CN112159413A

CN112159413A - Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof

Info

Publication number: CN112159413A
Application number: CN202010876482.2A
Authority: CN
Inventors: 陈爱华; 赵文朵
Original assignee: Yancheng Institute of Technology
Current assignee: Yancheng Institute of Technology
Priority date: 2020-08-27
Filing date: 2020-08-27
Publication date: 2021-01-01
Anticipated expiration: 2040-08-27
Also published as: CN112159413B

Abstract

The invention discloses a gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and a preparation method and application thereof, wherein the multi-element nano hybrid material is prepared by axially and covalently connecting and modifying graphene oxide by GaClTPP or/and GaClTTP, and the multi-element nano hybrid material is GaTPP-GO, GaTTP-GO or GaTPP-GO-GaTTP; wherein the GaClTPP is a 5,10,15, 20-tetraphenylgallium porphyrin complex, and the GaClTTP is a 5,10,15, 20-tetra (2-thiophene) gallium porphyrin complex. The multielement nanometer hybrid material of the invention shows excellent NLO and OL response at 532nm, wherein the nonlinear optical response capability of GaTPP-GO-GaTTP is optimal.

Description

Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of graphene composite materials, and particularly relates to a gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material, and a preparation method and application thereof.

Background

Graphene has caused a wide spectrum of research enthusiasm due to its large pi-conjugation and excellent mechanical and optoelectronic properties. Graphene can be subjected to saturation absorption in a wide spectral range due to ultra-fast carrier dynamics and efficient absorption of incident light, and the graphene dispersion has a remarkable nonlinear optical (NLO) response in 532nm nanosecond laser pulses, which means that the graphene dispersion has potential application in the field of nonlinear Optical Limiting (OL). Meanwhile, Graphene Oxide (GO), a derivative of graphene family, also has NLO and OL characteristics. Because GO has chemically active oxygen functional groups, including carboxylic and ketone groups at the GO edge, and epoxy and hydroxyl groups at the substrate, chemical modification of graphene is actually mainly by chemical modification of GO. The material shows excellent OL response at 532nm due to the efficient combination of different NLO mechanisms.

Porphyrins (TPPs) and their numerous analogs and derivatives are materials of paramount importance in chemistry, material science, physics, biology, and medicine. The porphyrin structure has high structural flexibility, and the physical, photoelectric and chemical parameters of the porphyrin structure can be adjusted in a very wide range. By means of R_xThe chemical reactivity of the Ga-Cl bond in TPPGaCl (R is a peripheral substituent in the TPP macrocycle) allows the preparation of a series of highly soluble axially substituted and bridged porphyrin complexes. In axially substituted porphyrins, the axial substituents in the porphyrin advantageously affect nonlinear optical (NLO) absorption due to the presence of dipole moments perpendicular to the macrocycle. But no study on gallium porphyrin axially functionalized graphene oxide is reported at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a gallium porphyrin axially functionalized graphene oxide multi-element nano hybrid material, and a preparation method and application thereof. Due to the effective combination of different NLO mechanisms, the materials show excellent NLO and OL response at 532nm, wherein the nonlinear optical response capability of the ternary nano hybrid material (GaTPP-GO-GaTTP) is optimal.

The invention is realized by the following technical scheme:

a gallium porphyrin axially functionalized graphene oxide multi-element nano hybrid material is prepared by modifying graphene oxide through axial covalent connection of GaClTPP or/and GaClTTP, and the multi-element nano hybrid material is GaTPP-GO, GaTTP-GO or GaTPP-GO-GaTTP; wherein, the GaClTPP is 5,10,15, 20-tetraphenylgallium porphyrin complex, and the GaClTTP is 5,10,15, 20-tetra (2-thiophene) gallium porphyrin complex; the structural formulas of GaClTPP and GaClTTP are respectively as follows:

a preparation method of gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material comprises the following steps when the multi-element nano hybrid material is GaTPP-GO:

in a DMSO solvent system, 38.8mg GaClTPP, 70mg GO, 500mg K₂CO₃Mixing and sonicating the mixture at 37 ℃; 150W power for 30min to form a homogeneous solution; stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, performing ultrasonic standing, filtering to obtain a filter cake, and respectively adding deionized water and CH into the filter cake₂Cl₂And repeatedly washing with EtOH until filtrate is colorless, and drying a filter cake in vacuum at normal temperature to obtain the GaTPP-GO.

A preparation method of gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material comprises the following steps when the multi-element nano hybrid material is GaTTP-GO:

in DMSO solvent system, 40mg GaClTTP, 70mg GO, 500mg K₂CO₃Mixing and sonicating the mixture at 37 ℃; 150W power for 30min to form a homogeneous solution; stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, performing ultrasonic standing, filtering to obtain a filter cake, and respectively adding deionized water and CH into the filter cake₂Cl₂And repeatedly washing with EtOH until filtrate is colorless, and carrying out vacuum drying on a filter cake at normal temperature to obtain the GaTTP-GO.

A preparation method of gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material comprises the following steps when the multi-element nano hybrid material is GaTPP-GO-GaTTP:

in a DMSO solvent system, 19.4mg GaClTPP, 20mg GaClTTP, 70mg GO, 500mg K₂CO₃Mixing and sonicating the mixture at 37 ℃; 150W power for 30min to form a homogeneous solution; stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, performing ultrasonic standing, filtering to obtain a filter cake, and respectively adding deionized water and CH into the filter cake₂Cl₂And repeatedly washing with EtOH until filtrate is colorless, and drying a filter cake in vacuum at normal temperature to obtain the GaTPP-GO-GaTTP.

The application of the gallium porphyrin axially functionalized graphene oxide multi-element nano hybrid material in a nonlinear optical material is characterized in that the multi-element nano hybrid material is GaTPP-GO-GaTTP.

An application of gallium porphyrin axially functionalized graphene oxide multi-element nano hybrid material in optical amplitude limiting and optical switches is disclosed, wherein the multi-element nano hybrid material is GaTPP-GO-GaTTP.

The invention has the following beneficial effects:

the invention designs and successfully prepares two kinds of metalloporphyrin GaClTPP and GaClTTP, then carries out axial covalent connection modification on the two kinds of porphyrin and Graphene Oxide (GO), synthesizes binary and ternary nano hybrid materials GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP, and proves that the two kinds of metalloporphyrin and GO are subjected to axial covalent modification. The nonlinear optical response capability and the optical amplitude limiting performance of the nano hybrid material are explored through a Z-scanning test means. The test result shows that the nonlinear optical absorption of the binary and ternary nano hybrid materials relative to the monomer is improved to a certain extent. Meanwhile, GO is modified by two porphyrins GaClTPP and GaClTTP together, so that the electron/energy transfer capability between the two porphyrins is stronger, and the nano hybrid material has more excellent nonlinear optical absorption and optical amplitude limiting performance compared with a monomer, wherein the performance of GaTPP-GO-GaTTP is the most excellent. Various research results show that the ternary nano hybrid material prepared by modifying graphene oxide with different porphyrins has potential application in related fields such as optical amplitude limiting, optical switches and the like.

Drawings

FIG. 1 is a scanning electron microscope image of GO (a), GaTPP-GO (b), GaTTP-GO (c), and GaTPP-GO-GaTTP (d);

FIG. 2 is an infrared spectrum of GO, GaClTPP, GaClTTP, GaTPP-GO, GaTTP-GO, GaTPP-GO-GaTTP;

FIG. 3 is a Raman spectrum of GO, GaTPP-GO, GaTTP-GO, GaTPP-GO-GaTTP;

FIG. 4 is a Z-scan plot of apertures for GaClTPP, GaClTTP, GO, GaTPP-GO, GaTTP-GO, and GaTPP-GO-GaTTP;

FIG. 5 is a comparison of the optical clipping performance of GaTTP-GO, GaTPP-GO and GaTPP-GO-GaTTP.

Detailed Description

The invention is described in further detail below with reference to specific embodiments and with reference to the following drawings.

Example 1

A preparation method of gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material comprises the following specific steps:

(1) preparation of Graphene Oxide (GO)

The method for preparing graphene oxide adopts a classical Hummers method. Weighing 6g of graphite powder, putting the graphite powder into a three-neck round-bottom flask with the volume of 1L, placing the round-bottom flask in an ice bath environment, sequentially adding 66mL and 60mL of concentrated phosphoric acid and concentrated sulfuric acid into the three-neck round-bottom flask, simultaneously carrying out rapid stirring in the process of adding the concentrated acid, simultaneously keeping the temperature range of the ice bath environment at 0-10 ℃, and slowly adding 30g of potassium permanganate into the three-neck flask for ten times. After potassium permanganate is completely put into the three-neck round-bottom flask, the reaction temperature is increased to 35 ℃, the reaction is carried out for 2 hours, after the reaction is carried out for 2 hours, the reaction temperature is continuously increased to 50 ℃, and the reaction is carried out for 12 hours. After the reaction was completed, the reaction product was poured into two 1L beakers filled with ice cubes and deionized water, and then a hydrogen peroxide solution was added to the beakers under stirring to remove the unreacted potassium permanganate. During the addition of the hydrogen peroxide solution, the solution color of the reaction product is changed remarkably, and the color is gradually lightened from black at the end of the reaction and finally appears golden yellow. The solution was allowed to stand, and the supernatant was removed. And (3) washing the obtained product for 3-5 times by using a 5% hydrochloric acid solution and deionized water respectively, and dialyzing and standing the obtained product after the washing is finished, wherein the standing time is about 7 days. After dialysis, ultrasound was performed. And finally, freeze-drying the dialysis product for 3d today to obtain the nano-scale graphene oxide.

(2) Preparation of 5,10,15, 20-Tetraphenylporphyrin (TPP)

150mL of propionic acid and 7.2mL of benzaldehyde are added into a three-neck flask with the volume of 500mL, stirring and heating are carried out for reflux at the temperature of 140 ℃, after the solution is refluxed, 3mL of mixed solution of freshly distilled pyrrole and 40mL of propionic acid is added into the flask through a constant pressure dropping funnel within 30min, and heating and refluxing are carried out for 60 min. During the dropwise addition of the mixed solution, the color change of the solution in the flask was colorless-yellowish brown-purple black. After the reaction is finished, 150mL of ethanol solution is added into the flask, ultrasonic treatment is carried out for 30min, and the flask is transferred to a refrigerator to be cooled for 12 h. Performing suction filtration, repeatedly washing with ethanol and n-hexane for several times until purple solid is washed out, dissolving the solid, adding silica gel powder, spin-drying, and separating and purifying by chromatographic column to obtain TPP 2g, wherein the eluent is dichloromethane: petroleum ether is 1: 3.

(3) Preparation of 5,10,15, 20-tetrakis (2-thienylporphyrin (TTP)

40mL of propionic acid, 40mL of nitrobenzene and 60mL of glacial acetic acid (solvent) are respectively added into a three-neck flask with the volume of 500mL, 4.5g of 2-thiophenecarboxaldehyde is added into the flask for ultrasonic treatment, stirring and heating reflux are carried out at 140 ℃, after the solution is refluxed, 3mL of a mixed solution of freshly distilled pyrrole and 40mL of glacial acetic acid is added into the flask through a constant-pressure dropping funnel within 30min, and heating reflux is carried out for 60 min. During the dropwise addition of the mixed solution, the color of the solution in the flask changed to yellowish-reddish brown-purplish black. After the reaction is finished, 150mL of ethanol solution is added into the flask, ultrasonic treatment is carried out for 30min, and the flask is transferred to a refrigerator to be cooled for 12 h. Performing suction filtration, repeatedly washing with ethanol and n-hexane for several times until purple solid is washed out, dissolving the solid, adding silica gel powder, spin-drying, and separating and purifying by chromatographic column to obtain TTP 2g, wherein the eluent is dichloromethane: petroleum ether is 1: 3.

(4) Preparation of 5,10,15, 20-tetraphenylgallium porphyrin complex (GaClTPP)

90mg of TPP, 500mg of anhydrous sodium acetate and 300mg of GaCl were added to the mixture, respectively₃Adding into 150mL single-neck round bottom flask, stirring with 70mL acetic acid as solvent at 120 deg.C, heating under reflux, tracking on point plate during reaction, stopping reaction when no material point is observed on silica gel plate, spin drying, extracting to obtain crude product, adding neutral Al into the extract₂O₃Spin-drying and purifying by chromatography to obtain 100mg of product (GaClTPP) with dichloromethane as eluent.

(5) Preparation of 5,10,15, 20-tetrakis (2-thienyl) gallium porphyrin complex (GaClTTP)

90mg of TTP, 500mg of anhydrous sodium acetate and 300mg of GaCl₃Adding into 150mL single-neck round bottom flask, stirring with 70mL acetic acid as solvent at 120 deg.C, heating under reflux, tracking on point plate during reaction, stopping reaction when no material point is observed on silica gel plate, spin drying, extracting to obtain crude product, adding neutral Al into the extract₂O₃Spin-dry and purify by column chromatography to give 100mg of product (GaClTTP) with dichloromethane as eluent.

(6) Preparation of GaClTPP covalent functionalized GO (GaTPP-GO)

38.8mg of GaClTPP, 70mg of GO and 500mg of K, respectively₂CO₃Into a 100mL single-necked round-bottomed flask, 50mL of dimethyl sulfoxide (DMSO) was used as a solvent, and the mixture was subjected to sonication at 37 ℃. 150W power lasting 30min to formTo form a uniform solution. Stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, carrying out ultrasonic standing, filtering to obtain a filter cake, repeatedly washing the filter cake with deionized water, dichloromethane and ethanol respectively until the filtrate is colorless, and carrying out vacuum drying on the filter cake for 1d at normal temperature to obtain 38mg of GaTPP-GO.

(7) Preparation of GaClTTP covalent functionalized GO (GaTTP-GO)

40mg of GaClTTP, 70mg of GO and 500mg of K, respectively₂CO₃Add to a 100mL single-necked round-bottomed flask with 50mL DMSO as solvent and sonicate the mixture at 37 ℃. The 150W power was continued for 30min to form a homogeneous solution. Stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, carrying out ultrasonic standing, filtering to obtain a filter cake, repeatedly washing the filter cake with deionized water, dichloromethane and ethanol respectively until the filtrate is colorless, and carrying out vacuum drying on the filter cake for 1d at room temperature to obtain 42mg of GaTTP-GO.

(8) Preparation of GaClTPP and GaClTTP covalently functionalized GO (GaTPP-GO-GaTTP)

19.4mg GaClTPP, 20mg GaClTTP, 70mg GO and 500mg K, respectively₂CO₃Add to a 100mL single-necked round-bottomed flask with 50mL DMSO as solvent and sonicate the mixture at 37 ℃. The 150W power was continued for 30min to form a homogeneous solution. Stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, ultrasonically standing, filtering to obtain a filter cake, repeatedly washing the filter cake with deionized water, dichloromethane and ethanol respectively until the filtrate is colorless, and heating the filter cake at room temperatureVacuum drying for 1d to obtain 44mg of GaTPP-GO-GaTTP.

Example 2 SEM analysis of GaClTPP, GaClTTP and GaTPP-GO-GaTTP

The shape analysis of GO, GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP is carried out by a Scanning Electron Microscope (SEM) to research the changes of the shapes of porphyrin and graphene oxide after covalent functionalization, and FIG. 1 is a scanning electron microscope image of GO (a), GaTPP-GO (b), GaTTP-GO (c) and GaTPP-GO-GaTTP (d). From FIG. 1(a), GO can be observed to be in a sheet-like folded structure and the surface is smooth, but from FIG. 1(b), FIG. 1(c) and FIG. 1(d), the GO is observed to be in a stacked state, the surface is obviously rough, but a folded state also exists, which indicates that the nano-hybrid material contains two components of porphyrin and GO at the same time, and indicates the successful preparation of the nano-hybrid material.

Example 3 Infrared Spectroscopy analysis of GaClTPP, GaClTTP and GaTPP-GO-GaTTP

FIG. 2 is an infrared spectrum of samples GO, GaClTPP, GaClTTP, GaTPP-GO, GaTTP-GO, GaTPP-GO-GaTTP, as seen in FIG. 2 at 3095cm^-1An absorption peak is formed, wherein the absorption peak is C-H stretching vibration on a thiophene group and ranges from 1590 cm to 1645cm^-1The absorption peaks at (B) correspond to the absorption peaks of stretching vibration with C being C, C being N and at 3330cm^-1、965cm^-1And 752cm^-1The absorption peak is the characteristic absorption peak of N-H, which is the absorption peak of N-H on the pyrrole ring. At 1260cm^-1And 1198cm^-1The band at (b) corresponds to the stretching vibration of the pyrrole C-N unit. A series of from 1410cm^-1To 1655cm^-1Can be attributed to the tensile vibration of the porphyrin phenyl C ═ C bond, and is 660-900 cm^-1The band observed corresponds to the bending vibration of the out-of-plane phenyl C-H unit. When the metal ions and the N-H in the porphyrin ring are subjected to coordination reaction, the absorption peaks of the N-H of TPP and TTP disappear, and a new absorption peak of the N-Ga is generated. GaClTPP and GaClTTP are respectively at 988cm^-1And 990cm^-1An N-Ga stretching vibration absorption peak is shown, which indicates that Ga ions are successfully coordinated with N in a porphyrin ring to form metalloporphyrins GaClTPP and GaClTTP. The work of porphyrin and graphene oxide can also be observed from fig. 2Characteristic peaks of GO, GaClTPP and GaClTTP appear in the binary nano hybrid materials (GaTPP-GO and GaTTP-GO) after being converted, and the characteristic peaks of GO, GaClTPP and GaClTTP simultaneously exist in the infrared spectrogram of the ternary nano hybrid materials (GaTPP-GO-GaTTP), so that the successful preparation of the binary and ternary nano hybrid materials can be confirmed.

Example 4 Raman Spectroscopy of GaClTPP, GaClTTP and GaTPP-GO-GaTTP

Raman spectroscopy is a scattering spectrum and can be used to study defects and the degree of functionalization of carbonaceous materials such as graphene. FIG. 3 is Raman spectra of GO, GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP nano hybrid materials, respectively. From FIG. 3, it can be observed that GO is 1348.84cm respectively^-1And 1599.54cm^-1There are two peaks corresponding to the D and G bands of GO. This is because during the oxidation of graphite, graphene oxide reacts to form a large number of oxygen-containing functional groups, and carbon atoms are separated from original single sp²Hybridization is changed into sp²And sp³Two hybridization modes, i.e., the carbon atoms in GO have two hybridization forms. According to the report, the peak ratio (I) of the D band and the G band can be passed_D/I_G) To compare the degree of hybridization and defects of the carbonaceous materials. The peak ratio (I) of the D band and the G band of four materials including GO, GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP can be calculated_D/I_G) 0.981, 1.033, 1.066 and 1.047 respectively, this result indicates an increase in the degree of disorder of the GO surface, while being able to indicate a large number of sp²Carbon atom is changed into sp³A carbon atom. Therefore, the fact that the three nano hybrid materials successfully carry out covalent functionalization with GO and the binary and ternary nano hybrid materials are successfully prepared can be proved. The positions of the D band and the G band can also be used for proving the electron transfer process between materials, and it is seen from the following table 1 that the positions of the D band and the G band of three nano hybrid materials have certain blue shifts, wherein the blue shift degree of GaTPP-GO-GaTTP is maximum (the blue shift of the D band is 3nm, and the blue shift of the G band is 7nm), which indicates that the electron transfer exists between porphyrin and GO, and probably because the GaTPP-GO-GaTTP contains two kinds of porphyrin molecules, the electron transfer between the GaTPP-GO and GO is strongest under the combined action of the two kinds of porphyrin molecules. On the one hand, the nano hybrid material is proved by Raman spectrumThe successful preparation of the material, on the other hand, illustrates that there is a strong electron transfer effect between the porphyrin and GO.

TABLE 1 comparison of Raman data for GO and GaTPP-GO, GaTTP-GO, GaTPP-GO-GaTTP

Example 5 nonlinear optical Properties analysis of GaClTPP, GaClTTP and GaTPP-GO-GaTTP

Graphene and its derivatives are often used as the research benchmark for optical limiting materials because of their ability to transport carriers very fast and their good optical absorption ability. In the embodiment, a hole-opening Z-scanning technology is adopted to test the nonlinear optical performance of GaClTPP, GaClTTP, GO, GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP nano hybrid materials in a nanosecond range, and DMSO is used as a solvent under test conditions, so that the samples are uniformly dispersed in the solvent, and the influence of the solvent on an experimental result is eliminated. FIG. 4 shows the results of open-cell Z-scan testing of all samples at 532nm with 4ns laser pulses. It can be observed from FIG. 4 that the hybrid material and its monomer both exhibit a trough shape, indicating that the material produced is Reverse Saturable Absorption (RSA) in nature. The wave trough depth in fig. 4 represents the magnitude of the nonlinear absorption performance, and it can be observed that the normalized transmittances of the prepared porphyrin monomers GaClTPP and GaClTTP, GO and the nano-hybrid materials GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP at the position of maximum laser intensity (Z ═ 0) are 95%, 93%, 76%, 66%, 74% and 49%, respectively, wherein the valley depth of the ternary nano-hybrid material GaTPP-GO-GaTTP is the deepest, which indicates that the nonlinear absorption performance is the best. Meanwhile, the binary nano hybrid materials GaTPP-GO and GaTTP-GO can be observed to have larger amplification compared with porphyrin monomers GaClTPP, GaClTTP and GO, and the phenomenon shows that the porphyrin functionalized graphene oxide nano hybrid material has more excellent nonlinear optical performance. The reason is that electron/energy transfer exists between porphyrin and graphene oxide, and the electron/energy transfer capacity is increased under the combined action of the porphyrin and the graphene oxide, so that the photoelectric property of the material is improved. Research results show that the ternary nano hybrid material has certain potential application value in the field of nonlinear optics, and meanwhile, a thought is provided for researching more excellent nonlinear optical materials.

Example 6 optical limiting Performance analysis of GaClTPP, GaClTTP and GaTPP-GO-GaTTP

FIG. 5 shows the optical amplitude limiting performance of GaClTPP, GaClTTP and GaTPP-GO-GaTTP, for the convenience of comparing the performance of each sample, the scanning test is performed under the same linear transmittance, the ternary nano hybrid material GaTPP-GO-GaTTP has better optical amplitude limiting performance than the binary nano hybrid material GaTPP-GO and GaTTP-GO, and the result is consistent with the Z-scanning result of the open pore. The optical limiting threshold values of GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP are respectively 0.32J/cm²、0.45J/cm²And 0.64J/cm². Given the donor-acceptor relationship of excited states in GaTPP-GO, GaTTP-GO and GaTPP-GO-GaTTP nano-hybrid materials, the increase in optical clipping performance can be attributed to excited state charge separation resulting from photo-induced electron transfer from the electron-donor porphyrin to the electron-acceptor GO. In fact, the more effective charge transfer effect of the ternary nano hybrid material GaTPP-GO-GaTTP has been confirmed by fluorescence, so that the ternary nano hybrid material GaTPP-GO-GaTTP shows the best light amplitude limiting effect.

In conclusion, the GO is modified by the two porphyrins GaClTPP and GaClTTP together, so that the electron/energy transfer capability between the two porphyrins is stronger, and the nano hybrid material has more excellent nonlinear optical absorption and optical amplitude limiting performance compared with a monomer, wherein the GaTPP-GO-GaTTP has the most excellent performance. Various research results show that the ternary nano hybrid material prepared by modifying graphene oxide with different porphyrins has potential application in related fields such as optical amplitude limiting, optical switches and the like.

Claims

1. The gallium porphyrin axially functionalized graphene oxide multi-element nano hybrid material is characterized in that the multi-element nano hybrid material is prepared by carrying out axial covalent connection modification on graphene oxide by GaClTPP or/and GaClTTP, and the multi-element nano hybrid material is GaTPP-GO, GaTTP-GO or GaTPP-GO-GaTTP; wherein, the GaClTPP is 5,10,15, 20-tetraphenylgallium porphyrin complex, and the GaClTTP is 5,10,15, 20-tetra (2-thiophene) gallium porphyrin complex; the structural formulas of GaClTPP and GaClTTP are respectively as follows:

2. the preparation method of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material as claimed in claim 1, wherein when the multi-element nano-hybrid material is GaTPP-GO, the method comprises the following steps:

3. The preparation method of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material as claimed in claim 1, wherein when the multi-element nano-hybrid material is GaTTP-GO, the method comprises the following steps:

in DMSO solvent system, 40mg GaClTTP, 70mg GO, 500mg K₂CO₃Are mixed and are in 3Subjecting the mixture to ultrasonic treatment at 7 ℃; 150W power for 30min to form a homogeneous solution; stirring and heating at 120 ℃ for 3d, cooling to room temperature after reaction is stopped, adding 40mL of deionized water into a flask, performing ultrasonic standing, filtering to obtain a filter cake, and respectively adding deionized water and CH into the filter cake₂Cl₂And repeatedly washing with EtOH until filtrate is colorless, and carrying out vacuum drying on a filter cake at normal temperature to obtain the GaTTP-GO.

4. The preparation method of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material as claimed in claim 1, wherein when the multi-element nano-hybrid material is GaTPP-GO-GaTTP, the method comprises the following steps:

5. The application of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material in nonlinear optical materials as claimed in claim 1, wherein the multi-element nano-hybrid material is GaTPP-GO-GaTTP.

6. The application of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material in optical limiting and optical switching according to claim 1, wherein the multi-element nano-hybrid material is GaTPP-GO-GaTTP.