A TiMn-MOF luminescent material and preparation method thereof

Abstract

The present invention discloses a TiMn-MOF luminescent material and a preparation method thereof, belonging to the technical field of luminescent materials. The present invention comprises dissolving manganese chloride tetrahydrate and trimesic acid in a mixed solvent consisting of ethanol, water, and dimethyldiamide, and stirring to obtain a mixed solution A; adding tetrabutyl titanate to the mixed solution A, stirring evenly, then ultrasonically stirring, centrifuging, washing with ethanol, and drying to obtain TiMn-MOF. The TiMn-MOF luminescent material of the present invention is prepared by a stirring method, and the preparation process is simple. Moreover, the prepared TiMn-MOF luminescent material can be excited under 350nm light to emit red light.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a TiMn-MOF luminescent material and a preparation method thereof. Background Art

[0002] As a new type of porous crystalline material constructed from metal cations / clusters and organic ligands, luminescent metal-organic frameworks (MOFs) have clear high porosity, chemical and structural tunability, and different luminescence properties, and have great potential in the field of luminescence. By selecting different metal ions and organic ligands for reaction, metal-organic frameworks with different morphologies can be synthesized. The metal ions used to synthesize luminescent metal-organic frameworks (MOFs) are generally rare earth ions. In addition, luminescent MOF materials have significant advantages. The framework material has a rigid and repetitive porous structure, which allows the organic light-emitting bodies to be arranged in an orderly manner at appropriate spacings, increases the solid loading of the organic light-emitting bodies and is conducive to the excitation of the internal light-emitting bodies.

[0003] In recent years, rare earth metal organic framework luminescent materials have attracted more and more attention from the public. Patent application CN106832311A discloses that Eu-MOF multicolor luminescent crystal materials and Tb-MOF green light crystal materials not only have good thermal stability and light stability, but also have high luminescence efficiency, and are excellent new high-efficiency luminescent crystal materials. Patent application CN116925381A discloses a MOF material with a copper-lanthanum bimetallic structure. The bimetallic MOF material exhibits a fluorescence emission peak at 700nm under the excitation of 405nm blue light. Patent application CN115322389A synthesized a dual-emission europium-based AIE-MOF for the first time, which has both the emission wavelength of europium and the AIE emission wavelength of tetraphenylethylene tetracarboxylic acid, and has good application prospects. However, since rare earth metal organic frameworks can cause harm to the environment, the present invention needs to explore a non-rare earth metal organic framework luminescent material that can emit red light. Summary of the Invention

[0004] In view of the above shortcomings of the prior art, the present invention provides a TiMn-MOF luminescent material and a preparation method thereof.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0007] (1) dissolving manganese chloride tetrahydrate and trimesic acid in a mixed solvent consisting of ethanol, water and dimethyl diamide and stirring to obtain a mixed solution A;

[0008] (2) adding tetrabutyl titanate to the mixed solution A and stirring uniformly to obtain a mixed solution B;

[0009] (3) The mixed solution B was ultrasonically stirred, then centrifuged and washed with ethanol, and then dried to obtain TiMn-MOF.

[0010] As a preferred embodiment of the present invention, the volume ratio of ethanol, water and dimethyl diamide is 1:1:(1-2).

[0011] As a preferred embodiment of the present invention, the mass ratio of manganese chloride tetrahydrate to trimesic acid is 3-13:6-10.

[0012] As a preferred embodiment of the present invention, the concentration of manganese chloride tetrahydrate in the mixed solution A is 3-13 g / L, and the concentration of trimesic acid is 6-10 g / L.

[0013] As a preferred embodiment of the present invention, the volume ratio of the solution A to tetrabutyl titanate is (61-63):(1-3).

[0014] As a preferred embodiment of the present invention, in step (3), the ultrasonication time is not less than 10 minutes, and the stirring time is 3-8 hours.

[0015] The present invention also claims protection for the TiMn-MOF luminescent material prepared by the preparation method of the TiMn-MOF luminescent material.

[0016] As a preferred embodiment of the present invention, the excitation wavelength of the TiMn-MOF luminescent material is 350 nm, and the emission wavelength is 700 nm.

[0017] The luminescence principle of the material of the present invention:

[0018] After being excited by a 350nm wavelength, the TiMn-MOF material undergoes three stages: absorption, energy transfer, and light emission. When light is absorbed, electrons jump from a low energy level to a high energy level, and then emit photons when they jump back to a lower energy level or the ground state, producing visible light.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The TiMn-MOF luminescent material of the present invention is prepared by a stirring method, and the preparation process is simple. In addition, the prepared TiMn-MOF luminescent material can be excited under 350nm light and generate 700nm red light through three stages of absorption, energy transfer and light emission. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the X-ray diffraction pattern of TiMn-MOF prepared in Example 1.

[0022] Figure 2 These are scanning electron microscope images of the TiMn-MOF prepared in Example 1 and its elemental analysis diagram, where (a) is a scanning electron microscope image of TiMn-MOF at low magnification, (b) is a scanning electron microscope image of TiMn-MOF at high magnification, C is the mapping distribution diagram of the C element, O is the mapping distribution diagram of the O element, Ti is the mapping distribution diagram of the Ti element, and Mn is the mapping distribution diagram of the Mn element.

[0023] Figure 3 This is the thermogravimetric diagram of TiMn-MOF prepared in Example 1.

[0024] Figure 4 These are the excitation and emission spectra of TiMn-MOF prepared in Example 1. DETAILED DESCRIPTION

[0025] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0026] Example 1

[0027] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0028] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of manganese chloride tetrahydrate added to the mixed solvent is 3.8 g / L, and the amount of trimesic acid added is 7 g / L.

[0029] (2) Tetrabutyl titanate was added to 61 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 1.2 mL.

[0030] (3) The mixed solution B was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0031] from Figure 1 It can be concluded that TiMn-MOF contains TiO2 and Mn2O3 components, and no impurity peaks appear.

[0032] from Figure 2 It can be seen that the structure of TiMn-MOF is uniform and spherical, the particles are about 800nm, its surface presents a network texture, and the C, O, Ti, and Mn elements are evenly distributed, with a low Mn content.

[0033] like Figure 3 As shown in Figure 2, TiMn-MOF has good thermal stability, so it has application value in a wide range. Figure 4 It can be seen that the TiMn-MOF material prepared in this embodiment can be excited by 350nm light and emit 700nm red light, so the material emits red light under ultraviolet light.

[0034] Example 2

[0035] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0036] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of manganese chloride tetrahydrate added to the mixed solvent is 4.2 g / L, and the amount of trimesic acid added is 8 g / L.

[0037] (2) Tetrabutyl titanate was added to 63 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 1.6 mL.

[0038] (3) The mixed solution B was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0039] When the TiMn-MOF material prepared in this example was illuminated with a 4W handheld UV lamp, it was observed that the TiMn-MOF material emitted red light. The TiMn-MOF material prepared in this example can be excited by 350nm light and emits 700nm red light, thus emitting red light under UV light.

[0040] Example 3

[0041] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0042] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of manganese chloride tetrahydrate added to the mixed solvent is 4.8 g / L, and the amount of trimesic acid added is 9 g / L.

[0043] (2) Tetrabutyl titanate was added to 62 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 2.1 mL.

[0044] (3) The mixed solution B was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0045] When the TiMn-MOF material prepared in this example was illuminated with a 4W handheld UV lamp, it was observed that the TiMn-MOF material emitted red light. The TiMn-MOF material prepared in this example can be excited by 350nm light and emits 700nm red light, thus emitting red light under UV light.

[0046] Example 4

[0047] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0048] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of manganese chloride tetrahydrate added to the mixed solvent is 6 g / L, and the amount of trimesic acid added is 9.2 g / L.

[0049] (2) Tetrabutyl titanate was added to 61 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 2.4 mL.

[0050] (3) The mixed solution B was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0051] When the TiMn-MOF material prepared in this example was illuminated with a 4W handheld UV lamp, it was observed that the TiMn-MOF material emitted red light. The TiMn-MOF material prepared in this example can be excited by 350nm light and emits 700nm red light, thus emitting red light under UV light.

[0052] Example 5

[0053] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0054] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:2, the amount of manganese chloride tetrahydrate added to the mixed solvent is 13 g / L, and the amount of trimesic acid added is 10 g / L.

[0055] (2) Tetrabutyl titanate was added to 62 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 3 mL.

[0056] (3) The mixed solution B was ultrasonicated for 6 min, stirred for 8 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0057] When the TiMn-MOF material prepared in this example was illuminated with a 4W handheld UV lamp, it was observed that the TiMn-MOF material emitted red light. The TiMn-MOF material prepared in this example can be excited by 350nm light and emits 700nm red light, thus emitting red light under UV light.

[0058] Example 6

[0059] A method for preparing a TiMn-MOF luminescent material comprises the following steps:

[0060] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:2, the amount of manganese chloride tetrahydrate added to the mixed solvent is 3 g / L, and the amount of trimesic acid added is 6 g / L.

[0061] (2) Tetrabutyl titanate was added to 61 mL of mixed solution A and stirred for 10 min to obtain mixed solution B, wherein the amount of tetrabutyl titanate in solution B was 1 mL.

[0062] (3) The mixed solution B was ultrasonicated for 5 min, stirred for 3 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain TiMn-MOF.

[0063] When the TiMn-MOF material prepared in this example was illuminated with a 4W handheld UV lamp, it was observed that the TiMn-MOF material emitted red light. The TiMn-MOF material prepared in this example can be excited by 350nm light and emits 700nm red light, thus emitting red light under UV light.

[0064] Comparative Example 1

[0065] A method for preparing a Mn-MOF luminescent material comprises the following steps:

[0066] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of manganese chloride tetrahydrate added to the mixed solvent is 3.8 g / L, and the amount of trimesic acid added is 7 g / L.

[0067] (2) The mixed solution A was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain Mn-MOF.

[0068] The Mn-MOF prepared in Comparative Example 1 was excited by 350 nm light and emitted reddish-brown light.

[0069] Comparative Example 2

[0070] A method for preparing a Ti-MOF luminescent material comprises the following steps:

[0071] (1) Manganese chloride tetrahydrate and trimesic acid are dissolved in a mixed solvent consisting of ethanol, water and dimethyldiamide and stirred to obtain a mixed solution A; wherein the volume ratio of ethanol, deionized water and dimethyldiamide is 1:1:1, the amount of tetrabutyl titanate added to the mixed solvent is 1.2 mL, and the amount of trimesic acid added is 7 g / L.

[0072] (2) The mixed solution A was ultrasonicated for 10 min, stirred for 3.5 h, then centrifuged and washed with ethanol three times, and dried in a drying oven at 60 °C for 12 h to obtain Ti-MOF.

[0073] The Ti-MOF material prepared in Comparative Example 2 cannot be excited by 350nm light.

[0074] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a TiMn-MOF luminescent material, characterized in that: The steps include: (1) dissolving manganese chloride tetrahydrate and trimesic acid in a mixed solvent consisting of ethanol, water and dimethyl diamide and stirring to obtain a mixed solution A; (2) adding tetrabutyl titanate to the mixed solution A and stirring uniformly to obtain a mixed solution B; (3) The mixed solution B was ultrasonically stirred, then centrifuged and washed with ethanol, and then dried to obtain TiMn-MOF.

2. The method for preparing the TiMn-MOF luminescent material according to claim 1, wherein: The volume ratio of the ethanol, water and dimethyldiamide is 1:1:(1-2).

3. The method for preparing the TiMn-MOF luminescent material according to claim 1, wherein: The concentration of manganese chloride tetrahydrate in the mixed solution A is 3-13 g / L, and the concentration of trimesic acid is 6-10 g / L.

4. The method for preparing the TiMn-MOF luminescent material according to claim 1, wherein: The volume ratio of the solution A to tetrabutyl titanate is (61-63):(1-3).

5. The method for preparing the TiMn-MOF luminescent material according to claim 1, wherein: In the step (3), the ultrasonication time is not less than 10 minutes, and the stirring time is 3-8 hours.

6. The TiMn-MOF luminescent material prepared by the method for preparing the TiMn-MOF luminescent material according to any one of claims 1 to 5.

7. The TiMn-MOF luminescent material according to claim 6, characterized in that: The TiMn-MOF luminescent material has an excitation wavelength of 350 nm and an emission wavelength of 700 nm.

Images