A method for preparing high-brightness multicolor luminescent IRMOF-0 materials

Abstract

The application discloses a method for preparing high-brightness multi-color luminescent IRMOF-0 material, and belongs to the technical field of multi-color luminescent metal organic framework (MOFs) material. The method comprises the following steps: taking non-luminescent IRMOF-0 as initial material, pre-pressing a T301 stainless steel gasket by using a diamond anvil, then forming a micro-hole sample cavity with a diameter of about 120 microns at the center of the concave pit generated by pre-pressing by using a laser punch, putting the non-luminescent IRMOF-0 initial material into the sample cavity, putting a ruby ball into the sample cavity, calibrating the pressure in the sample cavity by using a ruby fluorescence spectrum, applying a pressure of 6-30 GPa to the diamond anvil, and then releasing the pressure of the diamond anvil to normal pressure, so as to obtain the IRMOF-0 material with bright and multi-color luminescent characteristics. The method has the advantages of simple preparation and environmental protection, and replaces a complex and toxic chemical synthesis process, thereby opening up a new application prospect for non-aromatic interpenetrating MOFs.

Description

Technical Field

[0001] This invention belongs to the technical field of multicolor luminescent metal-organic frameworks (MOFs) materials, and specifically relates to a method for preparing high-brightness multicolor luminescent IRMOF-0 materials. Background Technology

[0002] For a long time, constructing multicolor photoluminescent materials with tunable properties has been a highly anticipated research goal, as these materials have broad application potential in fields such as multicolor displays, sensors, and encryption. Metal-organic frameworks (MOFs) are composed of various inorganic nodes and designable organic ligands, and their infinite combinations provide a variety of charge / energy transfer pathways and fluorescence mechanisms, making them an excellent platform for achieving tunable and controllable optical behavior. Among them, non-aromatic interpenetrating MOFs, characterized by multi-lattice entanglement, are considered ideal choices for MOF design due to their low-toxicity ligands, ease of synthesis, and excellent structural stability. However, compared with the high luminescence efficiency of rigid π-conjugated organic molecules containing benzene rings, MOFs based on ligand center emission are extremely difficult to produce photoluminescence when non-aromatic small molecules composed of electron-rich heteroatoms (such as N, O, and S) are used as bridging ligands. This is due to the large band gap between the ground and excited states and the rapid intramolecular motion. The lack of non-emissivity and optical properties makes it challenging to generate tunable multicolor emission from non-aromatic interpenetrating IRMOF-0s based on ligand center emission. Therefore, developing effective strategies to achieve efficient tunable emission colors from initially non-emissive non-aromatic interpenetrating IRMOF-0s is crucial. Summary of the Invention

[0003] The technical problem to be solved by this invention is to overcome the non-emission problem inherent in IRMof-0 materials and to provide a method for preparing high-brightness multicolor luminescent IRMof-0 materials through pressure processing engineering.

[0004] This invention uses non-luminescent IRMOF-0 as the starting material. Different pressures are applied to the sample using a diamond anvil cell, and then the pressure is released to atmospheric pressure. In-situ high-pressure fluorescence spectra of the samples under these different pressures are then collected. By comparing the fluorescence intensity and peak positions before and after treatment, a series of IRMOF-0 materials with high brightness and multicolor luminescence properties have been successfully prepared. The specific technical solution is as follows:

[0005] A method for preparing high-brightness multicolor luminescent IRMof-0 material is carried out in a diamond anvil cell. Using non-luminescent IRMof-0 as the initial material, a T301 stainless steel gasket is pre-pressurized using the diamond anvil cell. Then, a microporous sample cavity with a diameter of approximately 120 μm is formed at the center of the pre-pressurized pit using a laser drill. The non-luminescent IRMof-0 initial material is placed into the sample cavity, and a ruby ​​ball is inserted. The pressure inside the sample cavity is calibrated using ruby ​​fluorescence spectroscopy. A pressure of 6–30 GPa is applied to the diamond anvil cell, and then the pressure is released to atmospheric pressure to obtain a bright IRMof-0 material with multicolor luminescence characteristics.

[0006] In a method for preparing high-brightness multicolor luminescent IRMO material according to the present invention, when the pressure applied to the diamond anvil cell is 6 GPa, an IRMO material with deep blue luminescence characteristics is finally obtained; when the pressure is 12 GPa, an IRMO material with sky blue luminescence characteristics is finally obtained; when the pressure is 18 GPa, an IRMO material with cool white luminescence characteristics is finally obtained; when the pressure is 24 GPa, an IRMO material with pale yellow luminescence characteristics is finally obtained; and when the pressure is 30 GPa, an IRMO material with yellow luminescence characteristics is finally obtained.

[0007] The non-luminescent IRMO-0 can be synthesized by referring to the relevant literature currently reported, or by the following method: First, butynediic acid and zinc acetate dihydrate are dissolved in DMF and stirred for 10 minutes until the solution is colorless and transparent to obtain a precursor solution of butynediic acid and zinc acetate dihydrate. Then, the two precursor solutions are mixed and stirred continuously. Triethylamine reagent is added during stirring. When the solution becomes turbid, stirring is stopped immediately. The precipitate is then collected by centrifugation and washed with DMF. Finally, it is vacuum dried overnight at 40°C to obtain the non-luminescent IRMO-0 material. The DMF is N,N-dimethylformamide, the molar ratio of butynediic acid and zinc acetate dihydrate is 1:2, and 0.3 mL of triethylamine reagent is used for every 1.0 mmol of butynediic acid.

[0008] Beneficial effects:

[0009] This study successfully prepared a series of high-brightness, multicolor luminescent IRMOF-0 materials using pressure engineering. The advantage of this method lies in its simple and environmentally friendly preparation, replacing complex and highly toxic chemical synthesis processes, and opening up new application prospects for non-aromatic interpenetrating MOFs. Attached Figure Description

[0010] Figure 1 This is a transmission electron microscope (TEM) image of the prepared non-luminescent IRMof-0 sample.

[0011] Figure 2 This is the in-situ synchrotron radiation XRD spectrum of the prepared non-luminescent IRMOF-0 sample.

[0012] Figure 3 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 6 GPa pressure.

[0013] Figure 4 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 12 GPa pressure.

[0014] Figure 5 These are fluorescence spectra of the IRMOF-0 sample before and after treatment with 18 GPa pressure.

[0015] Figure 6 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 24 GPa pressure.

[0016] Figure 7 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 30 GPa pressure. Detailed Implementation

[0017] The present invention will now be described in more detail with reference to the following embodiments. Unless otherwise specified, all reagents used are commercially available products and have not been further purified before use. All high-pressure experiments were conducted at room temperature.

[0018] Example 1: Preparation of non-luminescent IRMof-0 samples

[0019] The synthesis method of IRMOF-0 material was based on previously reported literature with slight modifications. First, 1.0 mmol of butynediic acid and 2.0 mmol of zinc acetate dihydrate were dissolved in N,N-dimethylformamide (DMF, 5 mL) and stirred for 10 minutes to obtain a colorless and transparent solution. Then, the two precursor solutions were mixed and stirred continuously, with 0.3 mL of triethylamine reagent added during stirring. Stirring was stopped immediately when the solution became turbid. The precipitate was then collected by centrifugation, washed repeatedly with DMF, and finally dried under vacuum overnight at 40 °C to obtain the IRMOF-0 material.

[0020] Example 2: Morphology and structural characterization of non-luminescent IRMof-0 samples

[0021] The non-emitting IRMOF-0 sample prepared in Example 1 was characterized by transmission electron microscopy and in-situ synchrotron radiation XRD.

[0022] Figure 1 This is a transmission electron microscope (TEM) image of the non-luminescent IRMof-0 material. The image shows that the synthesized IRMof-0 nanoparticles are very uniform, with an average particle size of ~5 nm. Figure 2This is the XRD pattern of the prepared IRMOF-0 sample.

[0023] Example 3: High-pressure preparation of high-brightness deep blue luminescent IRMof-0 material

[0024] This experiment employed a 300 μm diameter diamond anvil cell to apply high pressure. First, a 40 μm thick pit was created by pre-compressing a T301 stainless steel washer, and a microporous sample cavity with a diameter of approximately 120 μm was obtained at the center of the pit using a laser drill. The sample was then placed into the sample cavity, and a ruby ​​ball was added to determine the actual pressure. The pressure was calibrated using standard ruby ​​fluorescence. In-situ high-pressure fluorescence experiments were performed using a 10 mW 355 nm laser. Without adding any transfer medium, a pressure of 6 GPa was applied to the diamond anvil cell, subjecting the sample to compression cycles from 1 atm to 6 GPa. Fluorescence spectra at atmospheric pressure and after decompression were collected before and after the treatment. Figure 3 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 6 GPa pressure. Figure 3 It can be seen that high-brightness deep blue luminescent IRMO-0 material was obtained after the IRMO-0 sample was subjected to a 6 GPa pressure treatment.

[0025] Example 4: High-pressure preparation of high-brightness sky-blue luminescent IRMof-0 material

[0026] This experiment employed a 300 μm diameter diamond anvil cell to apply high pressure. First, a 40 μm thick pit was created by pre-compressing a T301 stainless steel washer, and a microporous sample cavity with a diameter of approximately 120 μm was obtained at the center of the pit using a laser drill. The sample was then placed into the sample cavity, and a ruby ​​ball was added to determine the actual pressure. The pressure was calibrated using standard ruby ​​fluorescence. In-situ high-pressure fluorescence experiments were performed using a 10 mW 355 nm laser. Without adding any transfer medium, a pressure of 12 GPa was applied to the diamond anvil cell, subjecting the sample to compression cycles from 1 atm to 12 GPa. Fluorescence spectra at atmospheric pressure and after decompression were collected before and after the treatment. Figure 4 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 12 GPa pressure. Figure 4 It can be seen that high-brightness sky-blue luminescent IRMO-0 material was obtained after the IRMO-0 sample was subjected to a 12 GPa pressure treatment.

[0027] Example 5: High-pressure preparation of high-brightness cold white luminescent IRMof-0 material

[0028] This experiment employed a 300 μm diameter diamond anvil cell to apply high pressure. First, a 40 μm thick pit was created by pre-compressing a T301 stainless steel washer, and a microporous sample cavity with a diameter of approximately 120 μm was obtained at the center of the pit using a laser drill. The sample was then placed into the sample cavity, and a ruby ​​ball was added to determine the actual pressure. The pressure was calibrated using standard ruby ​​fluorescence. In-situ high-pressure fluorescence experiments were performed using a 10 mW 355 nm laser. Without adding any transfer medium, a pressure of 18 GPa was applied to the diamond anvil cell, subjecting the sample to compression cycles from 1 atm to 18 GPa. Fluorescence spectra at atmospheric pressure and after decompression were collected before and after the treatment. Figure 5 These are fluorescence spectra of the IRMOF-0 samples before and after treatment with 18 GPa pressure. Figure 5 It can be seen that high-brightness cold white luminescent IRMO-0 material was obtained after the IRMO-0 sample was subjected to 18 GPa pressure treatment.

[0029] Example 6: High-pressure preparation of high-brightness pale yellow luminescent IRMof-0 material

[0030] This experiment employed a 300 μm diameter diamond anvil cell to apply high pressure. First, a 40 μm thick pit was created by pre-compressing a T301 stainless steel washer, and a microporous sample cavity with a diameter of approximately 120 μm was obtained at the center of the pit using a laser drill. The sample was then placed into the sample cavity, and a ruby ​​ball was added to determine the actual pressure. The pressure was calibrated using standard ruby ​​fluorescence. In-situ high-pressure fluorescence experiments were performed using a 10 mW 355 nm laser. Without adding any transfer medium, a pressure of 24 GPa was applied to the diamond anvil cell, subjecting the sample to compression cycles from 1 atm to 24 GPa. Fluorescence spectra at atmospheric pressure and after decompression were collected before and after the treatment. Figure 6 These are the fluorescence spectra of the IRMOF-0 samples before and after treatment with 24 GPa pressure. Figure 6 It can be seen that high-brightness pale yellow luminescent IRMO-0 material was obtained after the IRMO-0 sample was subjected to a pressure treatment of 24 GPa.

[0031] Example 7: High-pressure preparation of high-brightness yellow luminescent IRMof-0 material

[0032] This experiment employed a 300 μm diameter diamond anvil cell to apply high pressure. First, a 40 μm thick pit was created by pre-compressing a T301 stainless steel washer, and a microporous sample cavity with a diameter of approximately 120 μm was obtained at the center of the pit using a laser drill. The sample was then placed into the sample cavity, and a ruby ​​ball was added to determine the actual pressure. The pressure was calibrated using standard ruby ​​fluorescence. In-situ high-pressure fluorescence experiments were performed using a 10 mW 355 nm laser. Without adding any transfer medium, a pressure of 30 GPa was applied to the diamond anvil cell, subjecting the sample to compression cycles from 1 atm to 30 GPa. Fluorescence spectra at atmospheric pressure and after decompression were collected before and after the treatment. Figure 7 These are the fluorescence spectra of IRMOF-0 samples before and after treatment with 30 GPa pressure. Figure 7 It can be seen that high-brightness yellow luminescent IRMO-0 material was obtained after the IRMO-0 sample was subjected to a pressure treatment of 30 GPa.

Claims

1. A method for preparing high-brightness multi-color luminescent IRMOF-0 material, which is carried out in a diamond anvil cell, using non-luminescent IRMOF-0 as starting material, using a T301 stainless steel gasket to pre-press the diamond anvil cell, then using a laser drill to form a 120 μm diameter micro-hole sample cavity at the center of the pre-pressing pit, placing the non-luminescent IRMOF-0 starting material into the sample cavity and placing a ruby ball in the sample cavity, using ruby fluorescence spectroscopy to calibrate the pressure in the sample cavity, applying a pressure of 6 ~ 30 GPa to the diamond anvil cell, then releasing the pressure in the diamond anvil cell to atmospheric pressure, to obtain IRMOF-0 material that is bright and has multi-color luminescent properties. The non-luminescent IRMOF-0 was synthesized by first dissolving butyne diacid and zinc acetate dihydrate separately in DMF and stirring for 10 minutes until the solutions were clear and colorless to obtain precursor solutions of butyne diacid and zinc acetate dihydrate, then mixing the two precursor solutions and continuing to stir, adding triethylamine reagent during the stirring, stopping the stirring immediately when the solution became cloudy, then collecting the precipitate by centrifugation and washing with DMF, and finally drying the non-luminescent IRMOF-0 material under vacuum at 40 °C overnight; wherein, The DMF is N, N-dimethylformamide, the molar ratio of butynedioic acid and zinc acetate dihydrate is 1:2, and 0.3 mL of triethylamine reagent is used per 1.0 mmol of butynedioic acid.

2. The method of claim 1, wherein the high brightness multicolor luminescent IRMOF-0 material is prepared by the method, characterized in that, When the diamond anvil cell is applied with a pressure of 6 GPa, the final IRMOF-0 material has deep blue luminescent properties, when the pressure is 12 GPa, the final IRMOF-0 material has sky blue luminescent properties, when the pressure is 18 GPa, the final IRMOF-0 material has cold white luminescent properties, when the pressure is 24 GPa, the final IRMOF-0 material has pale yellow luminescent properties, and when the pressure is 30 GPa, the final IRMOF-0 material has yellow luminescent properties.

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