Perovskite / MOF composite luminescent material and preparation method and application thereof

Abstract

The invention relates to the technical field of luminescent materials, and discloses a perovskite / MOF composite luminescent material and a preparation method and application thereof. The invention provides a preparation method of a perovskite / MOF composite luminescent material. The preparation method comprises the following steps: 1, preparing an organic ligand; 2, preparing a metal-organic framework material by taking the organic ligand obtained in the step 1 as a raw material; and 3, preparing the perovskite / MOF composite luminescent material by taking the metal-organic framework material obtained in the step 2 as a raw material. The fluorescence intensity of the perovskite / MOF composite luminescent material provided by the invention can be maintained at 90% or above within 12-month storage days, and the perovskite / MOF composite luminescent material has good stability; the luminous efficiency of the perovskite / MOF composite luminescent material provided by the invention can reach 96%, and the perovskite / MOF composite luminescent material has good luminous efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and more specifically, to a perovskite / MOF composite luminescent material, a preparation method thereof, and an application thereof. Background Art

[0002] Luminescent materials have been widely used in many fields such as display, lighting, bioimaging, and sensing. Perovskite materials have received extensive attention due to their unique optoelectronic properties, such as high luminescence efficiency, narrow emission spectrum, adjustable bandgap, etc. However, perovskite materials have the problem of poor stability and are prone to decomposition under the influence of environmental factors such as humidity, light, and temperature, which limits their practical applications.

[0003] Metal-organic framework materials (MOFs) are porous materials with a periodic network structure formed by the self-assembly of metal ions or metal clusters and organic ligands. MOFs have the advantages of high specific surface area, designable pore structure, and tunable functionality, and can provide a stable confinement environment for guest molecules. Combining perovskite with MOF to form a perovskite / MOF composite luminescent material is expected to combine the advantages of both, improve the stability of perovskite, and endow the composite material with new properties.

[0004] Based on this, developing a perovskite / MOF composite luminescent material, a preparation method thereof, and an application thereof has become an urgent technical problem to be solved by those skilled in the art. Summary of the Invention

[0005] The purpose of the present invention is to provide a perovskite / MOF composite luminescent material, a preparation method thereof, and an application thereof.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] A preparation method of a perovskite / MOF composite luminescent material, comprising the following steps:

[0009] 1. Prepare an organic ligand;

[0010] 2. Use the organic ligand obtained in step 1 as a raw material to prepare a metal-organic framework material;

[0011] 3. Use the metal-organic framework material obtained in step 2 as a raw material to prepare a perovskite / MOF composite luminescent material.

[0012] Further, in step 1, the preparation of the organic ligand specifically includes the following steps:

[0013] 1) Use sodium borohydride to reduce compound A to compound B;

[0014] Among them, the structural formula of Compound A is The structural formula of Compound B is

[0015]

[0016] 2) According to the molar ratio of Compound B to Compound C being 1:1, place the Compound B and Compound C obtained in step 1) in an organic solvent, add a catalytic amount of base, and react to obtain Compound D, which is the organic ligand;

[0017] Among them, the structural formula of Compound C is The structural formula of Compound D is

[0018]

[0019] Furthermore, in step 1), the reduction is specifically: reducing at 40 - 60 °C for 1 - 3 h.

[0020] Furthermore, in step 2), the organic solvent is one or more of CH3CN, DMF, DMI, or DMSO.

[0021] Furthermore, in step 2), the base is one or more of EtONa, PrONa, i-PrONa, or t-BuONa.

[0022] Furthermore, in step 2), the reaction is specifically: reacting at room temperature for 4 - 6 h.

[0023] Further, in step 2, the preparation of the metal-organic framework material specifically includes the following steps:

[0024] Dissolve the organic ligand obtained in step 1 and ferric chloride hexahydrate in DMF, react, centrifuge, wash with water, and dry to obtain the metal-organic framework material.

[0025] Furthermore, the molar ratio of the organic ligand to ferric chloride hexahydrate is 1:(1 - 1.5).

[0026] Furthermore, the reaction is specifically: reacting at 100 - 140 °C for 12 - 36 h.

[0027] Further, in step 3, the preparation of the perovskite / MOF composite luminescent material specifically includes the following steps:

[0028] Place the metal-organic framework material obtained in step 2 in cesium bromide, stir and react under vacuum, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material.

[0029] Furthermore, the cesium bromide is a cesium bromide solution with a volume fraction of 99.5%.

[0030] Further, the molar ratio of cesium bromide to the metal-organic framework material is (2-4):1.

[0031] Further, the vacuum stirring reaction is specifically: controlling the vacuum degree to be 10 3 ~10 -1 Pa, and carrying out vacuum stirring reaction at 70-80 °C for 12-36 h.

[0032] The second technical solution of the present invention:

[0033] The perovskite / MOF composite luminescent material prepared by the above-mentioned preparation method of the perovskite / MOF composite luminescent material.

[0034] The third technical solution of the present invention:

[0035] The application of the above-mentioned perovskite / MOF composite luminescent material in the fields of display, lighting, biological imaging, and sensing.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] The perovskite / MOF composite luminescent material provided by the present invention can maintain the fluorescence intensity above 90% within 12 months of storage days, and has good stability;

[0038] The perovskite / MOF composite luminescent material provided by the present invention has a luminous efficiency of up to 96%, and has good luminous efficiency. Description of the Drawings

[0039] By reading the following detailed description of the preferred embodiments, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present invention. Moreover, throughout the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0040] Figure 1 It is the stability detection result. Detailed Embodiments

[0041] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered a limitation of the present invention, but rather should be understood as a more detailed description of certain aspects, characteristics, and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0042] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0043] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0044] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are merely exemplary.

[0045] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0046] In the following examples, experimental operations such as centrifugation, methanol washing, water washing, drying, etc. are all conventional operations in the art and do not limit the preparation of the perovskite / MOF composite luminescent material of the present invention. Those skilled in the art can freely control the corresponding conditions according to the actual situation.

[0047] In the following examples, a method for preparing a perovskite / MOF composite luminescent material includes the following steps:

[0048] 1. Preparation of organic ligand

[0049] 1) Using sodium borohydride to reduce compound A to compound B;

[0050] Among them, the structural formula of compound A is The structural formula of compound B is

[0051]

[0052] Among them, the reduction is specifically: reducing at 40 - 60 °C for 1 - 3 h;

[0053] 2) According to the molar ratio of compound B to compound C being 1:1, place compound B and compound C obtained in step 1) in an organic solvent, add a catalytic amount of base, and react to obtain compound D, which is the organic ligand;

[0054] Among them, the structural formula of compound C is The structural formula of compound D is

[0055]

[0056] Among them, the organic solvent is one or more of CH3CN, DMF, DMI or DMSO;

[0057] Among them, the base is one or more of EtONa, PrONa, i-PrONa or t-BuONa;

[0058] Among them, the specific reaction is: react at room temperature for 4 to 6 h;

[0059] 2. Preparation of metal-organic framework material

[0060] Dissolve the organic ligand obtained in step 1 and iron(III) chloride hexahydrate in DMF, react, centrifuge, wash with water, and dry to obtain the metal-organic framework material;

[0061] Among them, the molar ratio of the organic ligand to iron(III) chloride hexahydrate is 1:(1 - 1.5);

[0062] Among them, the specific reaction is: react at 100 - 140 °C for 12 - 36 h;

[0063] 3. Preparation of perovskite / MOF composite luminescent material

[0064] Place the metal-organic framework material obtained in step 2 in cesium bromide, carry out a vacuum stirring reaction, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material;

[0065] Among them, the cesium bromide is a cesium bromide solution with a volume fraction of 99.5%;

[0066] Among them, the molar ratio of cesium bromide to the metal-organic framework material is (2 - 4):1;

[0067] Among them, the specific vacuum stirring reaction is: control the vacuum degree to be 10 3 ~10 -1 Pa, and carry out a vacuum stirring reaction at 70 - 80 °C for 12 - 36 h.

[0068] Example 1

[0069] A perovskite / MOF composite luminescent material

[0070] 1. Preparation of Organic Ligand

[0071] 1) Reduce compound A to compound B by using sodium borohydride at 50 °C for 2 h;

[0072] 2) According to the molar ratio of compound B to compound C being 1:1, place compound B and compound C obtained in step 1) in DMF, add a catalytic amount of t-BuONa, and react at room temperature for 5 h to obtain compound D, which is the organic ligand;

[0073] 2. Preparation of Metal-Organic Framework Material

[0074] According to the molar ratio of the organic ligand to ferric chloride hexahydrate being 1:1, dissolve the organic ligand obtained in step 1) and ferric chloride hexahydrate in DMF, react at 100 °C for 12 h, centrifuge, wash with water, and dry to obtain the metal-organic framework material;

[0075] 3. Preparation of Perovskite / MOF Composite Luminescent Material

[0076] According to the molar ratio of cesium bromide to the metal-organic framework material being 2:1, place the metal-organic framework material obtained in step 2) in a cesium bromide solution with a volume fraction of 99.5%, control the vacuum degree to be 10 -1 Pa, stir and react under vacuum for 12 h, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material.

[0077] Example 2

[0078] A perovskite / MOF composite luminescent material

[0079] 1. Preparation of Organic Ligand

[0080] 1) Reduce compound A to compound B by using sodium borohydride at 50 °C for 2 h;

[0081] 2) According to the molar ratio of compound B to compound C being 1:1, place compound B and compound C obtained in step 1) in DMF, add a catalytic amount of t-BuONa, and react at room temperature for 5 h to obtain compound D, which is the organic ligand;

[0082] 2. Preparation of Metal-Organic Framework Material

[0083] According to the molar ratio of the organic ligand to ferric chloride hexahydrate being 1:1.2, dissolve the organic ligand obtained in step 1) and ferric chloride hexahydrate in DMF, react at 120 °C for 24 h, centrifuge, wash with water, and dry to obtain the metal-organic framework material;

[0084] 3. Preparation of Perovskite / MOF Composite Luminescent Materials

[0085] According to the molar ratio of cesium bromide to metal-organic framework material being 3:1, place the metal-organic framework material obtained in step 2 into a cesium bromide solution with a volume fraction of 99.5%, control the vacuum degree to be 10 -1 Pa, carry out vacuum stirring reaction for 24 h, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material.

[0086] Example 3

[0087] A perovskite / MOF composite luminescent material

[0088] 1. Preparation of Organic Ligand

[0089] 1) Use sodium borohydride to reduce compound A to compound B at 50 °C for 2 h;

[0090] 2) According to the molar ratio of compound B to compound C being 1:1, place compound B and compound C obtained in step 1) into DMF, and add a catalytic amount of t-BuONa, react at room temperature for 5 h to obtain compound D, which is the organic ligand;

[0091] 2. Preparation of Metal-Organic Framework Material

[0092] According to the molar ratio of organic ligand to ferric chloride hexahydrate being 1:1.5, dissolve the organic ligand obtained in step 1 and ferric chloride hexahydrate in DMF, react at 140 °C for 36 h, centrifuge, wash with water, and dry to obtain the metal-organic framework material;

[0093] 3. Preparation of Perovskite / MOF Composite Luminescent Materials

[0094] According to the molar ratio of cesium bromide to metal-organic framework material being 4:1, place the metal-organic framework material obtained in step 2 into a cesium bromide solution with a volume fraction of 99.5%, control the vacuum degree to be 10 -1 Pa, carry out vacuum stirring reaction for 36 h, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material.

[0095] Comparative Example 1

[0096] A perovskite / MOF composite luminescent material

[0097] 1. Preparation of Metal-Organic Framework Material

[0098] The metal-organic framework material was obtained by dissolving terephthalic acid (organic ligand) and ferric chloride hexahydrate in DMF according to the molar ratio of 1:1.2, reacting at 120 °C for 24 h, centrifuging, washing with water, and drying.

[0099] 2. Preparation of perovskite / MOF composite luminescent material

[0100] The metal-organic framework material obtained in step 1 was placed in a cesium bromide solution with a volume fraction of 99.5% according to the molar ratio of cesium bromide to the metal-organic framework material of 3:1, and the vacuum was controlled to be 10 -1 Pa, and vacuum stirring reaction was carried out for 24 h, centrifuging, washing with methanol, washing with water, and drying to obtain the perovskite / MOF composite luminescent material.

[0101] Comparative Example 2

[0102] A perovskite / MOF composite luminescent material

[0103] 1. Preparation of metal-organic framework material

[0104] The metal-organic framework material was obtained by dissolving 2,2'-bipyridine (organic ligand) and ferric chloride hexahydrate in DMF according to the molar ratio of 1:1.2, reacting at 120 °C for 24 h, centrifuging, washing with water, and drying.

[0105] 2. Preparation of perovskite / MOF composite luminescent material

[0106] The metal-organic framework material obtained in step 1 was placed in a cesium bromide solution with a volume fraction of 99.5% according to the molar ratio of cesium bromide to the metal-organic framework material of 3:1, and the vacuum was controlled to be 10 -1 Pa, and vacuum stirring reaction was carried out for 24 h, centrifuging, washing with methanol, washing with water, and drying to obtain the perovskite / MOF composite luminescent material.

[0107] Comparative Example 3

[0108] A luminescent material

[0109] 1. Preparation of organic ligand

[0110] 1) Compound A was reduced to compound B by using sodium borohydride at 50 °C for 2 h.

[0111] 2) Compound B and compound C obtained in step 1 were placed in DMF according to the molar ratio of 1:1, and a catalytic amount of t-BuONa was added, and the reaction was carried out at room temperature for 5 h to obtain compound D, that is, the organic ligand.

[0112] 2. Preparation of Metal-Organic Framework Materials

[0113] Dissolve the organic ligand obtained in Step 1 and ferric chloride hexahydrate in DMF according to a molar ratio of the organic ligand to ferric chloride hexahydrate of 1:1.2, react at 120 °C for 24 h, centrifuge, wash with water, and dry to obtain the metal-organic framework material, that is, the luminescent material.

[0114] Detect the stability of the luminescent materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the stability test results are as Figure 1 shown;

[0115] It can be Figure 1 seen that the fluorescence intensity of a perovskite / MOF composite luminescent material provided by the present invention can be maintained above 90% within 12 months of storage days, having good stability. However, changing the organic ligand in the metal-organic framework material and omitting the composite of perovskite will both lead to a significant decrease in fluorescence intensity within 12 months of storage days, that is, a significant decrease in stability.

[0116] Detect the luminous efficiency of the luminescent materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the luminous efficiency test results are shown in Table 1;

[0117] Table 1 Luminous Efficiency

[0118]

[0119] From the data in Table 1, the luminous efficiency of a perovskite / MOF composite luminescent material provided by the present invention can reach 96%, having good luminous efficiency. However, changing the organic ligand in the metal-organic framework material and omitting the composite of perovskite will both lead to a significant decrease in the luminous efficiency of the luminescent material.

[0120] 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 them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: the specific implementation manners of the present invention can still be modified or equivalently replaced, and any modification or equivalent replacement without departing from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A preparation method of a perovskite / MOF composite luminescent material, characterized in that, It includes the following steps:

1. Prepare an organic ligand; 2. Use the organic ligand obtained in step 1 as a raw material to prepare a metal-organic framework material; 3. Use the metal-organic framework material obtained in step 2 as a raw material to prepare a perovskite / MOF composite luminescent material.

2. The preparation method of a perovskite / MOF composite luminescent material according to claim 1, wherein, In step 1, the preparation of the organic ligand specifically includes the following steps: 1) Reduce compound A to compound B using sodium borohydride; Among them, the structural formula of compound A is The structural formula of compound B is 2) According to the molar ratio of compound B to compound C being 1:1, place the compound B obtained in step 1) and compound C in an organic solvent, add a catalytic amount of base, and react to obtain compound D, which is the organic ligand; Among them, the structural formula of compound C is The structural formula of compound D is 3. The preparation method of a perovskite / MOF composite luminescent material according to claim 2, wherein In step 1), the reduction is specifically: reduce at 40 - 60 °C for 1 - 3 h.

4. The preparation method of a perovskite / MOF composite luminescent material according to claim 2, characterized in that, In step 2), the organic solvent is one or more of CH3CN, DMF, DMI, or DMSO; the base is one or more of EtONa, PrONa, i-PrONa, or t-BuONa; the reaction is specifically: react at room temperature for 4 - 6 h.

5. The preparation method of a perovskite / MOF composite luminescent material according to claim 1, characterized in that, In step 2, the preparation of the metal-organic framework material specifically includes the following steps: Dissolve the organic ligand obtained in step 1 and ferric chloride hexahydrate in DMF, react, centrifuge, wash with water, and dry to obtain the metal-organic framework material.

6. The preparation method of a perovskite / MOF composite luminescent material according to claim 5, wherein, The molar ratio of the organic ligand to ferric chloride hexahydrate is 1:(1 - 1.5); the reaction is specifically: react at 100 - 140 °C for 12 - 36 h.

7. The preparation method of a perovskite / MOF composite luminescent material according to claim 1, wherein In step 3, the preparation of the perovskite / MOF composite luminescent material specifically includes the following steps: Place the metal-organic framework material obtained in step 2 in cesium bromide, stir and react under vacuum, centrifuge, wash with methanol, wash with water, and dry to obtain the perovskite / MOF composite luminescent material.

8. The preparation method of a perovskite / MOF composite luminescent material according to claim 7, characterized in that, The cesium bromide is a cesium bromide solution with a volume fraction of 99.5%; the molar ratio of the cesium bromide to the metal-organic framework material is (2-4):1; the vacuum stirring reaction specifically is: controlling the vacuum degree to be 10 3 ~10 -1 Pa, and carrying out a vacuum stirring reaction at 70-80 °C for 12-36 h.

9. A perovskite / MOF composite luminescent material prepared by the preparation method of the perovskite / MOF composite luminescent material according to any one of claims 1 - 8.

10. An application of the perovskite / MOF composite luminescent material according to claim 9 in the fields of display, lighting, biological imaging, and sensing.

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