Three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, and preparation method and application thereof

Abstract

The application provides a three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores, and a preparation method and application thereof, and the preparation method is as follows: a water solution of three-dimensional ordered macroporous carbon is mixed with a water solution of lanthanide acetate, and uniform solution is obtained by continuous stirring; potassium fluoroborate is added into the uniform solution, and turbid solution is obtained by continuous stirring; the pH value of the turbid solution is adjusted to 1-7, and centrifugal separation and freeze-drying are carried out after continuous stirring, and the three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores is obtained. The acetate-based lanthanide fluoride quantum dots are loaded on the inner surface of the pores of the three-dimensional ordered macroporous carbon material to form a material with a novel multi-level structure, which can not only avoid the blockage of the internal pores of the three-dimensional ordered macroporous material, but also fully utilize the excellent photo-thermal performance of the three-dimensional ordered macroporous carbon and the large capacity adsorption performance of the acetate-based lanthanide fluoride quantum dots on organic dyes, so that the organic dyes are in an effective high-temperature degradation region and the pollutant degradation is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparation of organic pollutant high-efficiency photothermal degradation materials, and in particular to a three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores, a preparation method thereof and application thereof. BACKGROUND

[0002] How to realize efficient degradation of organic pollutants has become one of the problems to be solved by environmental protection workers. In recent years, photothermal conversion technology has shown great application potential in tumor or wound treatment, catalytic conversion of carbon dioxide and organic synthesis (Journal of Materials Chemistry A, 2021, 9, 17569-17591). In the aspect of pollutant degradation, scholars have carried out very beneficial exploration work (Chemical Engineering Journal, 2024, 486, 150192). However, the biggest difficulty in limiting the degradation efficiency of pollutants is how to develop efficient photothermal conversion materials and make the organic pollutants be in the effective high-temperature degradation region to the greatest extent.

[0003] Multistage structure materials are composites of materials of various scales, which can maximize the advantages of each component material. At present, high-performance photothermal conversion materials based on multistage structure materials have attracted widespread attention from scholars. For example, Wang et al. developed a non-symmetrical bismuth selenide / cadmium selenide-gold (Bi2Se3 / CdSe-Au) multistage structure nanorod, which can improve the light conversion temperature difference by 4.3 times compared with non-multistage structure gold nanorods (Advanced Functional Materials, 2021, 31, 2104424); Chen et al. constructed a hollow copper sulfide-based (Cu7S4-Cu9S8) multistage structure material, which confirmed that the multistage structure design of copper sulfide material can significantly enhance the light-thermal conversion ability and catalytic performance of the material (Chemical Engineering Journal, 2019, 363, 247-258). In summary, the above results prove that multistage structure materials are expected to show great application potential in the development of high-performance photothermal conversion materials.

[0004] Three-dimensional ordered macroporous carbon is a new type of carbon material formed by uniformly arranged macropores (pore size above 50 nm) throughout the material interior, which has great advantages in accelerating material diffusion (Chemical Society Review., 2013, 42, 794-830). As a typical carbon material, photo irradiation can cause the transition and relaxation cycle of the π electrons in the material interior, and then lead to the conversion of photon energy into heat energy, so three-dimensional ordered macroporous carbon is expected to become a new type of photothermal material with great potential. Acetate-based lanthanide fluoride material is a new type of material formed by the ordered arrangement of acetate layers and lanthanide fluoride monatomic, which has great application potential in dye adsorption (Journal of the American Chemical society. 2019, 141, 33, 13134-13142; Applied Surface Science, 2023, 621, 156842).

[0005] Therefore, how to load acetate-based lanthanide fluoride material in three-dimensional ordered macroporous carbon to obtain a high-efficiency photothermal degradation material, and use it as a photothermal degrader of dye to realize the rapid and effective degradation of pollutants, is the research focus of the research group. SUMMARY

[0006] In order to solve the problems in the prior art, the present application provides a three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in the pore channel and a preparation method and application thereof. The acetate-based lanthanide fluoride quantum dots are loaded on the inner surface of the pore channel of the three-dimensional ordered macroporous carbon material to form a material with a new multi-level structure.

[0007] In order to achieve the above-mentioned purpose, the specific scheme adopted by the present application is as follows:

[0008] On the one hand, in view of the insufficient research on multi-level structure photothermal conversion materials at present, the present application provides a preparation method of three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in the pore channel, mainly comprising the following steps:

[0009] (1) mixing a three-dimensional ordered macroporous carbon aqueous solution with a lanthanide acetate aqueous solution and continuously stirring to obtain a uniform solution;

[0010] (2) adding potassium fluoroborate to the uniform solution obtained in step (1) and continuously stirring to obtain a turbid solution;

[0011] (3) adjusting the pH value of the turbid solution to 1-7, continuously stirring, and then centrifuging and freeze-drying to obtain three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in the pore channel.

[0012] Further, in step (1), the concentration of the aqueous solution of the three-dimensional ordered macroporous carbon is 0.01-10 mg / mL, and the volume is 0.1-100 ml.

[0013] The concentration of the aqueous solution of the lanthanide acetate salt is 0.01-1 mol / L, and the volume is 0.1-10 ml.

[0014] Further, in step (2), the mass of the potassium fluoroborate is 0.01-10 g.

[0015] Further, in step (1), the continuous stirring time is 10-100 min.

[0016] In step (2), the continuous stirring time is 3-72 h.

[0017] In step (3), the continuous stirring time is 0.1-6 h.

[0018] On the other hand, the application provides a three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores, which is prepared by the above method; the three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores is denoted as F-Ln@OMC, the acetate-based lanthanide fluoride quantum dots with a size of 2-10 nm are loaded on the inner surface of the pores with an average inner diameter of 70-600 nm in the three-dimensional ordered macroporous carbon, and the acetate-based lanthanide fluoride quantum dots do not significantly affect the pore size and appearance of the three-dimensional ordered macroporous carbon.

[0019] In another aspect, in view of the slow degradation rate and low degradation efficiency of existing organic pollutants, the application provides an application of the three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores in the field of photo-thermal degradation of organic dyes, so as to realize efficient degradation of the organic dyes.

[0020] Further, the photo-thermal degradation of the organic dyes mainly includes the following steps:

[0021] Step one, placing the F-Ln@OMC in an organic dye solution, centrifuging and drying after oscillation, to obtain F-Ln@OMC-CR adsorbed with the organic dyes;

[0022] Step two, placing the F-Ln@OMC-CR on the surface of the silica aerogel, and irradiating with laser for a certain time, so that the F-Ln@OMC generates local high temperature under the action of the laser, and the organic dyes are degraded.

[0023] Further, in step one, the organic dye is any one of Congo red, Coomassie brilliant blue, Rhodamine B, Orange G, methyl orange, methyl blue, and methylene blue.

[0024] Further, in step one, the volume of the organic dye solution is 20-100 ml, the concentration is 100-2000 mg / L, the pH is 4.00-7.00; the mass of F-Ln@OMC is 0.10-1.00 g; and the oscillation time is 0.1 h-6 h.

[0025] Further, in step two, the mass of F-Ln@OMC-CR is 0.1-10 mg, the laser wavelength is 220-1200 nm, the laser power is 0.4-3.0 W / cm 2 , and the laser irradiation time is 0.5-300 min.

[0026] Beneficial effects:

[0027] (1) The acetoxy lanthanide fluoride quantum dots are loaded in the inner surface of the three-dimensional ordered macroporous carbon material to form a material with a novel multi-level structure, which can not only avoid the blockage of the inner channel of the three-dimensional ordered macroporous material, but also make full use of the excellent photo-thermal performance of the three-dimensional ordered macroporous carbon and the large capacity adsorption performance of the acetoxy lanthanide fluoride quantum dots on the organic dye, so that the organic dye is in the effective high-temperature degradation region and the pollutant degradation is realized.

[0028] (2) In the preparation of F-Ln@OMC, the purpose of step (1) is to make the lanthanide metal ions uniformly distributed on the inner surface of the three-dimensional ordered macroporous carbon. After the fluorine ions and acetate ions react with the lanthanide metal ions to form acetoxy lanthanide fluoride quantum dots after the release of fluorine ions by the addition of potassium fluoroborate in step (2), the purpose of step (3) is to remove the impurities outside the three-dimensional ordered macroporous carbon by acidification, and finally obtain F-Ln@OMC with high purity.

[0029] (3) The preparation process of the material does not need to add additional surfactants or templates, which avoids the pollution of surfactants to the surface of the prepared material and reduces the cumbersome template post-processing steps.

[0030] (4) The prepared F-Ln@OMC can realize the rapid and efficient degradation of organic dyes, and is expected to provide a new idea for the degradation of organic pollutants.

[0031] (5) The preparation method of the material is simple, low in cost, environmentally friendly and reusable, and is expected to show great application potential in the development of high-performance photo-thermal degradation materials. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 A low-magnification TEM image of F-Ce@OMC prepared in Example 1.

[0033] Figure 2 A high-magnification TEM image of F-Ce@OMC prepared in Example 1.

[0034] Figure 3 UV-Vis spectra of the Congo red dye before and after photothermal degradation in Example 1 (solvent: dimethyl sulfoxide).

[0035] Figure 4 High-magnification TEM image of F-Nd@OMC prepared in Example 2.

[0036] Figure 5 UV-Vis spectra of the Congo red dye before and after photothermal degradation in Example 2 (solvent: dimethyl sulfoxide).

[0037] Figure 6 UV-Vis spectra of the Congo red dye before and after photothermal degradation in Example 3 (solvent: dimethyl sulfoxide).

[0038] Figure 7 UV-Vis spectra of the Congo red dye before and after photothermal degradation in Example 4 (solvent: dimethyl sulfoxide). DETAILED DESCRIPTION

[0039] The technical solutions of the present application will be described clearly and completely below in conjunction with specific embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the protection scope of the present application.

[0040] Example 1

[0041] A method for degrading organic dyes by using a three-dimensional ordered macroporous carbon loaded with acetate-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0042] (1) 1 ml of a 1 mg / ml aqueous solution of three-dimensional ordered macroporous carbon is mixed with 50 ml of a 50 mg / ml aqueous solution of cerium acetate (Ce), and a uniform solution is obtained after continuous stirring for 30 min;

[0043] (2) 0.2 g of potassium fluoroborate is added to the uniform solution obtained in step (1), and a turbid solution is obtained after continuous stirring for 24 h;

[0044] (3) The turbid solution obtained in step (2) is adjusted to pH=4.0, and after continuous stirring for 0.5 h, centrifugal separation and freeze-drying are performed to obtain F-Ce@OMC;

[0045] (4) 0.5 g of F-Ce@OMC is placed in 100 ml of a 100 mg / L aqueous solution of Congo red, and after 0.5 h of shaking, centrifugal separation and drying are performed to obtain F-Ce@OMC-CR adsorbed with Congo red dye.

[0046] (5) 1 mg F-Ce@OMC-CR was placed on the surface of silica aerogel, and after laser irradiation at a wavelength of 660 nm and a power density of 1.03 W / cm 2 for 5 min, Congo red dye was attached to the surface of F-Ce@OMC-CR. The UV-Vis spectra of Congo red dye dissolved in dimethyl sulfoxide before and after photothermal degradation are shown in Figure 3 , from which it can be seen that the degradation efficiency of the dye is 77.80 %. Figure 3

[0047] In step (3), the low-magnification TEM photograph of F-Ce@OMC is shown in Figure 1 , from which it can be seen that the circular macropores with a size of about 250 nm can be observed throughout the material, and the overall contrast is relatively uniform, which proves that the morphological structure of the three-dimensional ordered macroporous carbon does not change significantly after loading of the fluorocerium quantum dots; the high-magnification TEM picture is shown in Figure 2 , which clearly shows that the fluorocerium quantum dots with relatively high contrast (black dots in the figure, with a size of about 7 nm) are uniformly dispersed in the entire material, and no obvious aggregation phenomenon occurs. The experimental results shown in Figure 1 and Figure 2 clearly show that the material obtained in step (3) is three-dimensional ordered macroporous carbon with fluorocerium quantum dots loaded in the pores.

[0048] Example 2

[0049] A method for degrading organic dyes by using three-dimensional ordered macroporous carbon with acetate-based lanthanide fluoride quantum dots loaded in the pores, mainly includes the following steps:

[0050] (1) 1 ml of an aqueous solution of three-dimensional ordered macroporous carbon at a concentration of 1 mg / ml is mixed with 50 ml of an aqueous solution of neodymium acetate (Nd) at a concentration of 50 mg / ml, and after continuous stirring for 60 min, a uniform solution is obtained;

[0051] (2) 0.5 g of potassium fluoroborate is added to the uniform solution obtained in step (1), and after continuous stirring for 24 h, a turbid solution is obtained;

[0052] (3) The turbid solution obtained in step (2) is adjusted to pH=4.0, and after continuous stirring for 0.5 h, centrifugal separation and freeze-drying are performed to obtain F-Nd@OMC;

[0053] (4) 0.5 g of F-Nd@OMC is placed in 100 ml of an aqueous solution of Congo red at a concentration of 100 mg / L, and after 0.5 h of oscillation, centrifugal separation and drying are performed to obtain F-Nd@OMC-CR adsorbed with Congo red dye;

[0054] ​(5) Weigh 2 mg of F-Nd@OMC-CR and place it on the surface of silica aerogel. Then, pass it through a wavelength of 980 nm and a power density of 1.03 W / cm². 2 After 3 minutes of laser irradiation, attached Figure 5 The UV-Vis spectra of Congo red dye before and after photothermal degradation and its dissolution in dimethyl sulfoxide are given by [the following data]. Figure 5 It can be seen that the dye degradation efficiency is 73.93%.

[0055] Appendix Figure 4 This is a TEM image in high-magnification mode, clearly showing that neodymium fluoride quantum dots (approximately 2 nm in size) are uniformly dispersed throughout the material, without any obvious aggregation. (Attached) Figure 4 The experimental results clearly show that the material obtained in step (3) is a three-dimensional ordered macroporous carbon with fluorine-neodymium quantum dots loaded on the inner surface.

[0056] Example 3

[0057] A method for degrading organic dyes using three-dimensional ordered macroporous carbon loaded with lanthanide acetate quantum dots within its pores mainly includes the following steps:

[0058] (1) Mix 5 ml of 1 mg / ml three-dimensional ordered macroporous carbon aqueous solution with 100 ml of 50 mg / ml cerium acetate (Ce) aqueous solution and stir continuously for 30 min to obtain a homogeneous solution;

[0059] (2) Add 1.0 g of potassium fluoroborate to the homogeneous solution obtained in step (1) and stir continuously for 36 h to obtain a turbid solution;

[0060] (3) Adjust the pH of the turbid solution obtained in step (2) to 6.0, stir continuously for 0.5 h, centrifuge and freeze dry to obtain F-Ce@OMC;

[0061] (4) Place 0.5 g F-Ce@OMC in 100 ml of 100 mg / L Congo red aqueous solution, shake for 2.0 h, centrifuge and dry to obtain F-Ce@OMC-CR adsorbed with Congo red dye;

[0062] (5) Weigh 1 mg of F-Ce@OMC-CR and place it on the surface of silica aerogel. Then, pass it through a wavelength of 660 nm and a power density of 0.60 W / cm². 2 After 20 minutes of laser irradiation, the dye degradation efficiency was 77.80% (see attached image). Figure 6 ).

[0063] Example 4

[0064] A method for degrading organic dyes by using a three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0065] (1) 10 ml of a 0.5 mg / ml aqueous solution of three-dimensional ordered macroporous carbon is mixed with 100 ml of a 20 mg / ml aqueous solution of praseodymium acetate (Pr), and a uniform solution is obtained after continuous stirring for 60 min;

[0066] (2) 2.0 g of potassium fluoroborate is added to the uniform solution obtained in step (1), and a turbid solution is obtained after continuous stirring for 54 h;

[0067] (3) The turbid solution obtained in step (2) is adjusted to pH=3.0, and after continuous stirring for 2.0 h, centrifugal separation and freeze-drying are performed to obtain F-Pr@OMC;

[0068] (4) 0.5 g of F-Pr@OMC is placed in 100 ml of a 100 mg / L aqueous solution of Congo red, and after 5.0 h of oscillation, centrifugal separation and drying are performed to obtain F-Pr@OMC-CR adsorbed with Congo red dyes;

[0069] (5) 3 mg of F-Pr@OMC-CR is placed on the surface of silica aerogel, and after laser irradiation at a wavelength of 915 nm and a power density of 0.94 W / cm 2 for 30 min, the dye degradation efficiency is 78.90 % (see Figure 7 ).

[0070] Example 5

[0071] A method for degrading organic dyes by using a three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0072] (1) 20 ml of a 1 mg / ml aqueous solution of three-dimensional ordered macroporous carbon is mixed with 200 ml of a 20 mg / ml aqueous solution of cerium acetate (Ce), and a uniform solution is obtained after continuous stirring for 50 min;

[0073] (2) 5.0 g of potassium fluoroborate is added to the uniform solution obtained in step (1), and a turbid solution is obtained after continuous stirring for 72 h;

[0074] (3) The turbid solution obtained in step (2) is adjusted to pH=2.0, and after continuous stirring for 0.5 h, centrifugal separation and freeze-drying are performed to obtain F-Ce@OMC;

[0075] (4) 0.5 g F-Ce@OMC was placed in 100 ml 100 mg / L aqueous solution of Congo red, and after 2.0 h of oscillation, centrifugal separation and drying, F-Ce@OMC-CR adsorbed with Congo red dye was obtained;

[0076] (5) 1 mg F-Ce@OMC-CR was placed on the surface of silica aerogel, and after laser irradiation for 60 min at a wavelength of 660 nm and a power density of 0.71 W / cm 2 , the dye degradation efficiency was 91.74 %.

[0077] Example 6

[0078] A method for degrading organic dyes by a three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0079] (1) 1 ml of 0.5 mg / ml aqueous solution of three-dimensional ordered macroporous carbon was mixed with 20 ml of 20 mg / ml aqueous solution of praseodymium acetate (Pr), and after continuous stirring for 20 min, a uniform solution was obtained;

[0080] (2) 0.05 g of potassium fluoroborate was added to the uniform solution obtained in step (1), and after continuous stirring for 24 h, a turbid solution was obtained;

[0081] (3) The turbid solution obtained in step (2) was adjusted to pH=4.0, and after continuous stirring for 5.0 h, centrifugal separation and freeze-drying, F-Pr@OMC was obtained;

[0082] (4) 2.0 g F-Pr@OMC was placed in 100 ml 100 mg / L aqueous solution of Congo red, and after 5.0 h of oscillation, centrifugal separation and drying, F-Pr@OMC-CR adsorbed with Congo red dye was obtained;

[0083] (5) 1 mg F-Pr@OMC-CR was placed on the surface of silica aerogel, and after laser irradiation for 60 min at a wavelength of 1064 nm and a power density of 0.54 W / cm 2 , the dye degradation efficiency was 54.90 % (see Figure 7 ).

[0084] Example 7

[0085] A method for degrading organic dyes by a three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0086] (1) 20 ml of 0.1 mg / ml aqueous solution of three-dimensional ordered macroporous carbon was mixed with 100 ml of 50 mg / ml aqueous solution of neodymium acetate (Nd), and a uniform solution was obtained after continuous stirring for 60 min;

[0087] (2) 1.0 g of potassium fluoroborate was added to the uniform solution obtained in step (1), and a turbid solution was obtained after continuous stirring for 12 h;

[0088] (3) The turbid solution obtained in step (2) was adjusted to pH = 4.0, and a centrifugal separation and freeze-drying were performed after continuous stirring for 3.0 h, and F-Nd@OMC was obtained;

[0089] (4) 2.0 g of F-Nd@OMC was placed in 100 ml of 1000 mg / L aqueous solution of orange G, and a centrifugal separation and drying were performed after oscillation for 0.5 h, and F-Nd@OMC-CR adsorbed with orange G dye was obtained;

[0090] (5) 2 mg of F-Nd@OMC-CR was placed on the surface of silica aerogel, and the dye degradation efficiency was 98.94% after laser irradiation at a wavelength of 1064 nm and a power density of 2.00 W / cm 2

[0091] Example 8

[0092] A method for degrading organic dyes by a three-dimensional ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0093] (1) 1 ml of 1 mg / ml aqueous solution of three-dimensional ordered macroporous carbon was mixed with 50 ml of 50 mg / ml aqueous solution of lanthanum acetate (La), and a uniform solution was obtained after continuous stirring for 60 min;

[0094] (2) 0.5 g of potassium fluoroborate was added to the uniform solution obtained in step (1), and a turbid solution was obtained after continuous stirring for 24 h;

[0095] (3) The turbid solution obtained in step (2) was adjusted to pH = 4.0, and a centrifugal separation and freeze-drying were performed after continuous stirring for 0.5 h, and F-La@OMC was obtained;

[0096] (4) 0.5 g of F-La@OMC was placed in 100 ml of 100 mg / L aqueous solution of methylene blue, and a centrifugal separation and drying were performed after oscillation for 0.5 h, and F-La@OMC-CR adsorbed with methylene blue dye was obtained;

[0097] ​(5) 2 mg of F-La@OMC-CR was placed on the surface of silica aerogel, and after irradiation by laser with a wavelength of 980 nm and a power density of 1.20 W / cm2for 3 min, the degradation efficiency of the dye was 85.82%.

[0098] Example 9

[0099] A method for degrading organic dyes by using three-dimensionally ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0100] (1) 1 ml of an aqueous solution of three-dimensionally ordered macroporous carbon with a concentration of 0.5 mg / ml was mixed with 20 ml of an aqueous solution of praseodymium acetate (Pr) with a concentration of 20 mg / ml, and after continuous stirring for 20 min, a uniform solution was obtained;

[0101] (2) 0.05 g of potassium fluoroborate was added to the uniform solution obtained in step (1), and after continuous stirring for 24 h, a turbid solution was obtained;

[0102] (3) The turbid solution obtained in step (2) was adjusted to pH=4.0, and after continuous stirring for 5.0 h, centrifugal separation and freeze-drying were performed to obtain F-Pr@OMC;

[0103] (4) 2.0 g of F-Pr@OMC was placed in 100 ml of an aqueous solution of Coomassie brilliant blue with a concentration of 100 mg / L, and after 5.0 h of shaking, centrifugal separation and drying were performed to obtain F-Pr@OMC-CR adsorbed with Coomassie brilliant blue dye;

[0104] (5) 1 mg of F-Pr@OMC-CR was placed on the surface of silica aerogel, and after irradiation by laser with a wavelength of 1064 nm and a power density of 0.41 W / cm 2 for 60 min, the degradation efficiency of the dye was 11.54%.

[0105] Example 10

[0106] A method for degrading organic dyes by using three-dimensionally ordered macroporous carbon loaded with acetic acid-based lanthanide fluoride quantum dots in pores, mainly comprising the following steps:

[0107] (1) 20 ml of an aqueous solution of three-dimensionally ordered macroporous carbon with a concentration of 1 mg / ml was mixed with 200 ml of an aqueous solution of cerium acetate (Ce) with a concentration of 20 mg / ml, and after continuous stirring for 50 min, a uniform solution was obtained;

[0108] (2) 5.0 g of potassium fluoroborate was added to the uniform solution obtained in step (1), and after continuous stirring for 72 h, a turbid solution was obtained;

[0109] (3) The turbid solution obtained in step (2) is adjusted to pH=2.0, centrifuged and freeze-dried after continuous stirring for 0.5 h to obtain F-Ce@OMC;

[0110] (4) 0.5 g F-Ce@OMC is placed in 100 ml 100 mg / L rhodamine B aqueous solution, centrifuged and dried after oscillation for 2.0 h to obtain F-Ce@OMC-CR adsorbed with rhodamine B dyes;

[0111] (5) 1 mg F-Ce@OMC-CR is placed on the surface of silica aerogel, and the dye degradation efficiency is 96.53% after laser irradiation at a wavelength of 660 nm and a power density of 0.71 W / cm 2 for 60 min.

[0112] The above description is only a preferred embodiment of the present application, and is not intended to limit the present application in any form. Any equivalent transformation or modification according to the essence of the present application should be covered within the protection scope of the present application.

Claims

1. A method for preparing a three-dimensionally ordered macroporous carbon loaded with acetoxy lanthanide fluoride quantum dots in pores, characterized by, The method mainly comprises the following steps: (1) mixing a water solution of three-dimensional ordered macroporous carbon with a water solution of lanthanide acetate salt, continuously stirring to obtain a uniform solution; (2) adding potassium fluoroborate to the uniform solution obtained in step (1), continuously stirring to obtain a turbid solution; (3) adjusting the pH value of the turbid solution to 1-7, continuously stirring, centrifugal separation and freeze-drying, thereby obtaining three-dimensional ordered macroporous carbon loaded with lanthanide fluoride quantum dots with acetate groups in pores.

2. The method of claim 1, wherein the method is characterized by, In step (1), the concentration of the water solution of three-dimensional ordered macroporous carbon is 0.01-10 mg / mL, and the volume is 0.1-100 ml; The concentration of the water solution of lanthanide acetate salt is 0.01-1 mol / L, and the volume is 0.1-10 ml.

3. The method of claim 2, wherein the method is characterized by, In step (2), the mass of potassium fluoroborate is 0.01-10 g.

4. The method of claim 1, wherein the method is characterized by, In step (1), the continuous stirring time is 10-100 min; In step (2), the continuous stirring time is 3-72 h; In step (3), the continuous stirring time is 0.1-6 h.

5. A three-dimensionally ordered macroporous carbon loaded with acetoxy lanthanide fluoride quantum dots in the pores, characterized in that, The three-dimensional ordered macroporous carbon loaded with lanthanide fluoride quantum dots with acetate groups in pores is prepared by the method of any one of claims 1-4; the three-dimensional ordered macroporous carbon loaded with lanthanide fluoride quantum dots with acetate groups in pores is denoted as F-Ln@OMC, and the acetate lanthanide fluoride quantum dots with a size of 2-10 nm are loaded on the inner surface of the pores with an average inner diameter of 70-600 nm in the three-dimensional ordered macroporous carbon.

6. The use of the three-dimensional ordered macroporous carbon loaded with lanthanide fluoride quantum dots with acetate groups in pores according to claim 5 in the field of photothermal degradation of organic dyes.

7. Use according to claim 6, wherein The photothermal degradation of organic dyes mainly comprises the following steps: Step one, placing F-Ln@OMC in an organic dye solution, centrifugal separation and drying after shaking, thereby obtaining F-Ln@OMC-CR adsorbed with organic dyes; Step two, placing F-Ln@OMC-CR on the surface of silica aerogel, irradiating with laser for a certain time, and under the action of laser, F-Ln@OMC generates local high temperature, thereby degrading the organic dyes.

8. Use according to claim 7, wherein the compound is ###0002### In step one, the organic dye is any one of Congo red, Coomassie brilliant blue, Rhodamine B, Orange G, Methyl orange, Methyl blue and Methylene blue.

9. The use according to claim 7, wherein the compound is ###0002### In step one, the volume of the organic dye solution is 20-100 ml, the concentration is 100-2000 mg / L, the pH is 4.00-7.00; the mass of F-Ln@OMC is 0.10-1.00 g; and the shaking time is 0.1 h-6 h.

10. The use according to claim 7, wherein the compound is ###00003### or a pharmaceutically acceptable salt thereof. In step two, the mass of F-Ln@OMC-CR is 0.1 ~10 mg, the laser wavelength is 220~1200 nm, the laser power is 0.4~3.0 W / cm 2 , and the laser irradiation time is 0.5~300 min.

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