Anthraquinone-functionalized zirconium-based MOF photocatalyst, preparation method and application thereof
Anthraquinone-functionalized zirconium-based MOF photocatalysts were prepared by microwave synthesis, which solved the problems of low carrier separation efficiency and insufficient visible light utilization, achieved efficient VOCs removal, and reduced synthesis cost and time.
Patent Information
- Application Number
- CN202610521787.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-20
- Publication Date
- 2026-06-16
AI Technical Summary
Existing photocatalytic technologies suffer from low carrier separation efficiency and insufficient visible light utilization, resulting in low VOCs removal efficiency. Furthermore, the synthesis methods are time-consuming and costly.
Anthraquinone-functionalized zirconium-based MOF photocatalysts were prepared by microwave synthesis. A three-dimensional hierarchical flower-like microsphere structure of MOF material was constructed using zirconium ions, 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid as mixed organic ligands. The MOF material was grown in situ on a metal substrate and used for photocatalytic self-Fenton reaction to remove VOCs.
It achieves efficient removal of VOCs under visible light. The catalyst has a large specific surface area, excellent photoresponse performance, simple synthesis method, low cost, and a removal rate of up to 100%.
Smart Images
Figure CN122209485A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to photocatalytic environmental remediation technology, specifically to an anthraquinone-functionalized zirconium-based MOF photocatalyst, its preparation method, and its application. Background Technology
[0002] Metal-organic frameworks (MOFs) are a class of crystalline porous materials formed by the self-assembly of metal ions and organic ligands, possessing advantages such as large specific surface area, tunable pore structure, and abundant functional sites. For example, UIO-66, due to its high specific surface area, tunable pore structure, and excellent photoresponse performance, has become an ideal photocatalytic material. In particular, zirconium-based UIO-66 exhibits excellent structural stability and visible light response, making it suitable for photocatalytic self-Fenton systems.
[0003] Therefore, growing MOF materials on a conductive metal substrate is an ideal photocatalytic material that can be used for photocatalytic removal of pollutants.
[0004] Microwave chemical synthesis has advantages such as uniform heating, rapid reaction, low energy consumption, and good reproducibility, making it very suitable for the controllable synthesis of MOF materials.
[0005] Based on this, it is desirable to obtain a zirconium-based MOF constructed using the visible light-responsive ligands 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid, thereby developing a highly efficient, stable, and easily prepared material for the efficient removal of VOCs under visible light. Summary of the Invention
[0006] In order to overcome the shortcomings of the prior art, the present invention aims to provide anthraquinone-functionalized zirconium-based MOF photocatalyst, preparation method and application. In particular, the prepared anthraquinone-functionalized zirconium-based MOF photocatalyst can overcome the problems of low carrier separation efficiency and insufficient visible light utilization in the existing photocatalytic technology, and has the advantages of simple process, low cost and excellent catalytic performance.
[0007] To achieve the above objectives, the present invention proposes the following technical solution: In a first aspect, the present invention proposes an anthraquinone-functionalized zirconium-based MOF photocatalyst, wherein the anthraquinone-functionalized zirconium-based MOF photocatalyst is constructed with zirconium ions as the metal center and 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid as mixed organic ligands to obtain a metal-organic framework AQ / NH2-UIO-66, which is the anthraquinone-functionalized zirconium-based MOF photocatalyst.
[0008] Preferably, the anthraquinone-functionalized zirconium-based MOF photocatalyst has a three-dimensional hierarchical flower-like microsphere structure.
[0009] Secondly, this invention proposes a method for preparing the above-mentioned anthraquinone-functionalized zirconium-based MOF photocatalyst. The preparation method involves using zirconium ions as the metal center and 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid as mixed organic ligands, and growing the catalyst in situ on a metal substrate via microwave synthesis.
[0010] Preferably, the preparation method includes the following steps: Zirconium salt was dissolved in an organic solvent, mixed organic ligands were added, and the reaction was carried out at a higher temperature to obtain the reaction product. The reaction products from the above steps were washed and dried to obtain the anthraquinone-functionalized zirconium-based MOF photocatalyst.
[0011] Preferably, the zirconium salt is one or more of Zr(NO3)4·5H2O, ZrCl4, and ZrOCl2·8H2O.
[0012] Preferably, the organic solvent is N,N-dimethylformamide solution (DMF).
[0013] Preferably, in the mixed organic ligand, the molar ratio of 2-aminoterephthalic acid to anthraquinone-2-carboxylic acid is 20:3 to 20:6, more preferably 20:5.
[0014] Preferably, an acid is added before the reaction is heated, and the acid is one or more of hydrochloric acid, sulfuric acid, and glacial acetic acid.
[0015] It should be noted that, in the technical solution described in this invention, the addition of acid helps to generate corresponding ions on the metal substrate.
[0016] Preferably, during the heating reaction, the heating rate is 10~15 °C / min, the final reaction temperature is 100~140 °C, and the reaction time is 40~50 min.
[0017] In some embodiments, zirconium salts (e.g., zirconium chloride) can be ultrasonically dispersed in DMF. 2-Aminoterephthalic acid and anthraquinone-2-carboxylic acid are added as mixed organic ligands under continuous stirring. After complete dissolution, an appropriate amount of acid (e.g., concentrated hydrochloric acid) is added to adjust the acidity of the reaction system and promote the dissolution of metal substrate ions. Under microwave power of 500–1200 W and initial pressure of 5–35 bar, the reaction temperature is raised to 100–140 °C at a heating rate of 10 °C / min and maintained for 45 minutes. After the reaction, the mixture is allowed to cool naturally to room temperature. The composite material is then removed and washed repeatedly with DMF and ethanol to remove unreacted substances. Finally, it is vacuum dried to obtain a uniformly loaded anthraquinone-functionalized zirconium-based MOF photocatalyst. In the above method for preparing the anthraquinone-functionalized zirconium-based MOF photocatalyst, the amount of anthraquinone-2-carboxylic acid added is 0.3–0.6 mmol, with 0.5 mmol being optimal.
[0018] In some preferred embodiments, the amount of hydrochloric acid added in the preparation method of the above-mentioned anthraquinone-functionalized zirconium-based MOF photocatalyst is 0.1 to 0.68 ml, preferably 0.34 ml.
[0019] Thirdly, this invention proposes the application of the above-mentioned anthraquinone-functionalized zirconium-based MOF photocatalyst or the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared by the above-described preparation method in the photocatalytic removal of volatile organic compounds in the Fenton reaction.
[0020] Preferably, when the above-mentioned anthraquinone-functionalized zirconium-based MOF photocatalyst is used for photocatalytic oxidation of VOCs, the specific steps are as follows: In a photogenerated spectrometer, a metal substrate loaded with the MOF is used as a catalyst, a mixture of toluene and high-purity air at a certain concentration (40-300 ppm) is introduced, and a xenon lamp with a wavelength of 420 nm is used as a light source to initiate a photocatalytic self-Fenton reaction to degrade VOCs.
[0021] Compared with the prior art, the present invention has the following advantages and outstanding effects: The chemical reagents used in this invention are all commonly used. Compared with the currently used hydrothermal method, this method does not require a long reaction time, reduces energy consumption, and allows for the in-situ growth of MOF catalysts on the surface of metal substrates in a one-step process. The synthesized catalyst has a high specific surface area, tunable pore structure, and good photoresponse performance. The anthraquinone-functionalized zirconium-based MOF photocatalyst prepared in this invention can achieve a removal rate of up to 100% for the photocatalytic oxidation of toluene in a fixed gas phase under visible light (≥ 420 nm) at room temperature. Attached Figure Description
[0022] Figure 1 The figure shows the XRD pattern of the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared in Example 1. The figure shows that the diffraction peak of anthraquinone-2-carboxylic acid corresponds highly with the diffraction peak of NH2-UIO-66.
[0023] Figure 2 The graph shows the toluene removal rate of the anthraquinone-functionalized zirconium-based MOF photocatalyst sample prepared in Example 1.
[0024] Figure 3 This is a scanning electron microscope image of the anthraquinone-functionalized zirconium-based MOF photocatalyst sample prepared in Example 1. Detailed Implementation
[0025] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several changes and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.
[0026] Experimental methods in the following examples that do not specify specific conditions should be performed according to conventional methods and conditions, or according to the product instructions. All reagents and raw materials used in this invention are commercially available.
[0027] The present invention will be further described below with reference to the embodiments: Example 1 Take a clean quartz microwave reaction tube and add 40 mL of DMF and 446 mg of zirconium chloride (ZrCl4) sequentially, then disperse by ultrasonication. While continuously stirring, first add 362 mg of 2-aminoterephthalic acid, and after it dissolves, add 126 mg of anthraquinone-2-carboxylic acid. After stirring for 10 minutes, add 0.34 mL of concentrated hydrochloric acid. Seal the reaction tube in a microwave reactor. Set the reaction program: heat to 120°C at 10°C / min, microwave power 1000W, react for 45 minutes. After the reaction, allow it to cool naturally, remove the sample, wash it three times each with DMF and anhydrous ethanol, and vacuum dry it overnight at 60°C to obtain the dark-colored AQ / NH2-UIO-66 photocatalyst material.
[0028] Figure 1 The image shows the XRD pattern of the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared in Example 1. The diffraction peaks of anthraquinone-2-carboxylic acid and NH2-UIO-66 are highly correlated.
[0029] Figure 2 The graph shows the toluene removal rate of the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared in Example 1. Figure 2 As shown, the obtained sample has excellent photocatalytic activity for the decomposition and removal of stationary toluene. Under visible light at room temperature (λ≥420 nm), the catalyst showed the removal rate of toluene under different toluene concentration conditions (i.e., 40ppm, 80ppm, 150ppm, 220ppm and 300ppm).
[0030] Figure 3 This is a scanning electron microscope (SEM) image of the anthraquinone-functionalized zirconium-based MOF photocatalyst sample prepared in Example 1. Figure 3 As shown, NH2-UIO-66 (Zr) has a regular octahedral structure with uniform particle size. Combined with... Figure 3 , Figure 3As can be seen from A, its microstructure is a typical three-dimensional hierarchical flower-like microsphere structure, composed of self-assembled nanocrystals of 20-50 nm, with an average particle size of about 2-5 μm and a BET specific surface area of 80-150 m² / g; as the loading of active components increases from 5 wt% (see A...), .... Figure 3 The content of B) was increased to 20 wt% (see Figure 3 With C), the surface roughness of the microspheres increases, the edges become blunt, and the specific surface area decreases to 40~80 m² / g; when the loading exceeds 20 wt% (see C), the surface roughness of the microspheres increases, the edges become blunt, and the specific surface area decreases to 40~80 m² / g; Figure 3 The flower-like skeleton completely collapsed and agglomerated into irregular nanoparticle aggregates, further reducing the specific surface area to 20~40 m² / g and significantly decreasing the dispersibility.
[0031] It should be noted that, Figure 3 The products were tested and characterized using the following methods: X-ray diffraction was performed on a Rigaku D / Max-RB X-ray diffractometer in Japan for structural analysis of the samples; the toluene concentration change was analyzed online using a GASERA ONE analyzer developed by Beijing Duke Tech Technology Co., Ltd.; and scanning electron microscope images were obtained using a Zeiss Gemini 300 scanning electron microscope.
[0032] Examples 2, 3, 4, and 5 The difference from Example 1 is that the toluene concentration was kept constant, and the MOF precursor feed was changed to change the MOF loading. Examples 2, 3, 4, and 5 were 0.3 mmol, 0.4 mmol, 0.5 mmol, and 0.6 mmol, respectively. The highest toluene removal rate was achieved when the anthraquinone-2-carboxylic acid concentration was 0.5 mmol in Example 1.
[0033] Under the conditions of Example 1, in a photogenerated spectrometer, a metal substrate loaded with the MOF was used as a catalyst, and a mixture of toluene and high-purity air at a certain concentration (40-300 ppm) was introduced, and a xenon lamp with a wavelength of 420 nm was used as a light source to initiate a photocatalytic self-Fenton reaction to degrade VOCs.
[0034] The results show that the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared in this embodiment has a 100% toluene removal rate for the photocatalytic oxidation of toluene in the fixed gas phase under visible light (λ≥420 nm).
[0035] The above description is merely a preferred embodiment of the present invention, but the present invention should not be limited to the content disclosed in this embodiment. Therefore, any equivalent or modified versions made without departing from the principles disclosed in the present invention fall within the scope of protection of the present invention.
[0036] It should be noted that the prior art portion of the protection scope of this invention is not limited to the embodiments given in this application. All prior art that does not contradict the solution of this invention, including but not limited to prior patent documents, prior publications, prior public uses, etc., can be included in the protection scope of this invention.
[0037] Furthermore, the combination of the technical features in this case is not limited to the combination methods described in the claims of this case or the combination methods described in the specific embodiments. All technical features described in this case can be freely combined or combined in any way, unless they contradict each other.
[0038] Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention. Unless otherwise specified, the embodiments and features described in this application can be arbitrarily combined with each other.
Claims
1. An anthraquinone-functionalized zirconium-based MOF photocatalyst, characterized in that, The anthraquinone-functionalized zirconium-based MOF photocatalyst is constructed using zirconium ions as the metal center and 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid as mixed organic ligands to obtain the metal-organic framework AQ / NH2-UIO-66, which is the anthraquinone-functionalized zirconium-based MOF photocatalyst.
2. The anthraquinone-functionalized zirconium-based MOF photocatalyst according to claim 1, characterized in that, The anthraquinone-functionalized zirconium-based MOF photocatalyst has a three-dimensional hierarchical flower-like microsphere structure.
3. A method for preparing the anthraquinone-functionalized zirconium-based MOF photocatalyst as described in claim 1 or 2, characterized in that, The preparation method involves using zirconium ions as the metal center and 2-aminoterephthalic acid and anthraquinone-2-carboxylic acid as mixed organic ligands, and growing them in situ on a metal substrate via microwave synthesis.
4. The preparation method according to claim 3, characterized in that, The preparation method includes the following steps: Zirconium salt was dissolved in an organic solvent, mixed organic ligands were added, and the reaction was carried out at a high temperature to obtain the reaction product. The reaction products from the above steps were washed and dried to obtain the anthraquinone-functionalized zirconium-based MOF photocatalyst.
5. The preparation method according to claim 4, characterized in that, The zirconium salt is one or more of Zr(NO3)4·5H2O, ZrCl4, and ZrOCl2·8H2O.
6. The preparation method according to claim 4, characterized in that, The organic solvent is an N,N-dimethylformamide solution.
7. The preparation method according to claim 4, characterized in that, In the mixed organic ligand, the molar ratio of 2-aminoterephthalic acid to anthraquinone-2-carboxylic acid is 20:3 to 20:6, preferably 20:
5.
8. The preparation method according to claim 4, characterized in that, An acid is added before the reaction is heated, and the acid is one or more of hydrochloric acid, sulfuric acid, and glacial acetic acid.
9. The preparation method according to claim 4, characterized in that, During the heating reaction, the heating rate is 10~15℃ / min, the final reaction temperature is 100~140℃, and the reaction time is 40~50min.
10. The application of the anthraquinone-functionalized zirconium-based MOF photocatalyst as described in claim 1 or 2, or the anthraquinone-functionalized zirconium-based MOF photocatalyst prepared by any one of claims 3 to 9, in the photocatalytic removal of volatile organic compounds in the Fenton reaction.