ions, B is a combination of two ions of Pr, Tb and Tm according to an equal molar ratio, x is 0.01-0.03, y is 0.05-0.3, x is 0.01-0.03, y is 0.05-0.3, and Bi < 3 + > is 0.01-0.03. Therefore, the photo-thermal conversion nano material which is high in photo-thermal conversion efficiency, low in cost, non-toxic, environment-friendly and controllable in photo-thermal conversion temperature is obtained. The preparation method has the advantages of simple and convenient process, no need of high-temperature calcination, low cost, high yield and easy industrial production, and can be used as the most potential substitute of the traditional PTT photo-thermal therapeutic agent in many application fields of photo-thermal therapy, optical temperature measurement, up-conversion photoluminescence and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic functional materials, and in particular to a high-efficiency light-to-heat conversion nanomaterial and a preparation method and product thereof. Background Art

[0002] Nanoparticle-mediated tumor-targeted photothermal therapy (PTT) is a treatment method that heats up nanoheaters through in vitro infrared radiation, thereby heating and ablating tumor cells. Since the tolerance temperature of surrounding healthy cells is higher than that of cancer cells, this treatment method is very less invasive and is called "green therapy" by the international medical community. Generally, biological tissues have strong absorption of visible light (350-780nm) and infrared light (>1000nm), and the least absorption of near-infrared short-wave light (NIR) (700-1000nm). Since near-infrared light has good biological tissue penetration and almost no damage to tissues, near-infrared laser-driven photothermal therapy technology has received more attention. In order to improve the photothermal conversion efficiency of near-infrared lasers in photothermal therapy, it is necessary to study and develop efficient, biocompatible, and targeted near-infrared photothermal conversion materials. Generally, photothermal agents for PTT diagnosis and treatment are mainly concentrated in photothermal conversion materials and devices such as organic materials, metal-based nanomaterials, carbon-based nanomaterials, and semiconductor nanomaterials. However, these materials all have certain advantages and disadvantages: organic materials are low in cost, but have certain photobleaching properties and poor stability; metals such as gold nanostructured materials have good photothermal properties, but they may be deformed by heat during illumination, and the price of precious metals also restricts the widespread application of such photothermal conversion materials; carbon-based nanomaterials have very good photostability, but have relatively low near-infrared absorption coefficients and low photothermal conversion efficiency; semiconductor nanomaterials are low in cost and have high photothermal conversion efficiency, but their photostability is not as good as carbon. The above photothermal conversion materials have seriously affected the development and application of PTT diagnosis and treatment technology. Therefore, the urgent need to develop low-cost, non-toxic, environmentally friendly and efficient photothermal conversion nanomaterials has become a future development trend. Summary of the invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-efficiency photothermal conversion nanomaterial, which is obtained by introducing four rare earth metal ions to form a co-doped sodium fluoride matrix nanomaterial with high photothermal conversion efficiency, low cost, non-toxicity, environmental protection and controllable photothermal conversion temperature. Another purpose of the present invention is to provide a preparation method and product of the above-mentioned high-efficiency photothermal conversion nanomaterial.

[0004] The purpose of the present invention is achieved through the following technical solutions:

[0005] The present invention provides a highly efficient photothermal conversion nanomaterial, the chemical formula of which is NaA(1-x-y) F4:xB / yBi 3+ , A is Yb or Y ion, B is a combination of two ions of Pr, Tb, and Tm in an equimolar ratio, x=0.01~0.03, y=0.05~0.3.

[0006] Furthermore, the photothermal conversion nanomaterial of the present invention:

[0007] A is Yb ion; B is Pr and Tb ion, or Pr and Tm ion; x=0.015-0.025, y=0.08-0.25.

[0008] A is Yb ion; B is Tb and Tm ion; x=0.012~0.025, y=0.08~0.25.

[0009] A is Y ion; B is Pr and Tb ion, or Pr and Tm ion, or Tb and Tm ion; x=0.012-0.025, y=0.1-0.25. Preferably, A is Y ion; B is Pr and Tb ion; x=0.016-0.022, y=0.12-0.20.

[0010] Another object of the present invention is achieved by the following technical solutions:

[0011] The method for preparing the above-mentioned high-efficiency light-to-heat conversion nanomaterial provided by the present invention comprises the following steps:

[0012] (1) Using metal nitrate and NH4F as raw materials, the mixture is prepared according to the chemical formula, and NaNO3, A(NO3)3, B(NO3)3, and Bi(NO3)3 are first added in sequence and ground and mixed evenly, and then NH4 is added and ground until a white gel is obtained;

[0013] (2) The white gel is transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining, and a hydrothermal molten salt reaction is carried out at a temperature of 180 to 240° C. for 18 to 30 hours. The reaction product is centrifuged, washed, dried, and dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

[0014] Furthermore, in step (2) of the preparation method of the present invention, the drying is carried out at a temperature of 50 to 80° C. for 12 to 15 hours.

[0015] The product prepared by the preparation method of the high-efficiency photothermal conversion nanomaterial of the present invention has a regular hexagonal sheet structure grain, and the sheet diameter is 60-150nm; the photothermal conversion temperature is 35-155℃, the photothermal conversion slope efficiency is 43-142℃ / W, and the near-infrared light to blue light intensity ratio I NIR / I BlueIt is 760 to 1600.

[0016] The present invention has the following beneficial effects:

[0017] (1) The present invention controls the photothermal conversion nanomaterial NaA (1-x-y) F4:x B / y Bi 3+ (x = 0.01 ~ 0.03, y = 0.05 ~ 0.3) in which the types and doping amounts of A and B ions, as well as the relationship between A and B ions and Bi 3+ The molar ratio of Bi 3+ The special electronic energy level structure and charge migration state of ions can effectively regulate the electronic structure (band structure), crystal field structure symmetry and energy level structure changes of sodium fluoride NaAF4 matrix crystals, resulting in a bandgap width E g Narrow, Bi 3+ The ions also cause changes in the crystal field symmetry around the heat center B ion, resulting in changes in crystal morphology and lattice defects, which in turn affect the heat conversion efficiency of the sample. 3+ Ion Synergy A 3+ To B 3+ The significant sensitization of ions and the efficient energy transfer cause the emission peaks in the ultraviolet and visible light bands to weaken or even quench, thereby significantly improving the NaA (1-x-y) F4:x B / y Bi 3+ The near-infrared luminescence intensity of nanomaterials at 800nm ​​is NIR / I Blue ) ratio can be increased to nearly 1600 times to form monochromatic near-infrared light. The strong near-infrared band is located in the biological transparent window, which is conducive to application in organisms. The synthesized nanomaterial responds to 980nm near-infrared light, with an excitation power of 1.0W, and can achieve a controllable photothermal conversion temperature range of 35-155℃ for 10s. The conversion efficiency is expressed by the photothermal conversion slope efficiency, which can approach and reach 142℃ / W.

[0018] (2) The present invention is a high-efficiency photothermal conversion nanomaterial prepared by using four doping ion compositions, and utilizes doping ion lattice substitution, lattice distortion, and energy transfer between ions to regulate the crystal energy level structure and electronic structure of the material, thereby regulating the photothermal conversion performance of the prepared nanomaterial and the emission intensity of ultraviolet light, visible light, and near-infrared light.

[0019] (3) The present invention adopts hydrothermal molten salt technology to synthesize efficient photothermal conversion nanomaterials with hexagonal crystal structure, regular flaky morphology, and uniform particle size distribution. This method is simple and convenient, does not require high-temperature calcination, has low cost, high yield, and is easy to industrialize.

[0020] (4) The nanomaterial synthesized in the present invention with strong near-infrared monochromatic luminescence (800nm) and efficient optical heating ability is suitable for multifunctional upconversion photoluminescence and optical heater applications. It is a very promising fluorescent self-labeling nanoheater and the most promising alternative to traditional PTT photothermal therapeutic agents. It can be used in many application fields such as photothermal therapy, optical temperature measurement, upconversion photoluminescence, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings:

[0022] Figure 1 This is the XRD spectrum of the high-efficiency photothermal conversion nanomaterial prepared in Example 1 of the present invention;

[0023] Figure 2 This is a SEM photograph of the high-efficiency photothermal conversion nanomaterial prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0024] Embodiment 1:

[0025] This embodiment is a highly efficient light-to-heat conversion nanomaterial, the chemical formula of which is NaYb 0.83 F4:0.01Tm / 0.01Tb / 0.15Bi 3+ , the preparation method steps are as follows:

[0026] (1) Using metal nitrate and NH4F as raw materials, according to the above chemical formula, weigh 8.501g NaNO3, 29.803g Yb(NO3)3, 0.355g Tm(NO3)3, 0.345g Tb(NO3)3, 5.925g Bi(NO3)3, and 14.816g NH4F, first add NaNO3, Yb(NO3)3, Tm(NO3)3, Tb(NO3)3, and Bi(NO3)3 into an agate mortar in that order and grind and mix them evenly, then add NH4 and grind until a white gel is obtained;

[0027] (2) The white gel was transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining and placed in a vacuum oven at 180°C for 24 hours. After the reaction was completed, the hydrothermal reactor was naturally cooled to room temperature (~25°C) to extract the reaction product; the reaction product was centrifuged, washed with deionized water and ethanol, dried at 60°C for 12 hours, and then dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

[0028] like Figure 1 As shown in FIG. 1 , the embodiment of the present invention successfully prepared the high-efficiency photothermal conversion nanomaterial NaYb by using the improved molten salt method. 0.83 F4:0.01Tm / 0.01Tb / 0.15Bi3+ ;like Figure 2 As shown, the grains have a highly symmetrical regular hexagonal lamellar structure, and the flake diameters are mostly distributed between 80nm and 120nm.

[0029] Embodiment 2:

[0030] This embodiment is a highly efficient light-to-heat conversion nanomaterial, the chemical formula of which is NaYb 0.78 F4:0.01Tm / 0.01Pr / 0.2Bi 3+ , the preparation method steps are as follows:

[0031] (1) With metal nitrate and NH4F as raw materials, according to the above chemical formula, weigh 8.501g NaNO3, 28.007g Yb(NO3)3, 0.355g Tm(NO3)3, 0.341g Pr(NO3)3, 7.899g Bi(NO3)3, and 14.816g NH4F, first add NaNO3, Yb(NO3)3, Tm(NO3)3, Pr(NO3)3, and Bi(NO3)3 into an agate mortar in that order and grind and mix them evenly, then add NH4 and grind until a white gel is obtained;

[0032] (2) The white gel was transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining and placed in a vacuum oven at 200°C for 24 hours. After the reaction was completed, the hydrothermal reactor was naturally cooled to room temperature (~25°C) to extract the reaction product; the reaction product was centrifuged, washed with deionized water and ethanol, dried at 70°C for 12 hours, and then dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

[0033] Embodiment three:

[0034] This embodiment is a highly efficient light-to-heat conversion nanomaterial, whose chemical formula is NaY 0.78 F4:0.01Tm / 0.01Pr / 0.2Bi 3+ , the preparation method steps are as follows:

[0035] (1) Using metal nitrate and NH4F as raw materials, according to the above chemical formula, weigh 8.501g NaNO3, 21.444g Y(NO3)3, 0.355g Tm(NO3)3, 0.341g Pr(NO3)3, 7.899g Bi(NO3)3, and 14.816g NH4F, first add NaNO3, Y(NO3)3, Tm(NO3)3, Pr(NO3)3, and Bi(NO3)3 into an agate mortar in that order and grind and mix them evenly, then add NH4 and grind until a white gel is obtained;

[0036] (2) The white gel was transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining and placed in a vacuum oven at 240°C for 24 hours. After the reaction was completed, the hydrothermal reactor was naturally cooled to room temperature (~25°C) to extract the reaction product; the reaction product was centrifuged, washed with deionized water and ethanol, dried at 60°C for 15 hours, and then dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

[0037] Embodiment 4:

[0038] This embodiment is a highly efficient light-to-heat conversion nanomaterial, whose chemical formula is NaY 0.834 F4:0.008Pr / 0.008Tb / 0.15Bi 3+ , the preparation method steps are as follows:

[0039] (1) Using metal nitrate and NH4F as raw materials, according to the above chemical formula, weigh 8.501g NaNO3, 22.928g Y(NO3)3, 0.273g Pr(NO3)3, 0.276g Tb(NO3)3, 5.925g Bi(NO3)3, and 14.816g NH4F, first add NaNO3, Y(NO3)3, Pr(NO3)3, Tb(NO3)3, and Bi(NO3)3 into an agate mortar in that order and grind and mix them evenly, then add NH4 and grind until a white gel is obtained;

[0040] (2) The white gel was transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining and placed in a vacuum oven at 180°C for 30 hours. After the reaction was completed, the hydrothermal reactor was naturally cooled to room temperature (~25°C) to extract the reaction product; the reaction product was centrifuged, washed with deionized water and ethanol, dried at 60°C for 15 hours, and then dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

[0041] With the chemical formula of NaYb 0.98 F4:0.02Pr 3+ , the other conditions are the same as those in Example 1 as a comparative example, the photothermal conversion temperature, photothermal conversion slope efficiency and near-infrared light to blue light intensity ratio (I NIR / I Blue ) as shown in Table 1.

[0042] Table 1 Performance indicators of the photothermal conversion materials of the embodiments of the present invention and the comparative examples

[0043]

Claims

1. A highly efficient photothermal conversion nanomaterial, characterized by: The chemical formula of the nanomaterial is NaA (1-x-y) F4:xB / yBi 3+ , A is Yb or Y ion, B is a combination of two ions of Pr, Tb, and Tm in an equimolar ratio, x=0.01~0.03, y=0.05~0.

3.

2. The high-efficiency light-to-heat conversion nanomaterial according to claim 1, characterized in that: The chemical formula A is Yb ion; B is Pr and Tb ion, or Pr and Tm ion; x=0.015-0.025, y=0.08-0.

25.

3. The high-efficiency light-to-heat conversion nanomaterial according to claim 1, characterized in that: The chemical formula A is Yb ion; B is Tb and Tm ions; x=0.012-0.025, y=0.08-0.

25.

4. The high-efficiency light-to-heat conversion nanomaterial according to claim 1, characterized in that: The chemical formula A is Y ion; B is Pr and Tb ion, or Pr and Tm ion, or Tb and Tm ion; x=0.012-0.025, y=0.1-0.

25.

5. The high-efficiency light-to-heat conversion nanomaterial according to claim 4, characterized in that: The chemical formula A is Y ion; B is Pr and Tb ions; x=0.016-0.022, y=0.12-0.

20.

6. The method for preparing the high-efficiency photothermal conversion nanomaterial according to any one of claims 1 to 5, characterized in that The following steps are involved: (1) Using metal nitrate and NH4F as raw materials, the mixture is prepared according to the chemical formula, and NaNO3, A(NO3)3, B(NO3)3, and Bi(NO3)3 are first added in sequence and ground and mixed evenly, and then NH4 is added and ground until a white gel is obtained; (2) The white gel is transferred to a tightly sealed hydrothermal reactor with a polytetrafluoroethylene lining, and a hydrothermal molten salt reaction is carried out at a temperature of 180 to 240° C. for 18 to 30 hours. The reaction product is centrifuged, washed, dried, and dispersed and stored in a cyclohexane solution to obtain a high-efficiency photothermal conversion nanomaterial.

7. The method for preparing a highly efficient photothermal conversion nanomaterial according to claim 6, characterized in that: In the step (2), the mixture is dried at a temperature of 50 to 80° C. for 12 to 15 hours.

8. The product obtained by the method for preparing the high-efficiency light-to-heat conversion nanomaterial according to claim 6 or 7, characterized in that: The photothermal conversion nanomaterial has a morphology of regular hexagonal flake structure grains, and the flake diameter is 60-150 nm.

9. The product according to claim 8, characterized in that: The photothermal conversion temperature of the photothermal conversion nanomaterial is 35-155°C, the photothermal conversion slope efficiency is 43-142°C / W, and the near-infrared light to blue light intensity ratio I NIR / I Blue It is 760 to 1600.

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