Cu3 (HTTT) 2MOF film and preparation method thereof
The Cu3(HHTT)2MOF thin film was prepared by a step-by-step immersion method and controlled reaction conditions, which solved the problem of uneven film growth in the existing technology and achieved efficient and low-cost film preparation, which is suitable for optoelectronic and sensing applications.
Patent Information
- Application Number
- CN202511070237.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-31
- Publication Date
- 2025-10-10
AI Technical Summary
The existing Cu3(HHTT)2MOF thin film preparation method has limitations such as harsh reaction conditions, complex preparation process, and difficulty in achieving uniform thin film growth.
A step-by-step immersion method was adopted. The substrate was first immersed in a copper salt aqueous solution and then immersed in a mixed solution for static reaction. The reaction conditions were controlled by combining appropriate copper ion and hexahydroxytetrazonaphthalene concentrations and volume ratios. Finally, the Cu3(HHTT)2MOF film was prepared by rinsing with deionized water and organic solvents and vacuum drying.
The uniform growth of Cu3(HHTT)2MOF thin films was achieved, which has good crystal structure, high purity, low cost and easy operation, and is suitable for optoelectronics and sensing fields.
Smart Images
Figure CN120757795A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a Cu3(HHTT)2MOF film and a preparation method thereof, belonging to the technical field of metal organic framework (MOF) material preparation. Background Art
[0002] Metal-organic framework (MOF) materials have shown great application potential in gas storage, separation, catalysis, sensing and other fields due to their advantages such as high specific surface area, adjustable pore structure and abundant active sites. As a MOF material with excellent performance, the research on its preparation method is of great significance for expanding its application in various fields. However, existing preparation methods have some limitations, such as harsh reaction conditions, complex preparation process, and difficulty in achieving uniform growth of thin films. Therefore, there is an urgent need to develop a simple and efficient method for preparing Cu3(HHTT)2MOF thin films. Summary of the Invention
[0003] In order to overcome the shortcomings of the prior art, the present invention provides a Cu3(HHTT)2MOF thin film and a preparation method thereof, which has the advantages of simple operation, low cost, good repeatability, etc., and the prepared thin film has a good crystal structure.
[0004] The technical solution adopted by the present invention to solve its technical problem is:
[0005] In a first aspect, the present application provides a method for preparing a Cu3(HHTT)2MOF thin film, comprising the following steps:
[0006] Prepare copper salt aqueous solution;
[0007] Prepare hexahydroxytetrazoline organic solution;
[0008] mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution to obtain a mixed solution;
[0009] First immersing the substrate in the remaining copper salt aqueous solution, and then immersing the substrate in the mixed solution to allow it to react;
[0010] The substrate is taken out, and unreacted substances, water and organic solvents are removed to obtain the Cu3(HHTT)2MOF thin film on the substrate.
[0011] The MOF thin film preparation method provided in this application is simple, efficient, and has high film quality.
[0012] Furthermore, the copper ion concentration of the copper salt aqueous solution is 0.05 mol / L to 0.2 mol / L; the hexahydroxytetrazoline concentration of the hexahydroxytetrazoline organic solution is 0.01 mol / L to 0.1 mol / L.
[0013] An appropriate copper ion concentration allows the copper salt to fully dissolve in water, providing a sufficient and evenly dispersed copper ion source for subsequent reactions, preventing the copper ion content required for film formation from being insufficient due to low concentrations. A suitable hexahydroxytetrazonaphthalene concentration creates favorable conditions for the reaction with copper ions. When the substrate is first immersed in the remaining copper salt aqueous solution, copper ions at the appropriate concentration are adsorbed on the substrate surface, forming a relatively evenly distributed layer of copper ions. Subsequent immersion in a mixed solution of the appropriate concentration facilitates the orderly, smooth, and uniform growth of the film.
[0014] Furthermore, in the step of mixing the hexahydroxytetraazine organic solution with a portion of the copper salt aqueous solution, the volume ratio of the copper salt aqueous solution to the hexahydroxytetraazine organic solution is 1:1-3.
[0015] When the substrate is first immersed in a copper salt aqueous solution with a higher concentration (compared to the mixed solution), a certain amount of copper ions are adsorbed on the surface, and then immersed in this mixed solution, the evenly distributed reactants can combine with the copper ions on the substrate surface in an orderly manner, thereby promoting the uniform growth of the film on the substrate.
[0016] Furthermore, the copper ion concentration of the copper salt aqueous solution is twice the hexahydroxytetrazoline concentration of the hexahydroxytetrazoline organic solution; in the step of mixing the hexahydroxytetrazoline organic solution with part of the copper salt aqueous solution, the volume ratio of the copper salt aqueous solution to the hexahydroxytetrazoline organic solution is 1:2.
[0017] Using this concentration and volume ratio can maximize the reaction between the two, which is conducive to the formation of a more regular and single Cu3(HHTT)2MOF thin film structure.
[0018] Furthermore, in the step of preparing the copper salt aqueous solution, the pH is adjusted to 3-5 with an inorganic acid, and the solute is copper nitrate trihydrate or copper chloride dihydrate.
[0019] The selected metal salt has good solubility in water and can provide a stable source of copper ions for the reaction. Adjusting the appropriate pH value with inorganic acid helps the copper ions to exist in the solution in a stable form, ensuring the effectiveness of the copper ions in subsequent reactions.
[0020] Furthermore, in the step of preparing the hexahydroxytetraazine organic solution, the solvent is N,N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran, and the solute contains an additive in addition to the hexahydroxytetraazine, and the additive is acetic acid or triethylamine, and the concentration of the additive is less than one-fifth of the concentration of the hexahydroxytetraazine.
[0021] The appropriate concentration of additives can improve solubility and increase reactivity without excessively interfering with the reaction process.
[0022] Furthermore, in the step of mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution, the mixture is heated at 30° C. to 60° C. and stirred at a rotation speed of 300 rpm to 600 rpm for 10 min to 30 min.
[0023] Proper heating can increase the activity of copper ions and hexahydrophthalazine molecules, making them more likely to react and accelerating the reaction rate. A suitable stirring speed ensures that the two solutions are fully mixed, making the copper ions and hexahydrophthalazine molecules more evenly distributed in the solution and promoting the reaction.
[0024] Furthermore, the substrate is a glass sheet, a silicon wafer or a mica sheet, which undergoes plasma surface treatment before being immersed in the copper salt aqueous solution. The static reaction time is 12 hours to 48 hours, ensuring that the reaction can proceed fully, which is conducive to the gradual formation of a complete and dense MOF thin film structure.
[0025] Furthermore, the step of removing unreacted substances, water and organic solvents comprises:
[0026] Rinse the substrate with deionized water, and rinse the substrate with ethanol or acetone;
[0027] The mixture was vacuum dried at 40°C to 80°C for 6 to 12 hours.
[0028] This operation can fully evaporate the moisture and residual volatile substances while ensuring the stability of the film structure.
[0029] In a second aspect, the present application provides a Cu3(HHTT)2MOF thin film, which is made by the Cu3(HHTT)2MOF thin film preparation method described in the first aspect, and has a regular and uniform structure, high purity and good performance.
[0030] The beneficial effects of the present invention are: the reaction conditions are mild, and the invention has the advantages of simple operation, low cost, good repeatability, etc., which is conducive to achieving uniform growth of the thin film. The prepared thin film has a good and complete crystal structure, a regular and uniform film structure, high purity, good crystallinity and stability, and a smooth surface, which is conducive to application in optoelectronics, sensing and other fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 Schematic diagram of the process for preparing Cu3(HHTT)2MOF thin film in this application.
[0032] Figure 2 This is the SEM image of the Cu3(HHTT)2MOF film prepared in this application.
[0033] Figure 3This is the XRD pattern of the Cu3(HHTT)2MOF film prepared in this application. DETAILED DESCRIPTION
[0034] To make the purpose, technical solutions, and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure are clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0035] It should be understood that, under the premise of no conflict, any and all embodiments of the present invention can be combined with the technical features in any other embodiment or multiple other embodiments to obtain additional embodiments. The present invention includes such combinations to obtain additional embodiments.
[0036] Unless otherwise specified, all technical and scientific terms used herein have the standard meanings in the art to which the claimed subject matter belongs. If there are multiple definitions for a term, the definition herein shall prevail.
[0037] The present invention provides a method for preparing a Cu3(HHTT)2MOF thin film, comprising the following steps:
[0038] S1: Prepare copper salt aqueous solution.
[0039] S2: Prepare a hexahydroxytetrazoline organic solution.
[0040] S3: Mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution to obtain a mixed solution.
[0041] S4: Immerse the substrate in the remaining copper salt aqueous solution first, and then immerse it in the mixed solution to allow it to react.
[0042] S5: The substrate is removed, unreacted materials, water, and organic solvents are removed, and a Cu3(HHTT)2MOF thin film is obtained on the substrate.
[0043] This sequence of operations allows the substrate to first contact the copper ions, creating a certain number of copper ion active sites on its surface. When immersed in the mixed solution, the hexahydroxytetrazonaphthalene and its complexes can better react with the copper ions on the substrate in an orderly manner to form a thin film, helping to form a more regular crystal structure. This step-by-step immersion method avoids reaction disorder and improves reaction controllability.
[0044] In step S1, the solvent is, for example, deionized water, and the copper salt can be Cu(NO3)2·3H2O, CuCl2·2H2O, etc.
[0045] The copper ion concentration of the copper salt aqueous solution can be 0.05-0.2 mol / L, for example, 0.08 mol / L, 0.1 mol / L, 0.13 mol / L, 0.18 mol / L, etc.
[0046] The copper salt aqueous solution can be added with an appropriate amount of acid, such as nitric acid, hydrochloric acid, etc., to adjust the pH value of the solution to 3-5, so as to improve the solubility and stability of Cu 2+ .
[0047] The copper salt aqueous solution in step S1 is divided into two parts, the first part is used for directly soaking the substrate, and the second part is used for mixing with the hexahydroxy tetraaza naphthalene organic solution and then soaking the substrate.
[0048] In step S2, for example, a certain amount of HHTT (hexahydroxy tetraaza naphthalene) is dissolved in an organic solvent, and ultrasonic dispersion is performed for 30-60 minutes, so as to fully dissolve it.
[0049] The organic solvent can be N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), etc.
[0050] The concentration of the hexahydroxy tetraaza naphthalene organic solution is, for example, 0.01-0.1 mol / L, for example, 0.02 mol / L, 0.03 mol / L, 0.06 mol / L, 0.09 mol / L, etc.
[0051] A small amount of additive can be added to the hexahydroxy tetraaza naphthalene organic solution to improve the reaction activity and solubility of the ligand. The additive can be acetic acid, triethylamine, etc.
[0052] In step S3, for example, the copper salt aqueous solution and the hexahydroxy tetraaza naphthalene organic solution are mixed in a certain volume ratio (for example, 1:1-3), and stirred at a speed of 300-600 rpm for 10-30 minutes, so as to fully contact Cu 2+ with HHTT and cause coordination reaction, forming a homogeneous mixed solution.
[0053] During the stirring process, appropriate heating (for example, water bath heating to 30-60°C) can be performed to accelerate the reaction process and improve the uniformity of the reaction.
[0054] In step S4, for example, the substrate after cleaning treatment is placed in an ion treatment instrument for treatment, and then quickly placed in the first copper salt aqueous solution. Subsequently, the substrate is horizontally immersed in the reaction mixed solution C, the immersion depth is controlled to be 0.5-2 cm, and the substrate is left to stand at room temperature for 12-48 hours, so as to make the Cu3(HHTT)2MOF crystals nucleate and grow on the surface of the substrate to form a thin film.
[0055] The optional substrate can be a glass sheet, a silicon wafer, a mica sheet, etc.
[0056] During the static reaction process, the environment should be kept relatively stable to avoid drastic changes in temperature and humidity that may affect film growth.
[0057] In step S5, for example, the substrate on which the Cu3(HHTT)2MOF thin film is grown is taken out from the reaction solution and rinsed with deionized water and the second organic solvent for 2 to 3 times respectively to remove unreacted substances and impurities remaining on the surface.
[0058] The cleaned film is then placed in a vacuum drying oven and dried at 40° C. to 80° C. for 6 to 12 hours to further remove moisture and organic solvents to obtain a finished Cu 3 (HHTT) 2 MOF film.
[0059] The second organic solvent is, for example, ethanol, acetone, etc.
[0060] In a preferred embodiment, Cu(NO3)2·3H2O is used as the copper source, and its purity is ≥99%. The concentration of the prepared metal salt solution is 0.1 mol / L, and the pH value of the solution is controlled at about 4. 2+ The solubility of the hydroxybenzoic acid is good and it can coordinate with HHTT more effectively in subsequent reactions.
[0061] In step S2, DMF is preferably used as the solvent for HHTT, the concentration of the prepared organic ligand solution is 0.05 mol / L, the ultrasonic dispersion time is 45 minutes, and an appropriate amount of acetic acid is added as an additive to make HHTT more evenly dispersed in the solution and improve its reaction activity.
[0062] Preferably, in step S3, the volume ratio of the copper salt aqueous solution to the hexahydroxytetrazoline organic solution is 1:2, the stirring speed is 400 rpm, the water bath heating temperature is 40°C, and the stirring reaction time is 20 minutes, so that the Cu in the reaction mixture C can be 2+ The coordination with HHTT is more complete, forming a uniform and stable reaction system, which is beneficial to the subsequent growth of thin films.
[0063] In a preferred step S4, the cleaned substrate is placed in an ion treatment apparatus for 10 minutes and then quickly placed in a copper salt aqueous solution for 10 minutes. The immersion depth in the mixed solution is 1 cm, and the reaction time is 24 hours. Under these conditions, a Cu3(HHTT)2MOF film can grow uniformly on the substrate surface, forming a continuous and dense film with a controllable thickness within the range of 100 nm to 300 nm.
[0064] Preferably, in step S5, the film is rinsed with deionized water and ethanol three times each, the vacuum drying temperature is 60°C, and the drying time is 8 hours. The treated Cu3(HHTT)2MOF film has good crystallinity and stability, a complete crystal structure, and a smooth surface, which is conducive to applications in optoelectronics, sensing and other fields.
[0065] Implementation Cases
[0066] Prepare metal salt solution A (copper salt aqueous solution): Accurately weigh 0.1 mol of Cu(NO3)2·3H2O and place it in a beaker. Add an appropriate amount of deionized water and stir on a magnetic stirrer until completely dissolved. Then adjust the pH of the solution to 4 with nitric acid and finally adjust the volume to 1 L to obtain a 0.1 mol / L Cu(NO3)2 solution.
[0067] Prepare organic ligand solution B (hexahydroxytetrazonaphthalene organic solution): weigh 0.05 mol of HHTT and place it in another beaker, add 500 mL of DMF and 0.5 mL of acetic acid, and place it in an ultrasonic cleaner for ultrasonic dispersion for 45 minutes to fully dissolve it and form a uniform solution.
[0068] Reaction solution mixing: Take out appropriate amounts of the prepared metal salt solution A and organic ligand solution B in a volume ratio of 1:2, stir at 400 rpm at room temperature, heat in a water bath to 40°C, and react with stirring for 1.5 hours to obtain a homogeneous reaction mixed solution C (mixed solution).
[0069] Start here Figure 1 , Film preparation: After ultrasonic cleaning with acetone and ethanol for 15 minutes and drying, the glass piece was placed in an ion treatment instrument for 10 minutes, and then quickly placed in metal salt solution A for 10 minutes to allow the surface to adsorb Cu 2+ Then, it was horizontally immersed in the reaction mixed solution C with an immersion depth of 1 cm and allowed to react at room temperature for 24 hours to allow Cu3(HHTT)2MOF crystals to grow on the surface of the glass to form a thin film.
[0070] Film post-processing: The glass sheet with the film was taken out, rinsed with deionized water three times, then rinsed with ethanol three times, and finally placed in a vacuum drying oven and dried at 60°C for 8 hours to obtain the finished Cu3(HHTT)2MOF film.
[0071] The Cu3(HHTT)2MOF film prepared in the embodiment was analyzed by XRD. Figure 3 The XRD pattern shows that the prepared Cu3(HHTT)2MOF film has a good crystal structure. The Cu3(HHTT)2MOF film prepared in the embodiment is observed under an electron microscope. Figure 2,SEM images show that the film surface is dense and the thickness is about 200nm.
[0072] Throughout this specification, reference to terms such as "one embodiment," "certain embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that the specific features, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, illustrative uses of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
[0073] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.
Claims
1. A method for preparing a Cu3(HHTT)2MOF thin film, characterized in that: The following steps are involved: Prepare copper salt aqueous solution; Prepare hexahydroxytetrazoline organic solution; mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution to obtain a mixed solution; First immersing the substrate in the remaining copper salt aqueous solution, and then immersing the substrate in the mixed solution to allow it to react; The substrate is taken out, and unreacted substances, water and organic solvents are removed to obtain the Cu3(HHTT)2MOF thin film on the substrate.
2. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: The copper ion concentration of the copper salt aqueous solution is 0.05 mol / L to 0.2 mol / L; the hexahydroxytetrazoline concentration of the hexahydroxytetrazoline organic solution is 0.01 mol / L to 0.1 mol / L.
3. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 2, characterized in that: In the step of mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution, the volume ratio of the copper salt aqueous solution to the hexahydroxytetrazoline organic solution is 1:1-3.
4. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 3, characterized in that: The copper ion concentration of the copper salt aqueous solution is twice the hexahydroxytetrazoline concentration of the hexahydroxytetrazoline organic solution; in the step of mixing the hexahydroxytetrazoline organic solution with part of the copper salt aqueous solution, the volume ratio of the copper salt aqueous solution to the hexahydroxytetrazoline organic solution is 1:
2.
5. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: In the step of preparing the copper salt aqueous solution, the pH is adjusted to 3-5 with an inorganic acid, and the solute is copper nitrate trihydrate or copper chloride dihydrate.
6. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: In the step of preparing the hexahydroxytetraazine organic solution, the solvent is N,N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran, and the solute contains an additive in addition to the hexahydroxytetraazine. The additive is acetic acid or triethylamine, and the concentration of the additive is less than one-fifth of the concentration of the hexahydroxytetraazine.
7. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: In the step of mixing the hexahydroxytetrazoline organic solution with a portion of the copper salt aqueous solution, the mixture is heated at 30° C. to 60° C. and stirred at a rotation speed of 300 rpm to 600 rpm for 10 min to 30 min.
8. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: The substrate is a glass sheet, a silicon sheet or a mica sheet, which is subjected to plasma surface treatment before being immersed in the copper salt aqueous solution. The static reaction time is 12 hours to 48 hours.
9. The method for preparing the Cu3(HHTT)2MOF thin film according to claim 1, characterized in that: The step of removing unreacted substances, moisture and organic solvents comprises: Rinse the substrate with deionized water, and rinse the substrate with ethanol or acetone; The mixture was vacuum dried at 40°C to 80°C for 6 to 12 hours.
10. A Cu3(HHTT)2MOF thin film, characterized in that The Cu3(HHTT)2MOF thin film is prepared by the Cu3(HHTT)2MOF thin film preparation method according to any one of claims 1 to 9.