CN101386783B - Sulfotetraphenyl porphyrin nano luminescent material and preparation method thereof - Google Patents
Sulfotetraphenyl porphyrin nano luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sulfonic acid tetraphenyl porphyrin nano-fluorescent material and a preparation method thereof, which relate to a fluorescent porphyrin material and a preparation method thereof. The sectional shape of the material is of a rectangular sheet or strip or sheet and strip. The method comprises the following steps: preparing a TPRS alcohol solution first, preparing a TPPS nano-fluorescent material dispersion system, and obtaining a product through separation and drying. The material has smaller size and better photosensitivity, has good characteristics of a porphyrin monomer such as rigidity and flexibility, electronic buffer capacity, photosensitivity, high chemical stability, wide spectral response, and also has special properties after the nanometer treatment such as small-size effect, surface effect, quantum effect, interfacial effect. The method is simple, has low production cost, and is convenient for promotion and application. The material prepared by adopting the method can be widely used as markers, photosensitive materials as well as sensitive recognition elements and materials for constructing photoelectric devices, molecular devices and sensors.
Description
Technical field
The invention belongs to porphyrin nano material technology field, particularly porphyrin nano fluorescent material and preparation method thereof.
Background technology
Nanotechnology is after infotech and biotechnology, the great technology of another profound influence socio-economic development, and its fast development will impel nearly all industrial circle to produce a revolutionary variation in 21 century.The nanometer material has the not available physics-chem characteristic of traditional material: small-size effect, surface effects, quantum effect and interfacial effect.Thereby make it have some special performances that common material does not possess: to cause rerum naturas such as sound, light, electromagnetism, thermodynamics to present new small-size effect; Along with the specific surface area that diminishes of particle diameter will increase significantly.High like this specific surface makes the atomicity that is in the surface more and more, and surface energy increases sharply simultaneously, makes it have high reactivity; It is significant different or the like that quantum effect can cause nanoparticle magnetic, light, sound, heat, electricity and supraconductivity and macroscopic property to have.In addition, nano material also has superplasticity, diffustivity and extraordinary electricity, mechanics, optical property.These peculiar properties that nano material has and excellent performance make it have a wide range of applications in electronics, optics, medical science, biology, catalysis, ceramics and magnetic data storage or the like field.
The agent structure of porphyrin is a pyrrole ring, and it is by four pyrrole rings and four big pi-conjugated systems with 18 atoms, 18 electronics that the methyne bridging gets up.Substituent variation has formed different derivatives of porphyrin on the pyrrole ring.Porphyrin compound is the darker material of color.The special construction of porphyrin quasi-molecule has the chemicalstability and the wide characteristics of spectral response of hard and soft property, electronics resiliency, photo-electro-magnetic, photosensitivity and height; Because its particular structure and performance, aspects such as, photovaltaic material synthetic in anticancer, colour developing, analytical chemistry, biological chemistry, medical chemistry, simulated light, catalyzed oxidation, sensitive material are had broad application prospects.
Porphyrin monomer (the not porphyrin of nanometer) has excellent characteristics such as chemicalstability and the spectral response of hard and soft property, electronics resiliency, photo-electro-magnetic, photosensitivity and height be wide; It obviously increases through fluorescence quantum yield behind the nanometer; Embody good photosensitivity and possessed the specific physiques such as small-size effect, surface effects, quantum effect and interfacial effect that the porphyrin monomer did not have originally, this has indicated that it possesses application prospect widely at the aspects such as responsive recognition component, photoelectronics and analytical chemistry that transmitter, molecular device are constructed in the thing of marking, light sensitive material and conduct.
Have porphyrin nano material and preparation method thereof at present; " Method toPrepare Porphyrin Nanoparticles and its Application as Oxidation Catalyst " patent like Pub.No.:US 2003/0232982Al; The size of disclosed 12 kinds of porphyrin nano particles is 0～1000nm, as the catalyzer of oxidizing reaction.Its preparation method is: at a certain temperature, earlier a kind of porphyrin or porphyrin mixture are dissolved in a kind of solvent, add stablizer, and then other a kind of solvent is added wherein.Stir the preparation nanoparticle.The shortcoming of this method is: (1) can only obtain the indefinite nanoparticle of shape; (2) need to add stablizer, increased operation; (3) increased production cost; (4) can bring certain pollution.And for example publication number is " a kind of metalloporphyrin nanotube and nano wire and preparation method thereof " patent of CN1706844A; The cross section of disclosed metalloporphyrin nanotube, nano wire is a hexagon, is used for the specific use such as protection of catalyzer, drug delivery and biologically active substance.Its preparation method is: at room temperature, be 5,10 of 0.01～5mmol/L with concentration; 15; 20-four pyridyl porphyrin zinc (ZnTPyP) are injected in the water phase surfactant mixture that concentration is 0.1～100mmol/L, stir 10～30 minutes, through separation, the dry finished product that gets.The main drawback of this method is: (1) needs to add tensio-active agent, has increased operation; (2) increased production cost; (3) can bring certain pollution.Magazine J.AM.CHEM.SOC.2007 and for example; 129; " Self-Assembly and Self-Metallization of PorphyrinNanosheets " literary composition of 2440-2441; The disclosed length of side to pyridyl triphenyl porphyrin tin (SnPyTriPP) nanometer sheet, nanometer piece is 300～1000nm, is mainly used in catalysis and the photoelectronics.Its preparation method is: at room temperature, the SnPyTriPP ethanolic soln of 200uL is injected in the 10mL water, stirred 10 minutes, finished product.The nanometer sheet and the nanometer piece size of this method preparation are relatively large, and the single sulfonic group tetraphenylporphyrin (TPPS that utilizes the said condition of this method to prepare
1) fluorescence intensity of nano material also has only TPPS
1Monomeric about 8 times (seeing accompanying drawing 1), intensity is lower.
Summary of the invention
The objective of the invention is weak point, a kind of sulfonic group tetraphenylporphyrin (TPPS) nano-luminescent material and preparation method thereof is provided to existing porphyrin nano material and preparation method thereof.Material of the present invention is regular fluorescence nano sheet and nano strip, and it is less relatively to have size, and fluorescence intensity is high, the advantage that fluorescent characteristic is good; The inventive method has simple and easy to do, and is environment friendly and pollution-free, but industrialization, the characteristics that cost is low.
Principle of the present invention is: in ethanol/tri-distilled water mixed solution system, utilize the porphyrin with different substituents (according to sulfonic group substituted number difference on phenyl ring, to be divided into single sulfonic group tetraphenylporphyrin (TPPS
1), disulfonic acid base tetraphenylporphyrin (TPPS
2), trisulfonic acid base tetraphenylporphyrin (TPPS
3) and tetrasulfonic acid base tetraphenylporphyrin (TPPS
4) these four types) solubleness in this system and main self-assembly reactive force different; Regulate the concentration of porphyrin chemicals; The ratio of ethanol and tri-distilled water; Whipping temp, churning time and rotating speed are so that successfully prepare nanometer porphyrin fluorescent material and realize optical property, form and the big or small control to this material.
The objective of the invention is to realize like this: a kind of sulfonic group tetraphenylporphyrin (TPPS) nano-luminescent material, its cross section are rectangular sheet material or web or sheet material and web.Sheet material length is 350～450nm, wide 150～300nm, and web length is 500～850nm, the wide 70～90nm of being.Therefore its fluorescent characteristic is monomeric more than 15～40 times, has possessed better photosensitive property, is widely used as extraordinary affinity tag, photochromics or constructs transmitter and the responsive recognition component of molecular device etc., in the fields such as analytical chemistry.Wherein sulfonic group tetraphenylporphyrin (TPPS) is single sulfonic group tetraphenylporphyrin (TPPS
1) or disulfonic acid base tetraphenylporphyrin (TPPS
2) or trisulfonic acid base tetraphenylporphyrin (TPPS
3) or tetrasulfonic acid base tetraphenylporphyrin (TPPS
4).
A kind of sulfonic group tetraphenylporphyrin (TPPS) preparation of nano fluorescent material method, elder generation disposes the TPPS ethanolic soln, back preparation TPPS nano-luminescent material dispersion system, through separation, the dry product that gets, concrete steps are following again:
(1) configuration of TPPS ethanolic soln
TPPS is positioned in the container, adds ethanolic soln again, after stirring through whisking appliance, just configuring the TPPS mass concentration is the TPPS ethanolic soln of 0.38～0.58mmol/L, under 3～4 ℃ of temperature, keeps in Dark Place, subsequent use.Wherein sulfonic group tetraphenylporphyrin (TPPS) is single sulfonic group tetraphenylporphyrin (TPPS
1) or disulfonic acid base tetraphenylporphyrin (TPPS
2) or trisulfonic acid base tetraphenylporphyrin (TPPS
3) or tetrasulfonic acid base tetraphenylporphyrin (TPPS
4).
(2) preparation of TPPS nano-luminescent material dispersion system
After (1) step accomplished, by the TPPS ethanolic soln: the volume ratio of tri-distilled water is the ratio of 1:50～100, goes on foot the TPPS ethanolic soln of preparing and preserving with (1); Pass through sampler; Be injected into initial temperature and be in 3～4 ℃ the tri-distilled water, then with the thermostatic mixer heating and stir and constant temperature at 4～80 ℃, again with 1440～1600 rev/mins rotating speed; Stirred 5～15 minutes, and just prepared micro emulsion xanchromatic TPPS nano-luminescent material dispersion system.
(3) spinning
After (2) step accomplished, with the TPPS nano-luminescent material dispersion system that (2) step prepared, be positioned in the supercentrifuge after, with 10000～14000 rev/mins rotating speed, high speed centrifugation separates 20～40min, collects lower floor's solid matter.
(4) drying
(3) step went on foot the solid matter of collecting with (3) and is positioned in the vacuum drying oven after accomplishing, and under 84～86 ℃ of temperature, carried out drying, and be 23～25 hours time of drying, just prepares the TPPS nano-luminescent material.
Temperature or mixing speed or churning time when the mass concentration of the TPPS in (1) step of adjustment or the adding volume of the TPPS ethanol liquid in (2) step or stirring; Just prepare TPPS nano fluorescent sheet material or web or sheet material and web; The length of its sheet material is 350～450nm, wide 150～300nm, and web length is 500～850nm, the wide 70～90nm of being.
The present invention mainly contains following effect after adopting above-mentioned preparation scheme:
(1) size of TPPS nano-luminescent material of the present invention is less relatively.The width of the TPPS nano fluorescent sheet material that employing the inventive method is prepared is merely 150～300nm; The width of TPPS nano fluorescent web is merely 70～90nm; Size is less; Therefore possess better small-size effect, surface effects, quantum effect etc., so TPPS nano-luminescent material of the present invention possesses more special performance.
(2) fluorescent characteristic of TPPS nano-luminescent material is better.The fluorescence quantum yield of the TPPS nano-luminescent material that employing the inventive method is prepared is up to monomeric 15 times of former TPPS, so the TPPS nano material of the present invention's preparation possesses more excellent fluorescence.
(3) TPPS nano-luminescent material of the present invention had both had the good characteristic of porphyrin monomer (not passing through the porphyrin of nanometer), possessed the specific performance behind the nanometer again.Adopt the TPPS nano-luminescent material of the inventive method preparation; Both possessed advantages such as chemicalstability and the spectral response of hard and soft property, electronics resiliency, photo-electro-magnetic, photosensitivity and height of porphyrin monomer (not passing through the porphyrin of nanometer) be wide, possessed the specific performances such as small-size effect, surface effects, quantum effect and interfacial effect behind the nanometer again.
(4) simple, the non-environmental-pollution of method, production cost are low.The inventive method is simple, need not add tensio-active agent or stablizer, only needs water and ethanol to make solvent.In process of production, do not need complicated plant and instrument, only adopt simple glassware and whisking appliance, and non-environmental-pollution.Operate also simple, thereby reduce production costs greatly.
(5) easy to utilize.Because the inventive method is simple, easy and simple to handle, only adopt simple device and the nano-luminescent material performance prepared good.Thereby easy to utilize, the industrialization producing feasibility is higher.
The TPPS nano-luminescent material of the present invention that adopts the inventive method to prepare; Can be widely used in fields such as electricity, optics, biology, chemistry and senser element, be widely used as the responsive recognition component that transmitter, molecular device are constructed in affinity tag, light sensitive material and conduct.
Description of drawings
Fig. 1 is the 5-p-sulfonic acid base phenyl-10,15 according to the method preparation of " Self-Assembly and Self-Metallization of Porphyrin Nanosheets " literary composition, 20-triphenyl porphyrin (TPPS
1) nano material and do not pass through the monomeric fluorescence emission spectrogram of porphyrin of nanometer;
Among the figure: the TPPS of curve 1 for preparing according to the method for " Self-Assembly and Self-Metallization of Porphyrin Nanosheets " literary composition
1The fluorescence emission spectrogram of nano material; Curve 2 is not for passing through the TPPS of nanometer
1Monomeric fluorescence emission spectrogram.
The 5-p-sulfonic acid base phenyl-10,15 that Fig. 2 prepares for embodiment 2,20-triphenyl porphyrin (TPPS
1) nano-luminescent material and do not pass through the monomeric fluorescence emission spectrogram of porphyrin of nanometer;
Among the figure: the TPPS of curve 1 for preparing by embodiment 2
1The fluorescence emission spectrogram of nano material; Curve 2 is not for passing through the TPPS of nanometer
1Monomeric fluorescence emission spectrogram.
The 5-p-sulfonic acid base phenyl-10,15 that Fig. 3 makes for embodiment 2,20-triphenyl porphyrin (TPPS
1) electron scanning micrograph of nanometer sheet;
The 5-p-sulfonic acid base phenyl-10,15 that Fig. 4 makes for embodiment 2,20-triphenyl porphyrin (TPPS
1) electron scanning micrograph of nano strip.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) nano-luminescent material, be that the cross section is the fluorescence nano sheet material of rectangular length 400～450nm, wide 200～300nm.
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) concrete steps of preparation of nanomaterials are following:
(1) TPPS
1The configuration of ethanolic soln
With TPPS
1Be positioned in the container, add ethanolic soln again, after stirring through whisking appliance, just configure TPPS
1Mass concentration is the TPPS of 0.58mmol/L
1Ethanolic soln keeps in Dark Place under 3 ℃ of temperature, and is subsequent use.
(2) TPPS
1The preparation of nano-luminescent material dispersion system
(1) step was pressed TPPS after accomplishing
1Ethanolic soln: the volume ratio of tri-distilled water is the ratio of 1:60, goes on foot the TPPS for preparing and preserve with (1)
1Ethanolic soln through sampler, is injected into initial temperature and is in 3 ℃ the tri-distilled water, then with the thermostatic mixer heating and stir and constant temperature at 80 ℃, with 1440 rev/mins rotating speed, stirred 5 minutes again, just prepare micro emulsion xanchromatic TPPS
1The nano-luminescent material dispersion system.
(3) spinning
(2) step went on foot the TPPS for preparing with (2) after accomplishing
1The nano-luminescent material dispersion system, be positioned in the supercentrifuge after, with 10000 rev/mins rotating speed, high speed centrifugation separates 40min, collects lower floor's solid matter.
(4) drying
(3) step went on foot the solid matter of collecting with (3) and is positioned in the vacuum drying oven after accomplishing, and under 86 ℃ of temperature, carried out drying, and be 23 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 400～450nm, wide 200～300nm.
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) nano-luminescent material, be that the cross section is that fluorescence nano sheet material and the length of rectangular length 350～450nm, wide 150～300nm is the fluorescence nano web of 500～850nm, the wide 70～90nm of being.
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) concrete steps of preparation of nanomaterials are following:
(1) TPPS
1The configuration of ethanolic soln
With embodiment 1, characteristic is: make TPPS
1Mass concentration be 0.43mmol/L, the temperature that keeps in Dark Place is 4 ℃.
(2) TPPS
1Preparation of nano fluorescent material
With embodiment 1, characteristic is: TPPS
1Ethanolic soln: the volume ratio of tri-distilled water is 1:50, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 70 ℃, and stirring velocity is 1600rpm, and churning time is 10 minutes.
(3) spinning
With embodiment 1, characteristic is: the speed of spinning is 13000 rev/mins, and centrifugation time is 30min.
(4) drying
With embodiment 1, characteristic is: drying temperature is 85 ℃, and be 24 hours time of drying, and the powdery substance of preparing is the TPPS of long 350～450nm, wide 150～300nm
1The fluorescence nano sheet material is the fluorescence nano web of 500～850nm, the wide 70～90nm of being with length.
Embodiment 3
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) nano-luminescent material, be that the cross section is the fluorescence nano sheet material of rectangular length 350～400nm, wide 150～250nm.
A kind of single sulfonic group tetraphenylporphyrin (TPPS
1) concrete steps of preparation of nanomaterials are following:
(1) TPPS
1The configuration of ethanolic soln
With embodiment 1, characteristic is: make TPPS
1Mass concentration be 0.50mmol/L, the temperature that keeps in Dark Place is 4 ℃.
(2) TPPS
1Preparation of nano fluorescent material
With embodiment 1, characteristic is: TPPS
1Ethanolic soln: the volume ratio of tri-distilled water is 1:70, and the initial temperature of tri-distilled water is 4 ℃, and the homo(io)thermism that makes mixed solution is at 4 ℃, and stirring velocity is 1550rpm, and churning time is 15 minutes.
(3) spinning
With embodiment 1, characteristic is: the speed of spinning is 14000 rev/mins, and centrifugation time is 20min.
(4) drying
With embodiment 1, characteristic is: drying temperature is 84 ℃, and be 25 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 350～400nm, wide 150～250nm.
Embodiment 4
A kind of disulfonic acid base tetraphenylporphyrin (TPPS
2) nano-luminescent material, be that the cross section is the fluorescence nano web of rectangular length 550～850nm, wide 75～90nm.
A kind of disulfonic acid base tetraphenylporphyrin (TPPS
2) concrete steps of preparation of nanomaterials are following:
(1) TPPS
2The configuration of ethanolic soln
With embodiment 1, characteristic is: the porphyrin kind is changed to TPPS
2, the TPPS that makes
2Mass concentration is 0.38mmol/L, and the temperature that keeps in Dark Place is 3 ℃.
(2) TPPS
2Preparation of nano fluorescent material
With embodiment 1, characteristic is: TPPS
2Ethanolic soln: the volume ratio of tri-distilled water is 1:60, and the initial temperature of tri-distilled water is 3 ℃, heat and the homo(io)thermism that makes mixed solution at 4 ℃, stirring velocity is 1600rpm, churning time is 15 minutes.
(3) spinning
With embodiment 1, characteristic is: the speed of spinning is 14000 rev/mins, and centrifugation time is 35min.
(4) drying
With embodiment 1, characteristic is: drying temperature is 84 ℃, and be 25 hours time of drying, and the powdery substance of preparing is the fluorescence nano web of long 550～850nm, wide 75～90nm.
Embodiment 5
A kind of trisulfonic acid base tetraphenylporphyrin (TPPS
3) nano-luminescent material, be that the cross section is the fluorescence nano sheet material of rectangular length 380～450nm, wide 180～300nm.
A kind of trisulfonic acid base tetraphenylporphyrin (TPPS
3) concrete steps of preparation of nanomaterials are following:
(1) TPPS
3The configuration of ethanolic soln
With embodiment 1, characteristic is: the porphyrin kind is changed to TPPS
3, the TPPS that makes
3Mass concentration is 0.47mmol/L, and the temperature that keeps in Dark Place is 4 ℃.
(2) TPPS
3Preparation of nano fluorescent material
With embodiment 1, characteristic is: TPPS
3Ethanolic soln: the volume ratio of tri-distilled water is 1:70, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 70 ℃, and stirring velocity is 1550rpm, and churning time is 10 minutes.
(3) spinning
With embodiment 1, characteristic is: the speed of spinning is 12000 rev/mins, and centrifugation time is 35min.
(4) drying
With embodiment 1, characteristic is: drying temperature is 86 ℃, and be 23 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 380～450nm, wide 180～300nm.
Embodiment 6
A kind of tetrasulfonic acid base tetraphenylporphyrin (TPPS
4) nano-luminescent material, be that the cross section is the rectangular parallelepiped fluorescence nano sheet material of rectangular length 390～450nm, wide 200～300nm.
A kind of tetrasulfonic acid base tetraphenylporphyrin (TPPS
4) concrete steps of preparation of nanomaterials are following:
(1) TPPS
4The configuration of ethanolic soln
With embodiment 1, characteristic is: the porphyrin kind is changed to TPPS
4, the TPPS that makes
4Mass concentration is 0.54mmol/L, and the temperature that keeps in Dark Place is 4 ℃.
(2) TPPS
4Preparation of nano fluorescent material
With embodiment 1, characteristic is: TPPS
4Ethanolic soln: the volume ratio of tri-distilled water is 1:100, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 80 ℃, and stirring velocity is 1440rpm, and churning time is 5 minutes.
(3) spinning
With embodiment 1, characteristic is: the speed of spinning is 10000 rev/mins, and centrifugation time is 40min.
(4) drying
With embodiment 1, characteristic is: drying temperature is 85 ℃, and be 24 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 390～450nm, wide 200～300nm.
Experimental result
1. press magazine J.AM.CHEM.SOC.2007,129, the method for 2440-2441 " Self-Assembly andSelf-Metallization of Porphyrin Nanosheets " literary composition and prepare a kind of TPPS respectively with embodiment 2
1Nano material and a kind of TPPS
1Fluorescent nano material carries out the fluorescent spectrophotometer assay experiment, and it is as depicted in figs. 1 and 2 respectively to record its fluorescence emission spectrogram.
2. a kind of TPPS for preparing with embodiment 2
1Nano-luminescent material carries out the sem experiment, and the electron scanning micrograph that draws Nano sheet material is as shown in Figure 3, and the electron scanning micrograph that draws the nanometer web is as shown in Figure 4.
Interpretation:
See TPPS from Fig. 2
1Monomer (TPPS
1Monomer) 602,668nm has 2 emission peaks, and fluorescence intensity is respectively: 41.772,4.302; TPPS
1Nano-luminescent material has 2 emission peaks 602,669, and fluorescence intensity is respectively: 704.164,5.044.Nano material (nano-TPPS thus
1) fluorescence spectrum figure explain that tentatively it is by TPPS
1Molecular.Calculate TPPS by figure
1Monomeric fluorescence quantum yield is: 0.02738; TPPS
1The fluorescence quantum yield of nano-luminescent material is: 0.41712.Therefore draw TPPS
1The fluorescence intensity of nano-luminescent material and fluorescence quantum yield are respectively TPPS
1Monomeric 17 and 15 times.Fluorescence property is far superior to TPPS
1Monomer; And the fluorescence intensity of TPPS nano material at the 602nm place that we calculate the method preparation of usefulness " Self-Assembly and Self-Metallization of Porphyrin Nanosheets " one literary composition through Fig. 1 is less than TPPS
1Monomeric 8 times (7.6 times).Through contrast, obviously draw TPPS with the inventive method preparation
1Nano material has excellent more photosensitive property.Analytical chemistry be can be widely used in and special marking thing, sensitive material and sensor are used as.
See TPPS from Fig. 3
1Nano-luminescent material is to be made up of a large amount of regular nanocubes sheet and nano strips.The mean length that is drawn nanometer sheet by Fig. 3 is about: 391nm, and width average is about: 214nm, so long-width ratio is: 1.8.
The length that is calculated nano strip by Fig. 4 is 500～850nm, and wide is 70～90nm.
In sum, the TPPS of method preparation of the present invention
1Nano-luminescent material not only can be used for analytical chemistry, photoelectronics and as special marking thing, sensitive material, also can be used for constructing nano-device.
Claims (10)
1. sulfonic group tetraphenylporphyrin nano-luminescent material; It is characterized in that the cross section is rectangular sheet material or web or sheet material and web; Sheet material length is 350～450nm, wide 150～300nm; Web length is 500～850nm, the wide 70～90nm of being, wherein the sulfonic group tetraphenylporphyrin is single sulfonic group tetraphenylporphyrin or disulfonic acid base tetraphenylporphyrin or trisulfonic acid base tetraphenylporphyrin or tetrasulfonic acid base tetraphenylporphyrin.
2. according to the described a kind of sulfonic group tetraphenylporphyrin nano-luminescent material of claim 1; It is characterized in that a kind of single sulfonic group tetraphenylporphyrin nano-luminescent material, is that the cross section is that fluorescence nano sheet material and the length of rectangular length 350～450nm, wide 150～300nm is the fluorescence nano web of 500～850nm, the wide 70～90nm of being.
3. according to the described a kind of sulfonic group tetraphenylporphyrin nano-luminescent material of claim 1, it is characterized in that a kind of disulfonic acid base tetraphenylporphyrin nano-luminescent material, is that the cross section is the fluorescence nano web of rectangular length 550～850nm, wide 75～90nm.
4. according to the described a kind of sulfonic group tetraphenylporphyrin nano-luminescent material of claim 1, it is characterized in that a kind of trisulfonic acid base tetraphenylporphyrin nano-luminescent material, is that the cross section is the fluorescence nano sheet material of rectangular length 380～450nm, wide 180～300nm.
5. according to the described a kind of sulfonic group tetraphenylporphyrin nano-luminescent material of claim 1, it is characterized in that a kind of tetrasulfonic acid base tetraphenylporphyrin nano-luminescent material, is that the cross section is the fluorescence nano sheet material of rectangular length 390～450nm, wide 200～300nm.
6. sulfonic group tetraphenylporphyrin preparation of nano fluorescent material method is characterized in that concrete method steps is following:
(1) configuration of sulfonic group tetraphenylporphyrin ethanolic soln
The sulfonic group tetraphenylporphyrin is positioned in the container; Add ethanolic soln again; After stirring through whisking appliance; Just configuring sulfonic group tetraphenylporphyrin mass concentration is the sulfonic group tetraphenylporphyrin ethanolic soln of 0.38～0.58mmol/L, under 3～4 ℃ of temperature, keeps in Dark Place, even wherein the sulfonic group tetraphenylporphyrin is single sulfonic group tetraphenylporphyrin or disulfonic acid base tetraphenylporphyrin trisulfonic acid base tetraphenylporphyrin or tetrasulfonic acid base tetraphenylporphyrin;
(2) preparation of sulfonic group tetraphenylporphyrin nano-luminescent material dispersion system
After the completion of (1) step; In sulfonic group tetraphenylporphyrin ethanolic soln: the volume ratio of tri-distilled water is 1: 50～100 ratio; With (1) the step sulfonic group tetraphenylporphyrin ethanolic soln preparing and preserve,, be injected into initial temperature and be in 3～4 ℃ the tri-distilled water through sampler; Then with thermostatic mixer heating and stir and constant temperature at 4～80 ℃; With 1440～1600 rev/mins rotating speed, stirred 5～15 minutes again, just prepare micro emulsion xanchromatic sulfonic group tetraphenylporphyrin nano-luminescent material dispersion system;
(3) spinning
After (2) step accomplished, with the sulfonic group tetraphenylporphyrin nano-luminescent material dispersion system that (2) step prepared, be positioned in the supercentrifuge after, with 10000～14000 rev/mins rotating speed, high speed centrifugation separates 20～40min, collects lower floor's solid matter;
(4) drying
After the completion of (3) step; The solid matter that (3) step was collected is positioned in the vacuum drying oven; Under 84～86 ℃ of temperature, carry out drying, be 23～25 hours time of drying, just prepares sulfonic group tetraphenylporphyrin nano fluorescent sheet material or web or sheet material and web; The length of its sheet material is 350～450nm, wide 150～300nm, and web length is 500～850nm, the wide 70～90nm of being.
7. according to the described a kind of sulfonic group tetraphenylporphyrin preparation of nano fluorescent material method of claim 6, it is characterized in that a kind of concrete steps of single sulfonic group tetraphenylporphyrin preparation of nanomaterials are following:
In (1) step, the mass concentration that makes single sulfonic group tetraphenylporphyrin is 0.43mmol/L, and the temperature that keeps in Dark Place is 4 ℃;
In (2) step, single sulfonic group tetraphenylporphyrin ethanolic soln: the volume ratio of tri-distilled water is 1: 50, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 70 ℃, and stirring velocity is 1600rpm, and churning time is 10 minutes;
In (3) step, the speed of spinning is 13000 rev/mins, and centrifugation time is 30min;
In (4) step, drying temperature is 85 ℃, and be 24 hours time of drying, and the powdery substance of preparing is the fluorescence nano web of 500～850nm, the wide 70～90nm of being for fluorescence nano sheet material and the length of long 350～450nm, wide 150～300nm.
8. according to the described a kind of sulfonic group tetraphenylporphyrin preparation of nano fluorescent material method of claim 6, it is characterized in that a kind of concrete steps of disulfonic acid base tetraphenylporphyrin preparation of nanomaterials are following:
In (1) step, the porphyrin kind is changed to disulfonic acid base tetraphenylporphyrin, and the disulfonic acid base tetraphenylporphyrin mass concentration that makes is 0.38mmol/L, and the temperature that keeps in Dark Place is 3 ℃;
In (2) step, disulfonic acid base tetraphenylporphyrin ethanolic soln: the volume ratio of tri-distilled water is 1: 60, and the initial temperature of tri-distilled water is 3 ℃, and the homo(io)thermism of mixed solution is at 4 ℃, and stirring velocity is 1600rpm, and churning time is 15 minutes;
In (3) step, the speed of spinning is 14000 rev/mins, and centrifugation time is 35min;
In (4) step, drying temperature is 84 ℃, and be 25 hours time of drying, and the powdery substance of preparing is the fluorescence nano web of long 550～850nm, wide 75～90nm.
9. according to the described a kind of sulfonic group tetraphenylporphyrin preparation of nano fluorescent material method of claim 6, it is characterized in that a kind of concrete steps of trisulfonic acid base tetraphenylporphyrin preparation of nanomaterials are following:
In (1) step, the porphyrin kind is changed to trisulfonic acid base tetraphenylporphyrin, and the trisulfonic acid base tetraphenylporphyrin mass concentration that makes is 0.47mmol/L, and the temperature that keeps in Dark Place is 4 ℃;
In (2) step, trisulfonic acid base tetraphenylporphyrin ethanolic soln: the volume ratio of tri-distilled water is 1: 70, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 70 ℃, and stirring velocity is 1550rpm, and churning time is 10 minutes;
In (3) step, the speed of spinning is 12000 rev/mins, and centrifugation time is 35min;
In (4) step, drying temperature is 86 ℃, and be 23 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 380～450nm, wide 180～300nm.
10. according to the described a kind of sulfonic group tetraphenylporphyrin preparation of nano fluorescent material method of claim 6, it is characterized in that a kind of concrete steps of tetrasulfonic acid base tetraphenylporphyrin preparation of nanomaterials are following:
In (1) step, the porphyrin kind is changed to tetrasulfonic acid base tetraphenylporphyrin, and the tetrasulfonic acid base tetraphenylporphyrin mass concentration that makes is 0.54mmol/L, and the temperature that keeps in Dark Place is 4 ℃;
In (2) step, tetrasulfonic acid base tetraphenylporphyrin ethanolic soln: the volume ratio of tri-distilled water is 1: 100, and the initial temperature of tri-distilled water is 4 ℃, and the temperature of mixed solution is 80 ℃, and stirring velocity is 1440rpm, and churning time is 5 minutes;
In (3) step, the speed of spinning is 10000 rev/mins, and centrifugation time is 40min;
In (4) step, drying temperature is 85 ℃, and be 24 hours time of drying, and the powdery substance of preparing is the fluorescence nano sheet material of long 390～450nm, wide 200～300nm.
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