Preparation method of low-cost, easy-to-form flexible magneto-optical composite material

Abstract

The application discloses a preparation method of a low-cost and easy-to-form flexible magneto-optical composite material, adopts in-situ symbiotic technology to uniformly disperse Fe3O4 or CoFe2O4 or NiFe2O4 nanoparticles which have strong magneto-optical effects and are extremely easy to agglomerate in ZIF-8 with fixed pores, and uses PgC5Cu to modify the ZIF-8 surface as a bridging agent, so that the ZIF-8 is uniformly dispersed in PMMA, and a composite material with excellent magneto-optical properties is successfully constructed. The innovative design not only maintains the original structural stability and optical transparency of the material, but also endows the material with unprecedented flexibility and processability, which provides the possibility for realizing the light weight, portability and flexibility of magneto-optical devices. Compared with traditional pure inorganic magneto-optical crystals, magneto-optical glasses and other materials, the application has the advantages of simple preparation method, short production cycle, significantly reduced energy consumption and cost, easy forming, high flexibility and the like, so that the application can adapt to more extensive application scenarios.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flexible magneto-optical composite materials, and particularly relates to a preparation method of a low-cost and easy-to-form flexible magneto-optical composite material. BACKGROUND

[0002] In the field of optical information, magneto-optical materials, as a kind of key functional materials, have been widely used in the development of various high-performance devices such as modulators, isolators, circulators, magneto-optical switches and sensors due to their unique magneto-optical effects such as Faraday rotation effect. These devices play an irreplaceable role in communication, laser technology, military and national defense and other important fields. At present, bismuth-doped rare earth iron garnet (BRIG) crystals have become one of the most widely used magneto-optical materials due to their excellent transmittance and significant Faraday effect in the near-infrared region, which has promoted the rapid development of optical communication, laser radar and Internet of Things technologies. At the same time, in response to the demand for visible to near-infrared band, researchers have developed magneto-optical crystals such as terbium gallium garnet (TGG), terbium scandium aluminum garnet (TSAG) and potassium terbium fluoride (KTF), which provide efficient high-power optical isolation solutions for industrial laser systems. In addition, with the rise of terahertz technology, the development of terahertz band magneto-optical crystals such as terbium erbium bismuth rare earth iron garnet (TbErBi:RIG), cerium fluoride (CeF3), holmium ferrite (HoFeO3) and indium antimonide (InSb) has further expanded the application range of magneto-optical materials, which are applied to new generation of magneto-optical devices such as terahertz magnetic polarization conversion, magneto-optical sensors / imagers, non-reciprocal phase shifters and isolators. Another indispensable magneto-optical material, magneto-optical glass, such as terbium-doped, cerium-doped and lead borate, has a broad application prospect in magneto-optical waveguides, optical fibers, modulators and optical fiber current sensors due to its unique performance advantages.

[0003] Although magneto-optical crystals and glass materials play an important role in traditional applications, there are still several core challenges to be solved. First, traditional crystal and glass magneto-optical materials often have long preparation cycles, high energy consumption and high material preparation costs. Second, crystal and glass magneto-optical materials have rigid structures, are difficult to form, and are not easy to make into special devices. Most importantly, when designing integrated optical systems, it is difficult to achieve integration of optical elements on a very small scale due to the limitations of the physical properties of traditional crystal materials and processing technology. If the particle size of the magnetic base element is prepared small enough and highly uniform dispersion in a transparent polymer, it is possible to obtain a high-transparency and strong magneto-optical material.

[0004] The patent first proposes a low-cost, easy-to-form flexible magneto-optical material, disperses Fe3O4 or CoFe2O4 or NiFe2O4 with strong magneto-optical effect in ZIF-8, and then realizes the uniform dispersion of the nanoparticles with strong magneto-optical effect in the transparent polymer material through PgC5Cu metal organic nanocapsule as the bridging agent between MOF and polymer in steps, prepares a high-transparency flexible magneto-optical composite material, and discusses the optical, magnetic and magneto-optical properties of the flexible magneto-optical composite material. The material successfully combines flexibility and significant magneto-optical effect, breaks the rigid binding of traditional magneto-optical materials, and is expected to be used for developing low-cost, high-integration and special-shaped new magneto-optical devices. SUMMARY

[0005] In view of the problems of long preparation period, high cost, difficult forming, difficulty in making special devices, and difficulty in optical integration of traditional crystal and glass magneto-optical materials, the application provides a low-cost, easy-to-form flexible inorganic-polymer composite magneto-optical material, a preparation method and application thereof. Fe3O4 or CoFe2O4 or NiFe2O4 with strong magneto-optical effect is dispersed in ZIF-8 by co-precipitation, and then PgC5Cu metal organic nanocapsule is used as a bridging agent between MOF and polymer to realize the uniform dispersion of nanoparticles with strong magneto-optical effect in transparent polymer material in steps. The high-transparency flexible magneto-optical composite material is prepared by forming in a specific mold after solvent volatilization. The composite material is expected to be applied in optical fiber communication, integrated optical devices, miniaturization and new special-shaped magneto-optical devices.

[0006] To achieve the above-mentioned application purposes, the application adopts the following technical solutions:

[0007] A low-cost, easy-to-form flexible magneto-optical composite material, the molecular formula of the composite material is: AB2O4-ZIF-8@PgC5Cu / PMMA, wherein A is Fe, Co, Ni; B is Fe. The AB2O4 nanoparticles belong to cubic crystal system, and the space group is . Specifically, the flexible magneto-optical composite material is Fe3O4-ZIF-8@PgC5Cu / PMMA or CoFe2O4-ZIF-8@PgC5Cu / PMMA or NiFe2O4-ZIF-8@PgC5Cu / PMMA; wherein the Fe3O4 or CoFe2O4 or NiFe2O4 nanoparticles are uniformly dispersed in ZIF-8 with fixed pores, and PgC5Cu is used to modify the surface of ZIF-8 as a bridging agent, so that the nanoparticles are uniformly dispersed in PMMA, and a flexible magneto-optical composite material is successfully constructed.

[0008] A low-cost, easy-to-form flexible magneto-optical composite material, comprising the following specific steps:

[0009] (1) Preparation of inorganic-organic nanocomposites: FeSO4·7H2O, (CH3COO)2Zn·2H2O (molar ratio of FeSO4·7H2O:(CH3COO)2Zn·2H2O not more than 0.43 / 0.55) were added to an appropriate amount of deionized water and mixed uniformly to prepare solution A; 2-methylimidazole C4H6N2 was added to an appropriate amount of deionized water and mixed uniformly to prepare solution B; solution B was quickly poured into solution A and stirred for 30 min, then washed with water, methanol, dichloromethane (DCM) three times in turn, and the sample Fe3O4-ZIF-8 was sealed with DCM, abbreviated as Fe-ZIF-8;

[0010] (2) Preparation of raw materials CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8: FeSO4·7H2O, Co(NO3)2·6H2O or Ni(NO3)2·6H2O, (CH3COO)2Zn·2H2O were added to deionized water and mixed uniformly to prepare solution C; 2-methylimidazole was added to deionized water and mixed uniformly to prepare solution D; solution D was quickly poured into solution C and stirred for 30 min, then transferred to a reaction kettle containing a polytetrafluoroethylene liner, heated at 120°C for 2 h, cooled to room temperature, then washed with water, methanol, dichloromethane three times in turn, and the sample CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8 was sealed with dichloromethane;

[0011] (3) Preparation of organic-inorganic polymer flexible magneto-optical composite material: two raw materials were accurately weighed according to the mass ratio of pentyl o-phenylcopper PgC5Cu to Fe3O4-ZIF-8 or CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8 1:20, and were placed in centrifuge tubes A and B respectively. Dichloromethane (DCM) was added to centrifuge tube B in a mass ratio of 1:10 and was ultrasonically mixed. DCM was added to centrifuge tube A in a mass ratio of 1:5. After PgC5Cu was dissolved, it was added to the sample in centrifuge tube B. After ultrasonic reaction for 3 min, centrifugation was performed. After DCM washing for 3 times, the sample Fe3O4-ZIF-8@PgC5Cu or CoFe2O4-ZIF-8@PgC5Cu or NiFe2O4-ZIF-8@PgC5Cu was sealed with DCM. Then, the DCM-sealed PgC5Cu modified AB2O4-ZIF-8 was added to the polymethyl methacrylate (PMMA) solution (dissolved and prepared according to 1 g PMMA / 5 ml DCM) in a mass ratio of the sample Fe3O4-ZIF-8@PgC5Cu or CoFe2O4-ZIF-8@PgC5Cu or NiFe2O4-ZIF-8@PgC5Cu to PMMA solution (0.003:1, 0.005:1, 0.01:1, 0.015:1). After stirring uniformly, the AB2O4-ZIF-8@PgC5Cu / PMMA flexible material dissolved in DCM solvent was prepared.

[0012] Further, the reaction conditions in steps (1) and (2) are synthesized at room temperature.

[0013] Further, the pentyl o-phenylcopper PgC5Cu is synthesized according to the literature (Engineering Plasticization Resistant Gas Separation Membranes Using Metal-Organic Nanocapsules. DOI: 10.1039 / d0sc01498b).

[0014] Further, after the dichloromethane solvent volatilizes, the flexible material can be solidified and formed. The flexible material can be used to prepare special-shaped magneto-optical elements according to the requirements of special-shaped magneto-optical devices.

[0015] Further, the AB2O4-ZIF-8@PgC5Cu / PMMA, wherein A is Co, Ni; B is Fe. The synthesis of the composite material is as follows: accurately weigh FeSO4·7H2O, (CH3COO)2Zn·2H2O, Co(NO3)2·6H2O or Ni(NO3)2·6H2O (molar ratio FeSO4·7H2O + Co(NO3)2·6H2O: (CH3COO)2Zn·2H2O is not more than 0.43 / 0.55 or molar ratio FeSO4·7H2O + Ni(NO3)2·6H2O: (CH3COO)2Zn·2H2O is not more than 0.43 / 0.55) in a beaker, add an appropriate amount of deionized water and mix uniformly to prepare solution A; accurately weigh C4H6N2 in a beaker, add an appropriate amount of deionized water and mix uniformly to prepare solution B; quickly pour solution B into solution A, stir for 30 min, then transfer to a polytetrafluoroethylene liner, react in a reaction kettle at 120 DEG C for 2 h, and then wash with water, methanol and dichloromethane (DCM) for three times respectively, and then store the sample with DCM;

[0016] Further, the composite material is expected to be applied in optical fiber communication, integrated optical devices, miniaturization and new-shaped magnetic-optical devices.

[0017] The present application uses in-situ symbiotic technology to uniformly disperse Fe3O4 or CoFe2O4 or NiFe2O4 nanoparticles which have strong magneto-optical effect but are prone to agglomeration in MOF (metal organic framework ZIF-8) with fixed pores, and modifies the surface of ZIF-8 with PgC5Cu (a specific configuration of copper complex, a bridging agent of ZIF-8 and PMMA), so that it is uniformly dispersed in PMMA, and a composite material with excellent magneto-optical properties is successfully constructed. This innovative design not only maintains the original structural stability and optical transparency of the material, but also endows it with unprecedented flexibility and processability, which provides the possibility for the lightweight, portable and flexible magneto-optical devices. Compared with traditional pure inorganic magneto-optical crystals and magneto-optical glasses, the present application has the advantages of simple preparation method, short production cycle, significantly reduced energy consumption and cost, easy molding, high flexibility and the like, so that it can adapt to more extensive application scenarios.

[0018] The present application has the following advantages:

[0019] (1) The flexible magneto-optical composite material AB2O4-ZIF-8@PgC5Cu / PMMA prepared by the present application has an optical transmittance of up to 80% in the 800-1500 nm waveband.

[0020] (2) The flexible magneto-optical composite material AB2O4-ZIF-8@PgC5Cu / PMMA prepared by the present invention has low preparation cost and short cycle, and also exhibits excellent magnetic and optical properties, providing a high-performance and low-cost solution for fields such as magneto-optics and optical integration.

[0021] (3) The flexible magneto-optical composite material AB2O4-ZIF-8@PgC5Cu / PMMA prepared by the present invention is unique in that the preparation process is simple and efficient. It can be directly molded without additional processing steps after the solvent (DCM) has naturally evaporated, showing excellent self-assembly performance and material molding convenience. Attached Figure Description

[0022] Figure 1 X-ray diffraction (XRD) spectra of ZIF-8, Fe-ZIF-8, and Fe-ZIF-8@PgC5Cu powders;

[0023] Figure 2 Raman spectra of ZIF-8, Fe-ZIF-8, and Fe3O4 powders;

[0024] Figure 3 xFe-ZIF-8@PgC5Cu / PMMA(x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5, 10, 15×10 -3 VSM spectrum of the thin film at room temperature;

[0025] Figure 4 xFe-ZIF-8@PgC5Cu / PMMA(x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5, 10, 15×10 -3 Transmission spectra of thin films and pure PMMA thin films;

[0026] Figure 5 xFe-ZIF-8@PgC5Cu / PMMA(x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5×10 -3 The Faraday rotation angle of the thin film at 1064 nm;

[0027] Figure 6 xFe-ZIF-8@PgC5Cu / PMMA(x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5×10 -3 The Faraday rotation angle of the thin film at 1550 nm;

[0028] Figure 7 X-ray diffraction (XRD) spectra of NiFe2O4-ZIF-8 and CoFe2O4-ZIF-8 powders;

[0029] Figure 8VSM spectra of Fe-ZIF-8, NiFe2O4-ZIF-8 and CoFe2O4-ZIF-8 powders before and after modification by PgC5Cu at room temperature;

[0030] Figure 9 The specific Faraday rotation angles of xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ), xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) and PMMA at 1064 nm and 1550 nm.

[0031] Figure 10 The specific Faraday rotation angles of xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) and xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) at 1064 nm and 1550 nm. DETAILED DESCRIPTION

[0032] In order to make the content of the present application more convenient to understand, the technical solutions of the present application will be further described below in combination with the embodiments of specific examples, but the present application is not limited to the examples given here.

[0033] Embodiment case 1

[0034] A preparation method of a low-cost, easy-to-form flexible magneto-optical composite material Fe-ZIF-8@PgC5Cu / PMMA, the specific steps are as follows:

[0035] (1) Preparation of inorganic-organic nanocomposite: 0.43 mmol FeSO4·7H2O, 0.55 mmol (CH3COO)2Zn·2H2O were added to 5 mL of deionized water and mixed uniformly to prepare solution A; 0.55 mmol 2-methyl imidazole C4H6N2 was added to 10 mL of deionized water and mixed uniformly to prepare solution B; solution B was quickly poured into solution A and stirred for 30 min, then washed with water, methanol and dichloromethane (DCM) for three times respectively, and then the sample Fe-ZIF-8 was sealed with DCM;

[0036] (2) Preparation of organic-inorganic polymer flexible magneto-optical composite material: two kinds of raw materials were accurately weighed according to the mass ratio of pentyl o-phenylcopper PgC5Cu to Fe-ZIF-8 of 1:20, and were placed in centrifuge tubes A and B, respectively. Dichloromethane (DCM) was added to centrifuge tube B in a mass ratio of 1:10 and was ultrasonically mixed, DCM was added to centrifuge tube A in a mass ratio of 1:5, and after PgC5Cu was dissolved, it was added to the sample in centrifuge tube B. After ultrasonic reaction for 3 min, centrifugation was performed, and the sample Fe-ZIF-8@PgC5Cu was stored in DCM after being washed with DCM for 3 times. Then, the DCM-stored PgC5Cu modified Fe-ZIF-8 was added to a polymethyl methacrylate (PMMA) solution (dissolved in DCM according to 1 g PMMA / 5 ml DCM) in a mass ratio of sample to PMMA solution (0.003:1, 0.005:1, 0.01:1, 0.015:1), and was stirred uniformly to prepare a Fe-ZIF-8@PgC5Cu / PMMA flexible material dissolved in DCM solvent.

[0037] The phase of Fe-ZIF-8 and Fe-ZIF-8@PgC5Cu was characterized, and the X-ray diffraction (XRD) spectrum (see Figure 1 ) showed that the characteristic peaks of Fe-ZIF-8 and Fe-ZIF-8@PgC5Cu were consistent with those of ZIF-8, but the characteristic peaks of Fe3O4 were not obvious in the XRD spectra of Fe-ZIF-8 and Fe-ZIF-8@PgC5Cu, while the Raman spectrum (see Figure 2 ) showed that Fe-ZIF-8 had obvious characteristic peaks of Fe3O4, indicating that the material Fe3O4 was successfully compounded with ZIF-8.

[0038] Figure 3 The VSM spectrum of the xFe-ZIF-8@PgC5Cu / PMMA (x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5, 10, 15×10 -3 ) thin film at room temperature showed that the magnetic property increased with the increase of x, and when x=15×10 -3 , the magnetic property of the thin film was 0.08 emμ·g -1 .

[0039] Figure 4 The transmittance spectrum of the xFe-ZIF-8@PgC5Cu / PMMA (x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5, 10, 15×10 -3 ) thin film showed that the optical transmittance was as high as 80% in the wavelength range of 800-1500 nm.

[0040] The extinction method was used to test the xFe-ZIF-8@PgC5Cu / PMMA (x (Fe-ZIF-8@PgC5Cu: PMMA) =3, 5×10-3 ) the specific Faraday rotation angle of the film at 1064 nm, the results are shown in Figure 5 Figure 6. The saturation applied magnetic field of the film is 300 mT, and the specific Faraday rotation angle of the film is 14.08 deg·cm (Fe-ZIF-8@PgC5Cu: PMMA) -3 at 1550 nm is 4.62 deg·cm -1 -1 The optimal value of x is 0.015:1.

[0041] Embodiment 2

[0042] A preparation method of a low-cost, easy-to-form flexible magneto-optical composite material CoFe2O4-ZIF-8@PgC5Cu / PMMA, the specific steps are as follows:

[0043] (1) Preparation of inorganic-organic nanocomposite: 0.28 mmol FeSO4·7H2O, 0.14 mmol Co(NO3)2·6H2O, and 0.55 mmol (CH3COO)2Zn·2H2O were added to 5 mL of deionized water and mixed uniformly to prepare solution A; 0.55 mmol 2-methyl imidazole C4H6N2 was added to 10 mL of deionized water and mixed uniformly to prepare solution B; solution B was quickly poured into solution A and stirred for 30 min, then transferred to a reaction kettle containing a polytetrafluoroethylene liner, heated at 120°C for 2 h, and cooled to room temperature. After washing with water, methanol, and dichloromethane three times each, the sample CoFe2O4-ZIF-8 was sealed with dichloromethane.

[0044] ​​(2) Preparation of organic-inorganic polymer flexible magneto-optical composite material: two kinds of raw materials were accurately weighed according to the mass ratio of pentyl o-phenylcopper PgC5Cu to CoFe2O4-ZIF-8 of 1:20 and were placed in centrifuge tubes A and B, respectively. Dichloromethane (DCM) was added to centrifuge tube B in a mass ratio of 1:10 and was ultrasonically mixed, DCM was added to centrifuge tube A in a mass ratio of 1:5, and after PgC5Cu was dissolved, it was added to the sample in centrifuge tube B. After ultrasonic reaction for 3 min, centrifugation was performed, and after DCM washing for 3 times, the sample CoFe2O4-ZIF-8@PgC5Cu was sealed with DCM. Then, the DCM-sealed PgC5Cu modified CoFe2O4-ZIF-8 was taken in a mass ratio of 0.005:1 of the sample to PMMA solution, was added to a polymethyl methacrylate (PMMA) solution (dissolved in DCM solvent at a mass ratio of 1 g PMMA to 5 ml DCM), was uniformly stirred, and was prepared into a CoFe2O4-ZIF-8@PgC5Cu / PMMA flexible material dissolved in DCM solvent. The material was transferred to a 1 cm cuvette for Faraday rotation angle test.

[0045] The phase of CoFe2O4-ZIF-8 and CoFe2O4-ZIF-8@PgC5Cu was characterized, and X-ray diffraction (XRD) spectrum (see Figure 7 ) showed that CoFe2O4-ZIF-8 and CoFe2O4-ZIF-8@PgC5Cu had characteristic peaks of ZIF-8 and characteristic peaks of CoFe2O4, indicating that the material CoFe2O4 was successfully compounded with ZIF-8.

[0046] Figure 8 The VSM spectrum of Fe-ZIF-8, NiFe2O4-ZIF-8 and CoFe2O4-ZIF-8 powder at room temperature, CoFe2O4-ZIF-8 has larger magnetism than Fe-ZIF-8, and the saturation magnetization can reach 11.22 emμ·g -1 , and after modification of CoFe2O4-ZIF-8 by PgC5Cu, the saturation magnetization is enhanced to 14.53 emμ·g -1 .

[0047] Figure 9 The transmittance spectrum of xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ), xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) and PMMA thin film, and xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) has a high optical transmittance of up to 75% in the wavelength range of 800-1500 nm.

[0048] Figure 10 xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10) -3 ) and xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10) -3 The Faraday rotation angles at 1064 nm and 1550 nm. xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5 × 10⁻⁶) -3 The saturated applied magnetic field of the thin film is 300 mT, xCoFe2O4-ZIF-8@PgC5Cu / PMMA(x (Fe-ZIF-8@PgC5Cu: PMMA) =5×10 -3 The film has a Faraday rotation angle of 15.03 deg·cm at 1064 nm. -1 The Faraday rotation angle at 1550 nm is 5.17 deg·cm. -1 .

[0049] Implementation Case 3

[0050] A low-cost, easily formable flexible magneto-optical composite material NiFe2O4-ZIF-8@PgC5Cu / PMMA and Ni preparation method are disclosed, with the specific steps as follows:

[0051] (1) Preparation of inorganic-organic nanocomposite materials: 0.28 mmol FeSO4·7H2O, 0.14 mmol Ni(NO3)2·6H2O and 0.55 mmol (CH3COO)2Zn·2H2O were added to 5 mL of deionized water and mixed evenly to prepare solution A; 0.55 mmol 2-methylimidazolium C4H6N2 was added to 10 mL of deionized water and mixed evenly to prepare solution B; solution B was quickly poured into solution A and stirred for 30 min, then transferred to a reaction vessel with a polytetrafluoroethylene liner, heated at 120℃ for 2 h, cooled to room temperature, washed three times each with water, methanol and dichloromethane, and then sealed with dichloromethane to preserve the sample NiFe2O4-ZIF-8.

[0052] (2) Preparation of organic-inorganic polymer flexible magneto-optical composite material: two kinds of raw materials were accurately weighed according to the mass ratio of pentyl o-phenylcopper PgC5Cu to NiFe2O4-ZIF-8 of 1:20 and were placed in centrifuge tubes A and B, respectively. Dichloromethane (DCM) was added to centrifuge tube B in a mass ratio of 1:10 and was ultrasonically mixed, DCM was added to centrifuge tube A in a mass ratio of 1:5, and after PgC5Cu was dissolved, it was added to the sample in centrifuge tube B. After ultrasonic reaction for 3 min, centrifugation was performed, and after DCM washing for 3 times, the sample NiFe2O4-ZIF-8@PgC5Cu was sealed with DCM. Then, the DCM-sealed PgC5Cu modified NiFe2O4-ZIF-8 was taken in a mass ratio of 0.005:1 of the sample to PMMA solution, was added to a polymethyl methacrylate (PMMA) solution (dissolved and prepared according to 1 g PMMA / 5 ml DCM), was uniformly stirred, and was prepared into a NiFe2O4-ZIF-8@PgC5Cu / PMMA flexible material dissolved in DCM solvent. The material was transferred to a 1 cm cuvette for Faraday rotation angle test.

[0053] The phase of NiFe2O4-ZIF-8 and NiFe2O4-ZIF-8@PgC5Cu was characterized, and the X-ray diffraction (XRD) spectrum (see Figure 7 ) shows that NiFe2O4-ZIF-8 and NiFe2O4-ZIF-8@PgC5Cu have characteristic peaks of ZIF-8 and characteristic peaks of NiFe2O4, indicating that the material NiFe2O4 is successfully compounded with ZIF-8.

[0054] Figure 8 The VSM spectrum of Fe-ZIF-8, NiFe2O4-ZIF-8 and CoFe2O4-ZIF-8 powders before and after modification by PgC5Cu at room temperature, compared with Fe-ZIF-8 and CoFe2O4-ZIF-8, the magnetic property of NiFe2O4-ZIF-8 is the largest, and the saturation magnetization can reach 17.51 emμ·g -1 , and the magnetic property of NiFe2O4-ZIF-8@PgC5Cu is 16.24 emμ·g -1 .

[0055] Figure 9 The transmittance spectrum of xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ), xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) and PMMA thin films, xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3The film has an optical transmittance of up to 78% in the 800-1500 nm waveband.

[0056] Figure 10 xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) and xCoFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) at 1064 nm and 1550 nm. The specific Faraday rotation angle of the xNiFe2O4-ZIF-8@PgC5Cu / PMMA (x is 5×10 -3 ) film is 16.93 deg·cm (Fe-ZIF-8@PgC5Cu: PMMA) -1 at 1064 nm and 5.70 deg·cm -3 -1 at 1550 nm under a saturation applied magnetic field of 300 mT. -1 -1 .

[0057] The above merely describes preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.​

Claims

1. A low cost, easy-to-form flexible magneto-optic composite material, characterized by: The composite material is Fe3O4-ZIF-8@PgC5Cu / PMMA or CoFe2O4-ZIF-8@PgC5Cu / PMMA or NiFe2O4-ZIF-8@PgC5Cu / PMMA; wherein, Fe3O4 or CoFe2O4 or NiFe2O4 nanoparticles are uniformly dispersed in ZIF-8 with fixed pores, and PgC5Cu is used to modify the surface of ZIF-8 as a bridging agent, so that it is uniformly dispersed in PMMA, and a flexible magneto-optical composite material is successfully constructed.

2. A process for the preparation of a low cost, easy to shape, flexible magneto-optic composite material as claimed in claim 1, characterized in that, Comprising the following steps: (1) Preparation of raw material Fe3O4-ZIF-8: FeSO4·7H2O, (CH3COO)2Zn·2H2O are added to deionized water and mixed uniformly to prepare solution A; 2-methylimidazole is added to deionized water and mixed uniformly to prepare solution B; solution B is quickly poured into solution A and stirred for 30 min, then washed with water, methanol and dichloromethane three times each, and then the sample Fe3O4-ZIF-8 is sealed with dichloromethane; (2) Preparation of raw material CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8: FeSO4·7H2O, Co(NO3)2·6H2O or Ni(NO3)2·6H2O, (CH3COO)2Zn·2H2O are added to deionized water and mixed uniformly to prepare solution C; 2-methylimidazole is added to deionized water and mixed uniformly to prepare solution D; solution D is quickly poured into solution C and stirred for 30 min, then transferred to a reaction kettle containing a polytetrafluoroethylene liner, heated at 120°C for 2 h, cooled to room temperature, then washed with water, methanol and dichloromethane three times each, and then the sample CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8 is sealed with dichloromethane; (3) Preparation of the organic-inorganic polymer flexible magneto-optical composite material: two raw materials are accurately weighed according to the mass ratio of amyl phenyl copper PgC5Cu to Fe3O4-ZIF-8 or CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8 of 1:20, and are respectively placed in centrifugal tubes, dichloromethane is respectively added and ultrasonic mixing is performed, after PgC5Cu is dissolved, the dichloromethane dispersion liquid of Fe3O4-ZIF-8 or CoFe2O4-ZIF-8 or NiFe2O4-ZIF-8 is added, ultrasonic reaction is performed for 3 min, centrifugation is performed, dichloromethane is washed for 3 times, and then the sample Fe3O4-ZIF-8@PgC5Cu or CoFe2O4-ZIF-8@PgC5Cu or NiFe2O4-ZIF-8@PgC5Cu is sealed with dichloromethane; then the sample Fe3O4-ZIF-8@PgC5Cu or CoFe2O4-ZIF-8@PgC5Cu or NiFe2O4-ZIF-8@PgC5Cu is added into the PMMA solution, stirring is uniformly performed, and the Fe3O4-ZIF-8@PgC5Cu / PMMA or CoFe2O4-ZIF-8@PgC5Cu / PMMA or NiFe2O4-ZIF-8@PgC5Cu / PMMA flexible magneto-optical composite material dissolved in dichloromethane solvent is prepared.

3. The production method according to claim 2, characterized by, The PMMA solution in step (2) is dissolved and configured according to 1 g PMMA / 5 ml dichloromethane.

4. The production method according to claim 2, characterized by, The mass ratio of Fe3O4-ZIF-8@PgC5Cu or CoFe2O4-ZIF-8@PgC5Cu or NiFe2O4-ZIF-8@PgC5Cu to the PMMA solution in step (3) is 0.003-0.015:

1.

5. The preparation method according to claim 2, characterized in that, After the dichloromethane solvent is volatilized, the flexible magneto-optical composite material can be solidified and formed.

6. The preparation method according to claim 2, characterized in that, The flexible magneto-optical composite material can prepare a special-shaped magneto-optical element according to the requirements of a special-shaped magneto-optical device.

7. Use of a low cost, easy to shape, flexible magneto-optic composite material as claimed in claim 1 for the production of magneto-optic devices, characterized in that: The magneto-optical device includes a magneto-optical isolator, a miniaturized or integrated optical integrated device, an optical circulator or a magneto-optical modulator.

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