M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3-based nanophotothermal materials and their preparation and applications

Abstract

The present invention belongs to the field of photothermal materials, and particularly relates to M (2‑x‑y‑z) Zn (2‑x‑y‑z) N x Yb y Tm z O3 nanophotothermal materials and their preparation and application. In the M (2‑x‑y‑z) Zn (2‑x‑y‑z) N x Yb y Tm z O3 nanophotothermal material, M is a Group I main group metal element, N is a rare earth metal element, x is 0.5 - 1.78, y is 0.05 - 0.25, and z is 0.001 - 0.03; the sum of x + y + z is less than 2. The present invention provides a nanophotothermal material with a brand-new chemical formula, and the new material unexpectedly has excellent near-infrared luminescence effect. Moreover, it also has excellent heat generation effect.

Description

Technical Field

[0001] The present invention relates to the field of functional nanomaterials, and particularly to the technical field of photothermal multifunctional materials. Background Art

[0002] Lanthanide ion-doped fluorescent nanoparticles can be used in the fields of bioimaging, photovoltaic technology, optical nanothermometers, anti-counterfeiting, etc., and have received extensive attention. So far, a variety of strategies have been developed to regulate the emission color, fluorescence lifetime, absolute emission intensity, and relative intensity of each fluorescence peak of lanthanide ion-doped fluorescent nanoparticles, such as antenna effect, fluorescence resonance energy transfer, cross-relaxation process control, surface effect, energy migration-mediated process, and so on.

[0003] Since lanthanide ion-doped fluorescent nanoparticles usually exhibit a multi-peak emission spectrum, the challenge lies in achieving fine-tuning of the upconversion or downconversion emission color in a wide spectral range, as well as single-band emission with a selected chromaticity. Recently, the near-infrared second-window emission observed in fluoride nanocrystals doped with Yb3+, Er3+, and Tm3+ has brought new opportunities for bioimaging applications and can image deep biological tissues. However, the exploration of controlling the color output of UCNPs cannot ignore the research on new matrix materials and their operations, which depends on the matrix properties and luminescent dopant concentrations.

[0004] In the past few years, oxide materials have attracted great attention due to their low toxicity, excellent optical properties, stability, and performance with broad application prospects, such as in the fields of LED phosphors, photocatalysts, fuel cells, multiferroics, pressure sensors, topological insulators, and biology. The broadband gap tunability of oxide materials is used in electronic and energy applications. However, there is little prior art on using this property to manipulate near-infrared emission and simultaneously regulate its photothermal properties. Summary of the Invention

[0005] The first object of the present invention is to provide a novel M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nanophotothermal material, aiming to provide a new material with both excellent luminescence and heat generation performance.

[0006] The second object of the present invention is to provide a preparation method of the M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nanophotothermal material and its application in the photothermal material.

[0007] A kind of M(2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nanophotothermal material, where M is a Group I main metal element, N is a rare earth metal element, x is 0.5 to 1.78, y is 0.05 to 0.25, and z is 0.001 to 0.03; the sum of x + y + z is less than 2.

[0008] The present invention provides a nanophotothermal material with a brand-new chemical formula, and the new material unexpectedly has excellent near-infrared luminescence effect. Moreover, it also has excellent heat generation effect.

[0009] The research of the present invention also shows that jointly optimizing and controlling M, N, x, y, and z helps to unexpectedly further achieve synergy and helps to further improve its photothermal performance.

[0010] Preferably, M includes at least one of Li, Na, and K, and preferably Na. The research of the present invention shows that using Na as M has better compatibility with Zn and can further synergistically improve the photothermal performance of the material.

[0011] In the present invention, N includes at least one of Y, Lu, Gd, La, and Kc; preferably Y. The research of the present invention shows that using Y as N helps to further improve the photothermal performance of the new material.

[0012] Preferably, x is 1.5 to 1.78, more preferably 1.64 to 1.76; y is 0.15 to 0.25, more preferably 0.18 to 0.2; z is 0.01 to 0.03, more preferably 0.01 to 0.02. x + y + z equals 1.84 to 1.96. The research of the present invention shows that under the preferred x, y, and z, it helps to further enhance the photothermal performance of the material.

[0013] The present invention also provides a brand-new Na (1.8-x) Zn (1.8-x) Y x Yb 0.19 Tm 0.01 O3 nanomaterial, where x is 1.6 to 1.76. In the preferred material of the present invention, sodium (Na) and zinc (Zn) can synergistically regulate its lattice strain and crystal field symmetry, and can enable the material to exhibit excellent photothermal heating characteristics while maintaining efficient infrared luminescence characteristics.

[0014] M as described in the present invention (2-x-y-z) Zn (2-x-y-z) N x Yb y Tmz The O3 nanophotothermal material is cubic-phase nanosingle crystal particles with a grain size of 14-18 nm.

[0015] The present invention also provides an M as described above (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z The preparation method of the O3 nanophotothermal material is obtained by heat-treating a mixed raw material containing an M source, a Zn source, an N source, a Yb source, and a Tm source.

[0016] In the present invention, the heat treatment method is solid-phase heat treatment or solvothermal treatment, preferably solvothermal treatment.

[0017] In the present invention, the steps of the solvothermal treatment are as follows: mixing the raw material solutions of the M source, Zn source, N source, Yb source, and Tm source with an auxiliary solution, then heating to a temperature of 100-300 °C for heat preservation solvothermal treatment, and then separating to obtain the M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nanophotothermal material;

[0018] The auxiliary solution includes component A, component B, and component C; wherein, component A is a saturated or unsaturated fatty acid of C 15 ~C 20 ; component B is an olefin containing 1-2 unsaturated bonds of C 15 ~C 20 ; component C is a saturated or unsaturated primary amine of C 15 ~C 20 Research shows that solvothermal treatment under the conditions of the present invention helps to optimize the grains and crystal phases of the new material described in the present invention and further strengthen the photothermal performance of the material.

[0019] Component A includes at least one of oleic acid, hexadecenoic acid, and eicosenoic acid.

[0020] Component B includes at least one of octadecene, nonadecene, eicocene, octadecene, heptadecene, hexadecene, and pentadecene.

[0021] Component C includes at least one of octadecylamine, oleylamine, and hexadecylamine; preferably includes oleylamine and octadecylamine with a volume ratio of 1-3:1. Research in the present invention shows that the preferred combined component C helps to cooperate synergistically with other components, helps to optimize the grains and crystal phases of the new material described in the present invention, and further strengthens the photothermal performance of the material.

[0022] Preferably, in the auxiliary agent solution, the volume ratio of component A, component B, and component C is 1 to 10: 1 to 10: 1 to 10; more preferably 1: 1.5 to 2: 1 to 1.5.

[0023] The M source includes at least one of sodium hydroxide, NaHCO3, Na2CO3, and CH3COONa.

[0024] Preferably, the Zn source includes at least one of ZnCl2, (CH3COO)2Zn, ZnCO3, Zn(NO3)2, and ZnSO4.

[0025] Preferably, the N source is at least one of the chlorides, nitrates, sulfates, and acetates of N metal.

[0026] Preferably, the Yb source is at least one of ytterbium chloride, ytterbium nitrate, ytterbium acetate, and ytterbium trifluoroacetate.

[0027] Preferably, the Tm source is at least one of thulium chloride, thulium nitrate, thulium acetate, and thulium trifluoroacetate.

[0028] In the present invention, the raw materials in the M source, Zn source, N source, Yb source, and Tm source are mixed with the auxiliary agent solution in the form of a separate solution or in a partially mixed or fully mixed form.

[0029] In the present invention, in the starting mixed solution for solvothermal treatment, the concentration of the total metal elements has no special requirements. For example, it can be 0.0005 mol / L to 0.5 mol / L, and further can be 0.01 to 0.05 mol / L.

[0030] In the present invention, the solvothermal process can be carried out in a closed container or an open container.

[0031] In the present invention, the temperature of the solvothermal treatment is 180 to 240 °C; further 200 to 220 °C. Research in the present invention shows that at the preferred solvothermal temperature, it helps to cooperate synergistically with other components, helps to optimize the crystal grains and crystal phases of the novel material described in the present invention, and helps to further enhance the photothermal performance of the material.

[0032] In the present invention, the heat preservation time at the solvothermal temperature is 10 to 30 h, preferably 20 to 30 h.

[0033] In the present invention, the temperature of the solid-phase heat treatment stage can be 400 to 600 °C, and the time can be 20 to 30 h.

[0034] The present invention also provides the M described above (2-x-y-z) Zn (2-x-y-z) N x Yb y Tmz The application of O3 nano-photothermal materials, using them as materials for photoluminescence and / or photothermal heating.

[0035] Beneficial effects

[0036] The present invention provides a kind of M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nano-photothermal materials, which take into account excellent photothermal performance. For example, they simultaneously have excellent infrared luminescence and heating characteristics.

[0037] The research of the present invention also shows that the combined optimization control of M, N, and x, y, z helps to unexpectedly further achieve synergy and helps to further improve its photothermal performance. Description of the drawings

[0038] Figure 1 It is the infrared photothermal heating spectrogram of Example 1.

[0039] Figure 2 It is the infrared photothermal heating spectrogram of Group A in Example 2.

[0040] Figure 3 It is the infrared photothermal heating spectrogram of Group B in Example 2.

[0041] Figure 4 It is the infrared photothermal heating spectrogram of Group A in Example 3.

[0042] Figure 5 It is the infrared photothermal heating spectrogram of Group B in Example 3.

[0043] Figure 6 It is the infrared photothermal heating spectrogram of Group C in Example 3.

[0044] Figure 7 It is the infrared photothermal heating spectrogram of Group A in Example 4.

[0045] Figure 8 It is the infrared photothermal heating spectrogram of Group B in Example 4.

[0046] Figure 9 It is the infrared photothermal heating spectrogram of Example 5.

[0047] Figure 10 It is the infrared photothermal heating spectrogram of Comparative Example 1.

[0048] Figure 11 It is the infrared photothermal heating spectrogram of Comparative Example 2.

[0049] Figure 12 It is the infrared photothermal heating spectrogram of Comparative Example 3.

[0050] Figure 13 It is the infrared light-induced heating spectrum of Comparative Example 4A.

[0051] Figure 14 It is the infrared light-induced heating spectrum of Comparative Example 4B. Detailed implementation mode

[0052] To better understand the present invention, the content of the present invention will be further elaborated below in conjunction with the drawings and embodiments, but the present invention is not limited to the following examples.

[0053] The M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z The preparation method of O3 nanophotothermal material can be obtained by heat-treating a mixed raw material containing M source, Zn source, N source, Yb source, and Tm source.

[0054] For example, an optional oxide of the present invention, Na (1.8-x) Zn (1.8-x) Y x Yb 0.19 Tm 0.01 The preparation method of O3 photothermal bifunctional nanomaterial includes the following steps:

[0055] 1) Add oleic acid, octadecene, oleylamine, and octadecylamine into a three-necked flask, and heat and stir to form a homogeneous solvent;

[0056] 2) Drop the aqueous solutions of sodium hydroxide, ytterbium chloride, yttrium chloride, thulium chloride, and zinc acetate into the solvent obtained in step 1) in sequence;

[0057] 3) Heat and stir the solution obtained in step 2) evenly;

[0058] 4) Transfer the emulsion obtained in step 3) into a reaction kettle, and keep it warm and react under closed conditions;

[0059] 5) Naturally cool the reaction product obtained in step 4) to room temperature, and obtain the oxide Na (1.8-x) Zn (1.8-x) Y x Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0060] In an optional scheme of the present invention, the volume ratio of oleic acid, octadecene, oleylamine, and octadecylamine in step 1) is 25:45:20:10.

[0061] In an alternative embodiment of the present invention, in step 3), the reaction temperature is 180~240°C and the reaction time is 10~30 h.

[0062] In an alternative embodiment of the present invention, the heating rate in step 3) is controlled at 3~5°C per minute, aiming to form a relatively uniform solvent system in the reaction vessel before reaching the reaction temperature of 180~240°C.

[0063] In an alternative embodiment of the present invention, in step 5), the vacuum drying temperature is 50~65°C and the drying time is 20~40 h.

[0064] Example 1

[0065] Step 1: Add oleic acid, octadecene, oleylamine, and octadecylamine to a three-necked flask in a volume ratio of 25:45:20:10, and heat and stir to form a uniform solvent.

[0066] Step 2: Sequentially drop aqueous solutions of sodium hydroxide (M source), zinc chloride, yttrium chloride (N source), ytterbium chloride, and thulium chloride into the solvent obtained in step 1) according to the molar ratio of metal elements Na, Zn, Y, Yb, Tm = 0.04:0.04:1.76:0.19:0.01.

[0067] Step 3: Heat and stir the solution obtained in step 2) evenly to obtain an emulsion (the concentration of metal elements in the mixed emulsion is 0.01 mol / L).

[0068] Step 4: Transfer the emulsion obtained in step 3) to a reaction kettle and keep it at 210°C for 24 h under closed conditions.

[0069] Step 5: Naturally cool the reaction product obtained in step 4) to room temperature, and after centrifugal separation, washing, vacuum drying and other processes, obtain oxide Na 0.04 Zn 0.04 Y 1.76 Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0070] The photothermal test performance of the material is shown in Figure 1 . The irradiation laser wavelength is 980 nm and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24°C to 41.1°C, indicating its good infrared and photothermal performance.

[0071] Example 2

[0072] Compared with Example 1, the only difference is that the M source is changed. The experimental groups are as follows:

[0073] A source: The M source is LiOH, and finally Li0.04 Zn 0.04 Y 1.76 Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0074] B source: M source is KOH, and finally K is obtained 0.04 Zn 0.04 Y 1.76 Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0075] Test according to the method of Example 1, and the results are as follows:

[0076] Group A: The photothermal test results of Group 2A of the example are shown in Figure 2 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 37.6 °C.

[0077] Group B: The photothermal test results of Group 2B of the example are shown in Figure 3 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 39.7 °C.

[0078] It can be seen from Examples 1 and 2 that M = Na can achieve the coordination of composition and lattice matching, and can unexpectedly further improve its photothermal performance.

[0079] Example 3

[0080] Compared with Example 1, the difference is only that the N source (oxide of N element) is changed, and the experimental groups are as follows:

[0081] Source A: The N source is Gd, and finally Li is obtained 0.04 Zn 0.04 Gd 1.76 Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0082] Source B: The N source is Lu, and finally Li is obtained 0.04 Zn 0.04 Lu 1.76 Yb 0.19 Tm 0.01 O3 photothermal bifunctional nanocrystal powder.

[0083] Source C: The N source is La, and finally Li is obtained 0.04 Zn 0.04 La 1.76 Yb 0.19Tm 0.01 O3 photothermal dual-functional nanocrystal powder.

[0084] Tested according to the method of Example 1, the results are as follows:

[0085] Group A: The photothermal test results of Group A in Example 3 are shown in Figure 4 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of the photothermal material rises from 24 °C to 38.2 °C.

[0086] Group B: The photothermal test results of Group B in Example 3 are shown in Figure 5 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of the photothermal material rises from 24 °C to 38.6 °C.

[0087] Group C: The photothermal test results of Group C in Example 3 are shown in Figure 6 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of the photothermal material rises from 24 °C to 38.9 °C.

[0088] It can be seen from Examples 1 and 3 that N = Y, which can achieve the coordination of composition and lattice matching, and can unexpectedly further improve its photothermal performance.

[0089] Example 4

[0090] Compared with Example 1, the difference is only that the element ratio in Step 2 is changed. The experimental groups are as follows:

[0091] Group A: Na, Zn, Y, Yb, Tm = 0.1:0.1:1.7:0.19:0.01, and finally obtained Na 0.1 Zn 0.1 Y 1.7 Yb 0.19 Tm 0.01 O3 photothermal dual-functional nanocrystal powder.

[0092] Group B: Na, Zn, Y, Yb, Tm = 0.16:0.16:1.64:0.19:0.01; finally obtained Na 0.16 Zn 0.16 Y 1.64 Yb 0.19 Tm 0.01 O3 photothermal dual-functional nanocrystal powder.

[0093] Tested according to the method of Example 1, the results are as follows:

[0094] Group A: The photothermal test results of Group A in Example 4 are shown in Figure 7。The wavelength of the irradiation laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 41.9 °C.

[0095] The photothermal test results of Example 4 in Group B are shown in Figure 8 。The wavelength of the irradiation laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 41.3 °C.

[0096] Example 5

[0097] Compared with Example 1, the difference is only that instead of carrying out the solvothermal reaction, the metal raw materials in Step 2 are directly mixed in solid state and then calcined in air at 500 °C for 24 h to obtain the product. The photothermal test results are shown in Figure 9 。The wavelength of the irradiation laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 34 °C.

[0098] It can be seen from Examples 1 and 5 that by using the solvothermal reaction described in the present invention, the phase and grain control of the new material can be further strengthened, which is helpful for further enhancing the photothermal performance of the prepared material.

[0099] Example 6

[0100] Compared with Example 1, the difference is only that in Step 1, the solvents are oleic acid, octadecene, oleylamine and octadecylamine in a volume ratio of 25:45:30; other operations and parameters are as in Example 1. The test results are as follows: the wavelength of the irradiation laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 38.4 °C.

[0101] It can be seen from Examples 1 and 6 that using the quaternary solvent for solvothermal treatment is helpful for further strengthening the lattice and grain control of the new material described in the present invention, and is helpful for further improving the photothermal performance of the material.

[0102] Example 7

[0103] Compared with Example 1, the difference is only that in Step 1, the solvents are oleic acid, eicosene and oleylamine in a volume ratio of 1:1.5:1; the metal solution in Step 2 is controlled to be 0.02 M; the temperature in Step 4 is 190 °C and the time is 28 h. Other operations and parameters are the same as in Example 1. The test results are as follows: the wavelength of the irradiation laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 s, the temperature of the photothermal material rises from 24 °C to 37.8 °C.

[0104] Comparative Example 1

[0105] Compared with Example 1, the only difference is that in Step 2, the Na source and the zinc source are missing, and in Step 2, the ratio of Y, Yb, and Tm is 1.8:0.19:0.01. Other operations and parameters are the same as in Example 1. Finally, Y 1.8 Yb 0.19 Tm 0.01 O3 nanocrystal powder.

[0106] The results of its photothermal test are shown in Figure 10 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of this photothermal material rises from 24 °C to 32.1 °C.

[0107] Comparative Example 2

[0108] Compared with Example 1, the only difference is that zinc is missing, and the missing charge is supplemented by Na. The finally obtained material is Na 0.12 Y 1.76 Yb 0.19 Tm 0.01 O3.

[0109] The results of the photothermal test of Comparative Example 2 are shown in Figure 11 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of this photothermal material rises from 24 °C to 31.8 °C.

[0110] Comparative Example 3

[0111] Compared with Example 1, the only difference is that Na is missing, and the missing charge is supplemented by Zn. The finally obtained material is Zn 0.06 Y 1.76 Yb 0.19 Tm 0.01 O3. The results of the photothermal test of Comparative Example 3 are shown in Figure 12 . The irradiation laser wavelength is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of this photothermal material rises from 24 °C to 31.5 °C.

[0112] Comparative Example 4

[0113] Compared with Example 1, the only difference is that other divalent elements are used to replace Zn in an equimolar amount. Other operations and parameters are the same as in Example 1. The experimental groups are as follows:

[0114] Group A: Calcium chloride is used to replace the zinc chloride in an equimolar amount;

[0115] Group B: Manganese chloride is used to replace the zinc chloride in an equimolar amount;

[0116] The tests are as follows:

[0117] Group A: The results of the photothermal test are shown in Figure 13 . The wavelength of the irradiated laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of the photothermal material rises from 24 °C to 30.2 °C.

[0118] Group B: The results of the photothermal test are shown in Figure 14 . The wavelength of the irradiated laser is 980 nm, and the power density is 1.0 W / mm². After continuous irradiation for 10 seconds, the temperature of the photothermal material rises from 24 °C to 30.7 °C.

Claims

1. A kind of M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z The preparation method of O3 nano-photothermal material is characterized in that, It is obtained by heat-treating a mixed raw material of an M source, a Zn source, an N source, a Yb source, and a Tm source with a stoichiometry of O3; wherein the M includes at least one of Li, Na, and K; (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z It is obtained by heat-treating a mixed raw material of an M source, a Zn source, an N source, a Yb source, and a Tm source with a stoichiometry of O3; wherein the M includes at least one of Li, Na, and K; The N described above includes at least one of Y, Lu, Gd, and La; The x is 1.5 - 1.78, the y is 0.15 - 0.25, and the z is 0.01 - 0.03; the sum of x + y + z is less than 2; The heat treatment method described is solvothermal; the steps of the solvothermal method are as follows: Mix the raw material solutions of the M source, Zn source, N source, Yb source, and Tm source and the additive solution, then heat to a temperature of 180-240 °C and keep warm for 10-30 h, and then separate to obtain the M (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z O3 nanophotothermal material; The auxiliary agent solution described above comprises component A, component B, and component C; wherein, component A is a saturated or unsaturated fatty acid with carbon number from C 15 to C 20 ; component B is an olefin with carbon number from C 15 to C 20 and having 1 to 2 unsaturated bonds; component C is a saturated or unsaturated primary amine with carbon number from C 15 to C 20 . In the auxiliary agent solution, the volume ratio of component A, component B, and component C is 1 - 10:1 - 10:1 - 10.

2. The preparation method according to claim 1, characterized in that, The M source includes at least one of sodium hydroxide, NaHCO3, Na2CO3, and CH3COONa; The Zn source includes at least one of ZnCl2, (CH3COO)2Zn, ZnCO3, Zn(NO3)2, and ZnSO4; The N source is at least one of the chlorides, nitrates, sulfates, and acetates of N metal; The Yb source is at least one of ytterbium chloride, ytterbium nitrate, ytterbium acetate, and ytterbium trifluoroacetate; The Tm source is at least one of thulium chloride, thulium nitrate, thulium acetate, and thulium trifluoroacetate; In the starting mixed solution of solvothermal reaction, the concentration of the total metal element is 0.0005 mol / L - 0.5 mol / L.

3. The preparation method according to claim 1, characterized in that, Its preparation steps include: Step 1: Add oleic acid, octadecene, oleylamine, and octadecylamine to a three-necked flask according to a volume ratio of 25:45:20:10, and heat and stir to form a uniform solvent; Step 2: Drop the aqueous solutions of the M source, zinc chloride, N source, ytterbium chloride, and thulium chloride into the solvent obtained in Step 1 in sequence according to the molar ratio of metal elements Na:Zn:Y:Yb:Tm = 0.04:0.04:1.76:0.19:0.01; the M source is sodium hydroxide; the N source is yttrium chloride; Step 3: Heat and stir the solution obtained in Step 2 evenly to obtain an emulsion, and the concentration of the metal elements in the mixed emulsion is 0.01 mol / L; Step 4: Transfer the emulsion obtained in Step 3 into a reaction kettle, and keep it warm and react at 210 °C for 24 h under airtight conditions; Step 5: Naturally cool the reaction product obtained in Step 4 to room temperature, and obtain it through centrifugal separation, washing, and vacuum drying.

4. The preparation method according to claim 3, characterized in that, Replace Na, Zn, Y, Yb, and Tm in Step 2 with 0.1:0.1:1.7:0.19:0.01 or 0.16:0.16:1.64:0.19:0.

01.

5. The preparation method according to claim 3, characterized in that, Replace the M source in Step 2 with lithium hydroxide or potassium hydroxide.

6. The preparation method according to claim 3, characterized in that, Replace the N source in Step 2 with gadolinium chloride, lutetium chloride, or lanthanum chloride.

7. M prepared by the preparation method according to any one of claims 1 to 6 (2-x-y-z) Zn (2-x-y-z) N x Yb y Tm z Application of O3 nano-photothermal material, characterized in that Use it as a material for photothermal heating.

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