Zn-MOF material, fly ash-coated MOF composite material and preparation method and application thereof
By preparing Zn-MOF and fly ash@MOF composite materials, the problems of low fly ash resource utilization and low photocatalytic efficiency were solved, realizing the reuse of fly ash and the rapid and efficient degradation of the antibiotic furacilin.
Patent Information
- Application Number
- CN202511458661.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-13
- Publication Date
- 2026-02-24
AI Technical Summary
Existing technologies are difficult to effectively utilize fly ash resources, and photocatalytic materials have low efficiency in degrading antibiotics.
A composite material was prepared by combining Zn-MOF material with fly ash. Zn-MOF and fly ash@MOF were prepared by solvothermal and hydrothermal reactions and applied to the photocatalytic degradation of the antibiotic furacilin.
This technology enables the resource reuse of fly ash and improves the efficiency of photocatalytic degradation of antibiotics, especially the rapid and efficient degradation of furacilin.
Smart Images
Figure CN121554751A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalytic materials technology, specifically to a Zn-MOF material and a fly ash@MOF composite material, as well as their preparation method and application. Background Technology
[0002] Antibiotic pollution has always been a serious environmental problem, and people have been searching for various methods to degrade antibiotics in the environment. Photocatalytic degradation of antibiotics is a technology that can make full use of solar energy and help solve the problem of antibiotic disposal, and is considered one of the most promising antibiotic degradation technologies. Photocatalytic materials are key to achieving antibiotic degradation; therefore, designing and synthesizing environmentally friendly, inexpensive, and pollution-free catalyst materials is an urgent task for antibiotic degradation.
[0003] Fly ash is a solid waste, and its emissions are increasing year by year. Fly ash not only occupies a large amount of land and causes enormous resource waste, but also seriously pollutes and harms the human living environment, disrupting the ecological balance. Therefore, the reuse of fly ash as a secondary resource has received attention from countries around the world.
[0004] Metal-organic frameworks (MOFs) are a new type of porous material, referring to coordination polymers with cavity structures possessing regular pore sizes and shapes, obtained through molecular assembly and crystal engineering methods using inorganic metal centers or clusters and organic bridging ligands. Due to their high stability, tunable pore size, and large specific surface area, MOF polymers are attracting great interest from scientists.
[0005] This invention uses metal-organic frameworks and waste fly ash as raw materials to prepare a fly ash@MOF photocatalytic composite material, which enables the rapid degradation of antibiotics. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to provide a method for preparing Zn-MOF material and fly ash@MOF composite material, and to apply the obtained Zn-MOF material and fly ash@MOF composite material to the photocatalytic degradation of the antibiotic furazolidone.
[0007] The technical problem to be solved by this invention is achieved by the following technical solution:
[0008] One objective of this invention is to provide a method for preparing Zn-MOF materials, wherein 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene and zinc acetate are dissolved in an organic solvent, the pH of the solution is adjusted to 6-7 with acid, and then transferred to a reaction vessel for solvothermal reaction to obtain Zn-MOF materials.
[0009] Further, the organic solvent is at least one of N,N′-dimethylformamide (DMF) and N,N′-dimethylacetamide (DMA).
[0010] Furthermore, the molar ratio of 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene, and zinc acetate dihydrate is 1.5:1:2.
[0011] Furthermore, the temperature of the solvothermal reaction is 100–120°C.
[0012] The second objective of this invention is to provide a Zn-MOF material prepared by the aforementioned preparation method.
[0013] The third objective of this invention is to provide a method for preparing fly ash@MOF composite material, wherein 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene and zinc acetate are dissolved in an organic solvent, and fly ash photocatalyst is added. The pH of the solution is adjusted to 6-7 with acid, and then transferred to a reaction vessel for solvothermal reaction to obtain fly ash@MOF composite material.
[0014] Further, the organic solvent is at least one of N,N′-dimethylformamide (DMF) and N,N′-dimethylacetamide (DMA).
[0015] Furthermore, the molar ratio of 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene, and zinc acetate dihydrate is 1.5:1:2.
[0016] Furthermore, the temperature of the solvothermal reaction is 100–120°C.
[0017] The fourth objective of this invention is to provide a fly ash@MOF composite material prepared by the aforementioned preparation method.
[0018] The fifth objective of this invention is to provide a method for preparing a fly ash photocatalyst, which involves mixing fly ash with alkali, calcining, washing with water, filtering, drying, dissolving the resulting powder with acid, adjusting the pH of the solution to 7-8 with alkali, then transferring it to a reaction vessel for hydrothermal reaction, filtering, and drying to obtain the fly ash photocatalyst.
[0019] Furthermore, the alkali is sodium hydroxide or potassium hydroxide.
[0020] Furthermore, the calcination temperature is 600–700°C.
[0021] Furthermore, the acid is nitric acid, hydrochloric acid, or sulfuric acid.
[0022] Furthermore, the temperature of the hydrothermal reaction is 170–190°C.
[0023] The sixth objective of this invention is to provide the application of the Zn-MOF material or fly ash@MOF composite material in the photocatalytic degradation of antibiotics.
[0024] Furthermore, the antibiotic is furacilin.
[0025] The beneficial effects of this invention are as follows: This invention prepares a novel Zn-MOF material and a fly ash@MOF composite material, and applies them as photocatalysts for the photocatalytic degradation of the antibiotic nitrofurazone. Compared with fly ash photocatalysts, the fly ash@MOF composite material of this invention can rapidly and efficiently photocatalytically degrade the antibiotic nitrofurazone, and has significant application value. Attached Figure Description
[0026] Figure 1 This is a coordination pattern diagram of zinc atoms in compound 1;
[0027] Figure 2 This is a three-dimensional pore structure diagram of compound 1;
[0028] Figure 3 Thermogravimetric curve of compound 1;
[0029] Figure 4 The UV-Vis absorption spectrum of the photocatalytic degradation of furazolidone using fly ash@MOF composite material;
[0030] Figure 5 The UV-Vis absorption spectrum of furazolidone is shown below without the addition of a photocatalyst.
[0031] Figure 6 The UV-Vis absorption spectrum of the photocatalytic degradation of furazolidone using fly ash photocatalyst;
[0032] Figure 7 The diagram shows the cyclic performance of photocatalytic degradation of furazolidone using fly ash@MOFF composite material. Detailed Implementation
[0033] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments and illustrations.
[0034] Example 1
[0035] Preparation of fly ash photocatalyst:
[0036] Weigh 5g of sodium hydroxide and 0.4g of fly ash into a crucible, calcine at 650℃ for 30min, then wash with boiling water, sonicate, filter, dry, and grind to obtain a powder. Weigh 0.25g of the powder, add 5mL of nitric acid to dissolve it, adjust the pH to 7.0–7.5 with sodium hydroxide solution, then transfer to a reaction vessel and react at 180℃ for 10h. After the reaction is complete, allow the reaction solution to cool naturally to room temperature, filter, dry, and grind to obtain the fly ash photocatalyst.
[0037] Example 2
[0038] The fly ash photocatalyst was prepared according to the method in Example 1, except that the amount of sodium hydroxide was adjusted to 2g.
[0039] Example 3
[0040] The fly ash photocatalyst was prepared according to the method in Example 1, except that the calcination temperature was adjusted to 700℃ and the calcination time was adjusted to 20min.
[0041] Example 4
[0042] The fly ash photocatalyst was prepared according to the method in Example 1, except that the reaction temperature was adjusted to 190°C and the reaction time was adjusted to 8 hours.
[0043] Example 5
[0044] Compound [Zn2(PT)(DPP)] n Synthesis of H2O(1):
[0045] 37.2 mg of 2,5-bis(4′-pyridine)phenol (DPP, 0.15 mmol), 68.2 mg of 1,3,6,8-tetra(4-carboxyphenyl)pyrene (H4PT, 0.10 mmol), and 43.9 mg of zinc acetate dihydrate (0.20 mmol) were added to a glass bottle. 1 mL of DMF and 1 mL of DMA were added to the bottle, and nitric acid was added dropwise to adjust the pH to 6.5. The bottle was sealed and heated to 109 °C for 5 days. After the reaction, the solution was cooled to room temperature at a rate of 5 °C / h. Blocky crystals precipitated in the glass bottle. The solution was filtered and dried to obtain compound 1. The molecular formula of compound 1 is C1. 60 H 36 Zn2N2O 10 Elemental analysis calculated values (%): C 66.93; H 3.35; N 2.61. Experimental values (%): C 66.56; H 3.23; N 2.84%. The determination and refinement of compound 1 were performed using the SHELXL-97 software package. Relevant crystallographic data for compound 1 are listed in Table 1.
[0046] Table 1 Crystal data of compound 1
[0047]
[0048]
[0049] a R1=Σ||F o |-|F c |) / Σ|F o |;wR2=[Σw(F o 2 -F c 2 ) 2 / Σw(F o 2 ) 2 ] 1 / 2
[0050] Crystal structure of compound 1:
[0051] The structural unit of compound 1 is a fully protonated carboxylic acid ligand PT, a nitrogen-containing ligand DPP, two coordinated zinc atoms, and a free water molecule. Figure 1 This is a coordination pattern diagram of zinc atoms in compound 1. Figure 1 It is known that in compound 1, there are two independent zinc atoms, Zn1 and Zn2, which are coordinated with four oxygen atoms on four protonated PT ligands and one nitrogen atom on a DPP ligand, respectively, forming a deformed trigonal bipyramidal spatial configuration. In compound 1, each protonated PT ligand is connected to eight zinc atoms, and each DPP ligand is connected to two zinc atoms. Figure 2 This is a three-dimensional pore structure diagram of compound 1. (From...) Figure 2 It can be seen that compound 1 has a porous structure on all three surfaces.
[0052] Thermal stability of compound 1:
[0053] Figure 3 The thermogravimetric curve is for compound 1. Figure 3 It can be seen that the thermogravimetric curve of compound 1 has two weight loss stages. The first stage has a weight loss of 1.68%, which corresponds to the loss of free water molecules (theoretical value is 1.67%), and then the framework remains stable; when the temperature rises to 170℃, the sample begins to decompose.
[0054] Example 6
[0055] Preparation of fly ash@MOF composite materials:
[0056] 37.2 mg of 2,5-bis(4′-pyridine)phenol (DPP, 0.15 mmol), 68.2 mg of 1,3,6,8-tetra(4-carboxyphenyl)pyrene (H4PT, 0.10 mmol), and 43.9 mg of zinc acetate dihydrate (0.20 mmol) were dissolved in 1 mL of DMF and 1 mL of DMA. 100 mg of the fly ash photocatalyst prepared in Example 1 was added, and the pH of the solution was adjusted to 6.5 by adding nitric acid. The solution was then transferred to a reaction vessel and reacted at 109 °C for 8 h. After the reaction, the reaction solution was washed with DMF, filtered, and dried to obtain the fly ash@MOF photocatalyst.
[0057] Examples 7-10
[0058] Fly ash@MOF composite materials were prepared according to the method in Example 6, except that the amount of fly ash photocatalyst was adjusted to 20 mg, 50 mg, 80 mg, and 150 mg, respectively.
[0059] Example 11
[0060] Fly ash@MOF composite materials were prepared according to the method in Example 6, except that the reaction temperature was adjusted to 115°C and the reaction time was adjusted to 6 hours.
[0061] Example 12
[0062] Fly ash@MOF composite material for photocatalytic degradation of the antibiotic furazolidone:
[0063] 50 mg of the fly ash@MOF composite material prepared in Example 6 was dispersed in 100 mL of furacilin aqueous solution (concentration 2 mg / L) and stirred in the dark for 60 min to ensure adsorption-desorption equilibrium was established. Photocatalytic degradation of furacilin was carried out in a photochemical reactor equipped with a 400 W mercury lamp. 5 mL of sample was taken every 15 min, and the degradation was analyzed using a UV-Vis spectrophotometer. In addition, control experiments were conducted under the same conditions, using either the fly ash photocatalyst prepared in Example 1 or no photocatalyst.
[0064] Figure 4 The UV-Vis absorption spectrum of the photocatalytic degradation of furazolidone using fly ash@MOF composite material is shown. Figure 4 It is known that fly ash@MOF composite material can degrade about 90% of furazolidone within 90 minutes.
[0065] Figure 5 The UV-Vis absorption spectrum of furazolidone is shown below without the addition of a photocatalyst. Figure 5 It can be seen that furazolidone is basically not degraded when no photocatalyst is used.
[0066] Figure 6The UV-Vis absorption spectrum of the photocatalytic degradation of furazolidone using fly ash as a photocatalyst is shown. Figure 6 It was found that fly ash photocatalysts could only degrade about 40% of furacilin within 90 minutes. This indicates that the combination of fly ash photocatalysts and Zn-MOF materials can rapidly and efficiently degrade the antibiotic furacilin.
[0067] Figure 7 This is a cycle performance diagram of photocatalytic degradation of furazolidone using fly ash@MOFF composite material. Figure 7 It can be seen that the fly ash@MOF composite material still exhibits excellent catalytic performance after three cycles.
[0068] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing Zn-MOF materials, characterized in that: 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene and zinc acetate were dissolved in an organic solvent, the pH of the solution was adjusted to 6-7 with acid, and then transferred to a reaction vessel for solvothermal reaction to obtain Zn-MOF material.
2. The preparation method according to claim 1, characterized in that: The organic solvent is at least one of N,N′-dimethylformamide and N,N′-dimethylacetamide; Preferably, the molar ratio of 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene, and zinc acetate dihydrate is 1.5:1:2; Preferably, the temperature of the solvothermal reaction is 100–120°C.
3. The Zn-MOF material prepared by the preparation method described in claim 1 or 2.
4. A method for preparing fly ash@MOF composite material, characterized in that: 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene and zinc acetate were dissolved in an organic solvent, and fly ash photocatalyst was added. The pH of the solution was adjusted to 6-7 with acid, and then transferred to a reaction vessel for solvothermal reaction to obtain fly ash@MOF composite material.
5. The preparation method according to claim 4, characterized in that: The preparation method of the fly ash photocatalyst is as follows: fly ash is mixed with alkali, calcined, washed with water, filtered, dried, the resulting powder is dissolved in acid, the pH value of the solution is adjusted to 7-8 with alkali, and then transferred to a reaction vessel for hydrothermal reaction, filtered, dried, and the fly ash photocatalyst is obtained.
6. The preparation method according to claim 5, characterized in that: The alkali is sodium hydroxide or potassium hydroxide; Preferably, the calcination temperature is 600–700°C; Preferably, the acid is nitric acid, hydrochloric acid, or sulfuric acid; Preferably, the temperature of the hydrothermal reaction is 170–190°C.
7. The preparation method according to claim 4, characterized in that: The organic solvent is at least one of N,N′-dimethylformamide and N,N′-dimethylacetamide; Preferably, the molar ratio of 2,5-bis(4′-pyridine)phenol, 1,3,6,8-tetra(4-carboxyphenyl)pyrene, and zinc acetate dihydrate is 1.5:1:2; Preferably, the temperature of the solvothermal reaction is 100–120°C.
8. The fly ash@MOF composite material prepared by the preparation method according to any one of claims 4 to 7.
9. The application of the Zn-MOF material of claim 3 or the fly ash@MOF composite material of claim 8 in the photocatalytic degradation of antibiotics.
10. The application according to claim 9, characterized in that: The antibiotic in question is furacilin.