CN101387810B - Single layer oxidation graphite composite hybridization material and method for preparing same and applications - Google Patents
Single layer oxidation graphite composite hybridization material and method for preparing same and applications Download PDFInfo
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- CN101387810B CN101387810B CN2008101524723A CN200810152472A CN101387810B CN 101387810 B CN101387810 B CN 101387810B CN 2008101524723 A CN2008101524723 A CN 2008101524723A CN 200810152472 A CN200810152472 A CN 200810152472A CN 101387810 B CN101387810 B CN 101387810B
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- graphite oxide
- layer graphite
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- porphyrin
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Abstract
The invention relates to a single-layer graphite oxide composite hybrid material, a preparation method and an application. The single-layer graphite oxide composite hybrid material is made by using and connecting single-layer graphite oxide and pi electronic conjugate system donors as raw materials via amide linkage, wherein the mass ratio between the single-layer graphite oxide and the pi electronic conjugate system donor is 1:1. The single-layer graphite oxide is a two-dimension plane material of which the molecular skeleton is formed by single-layer graphite atoms arranged in a hexagonal lattice form and which comprises oxygen organic function groups, wherein the area of one graphite oxide sheet is 10nm2 to 400um2, and the single sheet is thick of 0.3 to 2nm. The inventive composite material has improved organic solubility, presents good nonlinear optical property and is used for producing nonlinear optical devices.
Description
Technical field
The present invention relates to the manufacturing of nonlinear optical material, particularly a kind of single layer oxidation graphite composite hybridization material and preparation method and application, it is with mono-layer graphite oxide (Graphene Oxide, GO) for being given body, the pi-electron conjugated system is (as porphyrin, porphyrin) composite hybridization material that forms as donor has application widely at non-linear optical field.
Background technology
Be about to the optoelectronics industry (optical communication of realization in 21 century, optical information processing, storage and holography, optical computer, laser weapon, laser accurate processing, laser chemistry, laser medicine or the like) be basic material with the nonlinear optical material in, so the development of nonlinear optical material is still current frontline subject.The development of nonlinear optical material is advanced by leaps and bounds.Chemistry shows that with the development of material science photoelectric properties such as electric conductivity, optical nonlinearity are not the proprietary attribute of inorganics.Organic non linear optical material has shown powerful vitality and the using value of organism in the optical function material field.But organic non-linear optical properties is the photoelectric functional material of MOLECULE DESIGN, and it all is rich in attractive aspect quick nonlinear optical response.
In organic non linear optical material, wherein a part is based on donor and is given body and form structural design.C
60, carbon nano-tube is that the organic material that is given the body material has shown good nonlinear optical property.(J.Mater.Chem.2006,16,3021.Adv.Mater.2007,19,2737.Macromolecule, 2003,36,6286). mono-layer graphite and C
60, carbon nano-tube has similar structure, has pi-conjugated system, be one preferably electronics given body, porphyrin be one to the highstrung molecule donor of light.When excited state, can produce in the molecule and shift with electron transferring between molecules and energy.
Summary of the invention
The purpose of this invention is to provide a kind of single layer oxidation graphite composite hybridization material and preparation method and application, the electronics of pi-conjugated system is given body be connected the composite hybridization material of making by amido link with pi-electron conjugated system donor (as porphyrin), increased the solubility property of material greatly, this hybrid material was both water-soluble, was dissolved in organic solvent again.This composite hybridization material is than the physical mixed sample (the controlled sample) and the C of mono-layer graphite and porphyrin
60Show the performance of better nonlinear optics.
A kind of single layer oxidation graphite composite hybridization material provided by the invention is to be that raw material is connected by amido link and makes with mono-layer graphite oxide and pi-electron conjugated system donor.The mass ratio that feeds intake of described mono-layer graphite oxide and pi-electron conjugated system donor is 1:1.
Described mono-layer graphite oxide is meant that its molecular skeleton is made up of the mono-layer graphite atom of sexangle lattice arrangement, and single oxidized graphite flake area is at 10nm
2To 400 μ m
2Between, single-sheet thickness contains the two dimensional surface material of the organic functional of aerobic between 0.3 to 2nm.Described organo-functional group is to contain carboxyl, at least a in hydroxyl or the epoxy functionality.
The mono-layer graphite oxide material can prepare in enormous quantities by the chemical oxidation method that document (Carbon, 2004,42,2929) provide.
Described pi-electron conjugated system donor can be: porphyrin, fluorenes, carbazole, polythiophene (molecular weight 1000-10000), polyaniline (molecular weight 1000-10000) or polypyrrole (molecular weight 1000-10000).
The preparation method of a kind of single layer oxidation graphite composite hybridization material provided by the invention may further comprise the steps:
1) the mono-layer graphite oxide material is added in entry or the organic solvent,, make mono-layer graphite oxide material dissolves or dispersion through ultrasonic Treatment 30-60 minutes.
2) donor fully is dissolved in and above-mentioned corresponding organic solvent;
3) with step 1,2 described two kinds of solution mix, stirred 0.5 hour, and ultrasonic again 0.5-3 hours, the physical blending compound product of formation.
Described organic solvent is N, dinethylformamide or acetone.
The preparation method of porphyrin provided by the invention and mono-layer graphite oxide hybrid material may further comprise the steps:
1) under 70 ℃, argon shield, reaction steamed excessive thionyl chloride after 24 hours in mono-layer graphite oxide and excessive thionyl chloride and the triethylamine;
2) then with TTP-NH
2(5-(4) aminocarbonyl phenyl)-10,15,20-triphenyl porphyrin) reacted 72 hours down at 130 ℃;
3) in the reactant liquor impouring ether, product is with 0.22 μ m membrane filtration, and filter residue is scattered in tetrahydrofuran, and is ultrasonic, filters; Be repeated below operation: filter residue is scattered in tetrahydrofuran once more, and is ultrasonic, filters repetitive operation 10 times.Filter residue is washed till with chloroform and does not contain TTP-NH
2, use a spot of washing, filter residue and drying gets porphyrin and is connected in porphyrin-mono-layer graphite hybrid material (TPP-NHCO-SPFGraphene) on the mono-layer graphite by amido link.
The mass ratio that feeds intake of described mono-layer graphite oxide and porphyrin is 1:1.
Mono-layer graphite oxide compound substance provided by the invention is used for the manufacturing of device for non-linear optical.
The present invention is that the electronics with pi-conjugated system is given body and is connected the composite hybridization material made from pi-electron conjugated system donor (as porphyrin) by amido link, has increased the solubility property of material greatly, and this hybrid material was both water-soluble, was dissolved in organic solvent again.Simultaneously, than the physical mixed sample and the C of mono-layer graphite and porphyrin
60Show the performance of better nonlinear optics, can be used for the manufacturing of device for non-linear optical.
Description of drawings
Fig. 1 is the synthetic and structural representation of single layer oxidation graphite composite hybridization material.
Fig. 2 is the solubility property curve of single layer oxidation graphite composite hybridization material.
Fig. 3 is the non-linear optical property curve of single layer oxidation graphite composite hybridization material.
Embodiment
Below by embodiment the present invention is specifically described; present embodiment only is used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention; those skilled in the art makes some nonessential improvement and adjustment according to foregoing, all belongs to protection domain of the present invention.
The mono-layer graphite oxide material that the present invention uses can prepare in enormous quantities by the chemical oxidation method that document (Carbon, 2004,42,2929) provide.
Embodiment 1: mono-layer graphite oxide-porphyrin hybrid material (TPP-NHCO-SPFGraphene) preparation
Mono-layer graphite oxide (30mg, average thickness 0.8nm, average area 400 μ m
2) (graphene oxide), thionyl chloride (20ml), triethylamine (0.5ml) reacted 24 hours under 70 ℃ of argon shields, after reaction finishes; excessive thionyl chloride subtracted to steam come, under argon shield, above-mentioned product; 5-(4) aminocarbonyl phenyl)-10,15,20-triphenyl porphyrin (TTP-NH
2) (30mg), N, dinethylformamide (DMF) (10ml) reacted 72 hours down at 130 ℃.After reaction finished, in the reactant liquor impouring ether (300ml), product was with 0.22 μ m film [AUTOMATIC SCIENCE (TIANJIN) INSTRUMENT CO., LTD] filter, filter residue is scattered in tetrahydrofuran, and is ultrasonic, filter, after the repetitive operation 10 times, filter residue is washed till with chloroform and does not contain TTP-NH
2End product is used a spot of washing again.Filter residue and drying gets individual layer TPP-NHCO-SPFGraphene material.Through infrared test, at 1640cm
-1The absorption peak that amido link C=O vibration occurs, 1260cm
-1The C-N vibration absorption peak of amido link appears in the place.Show that the TPP-NHCO-SPFGraphene hybrid material connects by amido link.
Embodiment 2: mono-layer graphite oxide-porphyrin Composite Preparation
At 5ml N, dinethylformamide (DMF) adds 1mg mono-layer graphite oxide, the deep yellow solution that obtains clarifying after ultrasonic 30-60 minutes.With 5mg TTP-NH
2Be dissolved among the 5mlDMF, with the DMF solution and the TTP-NH of mono-layer graphite oxide
2DMF solution mix, stirred 0.5 hour, ultrasonic again 0.5-3 hour, can obtain mono-layer graphite oxide and TTP-NH
2The solution of compound substance.
Embodiment 3: measure the experiment of hybrid material non-linear nature
Open aperture Z scanning light source is the Nd:YAG Q-switched laser of frequency multiplication.Laser is the line polarisation pulse width 5ns of 532nm.It behind filter plate nearly Gaussian beam.Laser is divided into two bundles, and reflected light shines pulse energy 23uj as the reference light transmitted light to sample behind the lens of 25 centimetres of focal lengths.Sample places the laser spot place, and focal radius is 30um.Reflection is measured with two energy detectors (model is Molectron J3S-10) simultaneously with transmission potential, and C60 is as standard.In order to calculate light amplitude limit effect, it is 75% that the adjusting sample concentration makes its linear transmittance at 532nm, the thick 1mm of container.Open aperture Z scanning survey sample is through the transmissivity of tension focused beam focus.When sample during near focus, along with the increase of light intensity, nonlinear effect increases thereupon, because factors such as anti-saturated absorption, two-photon absorption, nonlinear scatterings, transmissivity can descend thereupon.TPP-NHCO-SPFGraphene shows minimum transmissivity 45%, shows good nonlinear optical property.
Accompanying drawing 1 is the synthetic synoptic diagram of embodiment 1, and the basic structure of product TPP-NHCO-SPFGraphene.Accompanying drawing 2 is that product is respectively 40,35,32,27,21,14 in concentration, 12mgL
-1The uv absorption spectrogram.Accompanying drawing 2 (A) is the typical curve of corresponding ultraviolet absorptivity being done at 419nm place variable concentrations, and effectively extinction coefficient is 0.024Lmg
-1Cm
-1, the R value is the typical curve of under variable concentrations the ultraviolet absorptivity at corresponding mono-layer graphite oxide absorption maximum place being done for 0.992. accompanying drawing 2 (B).By typical curve as can be seen the mono-layer graphite oxide solubleness of functionalization tangible improvement has been arranged.Accompanying drawing three is spectrograms of the nonlinear optical property measured among the embodiment two.By spectrogram, at sample during near focus, the TPP-NHCO-SPFGraphene that connects by amido link as can be seen, fullerene (C
60), TTP-NH
2, the physical mixed sample (mono-layer graphite: porphyrin mass ratio 1:1), the transmissivity of mono-layer graphite oxide is respectively 45%, 59%, and 76%, 83%, 94%.TPP-NHCO-SPFGraphene shows minimum transmissivity, shows good nonlinear optical property.
Claims (7)
1. single layer oxidation graphite composite hybridization material, it is characterized in that it is is that raw material is connected by amido link and makes with mono-layer graphite oxide and pi-electron conjugated system donor, the mass ratio that feeds intake of described mono-layer graphite oxide and pi-electron conjugated system donor is 1: 1; Described pi-electron conjugated system donor is: porphyrin, fluorenes, carbazole, polyaniline or polypyrrole.
2. composite hybridization material according to claim 1 is characterized in that: described mono-layer graphite oxide is meant that its molecular skeleton is made up of the mono-layer graphite atom of sexangle lattice arrangement, and single oxidized graphite flake area is at 10nm
2To 400 μ m
2Between, single-sheet thickness is between 0.3 to 2nm and contain the two dimensional surface material of the organic functional of aerobic.
3. composite hybridization material according to claim 2 is characterized in that described organo-functional group is to contain at least a in carboxyl, hydroxyl or the epoxy functionality.
4. composite hybridization material according to claim 1 is characterized in that described pi-electron conjugated system donor is a porphyrin.
5. the preparation method of porphyrin and single layer oxidation graphite composite hybridization material is characterized in that may further comprise the steps:
1) under 70 ℃, argon shield, reaction steamed excessive thionyl chloride after 24 hours in mono-layer graphite oxide and excessive thionyl chloride and the triethylamine;
2) then with 5-(4-aminocarbonyl phenyl)-10,15,20-triphenyl porphyrin (TPP-NH
2) reacted 72 hours down for 130 ℃ at organic solvent N, N-dimethyl formyl;
3) in the reactant liquor impouring ether, product is with 0.22 μ m membrane filtration, and filter residue is scattered in tetrahydrofuran, and is ultrasonic, filters; Be repeated below operation: filter residue is scattered in tetrahydrofuran once more, and is ultrasonic, filters repetitive operation 10 times; Filter residue is washed till with chloroform and does not contain TTP-NH
2, use a spot of washing, filter residue and drying gets mono-layer graphite-porphyrin hybrid material.
6. preparation method according to claim 5 is characterized in that the mass ratio that feeds intake of described mono-layer graphite oxide and porphyrin is 1: 1.
7. the described mono-layer graphite oxide compound substance of claim 1 is used for the manufacturing of device for non-linear optical.
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| CN101831039B (en) * | 2010-05-11 | 2011-11-16 | 武汉工程大学 | Polyvinyl carbazole/graphene composite material and synthetic method and application thereof |
| CN102321254B (en) * | 2011-09-30 | 2013-02-06 | 西安交通大学 | Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film |
| US8623784B2 (en) | 2011-10-19 | 2014-01-07 | Indian Institute Of Technology Madras | Polyaniline-graphite nanoplatelet materials |
| CN109678892B (en) * | 2018-12-06 | 2021-08-03 | 江苏大学 | Preparation method and application of porphyrin-carboxylated graphene oxide nano hybrid nonlinear optical material |
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