阅读说明：本技术 一种石墨烯酞菁复合材料及其制备方法 (Graphene phthalocyanine composite material and preparation method thereof ) 是由 王春锐 陈星� 邵俊峰 陈飞 于 2019-09-26 设计创作，主要内容包括：本发明提供一种石墨烯酞菁复合材料及其制备方法,方法包括：将具有规则排布孔结构的改性石墨烯材料和改性酞菁材料复合,得到石墨烯酞菁复合材料。上述方法制得的复合材料中改性酞菁材料也有序排布,如规则矩阵方式或六角网格结构排布,进而使得复合材料的光限幅性能优异。复合材料在入射能量为1.5J/cm<Sup>2</Sup>时发生较明显光限幅现象,输出幅值为0.8J/cm<Sup>2</Sup>,非线性衰减倍率约7倍；或在入射能量为3.4J/cm<Sup>2</Sup>时发生较明显光限幅现象,输出幅值为1.4J/cm<Sup>2</Sup>,非线性衰减倍率约4倍；或入射能量为2J/cm<Sup>2</Sup>时发生较明显光限幅现象,输出幅值为1.1J/cm<Sup>2</Sup>,非线性衰减倍率约5倍。(The invention provides a graphene phthalocyanine composite material and a preparation method thereof, wherein the method comprises the step of compounding a modified graphene material with a regular arrangement hole structure and the modified phthalocyanine material to obtain the graphene phthalocyanine composite material, wherein the modified phthalocyanine material in the composite material prepared by the method is also orderly arranged, such as a regular matrix mode or a hexagonal grid structure, so that the optical amplitude limiting performance of the composite material is excellent, the composite material generates an obvious optical amplitude limiting phenomenon when the incident energy is 1.5J/cm 2 , the output amplitude is 0.8J/cm 2 , and the nonlinear attenuation ratio is about 7 times, or generates an obvious optical amplitude limiting phenomenon when the incident energy is 3.4J/cm 2 , the output amplitude is 1.4J/cm 2 and the nonlinear attenuation ratio is about 4 times, or generates an obvious optical amplitude limiting phenomenon when the incident energy is 2J/cm 2 , the output amplitude is 1.1J/cm 2 , and the nonlinear attenuation ratio is about 5 times.)

1. a preparation method of a graphene phthalocyanine composite material comprises the following steps:

And compounding the modified graphene material with the regular arrangement hole structure and the modified phthalocyanine material to obtain the graphene phthalocyanine composite material.

2. the preparation method according to claim 1, wherein the modified graphene material with the regularly-arranged pore structure is prepared by the following method:

A) Providing a template material with a regularly arranged pore structure;

B) Compounding a graphene material on the template material;

C) Preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;

D) removing the template to obtain the graphene material with the regularly-arranged pore structure;

E) and carrying out functionalization treatment on the graphene material with the regularly-arranged pore structure to obtain the modified graphene material with the regularly-arranged pore structure.

3. the preparation method according to claim 2, wherein the graphene material with the regularly arranged pore structure is functionalized by one or more of carboxylation, hydroxylation, oxidation, chlorination and fluorination.

4. The method of claim 1, wherein the modified phthalocyanine material is prepared by:

carrying out functionalization treatment on the phthalocyanine material to obtain a modified phthalocyanine material;

The phthalocyanine material is functionalized with one or more of amination, acylation, oxidation, hydroxylation, and carboxylation.

5. The production method according to claim 4, wherein the phthalocyanine material is selected from a metal phthalocyanine and/or a substituted phthalocyanine having a substituent; the substituents are selected from alkyl, amino and methoxy.

6. the preparation method according to claim 3, wherein the temperature of the compounding is 0-100 ℃; the compounding time is 1-100 min.

7. A graphene phthalocyanine composite material prepared by the preparation method of any one of claims 1 to 6, which comprises a modified graphene material with a regularly-arranged pore structure;

and a modified phthalocyanine material compounded at the regularly arranged pore structure.

8. The composite material according to claim 7, wherein the pores of the modified graphene material with the regular pore arrangement structure have a pore diameter of 0.1nm to 100 μm; the arrangement mode of the holes on the modified graphene material with the regular arrangement hole structure is regular matrix arrangement or hexagonal grid structure arrangement.

Technical Field

the invention belongs to the technical field of materials, and particularly relates to a graphene phthalocyanine composite material and a preparation method thereof.

background

The laser protection technology can be used for protecting human eyes and photoelectric detectors from being damaged by strong laser, and is significant in industrial and military applications. Aiming at the characteristic of high-power laser, the nonlinear laser protection material has the advantages of high weak light transmittance and low strong light transmittance (namely the light amplitude limiting characteristic), and has the most development potential. Among them, phthalocyanine materials have good transparency, wide protection spectrum, nanosecond-level response time, and are widely concerned. For a protected optical system, the improvement of the linear transmittance of the protective material is beneficial to the improvement of the imaging quality; the nonlinear attenuation factor is improved, so that the protection capability is enhanced. The main problems of the prior phthalocyanine materials are that: under the condition of high linear transmittance, the nonlinear attenuation factor is still low, and the practical requirement cannot be met. The protective capability can be improved by introducing a substituent containing a conjugated structure into a phthalocyanine structure, but related researches are not systematic enough, and the structure-activity relationship between the structure and the function is not clear.

Graphene has certain nonlinear optical properties, and the optical limiting characteristics of the graphene phthalocyanine composite material are reported. However, the composite material system is generally simple composite, and whether the ordered arrangement of the two materials under the microstructure can further improve the performance of the material is not studied.

Disclosure of Invention

In view of the above, the present invention provides a graphene phthalocyanine composite material and a preparation method thereof, and the method can obtain the graphene phthalocyanine composite material in an ordered arrangement, and the composite material has excellent optical limiting performance.

The invention provides a preparation method of a graphene phthalocyanine composite material, which comprises the following steps:

And compounding the modified graphene material with the regular arrangement hole structure and the modified phthalocyanine material to obtain the graphene phthalocyanine composite material.

Preferably, the modified graphene material with the regularly-arranged pore structure is prepared by the following method:

A) providing a template material with a regularly arranged pore structure;

B) compounding a graphene material on the template material;

C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;

D) removing the template to obtain the graphene material with the regularly-arranged pore structure;

E) And carrying out functionalization treatment on the graphene material with the regularly-arranged pore structure to obtain the modified graphene material with the regularly-arranged pore structure.

preferably, the graphene material with the regularly arranged pore structure is functionalized by one or more of carboxylation, hydroxylation, oxidation, chlorination and fluorination.

preferably, the modified phthalocyanine material is prepared by the following method:

Carrying out functionalization treatment on the phthalocyanine material to obtain a modified phthalocyanine material;

the phthalocyanine material is functionalized with one or more of amination, acylation, oxidation, hydroxylation, and carboxylation.

preferably, the phthalocyanine material is selected from metal phthalocyanine and/or substituted phthalocyanine containing substituent groups; the substituents are selected from alkyl, amino and methoxy.

Preferably, the temperature of the compounding is 0-100 ℃; the compounding time is 1-100 min.

the invention provides a graphene phthalocyanine composite material prepared by the preparation method in the technical scheme, which comprises a modified graphene material with a regularly-arranged pore structure;

and a modified phthalocyanine material compounded at the regularly arranged pore structure.

Preferably, the pore diameter of the pores on the modified graphene material with the regularly-arranged pore structure is 0.1 nm-100 μm; the arrangement mode of the holes on the modified graphene material with the regular arrangement hole structure is regular matrix arrangement or hexagonal grid structure arrangement.

^{2 2 2 2 2 2}the invention provides a preparation method of a graphene phthalocyanine composite material, which comprises the following steps of compounding a modified graphene material with a regular arrangement hole structure and a modified phthalocyanine material to obtain the graphene phthalocyanine composite material, wherein the modified phthalocyanine material with the regular arrangement hole structure is compounded with the modified phthalocyanine material, so that the modified phthalocyanine material in the prepared composite material is also orderly arranged, and further the optical amplitude limiting performance of the composite material is excellent.

drawings

Fig. 1 is a schematic diagram of a preparation process of a graphene phthalocyanine composite material provided by the present invention;

FIG. 2 is a graph showing the optical limiting performance of the composite material prepared in example 1 of the present invention;

FIG. 3 is a graph showing the optical limiting performance of the composite material prepared in example 2 of the present invention;

FIG. 4 is a graph showing the optical limiting performance of the composite material prepared in example 3 of the present invention;

Fig. 5 is a graph showing the optical limiting performance of the composite material prepared in example 4 of the present invention.

Detailed Description

the invention provides a preparation method of a graphene phthalocyanine composite material, which comprises the following steps:

and compounding the modified graphene material with the regular arrangement hole structure and the modified phthalocyanine material to obtain the graphene phthalocyanine composite material.

Fig. 1 is a schematic diagram of a preparation process of the graphene phthalocyanine composite material provided by the invention.

in the present invention, the modified graphene material having a regularly arranged pore structure is preferably prepared according to the following method:

A) Providing a template material with a regularly arranged pore structure;

B) Compounding a graphene material on the template material;

C) Preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;

D) Removing the template to obtain the graphene material with the regularly-arranged pore structure;

E) and carrying out functionalization treatment on the graphene material with the regularly-arranged pore structure to obtain the modified graphene material with the regularly-arranged pore structure.

The invention firstly provides a template material with a regularly arranged pore structure. Wherein, the template material is preferably selected from one or more of an alumina template, a polymer template, a metal template, a silicon dioxide template and a molecular sieve template.

the polymer template can be polystyrene, polyacrylate, etc.

The metal template may be Au, Al, Cu, etc.

The aperture of the template material is preferably 0.1 nm-100 nm; more preferably 1nm to 100 nm; most preferably 10nm to 100 nm; the arrangement mode of the template material is a regular matrix arrangement mode or a hexagonal grid structure; other regular arrangements are also possible, which are not limited by the present invention.

The source of the template material is not limited in the present invention, and the template material may be commercially available or may be prepared in a manner known to those skilled in the art.

According to the present invention, the template material is prepared by one or more methods selected from electrochemical deposition, chemical polymerization, direct spin coating, physical deposition and self-assembly. The present invention is not limited to the above-described embodiments, and those skilled in the art will be familiar with the present invention.

Compounding a graphene material on the template material; the compounding mode is specifically as follows: graphene is dissolved by a solvent and then spin-coated on a template material.

According to the invention, the solvent is preferably ethanol; the ratio of graphene to ethanol is 1 g: 1-1000mL, wherein the rotation speed of the spin coating is preferably 100-10000 r/min; more preferably 500 to 9000 r/min; most preferably 1000-8000 r/min; the time for the spin coating is preferably 10s to 100 s; more preferably 20s to 80 s; most preferably 30s to 70 s.

The thickness of the spin-on graphene material is preferably 1-100 micrometers; more preferably 10-90 microns

And obtaining a template material layer and a graphene layer arranged on the template material layer after compounding.

preparing a regularly-arranged pore structure on the graphene material by adopting a chemical corrosion or laser processing mode.

Specifically, a regularly-arranged pore structure equal to the pore diameter of the template is prepared on the graphene material by using the pores of the template as a reference and adopting a chemical corrosion or laser processing mode.

the chemical corrosion is specifically corrosion by adopting a KMnO ₄ solution, the concentration of the KMnO ₄ solution is 0.01-1mol/L, the corrosion treatment time is 0.1-100min, the laser treatment parameters are specifically laser power preferably 0.01-100 w, more preferably 1-90 w, most preferably 10-80 w, the treatment time preferably 1-100 s, more preferably 10-90 s, and most preferably 20-80 s.

And removing the template to obtain the graphene material with the regularly-arranged pore structure.

The template removing method specifically comprises the following steps: preferably performing ultrasonic treatment on the treated material for 1-100 s; more preferably, the ultrasonic treatment is carried out for 10-90 s;

Or:

Dissolving the treated material by 0.01-1mol/L acid for 1-100min to remove the acid; more preferably, 0.1-0.9 mol/L acid is adopted for dissolving for 10-90 min for removal; wherein the acid is preferably an organic acid; for example, oxalic acid, citric acid, acetic acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.; the concentration of the acid is preferably 0.1-1 mol/L; more preferably 0.4 to 0.8 mol/L; most preferably 0.5 to 0.7 mol/L.

After the graphene material with the regularly arranged pore structure is obtained, the graphene material with the regularly arranged pore structure is subjected to functionalization treatment, and the modified graphene material with the regularly arranged pore structure is obtained. In the present invention, the graphene material having the regularly arranged pore structure is functionalized by one or more of carboxylation, hydroxylation, oxidation, chlorination and fluorination. In a specific embodiment, the graphene material with regularly arranged pore structures is functionalized into a carboxylated graphene material with regularly arranged pore structures.

In the invention, the temperature of the functionalization treatment is preferably 0-100 ℃, and the time is preferably 1-100 min. The concentration of the solution containing the functional group adopted in the functionalization treatment of the graphene material is preferably 0.01-10 mol/L; the volume ratio of the mass of the graphene material to the solution containing the functional group is preferably (0.01-10) g: (1-100) mL.

In the present invention, the phthalocyanine material is selected from metal phthalocyanine and/or substituted phthalocyanine containing substituent; the substituents are selected from alkyl, amino and methoxy. In a particular embodiment, the phthalocyanine material is a phthalocyanine material having amino substitution in a branch chain.

In the invention, the temperature of the phthalocyanine material functionalization tube treatment is preferably 0-100 ℃, and the time is preferably 1-100 min. The concentration of the solution containing the functional group adopted for the functionalization treatment of the phthalocyanine material is preferably 0.01-10 mol/L; the ratio of the mass of the phthalocyanine material to the volume of the solution containing the functional group is preferably (0.01-10) g: (1-100) mL.

in the invention, the mass ratio of the modified graphene material with the regularly-arranged pore structure to the modified phthalocyanine material is preferably 0.01-10: 0.01-10; the compounding temperature of the modified graphene material with the regular arrangement hole structure and the modified phthalocyanine material is preferably 0-100 ℃; the compounding time is 1-100 min.

The invention provides a graphene phthalocyanine composite material prepared by the preparation method in the technical scheme, which comprises a modified graphene material with a regularly-arranged pore structure;

and a modified phthalocyanine material compounded at the regularly arranged pore structure.

In the invention, the aperture of the pores on the modified graphene material with the regularly-arranged pore structure is 0.1 nm-100 μm; the arrangement mode of the holes on the modified graphene material with the regular arrangement hole structure is regular matrix arrangement or hexagonal grid structure arrangement.

In order to further illustrate the present invention, the following examples are provided to describe a graphene phthalocyanine composite and a preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.