CN112159413B - Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof - Google Patents
Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112159413B CN112159413B CN202010876482.2A CN202010876482A CN112159413B CN 112159413 B CN112159413 B CN 112159413B CN 202010876482 A CN202010876482 A CN 202010876482A CN 112159413 B CN112159413 B CN 112159413B
- Authority
- CN
- China
- Prior art keywords
- gattp
- gatpp
- hybrid material
- graphene oxide
- gaclttp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
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 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-thienyl) 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
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 x The 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-thienyl) 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 K 2 CO 3 Mixing 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 cake 2 Cl 2 Repeatedly washing with EtOH until the filtrate is colorlessAnd (3) drying the 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 K 2 CO 3 Mixing and subjecting the mixture to ultrasonication 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 cake 2 Cl 2 And repeatedly washing with EtOH until the filtrate is colorless, and drying the filter cake in vacuum 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 K 2 CO 3 Mixing and sonicating the mixture at 37 ℃;150W of 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 cake 2 Cl 2 And 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 GaClTPP and GaClTTP together, so that the electron/energy transfer capacity between the two porphyrins is stronger, and the nano hybrid material has more excellent nonlinear optical absorption and optical limiting performance compared with a monomer, wherein the performance of GaTPP-GO-GaTTP is 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 and rapidly stirring in the process of adding the concentrated acid, simultaneously keeping the temperature range of the ice bath environment at 0-10 ℃, and then 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. In the addition process of the hydrogen peroxide solution, the solution color of the reaction product is obviously changed, and the color gradually becomes lighter from black at the end of the reaction and finally becomes golden yellow. The solution was allowed to stand, and the supernatant liquid was removed. Washing with 5% hydrochloric acid solution and deionized water for 3-5 times, dialyzing and standing after washing, wherein the standing time is about 7 d. 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 60min. 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 12h. 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 = 1.
(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, the mixture is stirred and heated under reflux at the temperature of 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 the mixture is heated and refluxed for 60min. 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 12h. 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 = 1.
(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 3 Adding 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 extract 2 O 3 Spin-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 GaCl 3 Adding 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 extract 2 O 3 Spin-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, respectively 2 CO 3 Into a 100mL single-neck round-bottom flask, 50mL dimethyl sulfoxide (DMSO) was used as a solvent, and the mixture was sonicated 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 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, respectively 2 CO 3 Add 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 deg.C for 3d, cooling to room temperature after reaction is stopped, adding 40mL deionized water into flask, ultrasonic standing, and filtering to obtain the final productAnd (3) washing the filter cake repeatedly with deionized water, dichloromethane and ethanol respectively until the filtrate is colorless, and drying the filter cake in vacuum for 1d at normal 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, respectively 2 CO 3 Add to a 100mL single-neck 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 normal temperature to obtain 44mg of GaTPP-GO-GaTTP.
Example 2 SEM analysis of GaClTPP, gaClTTP and GaTPP-GO-GaTTP
The appearance of GO, gaTPP-GO, gaTTP-GO and GaTPP-GO-GaTTP is analyzed through a Scanning Electron Microscope (SEM) to explore the appearance change 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 a sheet-folded structure and smooth surface, but from fig. 1 (b), fig. 1 (c) and fig. 1 (d), it is observed to be a stacked state, and the surface becomes rough obviously, but there is also a folded state, indicating that the nano-hybrid material contains both porphyrin and GO components, indicating the successful preparation of 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 can be seen in FIG. 2At 3095cm -1 Has an absorption peak, here is C-H stretching vibration on the thiophene group, and is 1590-1645 cm -1 The absorption peaks at (A) correspond to the absorption peaks of the stretching vibration of C = C and C = N, and are at 3330cm -1 、965cm -1 And 752cm -1 The absorption peak is the characteristic absorption peak of N-H, which is the absorption peak of N-H on the pyrrole ring. At 1260cm -1 And 1198cm -1 The band at (b) corresponds to the stretching vibration of the pyrrole C-N unit. A series of from 1410cm -1 To 1655cm -1 Can be attributed to the tensile vibration of the porphyrin's phenyl C = C bond and is in the range of 660 to 900cm -1 The 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 -1 And 990cm -1 An 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. From fig. 2, it can also be observed that characteristic peaks of GO, gaClTPP, and GaClTTP appear in the binary nano hybrid material (GaTPP-GO, gaTTP-GO) after the porphyrin and graphene oxide functionalization, respectively, and the characteristic peaks of GO, gaClTPP, and GaClTTP exist in the infrared spectrogram of the ternary nano hybrid material (GaTPP-GO-GaTTP) at the same time, which can prove the successful preparation of the binary and ternary nano hybrid material.
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 are 1348.84cm respectively -1 And 1599.54 cm -1 There 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 sp 2 Hybridization is changed into sp 2 And sp 3 Two hybridization modes, i.e. the carbon atom in GO has twoHybrid 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 ) Respectively 0.981, 1.033, 1.066 and 1.047, which indicates an increase in the degree of disorder of the GO surface, while indicating a high number of sp 2 Carbon atom is changed into sp 3 A carbon atom. Therefore, the three nano hybrid materials can be proved to be successfully subjected to covalent functionalization with GO, and binary and ternary nano hybrid materials can be successfully prepared. 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 the three nano hybrid materials have certain blue shifts, wherein the blue shift degree of GaTPP-GO-GaTTP is maximum (3 nm for the D band and 7nm for the G band), which indicates that the electron transfer exists between porphyrin and GO, and probably because two kinds of porphyrin molecules are contained in GaTPP-GO-GaTTP, the electron transfer between the two kinds of porphyrin molecules and GO is strongest under the combined action of the two kinds of porphyrin molecules. On one hand, the successful preparation of the nano hybrid material is proved through Raman spectroscopy, and on the other hand, the strong electron transfer effect between porphyrin and GO is illustrated.
TABLE 1 comparison of Raman data for GO, gaTPP-GO, gaTTP-GO, and 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 in 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-hole Z-scan tests of all samples at 532nm, 4ns laser pulse. From FIG. 4, it can be observed that the hybrid material and its monomer both show a trough shape, indicating that the materials prepared are 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 deepest trough depth of the ternary nano-hybrid material GaTPP-GO-GaTTP indicates the best nonlinear absorption performance. 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/cm 2 、0.45J/cm 2 And 0.64J/cm 2 . Considering the donor-acceptor relationship of the excited states in GaTPP-GO, gaTTP-GO and GaTPP-GO-GaTTP nanohybrid materials, the increase in optical clipping performance can be attributed to the photo-induced electron transfer from the electron donor porphyrin to the electron acceptor GOAnd separating the excited charges. 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 (3)
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 performing axial covalent connection on GaClTPP and GaClTTP to modify graphene oxide, and the multi-element nano hybrid material is GaTPP-GO-GaTTP; wherein the GaClTPP is 5,10,15,20-tetraphenylgallium porphyrin complex, and the GaClTTP is 5,10,15,20-tetra (2-thienyl) gallium porphyrin complex; the structural formulas of GaClTPP and GaClTTP are respectively as follows:
the preparation method comprises the following steps:
in a DMSO solvent system, 19.4mg GaClTPP, 20mg GaClTTP, 70mg GO, 500mg K 2 CO 3 Mixing and sonicating the mixture at 37 ℃;150W of power for 30min to form a homogeneous solution; stirring and heating at 120 ℃ for 3d, cooling to room temperature after the reaction is stopped, adding 40mL of deionized water into a flask, ultrasonically standing,filtering to obtain filter cake, and adding deionized water and CH 2 Cl 2 And repeatedly washing with EtOH until filtrate is colorless, and drying a filter cake in vacuum at normal temperature to obtain the GaTPP-GO-GaTTP.
2. The application of gallium porphyrin axially functionalized graphene oxide polynary nano-hybrid material in nonlinear optical materials as claimed in claim 1, wherein the polynary nano-hybrid material is GaTPP-GO-GaTTP.
3. The application of gallium porphyrin axially functionalized graphene oxide multi-element nano-hybrid material in optical amplitude limiting and optical switching, as claimed in claim 1, wherein the multi-element nano-hybrid material is GaTPP-GO-GaTTP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876482.2A CN112159413B (en) | 2020-08-27 | 2020-08-27 | Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876482.2A CN112159413B (en) | 2020-08-27 | 2020-08-27 | Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112159413A CN112159413A (en) | 2021-01-01 |
| CN112159413B true CN112159413B (en) | 2023-01-10 |
Family
ID=73859431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010876482.2A Active CN112159413B (en) | 2020-08-27 | 2020-08-27 | Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112159413B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461696B (en) * | 2021-04-16 | 2022-11-01 | 同济大学 | Porphyrin phthalocyanine covalent dual-functionalized graphene nonlinear nano hybrid material and preparation method thereof |
| CN113773835B (en) * | 2021-09-22 | 2022-07-05 | 同济大学 | Cationic porphyrin functionalized Ti3C2TxNano-sheet nonlinear nano hybrid material and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254640A (en) * | 2015-09-25 | 2016-01-20 | 江苏大学 | Stannum porphyrin axial covalent functionalized reduced graphene oxide nonlinear optical materials, and preparation method thereof |
| CN107056822A (en) * | 2017-05-23 | 2017-08-18 | 江苏大学 | Porphyrin N doping redox graphene nonlinear optical material and preparation method thereof |
-
2020
- 2020-08-27 CN CN202010876482.2A patent/CN112159413B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254640A (en) * | 2015-09-25 | 2016-01-20 | 江苏大学 | Stannum porphyrin axial covalent functionalized reduced graphene oxide nonlinear optical materials, and preparation method thereof |
| CN107056822A (en) * | 2017-05-23 | 2017-08-18 | 江苏大学 | Porphyrin N doping redox graphene nonlinear optical material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112159413A (en) | 2021-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112159413B (en) | Gallium porphyrin axial functionalized graphene oxide multi-element nano hybrid material and preparation method and application thereof | |
| CN109294557B (en) | Preparation method and application of composite nano material with aggregation-induced emission property and photothermal conversion property | |
| CN113200539B (en) | Porphyrin edge covalent fused graphene nonlinear nano hybrid material and preparation method thereof | |
| Abd-El-Aziz et al. | Aggregation enhanced excimer emission (AEEE) with efficient blue emission based on pyrene dendrimers | |
| Özceşmeci et al. | New phthalocyanines bearing tetra (hydroxyethylthio) functionalities | |
| Zhao et al. | The third order nonlinear optical properties of graphene oxide–zinc (II) naphthalocyanine hybrids and amino graphene oxide–zinc (II) naphthalocyanine hybrids | |
| CN110256450B (en) | Benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and preparation method thereof | |
| Lu et al. | Preparation and third order nonlinear optical properties of corrole functionalized GO nanohybrids | |
| Ferrero et al. | Dual-tweezer behavior of an octapodal pyrene porphyrin-based system as a host for fullerenes | |
| CN113735866B (en) | Tetraphenylporphyrin covalent functionalized titanium disulfide nonlinear nano hybrid material and preparation thereof | |
| Yu et al. | Near-infrared upper phenyl-fused BODIPY as a photosensitizer for photothermal–photodynamic therapy | |
| Yao et al. | New porphyrin-based dendrimers with alkene linked fluorenyl antennae for optics | |
| Ovchenkova et al. | Carbazole-functionalized cobalt (ii) porphyrin axially bonded with C 60/C 70 derivatives: synthesis and characterization | |
| Ke et al. | Acetylene bridged porphyrin–monophthalocyaninato ytterbium (III) hybrids with strong two-photon absorption and high singlet oxygen quantum yield | |
| CN112358493B (en) | Micromolecular photothermal reagent based on boron-fluorine complex and preparation method and application thereof | |
| Guo et al. | The synthesis, molecular structure and photophysical properties of 2, 9, 16, 23-tetrakis (7-coumarinoxy-4-methyl)-phthalocyanine sensitizer | |
| CN110922418B (en) | Pyrrolo-pyrrole-dione conjugated oligomer, nanoparticle based on pyrrolo-pyrrole-dione conjugated oligomer and preparation methods of pyrrolo-pyrrole-dione conjugated oligomer and nanoparticle | |
| CN115040650A (en) | Preparation and application methods of quinoline cyanine photo-thermal nanoparticles with aggregation-enhanced photo-thermal characteristics | |
| Oezcesmeci et al. | Tetranuclear supramolecular structures containing phthalocyanine cores | |
| Bodedla et al. | Self-assembly of Pt (ii)-tetrakis (pentafluorophenyl) porphyrin via F⋯ F interaction for efficient cocatalyst-free photocatalytic hydrogen evolution | |
| CN109336893B (en) | Naphthalocyanine-aminated graphene oxide composite nonlinear optical material and preparation method thereof | |
| CN113150017A (en) | Coupled double-BODIPY near-infrared absorption dye and preparation method thereof | |
| CN112457334A (en) | Preparation method of phenanthroline bridged dicarballo derivative | |
| Amakawa et al. | Self-aggregates of a synthetic cadmium chlorin in solid film as a photosynthetic antenna model | |
| CN112110931B (en) | Axial coordination composite material with two-photon absorption characteristic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |