CN108057406A - A kind of phthalocyanin nano material and preparation method thereof - Google Patents
A kind of phthalocyanin nano material and preparation method thereof Download PDFInfo
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- CN108057406A CN108057406A CN201711339713.0A CN201711339713A CN108057406A CN 108057406 A CN108057406 A CN 108057406A CN 201711339713 A CN201711339713 A CN 201711339713A CN 108057406 A CN108057406 A CN 108057406A
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- phthalocyanine
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/121—Coherent waves, e.g. laser beams
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The present invention provides a kind of preparation method of phthalocyanin nano material, including：S1) phthalocyanine and/or phthalocyanine-like compound with water are mixed, are ultrasonically treated, obtains phthalocyanine suspension；S2 the phthalocyanine suspension) is subjected to laser treatment with irradiation, after centrifugal drying, obtains phthalocyanin nano material.Compared with prior art, the present invention need not add in various doping reagents, surfactant, acid-base reagent etc. in preparation process, while the reaction units such as high temperature and pressure are not required, and equipment is simple, easy to operate, and required time is short, and preparation process is easy to control.
Description
Technical field
The invention belongs to technical field of nano material more particularly to a kind of phthalocyanin nano material and preparation method thereof.
Background technology
Phthalocyanine has higher chemical stability and thermal stability, acidproof, alkaline-resisting, resistance to water logging, and has uniqueness
The properties such as light, electricity, sound, thermal and magnetic, chemistry receive people and widely pay close attention to.Phthalocyanine is a macrocyclic compound, in center cavity
Two hydrogen atoms can be substituted by various metals and non-metallic atom, a variety of substituent groups can be introduced on the phenyl ring of phthalocyanine, from
And reach the modifying function to Phthalocyanine.At present phthalocyanine oneself be widely used in chemical sensor, solar cell, light and urge
In the various new function materials such as agent, optical limiting materials.
Since nano material has some unique properties, so when Pcs'application is in chemical sensor, solar cell
With photochemical catalyst when fields, it usually needs Phthalocyanine is assembled into the aggregation of various nanostructureds.At present, there are many
Method can prepare phthalocyanin nano material, including：Physical vaporous deposition, ultrasonic method, electrophoretic deposition and solvent-thermal method.
Wherein, physical vaporous deposition manufacturing cost is high, is unfavorable for mass producing；Ultrasonic method is compared with the micro-nano knot for being difficult to guarantee product
Structure；Electrophoretic deposition is needed by template；And solvent heat rule can introduce side reaction and other products.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide phthalocyanin nano material and preparation method thereof, should
Procedure is simple and easy to control.
The present invention provides a kind of preparation method of phthalocyanin nano material, including：
S1) phthalocyanine and/or phthalocyanine-like compound with water are mixed, are ultrasonically treated, obtains phthalocyanine suspension；
S2 the phthalocyanine suspension) is subjected to laser treatment with irradiation, after centrifugal drying, obtains phthalocyanin nano material.
Preferably, the mass ratio of the phthalocyanine and/or phthalocyanine-like compound and water is (0.01~10)：(0.1~100).
Preferably, the step S1) in be ultrasonically treated time be 1~30min.
Preferably, the step S1) in ultrasonic power be 1~100W.
Preferably, the step S2) in laser treatment with irradiation the power of laser be 0.01~10W.
Preferably, the step S2) in laser treatment with irradiation time be 1~1000min.
Preferably, the step S2) in laser treatment with irradiation the wavelength of laser be 193~1064nm.
Preferably, the step S2) in centrifugation rate be 100~50000 revs/min；The time of centrifugation is 1~60 point
Clock.
Preferably, the step S2) in dry temperature be 80 DEG C~180 DEG C；The time of the drying for 1~for 24 hours.
The present invention also provides a kind of phthalocyanin nano material, the phthalocyanin nano material is spherical；The phthalocyanin nano material
A diameter of 20~500nm of material.
The present invention provides a kind of preparation method of phthalocyanin nano material, including：S1) by phthalocyanine and/or phthalocyanines chemical combination
Object is mixed with water, is ultrasonically treated, and obtains phthalocyanine suspension；S2 the phthalocyanine suspension) is subjected to laser treatment with irradiation, from
After heart drying, phthalocyanin nano material is obtained.Compared with prior art, the present invention need not add in various doping examinations in preparation process
Agent, surfactant, acid-base reagent etc., while the reaction units such as high temperature and pressure are not required, equipment is simple, easy to operate, required
Time is short, and preparation process is easy to control.
Description of the drawings
Fig. 1 is the stereoscan photograph for the phthalocyanin nano material being prepared in embodiment 1；
Fig. 2 is the stereoscan photograph for the phthalocyanin nano material being prepared in embodiment 2.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation method of phthalocyanin nano material, including：S1) by phthalocyanine and/or phthalocyanines chemical combination
Object is mixed with water, is ultrasonically treated, and obtains phthalocyanine suspension；S2 the phthalocyanine suspension) is subjected to laser treatment with irradiation, from
After heart drying, phthalocyanin nano material is obtained.
Wherein, the present invention has no the source of all raw materials special limitation, is commercially available.
The present invention is using phthalocyanine and/or phthalocyanine-like compound as raw material, preferably using its powder as raw material；The phthalocyanine compound
For phthalocyanine compound well known to those skilled in the art, special limitation is had no, is preferably metal phthalocyanine in the present invention
Close object and/or substituted phthalocyanine；The metal phthalocyanine compound is that metal phthalocyanine compound well known to those skilled in the art is
Can, special limitation is had no, is preferably copper phthalocyanine and/or indium phthalocyanine in the present invention；Substituent group in the substituted phthalocyanine is excellent
Elect the one or more in methyl, methoxyl group and tertiary butyl as.
Phthalocyanine and/or phthalocyanine-like compound are mixed with water；The water is preferably deionized water；The phthalocyanine and/or phthalein
The mass ratio of cyanine compound and water is preferably (0.01~10)：(0.1~100), more preferably (0.01~5)：(0.1~
50) it is further preferably, (0.01~2)：(0.1~20) is further preferably (0.01~1)：(0.1~10), be most preferably (0.01~
0.1)：(0.1~1).
It after mixing, is ultrasonically treated, obtains phthalocyanine suspension；The power of the supersound process is preferably 1~100W, more
Preferably 10~80W is further preferably 10~60W, is further preferably 20~40W；The time of the supersound process is preferably 1~
30min, more preferably 5~20min, are further preferably 10~15min.
The phthalocyanine suspension is subjected to laser treatment with irradiation；The power of laser is preferably during the laser treatment with irradiation
0.01~10W, more preferably 0.1~5W, are further preferably 0.5~3W, are most preferably 1~2W；The laser treatment with irradiation when
Between be preferably 1~1000min, more preferably 10~800min, be further preferably 50~500min, be further preferably 100~300min,
Most preferably 100~150min；The wavelength of laser is preferably 193~1064nm during the laser treatment with irradiation, and more preferably 250
~1000nm is further preferably 400~800nm, is further preferably 500~600nm, is further preferably 550~600nm, is most preferably
589nm。
After laser treatment with irradiation, centrifugal drying obtains phthalocyanin nano material；The rate of the centrifugation is preferably 100~
50000 revs/min, more preferably 1000~20000 revs/min, be further preferably 1000~10000 revs/min, further preferably for
1000~8000 revs/min, be further preferably 2000~5000 revs/min, is most preferably 3000~4000 revs/min；It is described from
The time of the heart is preferably 1~60min, more preferably 10~50min, is further preferably 10~40min, is most preferably 15~30min；
Supernatant is preferably outwelled after centrifugation, then is dried；The temperature of the drying is preferably 80 DEG C~180 DEG C, and more preferably 80
DEG C~150 DEG C, it is further preferably 100 DEG C~140 DEG C, is most preferably 100 DEG C~120 DEG C；The time of the drying is preferably 1~
For 24 hours, 5~20h is more preferably, is further preferably 8~16h, is most preferably 10~12h.
The present invention need not add in various doping reagents, surfactant, acid-base reagent etc. in preparation process, be not required to simultaneously
The reaction units such as high temperature and pressure are wanted, equipment is simple, easy to operate, and required time is short, and preparation process is easy to control；This method is in phthalein
Multiple application fields of cyanines, such as medicine, sensor, optical Limiting, solar cell and photocatalysis have great importance.
The present invention also provides a kind of phthalocyanin nano materials prepared using the above method；The phthalocyanin nano material is ball
Shape；A diameter of 20~500nm of the phthalocyanin nano material, more preferably 50~500nm, are further preferably 100~400nm, most
Preferably 200~400nm.
In order to further illustrate the present invention, with reference to embodiments to a kind of phthalocyanin nano material provided by the invention and its
Preparation method is described in detail.
Reagent used is commercially available in following embodiment.
Embodiment 1
1.1 prepare phthalocyanine suspension：The phthalocyanine powder of 0.01g is added in the deionized water of 0.1g, ultrasonic 10min
(ultrasonic power 20W).
1.2 laser treatment：The use of wavelength is 589nm, power is that the phthalocyanine prepared in the laser irradiation step 1.1 of 1W is suspended
Liquid 100min.
1.3 centrifugal drying：The phthalocyanine suspension after laser treatment will be used to be centrifuged by 3000 revs/min in step 1.2
After 15min, supernatant liquor is outwelled, dry 10h is put into 100 DEG C of baking oven, finally obtains phthalocyanin nano material.
The phthalocyanin nano material obtained in embodiment 1 is detected using scanning electron microscope, obtains its scanning electricity
Mirror (SEM) photo is as shown in Figure 1.From figure 1 it appears that phthalocyanine granulates are regular chondritic, the diameter of ball is about
200~400nm.
Embodiment 2
In addition to phthalocyanine powder is become copper phthalocyanine powder, other preparation conditions are same as Example 1.
The copper phthalocyanine nano material obtained in embodiment 2 is detected using scanning electron microscope, obtains its scanning
Electronic Speculum (SEM) photo is as shown in Figure 2.From figure 2 it can be seen that phthalocyanine granulates are regular chondritic, the diameter of ball is about
For 100~400nm.
Embodiment 3
In order to examine the mass ratio of phthalocyanine powder and water for preparing the influence of phthalocyanin nano material, except phthalocyanine powder with
Outside the quality difference of water, other preparation conditions are same as Example 1.The result shows that when the quality of phthalocyanine powder and water is distinguished
For 10:0.1,5:0.1,2:0.1,1:0.1,0.1:0.1, it can obtain phthalocyanin nano particle, nanometer in the phthalocyanine granulates of gained
The accounting of ion is 10%, 20%, 40%, 60%, 80% respectively.Size is 200~400nm.
Embodiment 4
In order to examine optical maser wavelength for preparing the influence of phthalocyanin nano material, in addition to optical maser wavelength difference, other
Preparation condition is same as Example 1.The result shows that when optical maser wavelength is respectively 193nm, 260nm, 350nm, 690nm,
1060nm, can obtain phthalocyanin nano particle, and the accounting of nanoparticle reaches 99% in the phthalocyanine granulates of gained, nanoparticle
Distribution be respectively 300~400nm, 200~300nm, 140~400nm, 250~400nm, 300~500nm.
Embodiment 5
In order to examine the laser treatment time for preparing the influence of phthalocyanin nano material, except laser treatment time difference
Outside, other preparation conditions are same as Example 1.The result shows that when the laser treatment time is respectively 1min, 50min, 150min,
500min, can obtain phthalocyanin nano particle, and the accounting of nanoparticle is 10%, 80% respectively in the phthalocyanine granulates of gained,
99%, 99%, the distribution of nanoparticle is respectively 200~1000nm, 200~500nm, 200~400nm, 200~400nm.
Claims (10)
1. a kind of preparation method of phthalocyanin nano material, which is characterized in that including：
S1) phthalocyanine and/or phthalocyanine-like compound with water are mixed, are ultrasonically treated, obtains phthalocyanine suspension；
S2 the phthalocyanine suspension) is subjected to laser treatment with irradiation, after centrifugal drying, obtains phthalocyanin nano material.
2. preparation method according to claim 1, which is characterized in that the phthalocyanine and/or phthalocyanine-like compound and water
Mass ratio is (0.01~10)：(0.1~100).
3. preparation method according to claim 1, which is characterized in that the step S1) in time for being ultrasonically treated for 1~
30min。
4. preparation method according to claim 1, which is characterized in that the step S1) in ultrasonic power for 1~
100W。
5. preparation method according to claim 1, which is characterized in that the step S2) in laser in laser treatment with irradiation
Power be 0.01~10W.
6. preparation method according to claim 1, which is characterized in that the step S2) in laser treatment with irradiation time
For 1~1000min.
7. preparation method according to claim 1, which is characterized in that the step S2) in laser in laser treatment with irradiation
Wavelength be 193~1064nm.
8. preparation method according to claim 1, which is characterized in that the step S2) in centrifugation rate for 100~
50000 revs/min；The time of centrifugation is 1~60min.
9. preparation method according to claim 1, which is characterized in that the step S2) in dry temperature for 80 DEG C~
180℃；The time of the drying for 1~for 24 hours.
10. the phthalocyanin nano material prepared by any one of claim 1~9, which is characterized in that the phthalocyanin nano material is ball
Shape；A diameter of 20~500nm of the phthalocyanin nano material.
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| CN201711339713.0A CN108057406A (en) | 2017-12-14 | 2017-12-14 | A kind of phthalocyanin nano material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342468A (en) * | 2019-07-29 | 2019-10-18 | 中国科学院长春光学精密机械与物理研究所 | A kind of nano material of interface disorder and preparation method thereof |
| CN113135926A (en) * | 2021-04-23 | 2021-07-20 | 昆明学院 | Novel crystal structure indium phthalocyanine nanowire and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001113159A (en) * | 1999-10-14 | 2001-04-24 | Dainippon Ink & Chem Inc | Method for manufacturing particulate of organic compound |
| CN1671468A (en) * | 2002-08-30 | 2005-09-21 | 浜松光子学株式会社 | Process for producing nanoparticle, apparatus therefor and method of storing nanoparticle |
| CN1750870A (en) * | 2003-03-07 | 2006-03-22 | 浜松光子学株式会社 | Fine particles, method and device for preparation thereof, and agent for parenteral injection and method for production thereof |
| JP2009119379A (en) * | 2007-10-25 | 2009-06-04 | Ebara Corp | Device and system for laser ablation in solution |
| CN101528181A (en) * | 2006-05-15 | 2009-09-09 | 国立大学法人大阪大学 | Method of producing nanoparticle dispersion of medicinal component |
| CN101890164A (en) * | 2010-02-10 | 2010-11-24 | 上海蓝怡科技有限公司 | Method for laser preparation of nano-drug preparation |
| CN102847534A (en) * | 2012-09-03 | 2013-01-02 | 中国科学院大连化学物理研究所 | Light-driven regulation preparation method and electrocatalysis activity of nanometer material |
| CN102921961A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Method for producing metallic nanomaterials through femtosecond lasers |
| CN103664965A (en) * | 2013-09-10 | 2014-03-26 | 常州大学 | Method for preparing phthalocyanine micro-nano structure |
-
2017
- 2017-12-14 CN CN201711339713.0A patent/CN108057406A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001113159A (en) * | 1999-10-14 | 2001-04-24 | Dainippon Ink & Chem Inc | Method for manufacturing particulate of organic compound |
| CN1671468A (en) * | 2002-08-30 | 2005-09-21 | 浜松光子学株式会社 | Process for producing nanoparticle, apparatus therefor and method of storing nanoparticle |
| CN1750870A (en) * | 2003-03-07 | 2006-03-22 | 浜松光子学株式会社 | Fine particles, method and device for preparation thereof, and agent for parenteral injection and method for production thereof |
| CN101528181A (en) * | 2006-05-15 | 2009-09-09 | 国立大学法人大阪大学 | Method of producing nanoparticle dispersion of medicinal component |
| JP2009119379A (en) * | 2007-10-25 | 2009-06-04 | Ebara Corp | Device and system for laser ablation in solution |
| CN101890164A (en) * | 2010-02-10 | 2010-11-24 | 上海蓝怡科技有限公司 | Method for laser preparation of nano-drug preparation |
| CN102847534A (en) * | 2012-09-03 | 2013-01-02 | 中国科学院大连化学物理研究所 | Light-driven regulation preparation method and electrocatalysis activity of nanometer material |
| CN102921961A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Method for producing metallic nanomaterials through femtosecond lasers |
| CN103664965A (en) * | 2013-09-10 | 2014-03-26 | 常州大学 | Method for preparing phthalocyanine micro-nano structure |
Non-Patent Citations (2)
| Title |
|---|
| 孟宪赓 等: "飞秒激光在金属纳米材料制备和材料微结构加工中的应用", 《激光与光电子学进展》 * |
| 钟敏霖 等: "激光纳米制造技术的应用", 《中国激光》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342468A (en) * | 2019-07-29 | 2019-10-18 | 中国科学院长春光学精密机械与物理研究所 | A kind of nano material of interface disorder and preparation method thereof |
| CN110342468B (en) * | 2019-07-29 | 2021-05-04 | 中国科学院长春光学精密机械与物理研究所 | Nano material with disordered surface and preparation method thereof |
| CN113135926A (en) * | 2021-04-23 | 2021-07-20 | 昆明学院 | Novel crystal structure indium phthalocyanine nanowire and preparation method thereof |
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Application publication date: 20180522 |