CN110256450B - Benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and preparation method thereof - Google Patents
Benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and preparation method thereof Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 230000003287 optical effect Effects 0.000 title claims abstract description 47
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 4-hydroxymethyl benzyloxy Chemical group 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FTAYNAUDDYXYCO-UHFFFAOYSA-N OCC1=CC=C(COC2=C(C(=CC=C2)C#N)C#N)C=C1 Chemical compound OCC1=CC=C(COC2=C(C(=CC=C2)C#N)C#N)C=C1 FTAYNAUDDYXYCO-UHFFFAOYSA-N 0.000 claims description 4
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- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 claims description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 3
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 15
- 239000011701 zinc Substances 0.000 claims 14
- 150000003751 zinc Chemical class 0.000 claims 12
- 229910052725 zinc Inorganic materials 0.000 claims 12
- 230000004913 activation Effects 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 19
- 230000009102 absorption Effects 0.000 description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000006862 quantum yield reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- 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
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
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Abstract
The invention discloses a benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and a preparation method thereof, belongs to the field of composite nonlinear optical materials, and aims to solve the problem of poor three-order nonlinear optical performance of the existing nonlinear optical material. The nonlinear optical material is prepared by bonding tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine compound and graphite oxide. The preparation method comprises the following steps: firstly, 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, n-amyl alcohol and Zn (CH)3COO)2Adding DBU and the phthalocyanine into a reaction container, and heating and reacting at 120-160 ℃ to obtain tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine; II, preparing GO; and thirdly, placing the DMF solution of GO and DCC in a reaction container, adding tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine after activation, and reacting at normal temperature under the protection of nitrogen. The composite optical material has good three-order nonlinear optical performance.
Description
Technical Field
The invention belongs to the field of composite nonlinear optical materials, and particularly relates to a benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and a preparation method thereof.
Background
With the development of optical research, especially the gradual maturity of laser technology, materials with excellent nonlinear optical properties become one of the hot spots of scientific research. The phthalocyanine and the graphene oxide are good third-order nonlinear optical materials, and the phthalocyanine and the graphene oxide can form a nonlinear optical composite material with more excellent performance in a covalent bonding mode. However, few reports have been made on the correlation between the molecular structure of phthalocyanine and the nonlinear optical properties of phthalocyanine/graphene oxide composite.
Graphene oxide contains many oxygen-containing functional groups, which makes its chemical properties more active than graphene, and can improve its properties through various reactions with the oxygen-containing functional groups, and phthalocyanine has its own unique advantages: the phthalocyanine belongs to a plane conjugated macromolecule, has excellent chemical adjustability and good structure cutting property, introduces a proper substituent group on the periphery of a phthalocyanine macrocycle, and utilizes a newly introduced functional group to react with other materials to form a compound, thereby finally achieving the aim of modifying the graphene oxide.
Disclosure of Invention
The invention aims to solve the problem of poor three-order nonlinear optical performance of the existing nonlinear optical material, and provides a benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material and a preparation method thereof.
The benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is formed by combining a tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine compound and graphene oxide, and the structure of the synthesized tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine/graphene oxide compound (alpha-ZnTPPc-GO) is as follows:
the preparation method of the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is realized according to the following steps:
firstly, 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, anhydrous n-amyl alcohol and Zn (CH)3COO)2Adding DBU (1, 8-diazabicycloundecen-7-ene) into a reaction vessel, taking nitrogen as protective gas, heating to 120-160 ℃, continuously reacting for 6-12 h, carrying out reduced pressure rotary evaporation on the obtained liquid-solid mixture to obtain a phthalocyanine crude product, and carrying out centrifugal washing on the phthalocyanine crude product for several times by adopting ethyl acetate to obtain tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine;
secondly, preparing GO (graphene oxide);
placing a DMF solution of GO and a DMF solution of DCC (dicyclohexylcarbodiimide) in a reaction container, stirring and activating, adding a DMF solution of tetra-alpha- (4-hydroxymethylbenzyloxy) phthalocyanine, stirring at normal temperature for 3-7 days under the protection of nitrogen, then taking DMF as an eluent, removing unreacted phthalocyanine from the obtained product in a centrifugal mode, dispersing the reactant with ethanol, and drying to obtain the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material (alpha-ZnTPPc-GO).
The benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is prepared from tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine compound and graphene oxide, the used benzene ring phthalocyanine compound is tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine (alpha-ZnTPPc), and the selected graphene oxide is Graphene Oxide (GO) with good dispersibility prepared by a Hummers method. The preparation method of the composite nonlinear optical material is simple, the performance is stable, the composite nonlinear optical material has good three-order nonlinear optical performance, the composite nonlinear optical material is subjected to open-cell Z scanning test, the nonlinear absorption coefficient beta of alpha-ZnTPC is 1.53cm/GW, the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material shows obvious reverse saturation absorption property, and the nonlinear absorption coefficient is a positive value. The invention can be widely applied in the fields of photonics and photoelectric devices.
Drawings
FIG. 1 is the UV-visible absorption spectra of α -ZnTPPc and α -ZnTPPc-GO in the examples, wherein 1 represents α -ZnTPPc, and 2 represents α -ZnTPPc-GO;
FIG. 2 is a graph showing fluorescence spectra of α -ZnTPPc and α -ZnTPPc-GO in examples, wherein 1 represents α -ZnTPPc, and 2 represents α -ZnTPPc-GO;
FIG. 3 is the Raman spectra of GO and α -ZnTPPc-GO in the examples, where 3 represents GO and 2 represents α -ZnTPPc-GO;
FIG. 4 is the Z-scan curve of the open pore of α -ZnTPC-GO in the examples.
Detailed Description
The first embodiment is as follows: the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is synthesized by a tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine compound and a graphene oxide, and the synthesized tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine/graphene oxide compound (alpha-ZnTPPc-GO) has the structure:
in the embodiment, tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine with Zn as the central metal ion in the ring is prepared by a template method. The embodiment prepares the metal phthalocyanine composite material with better nonlinear optical performance by a substituent modification method.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is that the graphene oxide is prepared by Hummers method.
The third concrete implementation mode: the preparation method of the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is implemented according to the following steps:
firstly, 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, anhydrous n-amyl alcohol and Zn (CH)3COO)2Adding DBU (1, 8-diazabicycloundecen-7-ene) into a reaction vessel, taking nitrogen as protective gas, heating to 120-160 ℃, continuously reacting for 6-12 h, carrying out reduced pressure rotary evaporation on the obtained liquid-solid mixture to obtain a phthalocyanine crude product, and carrying out centrifugal washing on the phthalocyanine crude product for several times by adopting ethyl acetate to obtain tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine;
secondly, preparing GO (graphene oxide);
placing a DMF solution of GO and a DMF solution of DCC (dicyclohexylcarbodiimide) in a reaction container, stirring and activating, adding a DMF solution of tetra-alpha- (4-hydroxymethylbenzyloxy) phthalocyanine, stirring at normal temperature for 3-7 days under the protection of nitrogen, then taking DMF as an eluent, removing unreacted phthalocyanine from the obtained product in a centrifugal mode, dispersing the reactant with ethanol, and drying to obtain the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material (alpha-ZnTPPc-GO).
The tetra-alpha- (4-hydroxymethylbenzyloxy) metal phthalocyanine complex in the first step of the present embodiment is synthesized from a molecular fragment of 3- (4-hydroxymethylbenzyloxy) phthalodinitrile and a metal phthalocyanine complex.
The tetra-alpha- (4-hydroxymethylbenzyloxy) phthalocyanine according to the present embodiment is a tetra-alpha- (4-hydroxymethylbenzyloxy) phthalocyanine in which the metal ion at the center in the ring is Zn.
The fourth concrete implementation mode: the difference between the present embodiment and the third embodiment is that the preparation method of 3- (4-hydroxymethylbenzyloxy) phthalodinitrile in the first step is as follows:
a. placing 3-nitrophthalonitrile and 1, 4-benzenedimethanol into a reaction bottle, taking DMF solution as a reaction solvent and anhydrous potassium carbonate as a catalyst, placing the reaction bottle in a room temperature environment under the protection of nitrogen atmosphere, stirring and reacting for 90-100 hours, after the reaction is finished, removing a reacted solid phase substance through suction filtration, and collecting filtrate, namely the DMF solution of 3- (4-hydroxymethyl benzyloxy) phthalonitrile;
b. transferring a DMF solution of 3- (4-hydroxymethyl benzyloxy) phthalic nitrile to trichloromethane, standing in an ice water bath for 10-14 h, extracting with secondary water as an extractant to remove DMF, removing trichloromethane by reduced pressure distillation to obtain oily 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, recrystallizing with n-hexane as a solvent to obtain a white powdery solid, and performing reduced pressure suction filtration and vacuum drying to finally obtain (pure) 3- (4-hydroxymethyl benzyloxy) phthalic nitrile.
The fifth concrete implementation mode: this embodiment differs from the embodiment three or four in that in step one, 3- (4-hydroxymethylbenzyloxy) phthalonitrile and Zn (CH)3COO)2Is 4: 1.
The sixth specific implementation mode: the embodiment is different from one of the third to fifth embodiments in that the preparation method of GO (graphene oxide) in the second step is as follows:
step one, 5g of graphite powder and 50mL of concentrated H with the mass concentration of 98 percent2SO4、8g K2S2O8And 5g P2O5Uniformly mixing, heating in a water bath at 80 ℃ and mechanically stirring for 4-6 h, cooling to room temperature after the reaction is finished, adding distilled water to dilute the obtained mixture, continuously performing repeated suction filtration and washing on the reactant with the distilled water, washing for a plurality of times, and drying to obtain pre-oxidized graphene (black powder);
step two, transferring the pre-oxidized graphene to a solution containing 100mL of concentrated H with the mass concentration of 98%2SO4、2g NaNO3And 12g KMnO4The mixed solution is placed at 35 ℃ and mechanically stirred for 2-4H, and H is dropwise added into the reaction solution2O2And (3) filtering the solution (the mass fraction is 30%) until the reaction solution presents brown yellow, washing the solution by using a 0.5mol/L hydrochloric acid aqueous solution until brown yellow solids are not dissolved to form colloidal liquid, and obtaining a crude product of the graphene oxide, and performing centrifugal dialysis and purification to obtain the graphene oxide.
The seventh embodiment: the difference between this embodiment and one of the third to sixth embodiments is that the DMF solution of GO described in step three is obtained by dissolving GO in 10mL of DMF solution and performing ultrasonic dispersion.
The specific implementation mode is eight: the difference between this embodiment and one of the third to seventh embodiments is that the concentration of the DMF solution of GO is 4-6 mg/mL and the concentration of the DMF solution of DCC is 7-10 mg/mL in the third step.
The specific implementation method nine: the difference between this embodiment and one of the third to eighth embodiments is that the mass ratio of GO to tetra- α - (4-hydroxymethylbenzyloxy) phthalocyanine in step three is 1: 4.
The detailed implementation mode is ten: this embodiment differs from one of the third to ninth embodiments in that the drying in step three is carried out in a vacuum oven at 30 ℃.
The first embodiment is as follows: the preparation method of the benzene ring substituted phthalocyanine/graphene oxide composite nonlinear optical material is implemented according to the following steps:
firstly, placing 1.73g of 3-nitrophthalonitrile and 1.50g of 1, 4-benzenedimethanol in a two-neck round-bottom flask, using 30mL of DMF solution as a reaction solvent and anhydrous potassium carbonate as a catalyst (adding every 1h, accumulating for 3 times and totaling 4.50g), discharging oxygen in a device, placing the device in a room temperature environment under the protection of nitrogen atmosphere, stirring for 96h, after the reaction is finished, removing the reacted solid through suction filtration to obtain a pure filtrate, namely the DMF solution of the 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, transferring the DMF solution of the 3- (4-hydroxymethyl benzyloxy) phthalic nitrile to 150mL of trichloromethane, then placing the solution in an ice water bath for standing for 12h, performing sufficient extraction treatment on the solution by using secondary water as an extracting agent to remove DMF, removing the trichloromethane from the solution through reduced pressure distillation, obtaining oily 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, taking normal hexane as a solvent, obtaining a white powdery solid by a recrystallization method, and obtaining pure 3- (4-hydroxymethyl benzyloxy) phthalic nitrile under the conditions of reduced pressure filtration and vacuum drying;
a100 mL round-bottomed flask was taken, and 1g of 3- (4-hydroxymethylbenzyloxy) phthalodinitrile, 50mL of anhydrous n-pentanol, 0.7g of Zn (CH) were added to the prepared molecular fragments in this order3COO)2And 2mL of DBU, taking nitrogen as protective gas, heating to 140 ℃, continuously reacting for 10 hours, carrying out reduced pressure rotary evaporation on the obtained liquid-solid mixture to obtain a phthalocyanine crude product, selecting ethyl acetate, and carrying out centrifugal washing for several times to obtain tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine (alpha-ZnTPPc);
secondly, synthesizing GO by adopting a Hummers method;
preparing a tetra-alpha- (4-hydroxymethyl benzyloxy) phthalocyanine/graphene oxide (alpha-ZnTPPc-GO) compound: firstly weighing 50mg of GO to be dissolved in 10mL of DMF solution, obtaining the DMF solution of GO by ultrasonic treatment, placing the DMF solution (5mg/mL) containing GO and the DMF solution (8mg/mL) of DCC in a 100mL flask, stirring for 0.5h at normal temperature, activating oxygen-containing functional groups on graphene oxide by DCC, then adding 20mL of DMF solution (10mg/mL) of alpha-ZnTPC, stirring for 7 days at normal temperature under the protection of nitrogen, then taking DMF as an eluent, removing unreacted phthalocyanine by a centrifugal mode from the obtained product, dispersing the rest product by using a proper amount of ethanol, and placing the product in a vacuum drying oven at the temperature of 30 ℃ for drying to obtain the alpha-ZnTPPc-GO compound.
FIG. 1 shows the UV-visible absorption spectra of samples α -ZnTPPc and α -ZnTPPc-GO. α -ZnTPC shows two strong absorptions: one of the absorption peaks is wider and weaker and is located at 300-350nm, which is called Soret band (B band); the other is a relatively strong and sharp absorption peak near 700nm, accompanied by a small shoulder, called the Q-band. In fact, both the B band and the Q band are typical uv-visible absorption peaks of metal phthalocyanines, mainly caused by n-pi electron transitions and pi-pi electron transitions between HOMO orbitals and LUMO orbitals in highly conjugated planar structures in the phthalocyanine molecule. The Q-band maximum absorption peak wavelength of alpha-ZnTPC is at 706 nm.
The ultraviolet absorption peak of the alpha-ZnTPPc-GO compound is shown in figure 1, and the ultraviolet absorption peak of the alpha-ZnTPPc-GO compound is greatly changed compared with the absorption peak of the alpha-ZnTPPc molecule due to the introduction of GO. The alpha-ZnTPPc-GO presents a stronger and wider ultraviolet absorption band in the range of 270-320nm, which is caused by the synergistic effect of the Soret band of the alpha-ZnTPC and the pi-transition of GO; and the Q band peak of the alpha-ZnTPPc-GO is positioned at 710nm, and the position of the Q band peak of the alpha-ZnTPPc-GO generates weak red shift compared with the Q band peak position of the alpha-ZnTPPc, which means that the ground state electron interaction exists between the alpha-ZnTPPc and GO in the alpha-ZnTPPc-GO compound. alpha-ZnTPPc is an electron donor and GO is a good electron acceptor due to the charge transfer that exists between alpha-ZnTPC and GO.
FIG. 2 is a fluorescence spectrum of α -ZnTPPc and α -ZnTPPc-GO, both of which show fluorescence emission peaks due to electrons from S after the α -ZnTPPc is excited0Excited transition of state to S1State, again radiationless transition to S0Energy loss in the state. alpha-ZnTPPc shows a strong fluorescence peak at 725nm, as shown in the figure, the corresponding alpha-ZnTPPc-GO compound also shows fluorescence emission with certain intensity, which is caused by the existence of alpha-ZnTPPc molecules in the compound, but compared with the corresponding phthalocyanine compound, the peak intensity is greatly weakened, which shows that an electron transfer process exists between the phthalocyanine molecules and GO in the alpha-ZnTPPc-GO compound, so that the fluorescence intensity is quenched to different degrees.
Compared with the corresponding alpha-ZnTPC, the alpha-ZnTPPc-GO compound has large fluorescence quenching degree, which is consistent with the phthalocyanine fluorescence quantum yield and the fluorescence intensity thereof. Generally, the fluorescence quenching degree of the complex is closely related to the photoinduced electron transfer or energy transfer (PET/ET) process between phthalocyanine molecules and GO, GO in α -ZnTPPc-GO is the same component, the PET/ET process is greatly dependent on α -ZnTPPc parts with different fluorescence quantum yields, and the fluorescence quenching degree of α -ZnTPPc-GO is the greatest, which indicates that the electron transfer degree between α -ZnTPPc and GO is the greatest.
FIG. 3A shows that GO and α -ZnTPPc-GO samples were tested by confocal laser microscopy Raman spectroscopy (model number JYHR800 from HORIBA Jobin Yvon Co.) with excitation wavelength of 458 nm. And obtaining Raman spectra of GO and alpha-ZnTPPc-GO. By taking GO as a comparison standard, the D peak and the G peak can be observed by alpha-ZnTPPc-GO, but the red shift degree of the peak position is obvious. In previous reports, the intensity ratio of the D peak and the G peak is often used to indicate sp in the composite material2/sp3The ratio of the two hybridized carbons, and further to describe the relative density and degree of disorder of the defects in their structures. Furthermore, I of a-ZnTPPc-GO when GO and a-ZnTPPc are combinedD/IGAnd decreases. Based on the above results, it was further confirmed that GO and α -ZnTPPc molecules are connected into a whole through ester bonds.
Fig. 4 studies the third order nonlinear optical properties of tetra-a- (4-hydroxymethylbenzyloxy) phthalocyanine/graphene oxide (a-ZnTPPc-GO) composite using Z-scan technique using Brilliant Nd with a laser source of 532nm 4ns pulse width: YAG laser adopts open Z scanning technology to test the three-order non-linear properties of alpha-ZnTPPc and alpha-ZnTPPc-GO under the condition of 40.4uJ of energy intensity. With C60The samples are 2 multiplied by 10 for the standard liquid sample-4mol/L DMSO solution. The open Z-scan curve of alpha-ZnTPPc-GO is shown in the figure, and the alpha-ZnTPPc-GO shows a typical reverse saturation absorption valley, which is caused by excited state absorption. The Z-scan curve of alpha-ZnTPC-GO is shown in the figure, the normalized transmittance curve of GO changes along with the change of the Z value, and the curve shows the form from one shoulder to one valley and then from valley to one shoulder, namely, the curve is a conversion process from saturated absorption to reverse saturated absorption to saturated absorption. Therefore, when the alpha-ZnTPPc and the GO are bonded into a composite material, the nonlinear response of the composite material is much larger than that of the alpha-ZnTPPc and the GO, and the nonlinear absorption coefficient of the composite material is far larger than the sum of the two nonlinear absorption coefficients. This shows that the nonlinear response of the compound is not only the accumulation of the nonlinear effects of both alpha-ZnTPPc and GO, in addition, GO is a good electron acceptor, alpha-ZnTPPc is a good electron donor, andthe inter-electronic PET/ET process also plays a non-negligible critical role in improving the nonlinear response of the composite. It must be emphasized that, in combination with the results of the fluorescence spectrum analysis, it can be found that the PET/ET process between α -ZnTPPc and GO in the composite depends on the fluorescence quantum yield of the α -ZnTPPc moiety, which can be confirmed from the above-mentioned nonlinear optical properties of the composite and the α -ZnTPPc fluorescence quantum yield. The fluorescence quantum yield of the alpha-ZnTPC is the maximum, so the PET/ET process between the alpha-ZnTPPc and GO is the strongest, and the nonlinear improvement of the compound is greatly promoted, therefore, the alpha-ZnTPC-GO shows strong nonlinear response.
Claims (10)
1. The benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material is characterized in that the benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material is formed by combining a tetra-alpha- (4-hydroxymethyl benzyloxy) zinc phthalocyanine compound and graphene oxide, and the synthesized tetra-alpha- (4-hydroxymethyl benzyloxy) zinc phthalocyanine/graphene oxide compound has the following structure:
2. The benzene ring-substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 1, wherein the graphene oxide is prepared by a Hummers method.
3. The preparation method of the benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material is characterized by comprising the following steps:
firstly, 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, anhydrous n-amyl alcohol and Zn (CH)3COO)2Adding DBU into a reaction container, taking nitrogen as protective gas, heating to 120-160 ℃, andcontinuously reacting for 6-12 h, carrying out reduced pressure rotary evaporation on the obtained liquid-solid mixture to obtain a crude phthalocyanine product, and carrying out centrifugal washing on ethyl acetate for several times to obtain tetra-alpha- (4-hydroxymethyl benzyloxy) zinc phthalocyanine;
II, preparing GO;
placing a DMF solution of GO and a DMF solution of DCC in a reaction container, stirring and activating, adding a DMF solution of tetra-alpha- (4-hydroxymethyl benzyloxy) zinc phthalocyanine, stirring at normal temperature for 3-7 days under the protection of nitrogen, then taking DMF as an eluent, removing unreacted phthalocyanine from the obtained product in a centrifugal mode, dispersing reactants with ethanol, and drying to obtain the benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material.
4. The method for preparing the benzene ring-substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein the preparation method of the 3- (4-hydroxymethylbenzyloxy) phthalonitrile in the first step is as follows:
a. placing 3-nitrophthalonitrile and 1, 4-benzenedimethanol into a reaction bottle, taking DMF solution as a reaction solvent and anhydrous potassium carbonate as a catalyst, placing the reaction bottle in a room temperature environment under the protection of nitrogen atmosphere, stirring and reacting for 90-100 hours, after the reaction is finished, removing a reacted solid phase substance through suction filtration, and collecting filtrate, namely the DMF solution of 3- (4-hydroxymethyl benzyloxy) phthalonitrile;
b. transferring a DMF solution of 3- (4-hydroxymethyl benzyloxy) phthalic nitrile to trichloromethane, standing in an ice water bath for 10-14 h, extracting with secondary water as an extractant to remove DMF, removing trichloromethane by reduced pressure distillation to obtain oily 3- (4-hydroxymethyl benzyloxy) phthalic nitrile, recrystallizing with n-hexane as a solvent to obtain a white powdery solid, and performing reduced pressure suction filtration and vacuum drying to finally obtain the 3- (4-hydroxymethyl benzyloxy) phthalic nitrile.
5. The method for preparing benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein in the first step, 3- (4-hydroxymethyl benzyloxy group) Phthalic nitrile and Zn (CH)3COO)2Is 4: 1.
6. The preparation method of the benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein the preparation method of GO in step two is as follows:
step one, 5g of graphite powder and 50mL of concentrated H with the mass concentration of 98 percent2SO4、8g K2S2O8And 5g P2O5Uniformly mixing, heating in a water bath at 80 ℃, mechanically stirring for 4-6 h, cooling to room temperature after the reaction is finished, adding distilled water to dilute the obtained mixture, continuously performing repeated suction filtration and washing on the reactant with the distilled water, washing for a plurality of times, and drying to obtain pre-oxidized graphene;
step two, transferring the pre-oxidized graphene to a solution containing 100mL of concentrated H with the mass concentration of 98%2SO4、2g NaNO3And 12g KMnO4The mixed solution is placed at 35 ℃ and mechanically stirred for 2-4H, and H is dropwise added into the reaction solution2O2And (3) filtering the solution until the reaction solution presents brown yellow, washing the solution by using a 0.5mol/L hydrochloric acid aqueous solution until brown yellow solids are not dissolved to form colloidal liquid, obtaining a crude product of the graphene oxide, and performing centrifugal dialysis and purification to obtain the graphene oxide.
7. The method for preparing the benzene ring-substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein the DMF solution of GO in the step three is obtained by dissolving GO in 10mL of DMF solution and performing ultrasonic dispersion.
8. The preparation method of the benzene ring-substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein in the third step, the concentration of the DMF solution of GO is 4-6 mg/mL, and the concentration of the DMF solution of DCC is 7-10 mg/mL.
9. The preparation method of the benzene ring substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein the mass ratio of GO to tetra-alpha- (4-hydroxymethylbenzyloxy) zinc phthalocyanine in step III is 1: 4.
10. The method for preparing a benzene ring-substituted zinc phthalocyanine/graphene oxide composite nonlinear optical material according to claim 3, wherein the drying in the third step is performed in a vacuum drying oven at 30 ℃.
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