阅读说明：本技术 一种zif-8调控的近红外镓酸盐长余辉纳米材料的制备方法 (Preparation method of near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8 ) 是由 李玲玲 姚天琳 董高秋 于 2021-08-03 设计创作，主要内容包括：本发明属于纳米材料的制备技术领域,特别涉及一种ZIF-8调控的近红外镓酸盐长余辉纳米材料的制备方法,将金属-有机骨架ZIF-8与镓酸锌及掺杂离子的金属离子前体溶液混合后烘干,通过两次焙烧法制得近红外镓酸盐长余辉纳米材料；通过本发明的制备方法,可获得颗粒约100nm并且分布均匀、具有超长余辉的近红外镓酸盐长余辉纳米材料,能够很好的应用于生物成像领域。(The invention belongs to the technical field of preparation of nano materials, and particularly relates to a preparation method of a near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8, which comprises the steps of mixing a metal-organic framework ZIF-8 with zinc gallate and a metal ion precursor solution doped with ions, drying, and preparing the near-infrared gallate long-afterglow nano material by a twice baking method; the near-infrared gallate long-afterglow nano material with particles of about 100nm, uniform distribution and ultra-long afterglow can be obtained by the preparation method, and can be well applied to the field of biological imaging.)

1. A preparation method of a near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8 is characterized by comprising the following steps:

step 1, mixing ZIF-8 powder and a metal ion precursor solution, and drying to prepare a precursor A; the ratio of the ZIF-8 powder to the metal ion precursor solution is 100-200mg ZIF-8 powder/2-4 mL metal ion precursor solution, and the metal ion precursor solution is formed by mixing a gallium nitrate solution, a zinc acetate solution, a chromium nitrate solution and a tin chloride solution;

step 2, pre-sintering the precursor A to prepare a solid B;

step 3, roasting the solid B to prepare a solid C;

and 4, treating the solid C with hydrochloric acid to prepare the near-infrared gallate long-afterglow nano material.

2. The method according to claim 1, wherein the metal ion precursor solution is prepared by mixing a gallium nitrate solution, a zinc acetate solution, a chromium nitrate solution, and a tin chloride solution in a volume ratio of 80:5:5:2, wherein the gallium nitrate solution has a molar concentration of 0.25 to 0.3mol/L, the zinc acetate solution has a molar concentration of 0.1 to 0.2mol/L, the chromium nitrate solution has a molar concentration of 0.02 to 0.1mol/L, and the tin tetrachloride solution has a molar concentration of 0.05 to 0.1 mol/L.

3. The method of claim 1, wherein the pre-sintering temperature of step 2 is 600-.

4. The method as claimed in claim 1, wherein the calcination temperature in step 3 is 900-1000 ℃.

5. The preparation method according to claim 1, wherein the specific method of step 1 is: and (3) uniformly mixing ZIF-8 powder and a metal ion precursor solution by ultrasonic waves for 30-60min, and drying at 110 ℃ for 2-3h to obtain a precursor A.

6. The preparation method according to claim 1, wherein the specific method of step 2 is: and (3) putting the precursor A into a muffle furnace, heating the precursor A from room temperature to the pre-sintering temperature at the heating rate of 5 ℃/min, and reacting for 2h to obtain a solid B.

7. The preparation method according to claim 1, wherein the specific method of step 3 is: and cooling the solid B, grinding the solid B into fine powder, putting the fine powder into a muffle furnace, heating the fine powder from room temperature to the required temperature at the heating rate of 2 ℃/min, and reacting for 4 hours.

8. The preparation method according to claim 1, wherein the specific method of the step 4 is as follows: and treating the solid C with hydrochloric acid with the concentration of 0.01-1M for 1-8h, and centrifugally washing and drying to obtain the near-infrared gallate long-afterglow nano material.

9. The method of preparing of claim 1, wherein the ZIF-8 powder is prepared by:

step 01, mixing a zinc nitrate solution and a 2-methylimidazole solution to prepare a milky mixed solution;

and step 02, centrifuging, washing and drying the milky white mixed solution prepared in the step 01 to prepare ZIF-8 powder.

10. The preparation method according to claim 9, wherein in the step 01, the mass concentration of the zinc nitrate solution is 0.004 to 0.016g/mL, the mass concentration of the 2-methylimidazole solution is 0.01 to 0.04g/mL, and the volume ratio of the zinc nitrate solution to the 2-methylimidazole solution is 1: 1.

Technical Field

The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8.

Background

The long afterglow luminescent material is one new kind of luminescent material with afterglow performance after excitation is stopped. It can store energy from ultraviolet light, visible light, X-rays, or other excitation sources, and then gradually release energy through photon emission. The persistent emission may be after excitation has ceasedLasting minutes, hours or even days. Cr having especially near infrared emission³⁺The doped zinc gallate long afterglow luminescent material has good emission matching with the first biological window (650-. In addition, the near-infrared long-afterglow nano material has the advantages of no need of in-situ excitation, high signal-to-noise ratio, improvement of imaging sensitivity, deep tissue penetration and the like, can be used as an excellent biomarker probe, and has wide application prospects in the fields of biological imaging, medical diagnosis and treatment.

The traditional long afterglow luminescent material is generally synthesized by a high temperature solid phase method, but because the method relates to a high temperature sintering process, the obtained particles are seriously agglomerated and have very large sizes (between 1 and 100 micrometers), so that the application of the long afterglow luminescent material as a marking material in the field of biomedicine is limited. Although various wet chemical methods including hydrothermal method, solvothermal method, sol-gel method, etc. are available, the long-afterglow nano luminescent material can also be prepared. However, compared with a high-temperature solid-phase synthesis method, the material obtained by a wet chemical method has lower crystallization degree, more defects and weaker luminescence, and the application of the material in aspects such as biological imaging is influenced.

In order to further promote the biomedical application of the near-infrared long-afterglow material, the exploration and improvement technology is very significant for preparing the near-infrared long-afterglow nano material with high luminous efficiency, long afterglow time and uniform particle size distribution.

Disclosure of Invention

The invention solves the technical problems in the prior art and provides a preparation method of a near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8.

The technical scheme of the invention is as follows:

a preparation method of a near-infrared gallate long-afterglow nano material regulated and controlled by ZIF-8 comprises the following steps:

step 1, mixing ZIF-8 powder and a metal ion precursor solution, and drying to prepare a precursor A; the ratio of the ZIF-8 powder to the metal ion precursor solution is 100-200mg ZIF-8 powder/2-4 mL metal ion precursor solution, the metal ion precursor solution is formed by mixing a gallium nitrate solution, a zinc acetate solution, a chromium nitrate solution and a tin chloride solution according to the volume ratio of 80:5:5:2, the molar concentration of the gallium nitrate solution is 0.25-0.3mol/L, the molar concentration of the zinc acetate solution is 0.1-0.2mol/L, the molar concentration of the chromium nitrate solution is 0.02-0.1mol/L, and the molar concentration of the tin tetrachloride solution is 0.05-0.1 mol/L;

step 2, pre-sintering the precursor A to prepare a solid B, wherein the pre-sintering temperature is 600-800 ℃;

step 3, roasting the solid B to prepare a solid C, wherein the roasting temperature is 900-1000 ℃;

and 4, treating the solid C with hydrochloric acid, and centrifugally washing and drying to obtain the near-infrared gallate long-afterglow nano material.

Preferably, the ZIF-8 powder is prepared by the method of

Step 01, mixing a zinc nitrate solution and a 2-methylimidazole solution to prepare a milky mixed solution;

and step 02, centrifuging, washing and drying the milky white mixed solution prepared in the step 01 to prepare ZIF-8 powder.

Preferably, in the step 01, the mass concentration of the zinc nitrate solution is 0.004-0.016g/mL, the mass concentration of the 2-methylimidazole solution is 0.01-0.04g/mL, the volume ratio of the zinc nitrate solution to the 2-methylimidazole solution is 1:1, and water or methanol is adopted as a mixed system of the reaction; and (3) dripping the 2-methylimidazole aqueous solution into the zinc nitrate aqueous solution during mixing, and stirring for 15-120 min.

Preferably, in the step 02, the centrifugation rotation speed is 8000-10000r/min, the centrifugation time is 15-20min, the drying temperature is 60 ℃, and the drying time is 10-12 h.

Preferably, the specific method of step 1 is: and (3) uniformly mixing ZIF-8 powder and a metal ion precursor solution by ultrasonic waves for 30-60min, and drying at 110 ℃ for 2-3h to obtain a precursor A.

Preferably, the specific method of step 2 is: and (3) putting the precursor A into a muffle furnace, heating the precursor A from room temperature to the pre-sintering temperature at the heating rate of 5 ℃/min, and reacting for 2h to obtain a solid B.

Preferably, the specific method of step 3 is: and cooling the solid B, grinding the solid B into fine powder, putting the fine powder into a muffle furnace, heating the fine powder from room temperature to the required temperature at the heating rate of 2 ℃/min, and reacting for 4 hours.

Preferably, in the step 4, the concentration of the hydrochloric acid is 0.01-1M, the time for treating the solid C with the hydrochloric acid is 1-8h, the centrifugal rotation speed is 10000-12000r/min, the centrifugal time is 10-15min, and the drying time is 10-12 h.

Compared with the prior art, the invention has the advantages that,

1. by the preparation method, the near-infrared gallate long-afterglow nano material with uniform size (about 100 nm) and ultra-long afterglow can be obtained, and the preparation method can be well applied to the field of biological imaging;

2. in the preparation method, the metal ion raw material is easy to obtain, the precursor solution is simple to prepare, the equipment cost is low, the operation is simple, and the repeatability is good;

3. the preparation method of the invention can rapidly carry out multi-step reaction at room temperature, and the obtained nano material has high yield and excellent long afterglow performance.

Drawings

FIG. 1 is a transmission electron micrograph of ZIF-8 prepared in example 1 of the present invention;

FIG. 2 is a transmission electron micrograph of the gallate nanomaterial prepared in example 1 of the present invention;

FIG. 3 is a graph of the room temperature emission spectrum of the gallate long-afterglow nanomaterial prepared in example 1 of the present invention;

FIG. 4 is the long afterglow decay curve of the near infrared gallate long afterglow nano material prepared in the embodiment 1 of the present invention.

Detailed Description

Example 1:

(1) preparation of ZIF-8 powder:

20mL of 0.004g/mL zinc nitrate aqueous solution is taken and dropped into 20mL of 0.01g/mL 2-methylimidazole aqueous solution, and the mixture is stirred for 30min at room temperature to obtain milky white solution. Centrifuging at 10000r/min for 15min, and drying in an oven at 60 deg.C for 12h to obtain ZIF-8 powder;

(2) preparing a gallate long-afterglow nano luminophor @ ZIF-8 composite material:

adding 8mL of Ga (NO)₃)₃Solution (0.25mol/L), 0.5mL of Zn (CH)₃COO)₃(0.1mol/L), 0.5mL of Cr (NO)₃)₃Solution (0.02mol/L) and 0.2mL of SnCl₄(0.05mol/L) and stirring uniformly to form a metal ion precursor solution. Subsequently, 4mL of the metal ion precursor solution was mixed with 100mg of ZIF-8, uniformly mixed by sonication for 60min, and the mixture was dried in an oven at 110 ℃ for 3 h. And (3) putting the dried sample into a muffle furnace, heating the sample from room temperature to 600 ℃ at the heating rate of 5 ℃/min, reacting for 2h, cooling to room temperature, taking out, grinding for 20min to obtain fine powder, putting the fine powder into the muffle furnace, heating from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, reacting for 4h, treating the obtained product with 1M hydrochloric acid for 1h, centrifuging, washing with deionized water, and drying in an oven at 60 ℃ for 12h to obtain the final product.

By analyzing the material obtained in example 1 by using a TEM image, as shown in FIG. 1-2, the ZIF-8 powder has uniform morphology and good dispersibility, and the obtained gallate long afterglow material has uniform size of about 100nm, thereby verifying the successful synthesis of the material.

The material obtained in example 1 was analyzed by fluorescence spectroscopy, and its emission peak was at 700nm under 254nm uv excitation, as shown in fig. 3-4, and it appeared as red emission. And exhibits strong long afterglow emission characteristics after excitation is stopped.

Example 2:

(1) preparation of ZIF-8 powder:

5mL of 0.016g/mL zinc nitrate methanol solution is dropped into 5mL of 0.04g/mL 2-methylimidazole methanol solution, and the mixture is stirred at room temperature for 120min to obtain a milky white solution. Centrifuging at 10000r/min for 15min, and drying in an oven at 60 deg.C for 12h to obtain ZIF-8 powder;

(2) preparing a gallate long-afterglow nano luminophor @ ZIF-8 composite material:

adding 8mL of Ga (NO)₃)₃Solution (0.25mol/L), 0.5mL of Zn (CH)₃COO)₃(0.1mol/L), 0.5mL of Cr (NO)₃)₃Solution (0.02mol/L) and 0.2mL of SnCl₄(0.05mol/L) mixingAnd stirring uniformly to form the metal ion precursor solution. Subsequently, 4mL of the metal ion precursor solution was mixed with 100mg of ZIF-8, sonicated for 30min to mix well, and the mixture was dried in an oven at 110 ℃ for 2 h. And (3) putting the dried sample into a muffle furnace, heating the sample from room temperature to 800 ℃ at the heating rate of 5 ℃/min, reacting for 2h, cooling to room temperature, taking out, grinding for 10min to obtain fine powder, putting the fine powder into the muffle furnace, heating from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, reacting for 4h, treating the obtained product with 1mol/L hydrochloric acid for 2h, centrifuging, washing with deionized water, and drying in an oven at 60 ℃ for 10h to obtain the final product.

By analyzing the material obtained in example 2 by using a TEM image, the ZIF-8 powder has uniform morphology and uniform hexagonal shape, and the obtained gallate long afterglow material has uniform size which is about 100nm, thereby verifying the successful synthesis of the material.

The material obtained in example 2 was analyzed by a fluorescence spectrometer, and the emission peak was at 700nm under excitation of 254nm uv light, showing red emission. And exhibits strong long afterglow emission characteristics after excitation is stopped.

Example 3:

(1) preparation of ZIF-8 powder:

20mL of 0.004g/mL zinc nitrate aqueous solution is taken and dropped into 20mL of 0.01g/mL 2-methylimidazole aqueous solution, and the mixture is stirred for 30min at room temperature to obtain milky white solution. Centrifuging at 10000r/min for 15min, and drying in an oven at 60 deg.C for 12h to obtain ZIF-8 powder;

(2) preparing a gallate long-afterglow nano luminophor @ ZIF-8 composite material:

adding 8mL of Ga (NO)₃)₃Solution (0.25mol/L), 0.5mL of Zn (CH)₃COO)₃(0.1mol/L), 0.5mL of Cr (NO)₃)₃Solution (0.02mol/L) and 0.2mL of SnCl₄(0.05mol/L) and stirring uniformly to form a metal ion precursor solution. Then, 2mL of the metal ion precursor solution was mixed with 100mg of ZIF-8, uniformly mixed by sonication for 60min, and the mixture was dried in an oven at 110 ℃ for 3 hours. Putting the dried sample into a muffle furnace, heating the sample from room temperature to 600 ℃ at the heating rate of 5 ℃/min, reacting for 2h, cooling the sample to room temperature, taking out the sample, and grinding the sample20min, placing the mixture into a muffle furnace, heating the mixture from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, reacting for 4h, treating the obtained product with 1mol/L hydrochloric acid for 4h, centrifuging, washing with deionized water, and drying in an oven at 60 ℃ for 12h to obtain the final product.

By analyzing the material obtained in example 3 by using a TEM image, the ZIF-8 powder has uniform morphology and better dispersibility, and the obtained gallate long afterglow material has uniform size of about 100nm, thereby verifying the successful synthesis of the material.

The material obtained in example 3 was analyzed by a fluorescence spectrometer, and the emission peak was at 700nm under excitation of 254nm uv light, showing red emission. And exhibits strong long afterglow emission characteristics after excitation is stopped.

Example 4:

(1) preparation of ZIF-8 powder:

20mL of 0.004g/mL zinc nitrate aqueous solution is taken and dropped into 20mL of 0.01g/mL 2-methylimidazole aqueous solution, and the mixture is stirred for 30min at room temperature to obtain milky white solution. Centrifuging at 10000r/min for 15min, and drying in an oven at 60 deg.C for 12h to obtain ZIF-8 powder;

(2) preparing a gallate long-afterglow nano luminophor @ ZIF-8 composite material:

adding 8mL of Ga (NO)₃)₃Solution (0.25mol/L), 0.5mL of Zn (CH)₃COO)₃(0.1mol/L), 0.5mL of Cr (NO)₃)₃Solution (0.02mol/L) and 0.2mL of SnCl₄(0.05mol/L) and stirring uniformly to form a metal ion precursor solution. Subsequently, 4mL of the metal ion precursor solution was mixed with 200mg of ZIF-8, uniformly mixed by sonication for 60min, and the mixture was dried in an oven at 110 ℃ for 3 h. And (3) putting the dried sample into a muffle furnace, heating the sample from room temperature to 800 ℃ at the heating rate of 5 ℃/min, reacting for 2h, cooling to room temperature, taking out, grinding for 10min to obtain fine powder, putting the fine powder into the muffle furnace, heating from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, reacting for 4h, treating the obtained product with 1M hydrochloric acid for 8h, centrifuging, washing with deionized water, and drying in an oven at 60 ℃ for 12h to obtain the final product.

By analyzing the material obtained in the example 4 by using a TEM image, the ZIF-8 powder has uniform appearance and good dispersibility, and the obtained gallate long afterglow material has uniform size of about 100nm, thereby verifying the successful synthesis of the material.

The material obtained in example 4 was analyzed by a fluorescence spectrometer, and the emission peak was at 700nm under excitation of 254nm uv light, showing red emission. And exhibits strong long afterglow emission characteristics after excitation is stopped.

Example 5:

(1) preparation of ZIF-8 powder:

20mL of 0.004g/mL zinc nitrate aqueous solution is taken and dropped into 20mL of 0.01g/mL 2-methylimidazole aqueous solution, and the mixture is stirred for 15min at room temperature to obtain milky white solution. Centrifuging at 10000r/min for 15min, and drying in an oven at 60 deg.C for 12h to obtain ZIF-8 powder;

(2) preparing a gallate long-afterglow nano luminophor @ ZIF-8 composite material:

adding 8mL of Ga (NO)₃)₃Solution (0.3mol/L), 0.5mL of Zn (CH)₃COO)₃(0.2mol/L), 0.5mL of Cr (NO)₃)₃Solution (0.1mol/L) and 0.2mL of SnCl₄(0.1mol/L) and stirring uniformly to form a metal ion precursor solution. Subsequently, 4mL of the metal ion precursor solution was mixed with 100mg of ZIF-8, uniformly mixed by sonication for 60min, and the mixture was dried in an oven at 110 ℃ for 3 h. And (3) putting the dried sample into a muffle furnace, heating the sample from room temperature to 600 ℃ at the heating rate of 5 ℃/min, reacting for 2h, cooling to room temperature, taking out, grinding for 20min to obtain fine powder, putting the sample into the muffle furnace, heating from room temperature to 900 ℃ at the heating rate of 2 ℃/min, reacting for 4h, treating the obtained product with 0.01mol/L hydrochloric acid for 8h, centrifuging, washing with deionized water, and drying in an oven at 60 ℃ for 12h to obtain the final product.

By analyzing the material obtained in example 5 by using a TEM image, the ZIF-8 powder has uniform morphology and better dispersibility, and the obtained gallate long afterglow material has uniform size of about 100nm, thereby verifying the successful synthesis of the material.

The material obtained in example 1 was analyzed by a fluorescence spectrometer, and the emission peak was at 700nm under excitation of 254nm uv light, showing red emission. And exhibits strong long afterglow emission characteristics after excitation is stopped.

Comparative example 1:

just the pre-sintering temperature and the sintering temperature were modified to 500 and 800 c, respectively, as in example 1.

The material obtained in comparative example 1 was analyzed by fluorescence spectroscopy, and its emission peak was at 700nm under the excitation of 254nm uv light. Exhibits red emission, but the emission intensity is weaker than that of example 1, and the long afterglow emission time is significantly shortened after the excitation is stopped.

Comparative example 2:

just as in example 1, the mass of the ZIF-8 powder was changed to 50mg, and the volume of the metal ion precursor solution was changed to 1 mL.

The material obtained in comparative example 2 was analyzed by fluorescence spectroscopy, and its emission peak was at 700nm under the excitation of 254nm uv light. Exhibits red emission, but the emission intensity is weaker than that of example 1, and the long afterglow emission time is significantly shortened after the excitation is stopped.

It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.