Preparation method and application of composite porphyrin MOFs film

Abstract

The invention relates to the technical field of optical limiting materials, in particular to a preparation method and application of a composite porphyrin MOFs film, and the preparation method comprises the following steps: carrying out functional modification on a transparent substrate, alternately soaking the functionalized transparent substrate in a metal salt solution and a porphyrin ligand solution, and preparing a porphyrin-based MOFs film on the surface of the transparent substrate; the obtained porphyrin-based MOFs film is soaked in a Pt < 2 + > salt solution, and a Pt < 2 + > ion loaded porphyrin-based MOFs film is obtained; and carrying out reduction treatment on the obtained Pt < 2 + > ion loaded porphyrin-based MOFs film, so as to obtain the Pt nanoparticle loaded metalloporphyrin MOFs film. The invention provides an effective, novel and convenient method for preparing the composite porphyrin MOFs film meeting the laser development requirement, in the preparation process, the quantity of introduced object components is large, the loading efficiency is high, the process is controllable, and meanwhile, the problems that surface active substances in an existing device are poor in adhesive force, prone to falling off and the like are solved.

Description

Technical Field

[0001] The invention relates to the technical field of optical limiting materials, and in particular to a preparation method and application of a composite porphyrin MOFs film. Background Art

[0002] Optical limiting materials are laser protection materials based on the principle of nonlinear optics. They can be used to protect human eyes and sensitive optical devices from laser damage, so they have always received widespread attention. However, the current optical limiting materials are mainly in the form of powder or block materials, which are difficult to meet the requirements of device applications. In addition, a single optical limiting material is difficult to meet the performance indicators of an ideal optical limiting material.

[0003] Metal-organic framework materials (MOFs), as an inorganic-organic hybrid material, have rich pore structures and thus have a large load capacity. Functional guest substances can be embedded in their pores to increase or enhance the performance of their main body, which provides a construction strategy and candidate materials for the preparation of composite optical limiting materials, especially porphyrin MOFs materials constructed with porphyrin ligands. However, MOFs materials mostly exist in the form of powders / blocks, which are difficult to meet the application requirements of large areas and thin films.

[0004] Therefore, there is an urgent need for a high-quality method for preparing composite MOFs films to effectively improve and adjust the performance, enhance the laser protection effect of the material, and meet the needs of laser development. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a high-quality composite porphyrin MOFs film.

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

[0007] The present invention provides a method for preparing a composite porphyrin MOFs film, comprising the following steps:

[0008] (1) functionalizing a transparent substrate, alternately immersing the functionalized transparent substrate in a metal salt solution and a porphyrin ligand solution to prepare a porphyrin-based MOFs film on the surface of the transparent substrate;

[0009] (2) The obtained porphyrin-based MOFs film was deposited on Pt 2+ Soak in a salt solution to obtain Pt 2+ Ion-loaded porphyrin-based MOFs films;

[0010] (3) The obtained Pt 2+ The ion-loaded porphyrin-based MOFs film is reduced to obtain a Pt nanoparticle-loaded metalloporphyrin MOFs film.

[0011] Furthermore, the porphyrin ligand is selected from any one of carboxyl porphyrin or pyridine porphyrin.

[0012] Furthermore, the metal salt is selected from one or more of zinc acetate and zinc nitrate.

[0013] Furthermore, the functional modification of the transparent substrate specifically refers to: forming functional groups on the surface of the transparent substrate, and the functional groups include any one or more of hydroxyl, carboxyl or pyridyl.

[0014] Furthermore, the transparent substrate is a composite of one or more of quartz glass, conductive glass, PDMS, PMMA, and plastic.

[0015] Furthermore, the Pt 2+ Salt is K 2 PtCl 4 .

[0016] Furthermore, the reduction treatment is soaking in a reducing agent or treating with a reducing gas.

[0017] Furthermore, the reducing agent is formaldehyde; the reducing gas is H 2 .

[0018] Furthermore, the composite porphyrin MOFs film prepared by any of the above-mentioned preparation methods is used as an optical limiting device or in the preparation of an optical limiting device.

[0019] Compared with the prior art, the present invention provides an effective, novel and convenient method for preparing a composite porphyrin MOFs film that meets the needs of laser development. During the preparation process, a large amount of guest components are introduced, the loading efficiency is high, and the process is controllable. At the same time, the problems of poor adhesion and easy shedding of surfactants in existing devices are solved, providing broad prospects for its application in the fields of optical limiting devices and other devices.

[0020] Instruction Manual

[0021] Figure 1 This is the powder diffraction pattern of PtNPs@ZnTCPP(Pt) prepared in Example 1.

[0022] Figure 2 This is the SEM image of PtNPs@ZnTCPP(Pt) prepared in Example 1.

[0023] Figure 3 This is the Z-scan curve of PtNPs@ZnTCPP(Pt) prepared in Example 1.

[0024] Figure 4Z-scan curves of ZnTCPP, Pt@ZnTCPP and Pt NPs@ZnTCPP(Pt) prepared in Example 1. DETAILED DESCRIPTION

[0025] The technical scheme of the present invention is further described below in conjunction with specific examples. It should be understood that the following examples are only exemplary descriptions and explanations of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0026] Unless otherwise stated, the raw materials and reagents described in the examples are commercially available products, or are prepared by methods known to those skilled in the art, and will not be described in detail in the present invention.

[0027] Example 1

[0028] 1) Preparation of PtNPs@ZnTCPP(Pt) optical limiting devices

[0029] First, prepare 2mmol / L NaOH / H 2 O 2 (volume ratio 3:1) mixed aqueous solution for later use. Use distilled water and anhydrous ethanol to clean the quartz glass in turn to remove the oil and impurities on the surface of the substrate. Then soak the substrate in 2mmol / L NaOH / H 2 O 2 The mixed aqueous solution was heated in a water bath at 80° C. for 30 minutes. The substrate after the water bath was then rinsed with distilled water and anhydrous ethanol in sequence, and the rinsed substrate was blown dry with nitrogen to prepare hydroxyl-modified quartz glass.

[0030] Weigh zinc acetate (Zn(OAc) 2 ) and 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP), each of which was dissolved in an ethanol solution to prepare 500 ml of a solution with a concentration of 1 mmol / L and 0.05 mmol / L, respectively. The above hydroxyl-modified quartz glass was placed in Zn(OAc) 2 ethanol solution and TCPP ethanol solution in sequence; among them, in Zn(OAc) 2 The immersion time in the ethanol solution is 10 minutes, and after the reaction, the film is immersed in anhydrous ethanol for 3 minutes to remove the residual reaction raw materials; the immersion time in the TCPP ethanol solution is 20 minutes, and after the reaction, the film is immersed in anhydrous ethanol for 3 minutes to remove the residual reaction raw materials; the above operation is a complete cycle, which is repeated 10 times to obtain a ZnTCPP film of a certain thickness.

[0031] The ZnTCPP film successfully prepared above was 2 PtCl4 The film was immersed in K 2 PtCl 4 During the immersion process, a portion of Pt 2+ The ions are wrapped between MOFs sheets, and some Pt 2+ The ions coordinate with the nitrogen atom in the porphyrin center to form Pt 2+ Ion-loaded Pt@ZnTCPP thin films.

[0032] The Pt@ZnTCPP film was immersed in formaldehyde solution for reduction treatment for 6 hours. 2+ The ions are reduced to Pt nanoparticles, and Pt NPs@ZnTCPP (Pt) with highly dispersed Pt nanoparticles is obtained, that is, the composite porphyrin MOFs film of the present invention.

[0033] 2) Basic characterization of PtNPs@ZnTCPP(Pt) optical limiting devices

[0034] The Pt NPs@ZnTCPP(Pt) obtained in 1) was characterized by powder diffraction and scanning electron microscopy (SEM). Figure 1 and Figure 2 shown.

[0035] 3) Optical limiting performance test

[0036] The Z-scan curve of PtNPs@ZnTCPP(Pt) obtained in 1) above was tested by Z-scan test system. Figure 3 shown.

[0037] The ZnTCPP, Pt@ZnTCPP and PtNPs@ZnTCPP(Pt) prepared in 1) were tested by Z-scan test system. The obtained Z-scan curves are shown in Figure 4 shown.

[0038] Although the specific implementation modes of the present invention are described above, those skilled in the art should understand that the specific implementation modes described are only illustrative and are not intended to limit the scope of the present invention. Any modifications and changes made by those skilled in the art in accordance with the spirit of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a composite porphyrin MOFs film, characterized in that: The following steps are involved: (1) functionalizing a transparent substrate, alternately immersing the functionalized transparent substrate in a metal salt solution and a porphyrin ligand solution to prepare a porphyrin-based MOFs film on the surface of the transparent substrate; (2) The obtained porphyrin-based MOFs film was deposited on Pt 2+ Soak in a salt solution to obtain Pt 2+ Ion-loaded porphyrin-based MOFs films; (3) The obtained Pt 2+ The ion-loaded porphyrin-based MOFs film is reduced to obtain a Pt nanoparticle-loaded metalloporphyrin MOFs film.

2. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The porphyrin ligand is selected from any one of carboxyl porphyrin and pyridine porphyrin.

3. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The metal salt is selected from one or more of zinc acetate and zinc nitrate.

4. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The functional modification of the transparent substrate specifically refers to: forming a functional group on the surface of the transparent substrate, and the functional group includes any one or more of a hydroxyl group, a carboxyl group or a pyridyl group.

5. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The transparent substrate is a composite of one or more of quartz glass, conductive glass, PDMS, PMMA and plastic.

6. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The Pt 2+ The salt is K2PtCl4.

7. The method for preparing a composite porphyrin MOFs film according to claim 1, characterized in that: The reduction treatment is soaking in a reducing agent or treating with a reducing gas.

8. The method for preparing a composite porphyrin MOFs film according to claim 7, characterized in that: The reducing agent is formaldehyde; the reducing gas is H2.

9. Use of the composite porphyrin MOFs film prepared by the preparation method according to any one of claims 1 to 8 as an optical limiting device or in the preparation of an optical limiting device.

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