CN103293822B - The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material - Google Patents
The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material Download PDFInfo
- Publication number
- CN103293822B CN103293822B CN201310181051.4A CN201310181051A CN103293822B CN 103293822 B CN103293822 B CN 103293822B CN 201310181051 A CN201310181051 A CN 201310181051A CN 103293822 B CN103293822 B CN 103293822B
- Authority
- CN
- China
- Prior art keywords
- phthalocyanine
- compound
- particle
- carbon nano
- hybrid material
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses the preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material.The method is pressed into target-pulse laser through dag and phthalocyanine-like compound potpourri and bombards continuously and acquire aaerosol solution-add ammoniacal liquor or ethylenediamine and be heated to 70 ~ 240 DEG C and be incubated-removed by hydro-extractor particle large in suspending liquid and obtain supernatant-add silane coupling agent and be heated to 150-240 DEG C and be incubated and obtains colloidal sol-insert on mould or all kinds of carrier after drying and other steps, the finally transparent nonlinear optics carbon nano-particle of acquisition and phthalocyanine-like compound hybrid material film or block etc.Solid transparent hybrid material prepared by the present invention has the advantages such as strong and fast response time, the light limit threshold value of nonlinear optical properties is low, is the nonlinear optical material that a class has widespread use and is worth.
Description
Technical field
The invention belongs to inorganic-organic hybrid optical material and field of nanometer technology, particularly the preparation method of a kind of carbon nano-particle and phthalocyanine-like compound hybrid material.
Background technology
Increasingly extensive along with laser technology application, the laser threat that human eye and optoelectronic sensor are subject to is more and more serious, and therefore lasing safety is extremely paid attention to various countries.Linear optics effect cannot meet the demand of lasing safety, and how research steering utilizes the nonlinear optics limiting effect of material to realize lasing safety by people.In addition, nonlinear optics also demonstrates tempting application prospect in contemporary optics communication, data storing, optical information processing etc., so synthesis nonlinear optical properties is strong and new material that response speed is exceedingly fast has become current research emphasis.
Phthalocyanine has special two-dimentional conjugation л electronic structure, not only has higher stability to light, heat, and almost can form complex with all metallic element generation coordinations in the periodic table of elements.Phthalocyanine-like compound can by the intensity of Excited-state Absorption process restriction nanosecond laser pulses in quite broad ultraviolet-visible light spectral limit, having larger optical nonlinearity coefficient and very short photoelectric response time, is therefore a kind of well organic non linear optical material.
When carbon nano-particle size only has a few nanometer, after particularly using its surface of organic matter modified, unique optics and nonlinear optical property can be shown, in addition carbon nano-particle itself is not containing toxic element, therefore shows tempting application prospect in fields such as biological detection, photocatalysis, nonlinear optics and photoelectric conversions.The combination of the factor affecting carbon nano-particle optics and the nonlinear optical property mainly crystal structure of carbon nano-particle and the molecular structure of surface modification thereof and it and carbon nano-particle.Form hybrid inorganic-organic materials by the more excellent optics of acquisition and non-linear optical property with phthalocyanine and metal complex modified carbon nano particle thereof, at photoelectric device and non-linear optical field, there is important application.But phthalocyanine pole is insoluble in water-based liquid medium, even if solubleness is in organic solvent also very limited, so modify inorganic material with phthalocyanine and there is extreme difficulties, efficiency is also very low, can not give full play to the performance advantage of two class materials.Although phthalocyanine-like compound is carbon nano-structured with other at present, as fullerene, carbon nano-tube etc. achieve hybridization compounding, do not show gratifying non-linear optical property.
Summary of the invention
The above-mentioned technical barrier that the present invention exists to solve phthalocyanine-like compound and inorganic material compound, disclose a kind of solid transparent and represent the phthalocyanine-like compound of non-linear optical property excellence and the preparation method of carbon nano-particle hybrid material, can be used for making device for non-linear optical.
The present invention is by the following technical solutions:
A preparation method for nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material, is characterized in that comprising the following steps:
(1) dag is mixed with the mass ratio of phthalocyanine-like compound by 100:10-30, and be pressed into dag and phthalocyanine-like compound disk after making it mix by ball mill grinding 6-12 hour;
(2) configuration concentration is the dimethyl formamide ethanolic solution of 2-5mol/L, obtained dag and phthalocyanine-like compound disk is placed in dimethyl formamide ethanolic solution apart from liquid level 2-3mm place;
(3) power density is adopted to be 10
6-10
8wcm
-2pulsed laser beam bombard dag in dimethyl formamide ethanolic solution and phthalocyanine-like compound disk continuously, the container holding dimethyl formamide ethanolic solution and dag and phthalocyanine-like compound disk is put into ultrasonic cleaner simultaneously and carry out ultrasound wave dispersion, pulsed laser ablation and ultrasound wave dispersion continued after 3-6 hour, take out the dag and phthalocyanine-like compound disk not doing to be finished, obtain suspending liquid;
(4) obtained suspending liquid is put into closed reactor, add ammoniacal liquor or ethylenediamine by the 4-16% of suspension vol simultaneously, suspending liquid be heated to 70-240 DEG C and be incubated 2-6 hour, then suspending liquid being put into hydro-extractor and remove larger particle, obtaining supernatant;
(5) volume ratio by 50-100% in above-mentioned supernatant adds silane coupling agent, inserts in closed reactor and is heated to 150-240 DEG C and is incubated 1-3 hour, obtains the colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material;
(6) the above-mentioned colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material is inserted in mould or on all kinds of carrier, at 70-85 DEG C of air drying, obtain transparent nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material film or block.
Described dag granularity is 1 μm, and phthalocyanine-like compound is metal phthalocyanine compound and the chow ring substituents thereof such as ZnPc, copper phthalocyanine or aluminium phthalocyanine.
Described silane coupling agent is the silane coupling agents such as vinyl, amino or epoxy radicals.
The carbon nano-particle adopting the present invention to prepare generation and phthalocyanine-like compound hybrid material have that nonlinear optical properties is strong, fast response time, light limit the advantages such as threshold value is low, are the nonlinear optical materials that a class has widespread use value.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the preparation method of nonlinear optics carbon nano-particle of the present invention and phthalocyanine-like compound hybrid material;
Fig. 2 is carbon nano-particle of the present invention and phthalocyanine compound hybrid material linear transmittance under visible light.
Fig. 3 is the relation that carbon nano-particle of the present invention and copper phthalocyanine compound hybrid material laser input energy and exports between energy.
Fig. 4 is the relation that carbon nano-particle of the present invention and ZnPc compound hybrid material laser input energy and exports between energy.
Fig. 5 is the relation that the laser of carbon nano-particle of the present invention and copper phthalocyanine compound hybrid material inputs between energy and standard transmittance.
Fig. 6 is the relation that the laser of carbon nano-particle of the present invention and ZnPc compound hybrid material inputs between energy and standard transmittance.
Embodiment
Enumerate embodiment introduce detailed technology scheme of the present invention below in conjunction with accompanying drawing, following examples are several typical examples, the invention is not restricted to following examples:
Embodiment 1:
As shown in Figure 1, the preparation of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material is realized according to following steps:
(1) get by the mass ratio of 100:20 dag and the Copper phthalocyanine compound that granularity is 1 μm, mixed by bowl mill, drum's speed of rotation controls at 400 revs/min, and Ball-milling Time is 8 hours, then the material mixed is pressed into disk.
(2) dimethyl formamide (DMF) ethanolic solution that volume by volume concentration is 3mol/L is configured, obtained dag and phthalocyanine-like compound disk are placed in beaker, DMF ethanolic solution is poured in beaker, the amount of control DMF ethanolic solution, makes liquid level apart from dag and phthalocyanine-like compound disk 2mm.
(3) pulsed laser beam is adopted to bombard dag in DMF ethanolic solution and phthalocyanine-like compound disk continuously, the container holding DMF ethanolic solution and dag and phthalocyanine-like compound disk is put into ultrasonic cleaner simultaneously and carry out ultrasound wave dispersion, the power density of laser controls 10
7wcm
-2, irradiate after 5 hours, after taking out the dag and phthalocyanine-like compound disk not doing to be finished, obtain suspending liquid.
(4) obtained suspending liquid is put into closed reactor, add ammoniacal liquor by 10% of suspension vol simultaneously, be then heated to 200 DEG C and be incubated 4 hours.The suspending liquid that insulation obtains is removed larger particle by hydro-extractor, and centrifugal speed is 5000 revs/min, obtains supernatant.
(5) in above-mentioned supernatant, add 3-aminopropyl trimethoxysilane by the volume ratio of 100%, insert in closed reactor and be heated to 240 DEG C and be incubated 2 hours, obtain colloidal sol.
(6) colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material that insulation obtains is inserted square mould, at 80 DEG C of air dryings, obtain transparent carbon nano-particle and Copper phthalocyanine compound hybrid material film.
Embodiment 2:
(1) get by the mass ratio of 100:10 dag and the phthalocyanine compound that granularity is 1 μm, mixed by bowl mill, drum's speed of rotation controls at 300 revs/min, and Ball-milling Time is 6 hours.And then the material mixed is pressed into disk.
(2) volume by volume concentration 2mol/L DMF ethanolic solution is configured, obtained dag and phthalocyanine-like compound disk are placed in beaker, DMF ethanolic solution is poured in beaker, the amount of control DMF ethanolic solution, make liquid level apart from dag and phthalocyanine-like compound disk 2mm.
(3) pulsed laser beam is adopted to bombard dag in DMF ethanolic solution and phthalocyanine-like compound disk continuously, the container holding DMF ethanolic solution and dag and phthalocyanine-like compound disk is put into ultrasonic cleaner simultaneously and carry out ultrasound wave dispersion, the power density of laser controls 10
8wcm
-2, irradiate after 3 hours, after taking out the dag and phthalocyanine-like compound disk not doing to be finished, obtain suspending liquid.
(4) obtained suspending liquid is put into closed reactor, add ammoniacal liquor by 4% of suspension vol simultaneously, be then heated to 70 DEG C and be incubated 6 hours.The suspending liquid that insulation obtains is removed larger particle by hydro-extractor, and centrifugal speed is 3000 revs/min, obtains supernatant.
(5) in above-mentioned supernatant, add 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane by the volume ratio of 80%, insert in closed reactor and be heated to 150 DEG C and be incubated 3 hours, obtain colloidal sol.
(6) colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material that insulation obtains is inserted square mould, at 70 DEG C of air dryings, obtain transparent carbon nano-particle and phthalocyanine compound hybrid material film.
Embodiment 3:
(1) get by the mass ratio of 100:30 dag and the aluminum phthalocyanine compound that granularity is 1 μm, mixed by bowl mill, drum's speed of rotation controls at 500 revs/min, and Ball-milling Time is 12 hours.And then the material mixed is pressed into disk.
(2) volume by volume concentration 5mol/L DMF ethanolic solution is configured, obtained dag and phthalocyanine-like compound disk are placed in beaker, DMF ethanolic solution is poured in beaker, the amount of control DMF ethanolic solution, make liquid level apart from dag and phthalocyanine-like compound disk 3mm.
(3) pulsed laser beam is adopted to bombard dag in DMF ethanolic solution and phthalocyanine-like compound disk continuously, the container holding DMF ethanolic solution and dag and phthalocyanine-like compound disk is put into ultrasonic cleaner simultaneously and carry out ultrasound wave dispersion, the power density of laser controls 10
6wcm
-2, irradiate after 6 hours, after taking out the dag and phthalocyanine-like compound disk not doing to be finished, obtain suspending liquid.
(4) obtained suspending liquid is put into closed reactor, add ammoniacal liquor by 16% of suspension vol simultaneously, be then heated to 240 DEG C and be incubated 6 hours.The suspending liquid that insulation obtains is removed larger particle by hydro-extractor, and centrifugal speed is 5000 revs/min, obtains supernatant.
(5) volume ratio by 50% in above-mentioned supernatant adds vinyltrimethoxy silane, inserts in closed reactor and is heated to 200 DEG C and is incubated 1 hour, obtains colloidal sol.
(6) colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material that insulation obtains is inserted square mould, at 85 DEG C of air dryings, obtain transparent carbon nano-particle and aluminum phthalocyanine compound hybrid material film.
The carbon nano-particle prepare embodiment 1-3 and phthalocyanine compound hybrid material film carry out conventional Z scanning, obtain linear transmittance under the visible wavelength of 400-700nm as shown in Figure 2.In visible-range, the transmittance of gained solid material has exceeded 50%, meets the printing opacity needs of conventional photo material completely.
Carbon nano-particle and copper/ZnPc compounds hybrid material laser input energy and export relation between energy as shown in Figure 3-4; Relation between laser input energy and standard transmittance as seen in figs. 5-6.With the C of current document wide coverage
60, Graphene, carbon nano-tube and compared with phthalocyanine-like compound hybrid material etc., gained solid materials display has gone out lower light limit threshold value.
Claims (3)
1. a preparation method for nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material, is characterized in that comprising the following steps:
(1) dag is mixed with the mass ratio of phthalocyanine-like compound by 100:10-30, and be pressed into dag and phthalocyanine-like compound disk after making it mix by ball mill grinding 6-12 hour;
(2) configuration concentration is the dimethyl formamide ethanolic solution of 2-5mol/L, obtained dag and phthalocyanine-like compound disk is placed in DMF ethanolic solution apart from liquid level 2-3mm place;
(3) power density is adopted to be that the pulsed laser beam of 106-108Wcm-2 bombards dag in DMF ethanolic solution and phthalocyanine-like compound disk continuously, the container holding DMF ethanolic solution and dag and phthalocyanine-like compound disk is put into ultrasonic cleaner simultaneously and carry out ultrasound wave dispersion, pulsed laser ablation and ultrasound wave dispersion continued after 3-6 hour, take out the dag and phthalocyanine-like compound disk not doing to be finished, obtain suspending liquid;
(4) obtained suspending liquid is put into closed reactor, add ammoniacal liquor or ethylenediamine by the 4-16% of suspension vol simultaneously, suspending liquid be heated to 70-240 DEG C and be incubated 2-6 hour, then suspending liquid being put into hydro-extractor and remove larger particle, obtaining supernatant;
(5) volume ratio by 50-100% in above-mentioned supernatant adds silane coupling agent, inserts in closed reactor and is heated to 150-240 DEG C and is incubated 1-3 hour, obtains the colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material;
(6) the above-mentioned colloidal sol containing carbon nano-particle and phthalocyanine-like compound hybrid material is inserted in mould or on all kinds of carrier, at 70-85 DEG C of air drying, obtain transparent nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material film or block.
2. the preparation method of a kind of nonlinear optics carbon nano-particle according to claim 1 and phthalocyanine-like compound hybrid material, it is characterized in that: described dag granularity is 1 μm, phthalocyanine-like compound is metal phthalocyanine compound and the chow ring substituent thereof of ZnPc, copper phthalocyanine or aluminium phthalocyanine.
3. the preparation method of a kind of nonlinear optics carbon nano-particle according to claim 1 and phthalocyanine-like compound hybrid material, is characterized in that: described silane coupling agent is the silane coupling agent of vinyl, amino or epoxy radicals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310181051.4A CN103293822B (en) | 2013-05-16 | 2013-05-16 | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310181051.4A CN103293822B (en) | 2013-05-16 | 2013-05-16 | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103293822A CN103293822A (en) | 2013-09-11 |
| CN103293822B true CN103293822B (en) | 2015-10-28 |
Family
ID=49094952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310181051.4A Expired - Fee Related CN103293822B (en) | 2013-05-16 | 2013-05-16 | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103293822B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104898346B (en) * | 2015-05-12 | 2018-04-27 | 黑龙江大学 | A kind of metal-free phthalocyanine-graphene oxide composite nonlinear optical film material and preparation method thereof |
| CN111929758A (en) * | 2020-08-12 | 2020-11-13 | 中国科学院长春光学精密机械与物理研究所 | Laser protective equipment and protective system |
| CN115141397B (en) * | 2022-08-08 | 2023-05-26 | 西南石油大学 | Composite film, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349478A (en) * | 1999-04-16 | 2002-05-15 | 联邦科学和工业研究组织 | Multilayer carbon nanotube films |
| CN1429767A (en) * | 2001-10-04 | 2003-07-16 | 佳能株式会社 | Method for preparing nanometer carbon material |
| CN1512540A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院化学研究所 | Carbon nano tube/carbon niride nano tube with nano junction and preparation and use |
| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
| CN101254916A (en) * | 2008-04-11 | 2008-09-03 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
-
2013
- 2013-05-16 CN CN201310181051.4A patent/CN103293822B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349478A (en) * | 1999-04-16 | 2002-05-15 | 联邦科学和工业研究组织 | Multilayer carbon nanotube films |
| CN1429767A (en) * | 2001-10-04 | 2003-07-16 | 佳能株式会社 | Method for preparing nanometer carbon material |
| CN1512540A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院化学研究所 | Carbon nano tube/carbon niride nano tube with nano junction and preparation and use |
| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
| CN101254916A (en) * | 2008-04-11 | 2008-09-03 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
Non-Patent Citations (1)
| Title |
|---|
| 基于酞菁的非线性光学功能材料的设计和制备;何楠;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20110715(第7期);B014-18 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103293822A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Hydrophobic carbon dots with blue dispersed emission and red aggregation-induced emission | |
| Aziz et al. | A novel polymer composite with a small optical band gap: New approaches for photonics and optoelectronics | |
| CN102282229B (en) | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base | |
| He et al. | Sonochemical preparation of hierarchical ZnO hollow spheres for efficient dye‐sensitized solar cells | |
| JP4665499B2 (en) | Metal fine particles, production method thereof, composition containing the same, and use thereof | |
| Sun et al. | Preparation and characterization of polypyrrole/TiO2 nanocomposites by reverse microemulsion polymerization and its photocatalytic activity for the degradation of methyl orange under natural light | |
| Cheng et al. | Highly Efficient Photothermal Conversion of Ti3C2T x/Ionic Liquid Gel Pen Ink for Smoothly Writing Ultrasensitive, Wide-Range Detecting, and Flexible Thermal Sensors | |
| CN103293822B (en) | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material | |
| CN104449714B (en) | Conversion nano granule-graphene oxide composite material and preparation method thereof in one | |
| Wang et al. | Preparation, characterization, and nonlinear optical properties of graphene oxide-carboxymethyl cellulose composite films | |
| Mamidala et al. | Enhanced nonlinear optical responses in donor-acceptor ionic complexes via photo induced energy transfer | |
| CN101219859A (en) | Nano-oiliness ATO heat-insulating slurry, production method and uses thereof | |
| Zheng et al. | The effects of ultrasonication power and time on the dispersion stability of few-layer graphene nanofluids under the constant ultrasonic energy consumption condition | |
| JP4873864B2 (en) | Metal oxide dispersion and coating method thereof | |
| Zhang et al. | Hydrophobic modification of ZnO nanostructures surface using silane coupling agent | |
| Tadesse et al. | Natural dye-sensitized solar cells using pigments extracted from Syzygium guineense | |
| CN106433219A (en) | Tungsten/fluorine codoped vanadium dioxide nanometer heat insulation sizing agent, tungsten/fluorine codoped vanadium dioxide paint film by means of sizing agent and preparation method | |
| Brza et al. | Green coordination chemistry as a novel approach to fabricate polymer: Cd (II)-complex composites: Structural and optical properties | |
| Li et al. | Multifunctional carbon nitride nano-homojunction decorated g-C3N4 nanocomposites for optoelectronic performances | |
| CN102201643B (en) | Preparation method for graphene-based saturable adsorption mirror | |
| CN111621170A (en) | Water-based nano tin antimony oxide heat insulation slurry and preparation method and application thereof | |
| Senthamarai et al. | Synthesis and characterization of nickel doped TiO2 nanoparticles by green method and its performance as dye‐sensitized solar cells photoanodes | |
| Vieira et al. | Improving the performance of direct solar collectors and stills by controlling the morphology and size of plasmonic core–shell nanoheaters | |
| Eswaramoorthy et al. | Planar perovskite solar cells: Plasmonic nanoparticles‐modified ZnO as an electron transport layer for enhancing the device performance and stability at ambient conditions | |
| Jiao et al. | Efficient utilization of hybrid photovoltaic/thermal solar systems by nanofluid-based spectral beam splitting: A review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20160516 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |