CN108057406A - A kind of phthalocyanin nano material and preparation method thereof - Google Patents

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

A kind of phthalocyanine nano material and preparation method thereof

technical field

The invention belongs to the technical field of nanomaterials, and in particular relates to a phthalocyanine nanomaterial and a preparation method thereof.

Background technique

Phthalocyanine has high chemical and thermal stability, acid resistance, alkali resistance, water immersion resistance, and unique optical, electrical, acoustic, thermal, magnetic, chemical and other properties, which have attracted widespread attention. Phthalocyanine is a macrocyclic compound. The two hydrogen atoms in the central cavity can be replaced by various metal and non-metal atoms. Various substituents can be introduced on the benzene ring of phthalocyanine to achieve the modification of phthalocyanine molecules. . At present, phthalocyanine has been widely used in various new functional materials such as chemical sensors, solar cells, photocatalysts, and optical limiting materials.

Due to the unique properties of nanomaterials, when phthalocyanine is used in chemical sensors, solar cells, and photocatalysts, it is usually necessary to assemble phthalocyanine molecules into aggregates of various nanostructures. At present, there are many methods to prepare phthalocyanine nanomaterials, including physical vapor deposition, ultrasonic method, electrophoretic deposition and solvothermal method. Among them, the physical vapor deposition method has high preparation costs and is not conducive to large-scale production; the ultrasonic method is difficult to ensure the micro-nano structure of the product; the electrophoretic deposition method requires the use of templates; and the solvothermal method will introduce side reactions and other products.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a phthalocyanine nanomaterial and a preparation method thereof, the process of which is simple and easy to control.

The invention provides a preparation method of phthalocyanine nanomaterials, comprising:

S1) mixing phthalocyanine and/or phthalocyanine compound with water, and performing ultrasonic treatment to obtain a phthalocyanine suspension;

S2) subjecting the phthalocyanine suspension to laser irradiation treatment, and centrifuging and drying to obtain phthalocyanine nanomaterials.

Preferably, the mass ratio of the phthalocyanine and/or phthalocyanine compound to water is (0.01-10):(0.1-100).

Preferably, the ultrasonic treatment time in the step S1) is 1-30 min.

Preferably, the power of the ultrasound in the step S1) is 1-100W.

Preferably, the power of the laser in the laser irradiation treatment in the step S2) is 0.01-10W.

Preferably, the laser irradiation treatment time in the step S2) is 1-1000 min.

Preferably, the wavelength of the laser in the laser irradiation treatment in the step S2) is 193-1064 nm.

Preferably, the speed of centrifugation in the step S2) is 100-50000 rpm; the time of centrifugation is 1-60 minutes.

Preferably, the drying temperature in the step S2) is 80°C-180°C; the drying time is 1-24h.

The invention also provides a nano-phthalocyanine material, which is spherical; and the nano-phthalocyanine material has a diameter of 20-500 nm.

The invention provides a preparation method of a phthalocyanine nanomaterial, comprising: S1) mixing phthalocyanine and/or phthalocyanine compound with water, and performing ultrasonic treatment to obtain a phthalocyanine suspension; S2) mixing the phthalocyanine The suspension liquid is subjected to laser irradiation treatment, and after being centrifuged and dried, the phthalocyanine nanometer material is obtained. Compared with the prior art, the present invention does not need to add various doping reagents, surfactants, acid-base reagents, etc. in the preparation process, and does not need reaction devices such as high temperature and high pressure. The equipment is simple, the operation is convenient, and the required time is short. The preparation process is easy to control.

Description of drawings

Fig. 1 is the scanning electron micrograph of the phthalocyanine nanomaterial prepared in embodiment 1;

FIG. 2 is a scanning electron micrograph of the phthalocyanine nanomaterial prepared in Example 2.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides a preparation method of a phthalocyanine nanomaterial, comprising: S1) mixing phthalocyanine and/or phthalocyanine compound with water, and performing ultrasonic treatment to obtain a phthalocyanine suspension; S2) mixing the phthalocyanine The suspension liquid is subjected to laser irradiation treatment, and after being centrifuged and dried, the phthalocyanine nanometer material is obtained.

Wherein, the present invention has no special limitation on the sources of all raw materials, which can be commercially available.

The present invention uses phthalocyanine and/or phthalocyanine compound as raw material, preferably its powder as raw material; the phthalocyanine compound can be a phthalocyanine compound well known to those skilled in the art, and there is no special limitation, preferably in the present invention It is a metal phthalocyanine compound and/or a substituted phthalocyanine; the metal phthalocyanine compound is a metal phthalocyanine compound well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably copper phthalocyanine and/or Indium phthalocyanine; the substituent in the substituted phthalocyanine is preferably one or more of methyl, methoxy and tert-butyl.

Mix phthalocyanine and/or phthalocyanine compound with water; The water is preferably deionized water; The mass ratio of the phthalocyanine and/or phthalocyanine compound to water is preferably (0.01～10): (0.1～ 100), more preferably (0.01～5): (0.1～50), more preferably (0.01～2): (0.1～20), more preferably (0.01～1): (0.1～10), most preferably It is (0.01～0.1): (0.1～1).

After mixing, perform ultrasonic treatment to obtain a phthalocyanine suspension; the power of the ultrasonic treatment is preferably 1 to 100W, more preferably 10 to 80W, more preferably 10 to 60W, and more preferably 20 to 40W; the ultrasonic The treatment time is preferably 1 to 30 minutes, more preferably 5 to 20 minutes, and even more preferably 10 to 15 minutes.

The phthalocyanine suspension is subjected to laser irradiation treatment; the laser power during the laser irradiation treatment is preferably 0.01-10W, more preferably 0.1-5W, more preferably 0.5-3W, most preferably 1-2W; The time for the laser irradiation treatment is preferably 1 to 1000min, more preferably 10 to 800min, more preferably 50 to 500min, more preferably 100 to 300min, most preferably 100 to 150min; the wavelength of the laser during the laser irradiation treatment is preferably It is 193-1064 nm, more preferably 250-1000 nm, still more preferably 400-800 nm, still more preferably 500-600 nm, still more preferably 550-600 nm, most preferably 589 nm.

After laser irradiation treatment, centrifuge and dry to obtain phthalocyanine nanomaterials; the speed of the centrifugation is preferably 100 to 50,000 rpm, more preferably 1,000 to 20,000 rpm, more preferably 1,000 to 10,000 rpm, and more preferably 1000～8000 rev/min, more preferably 2000～5000 rev/min, most preferably 3000～4000 rev/min; the time of described centrifugation is preferably 1～60min, more preferably 10～50min, more preferably 10min ~ 40min, most preferably 15 ~ 30min; after centrifugation, it is preferable to pour off the supernatant clear night, and then dry; the drying temperature is preferably 80°C ~ 180°C, more preferably 80°C ~ 150°C, and more preferably 100°C ~ 140°C, most preferably 100°C-120°C; the drying time is preferably 1-24h, more preferably 5-20h, more preferably 8-16h, most preferably 10-12h.

The present invention does not need to add various doping reagents, surfactants, acid-base reagents, etc. during the preparation process, and does not need reaction devices such as high temperature and high pressure at the same time, the equipment is simple, the operation is convenient, the required time is short, and the preparation process is easy to control; the method Phthalocyanine is of great significance in many application fields, such as medicine, sensors, light limiting, solar cells and photocatalysis.

The present invention also provides a nano-phthalocyanine material prepared by the above method; the nano-phthalocyanine material is spherical; the nano-phthalocyanine material has a diameter of 20-500 nm, more preferably 50-500 nm, and more preferably 100 nm. ~400nm, most preferably 200~400nm.

In order to further illustrate the present invention, a phthalocyanine nanomaterial provided by the present invention and its preparation method are described in detail below in conjunction with examples.

The reagents used in the following examples are all commercially available.

Example 1

1.1 Preparation of phthalocyanine suspension: 0.01 g of phthalocyanine powder was added to 0.1 g of deionized water, and ultrasonicated for 10 min (ultrasonic power 20W).

1.2 Laser treatment: irradiate the phthalocyanine suspension prepared in step 1.1 with a laser with a wavelength of 589 nm and a power of 1 W for 100 min.

1.3 Centrifugal drying: centrifuge the phthalocyanine suspension treated with laser in step 1.2 at 3000 rpm for 15 minutes, pour off the supernatant, and dry in an oven at 100°C for 10 hours to finally obtain phthalocyanine nanomaterials.

The phthalocyanine nanomaterial obtained in Example 1 was detected by a scanning electron microscope, and its scanning electron microscope (SEM) photo was obtained as shown in FIG. 1 . It can be seen from Figure 1 that the phthalocyanine particles have a regular spherical structure, and the diameter of the ball is about 200-400nm.

Example 2

Except changing phthalocyanine powder into copper phthalocyanine powder, other preparation conditions are identical with embodiment 1.

The copper phthalocyanine nanomaterial obtained in Example 2 was detected by a scanning electron microscope, and its scanning electron microscope (SEM) photo was obtained as shown in FIG. 2 . It can be seen from Figure 2 that the phthalocyanine particles are regular spherical structures with a diameter of about 100-400 nm.

Example 3

In order to examine the influence of the mass ratio of phthalocyanine powder and water on the preparation of phthalocyanine nanomaterials, other preparation conditions were the same as in Example 1 except that the quality of phthalocyanine powder and water was different. The results show that when the quality of phthalocyanine powder and water is 10:0.1, 5:0.1, 2:0.1, 1:0.1, 0.1:0.1, phthalocyanine nanoparticles can be obtained, and the amount of nano-ions in the obtained phthalocyanine particles The proportions are 10%, 20%, 40%, 60%, and 80%, respectively. The size is 200-400nm.

Example 4

In order to examine the influence of the laser wavelength on the preparation of phthalocyanine nanomaterials, other preparation conditions were the same as in Example 1 except that the laser wavelength was different. The results show that when the laser wavelengths are 193nm, 260nm, 350nm, 690nm, and 1060nm, phthalocyanine nanoparticles can be obtained, the proportion of nano-ions in the obtained phthalocyanine particles reaches 99%, and the distribution of nano-ions is 300~ 400nm, 200~300nm, 140~400nm, 250~400nm, 300~500nm.

Example 5

In order to examine the effect of laser treatment time on the preparation of phthalocyanine nanomaterials, other preparation conditions were the same as in Example 1 except that the laser treatment time was different. The results show that when the laser treatment time is 1min, 50min, 150min, 500min, phthalocyanine nanoparticles can be obtained, and the proportion of nano-ions in the obtained phthalocyanine particles is 10%, 80%, 99%, 99%, respectively. The distribution of nanometer ions is 200-1000nm, 200-500nm, 200-400nm, 200-400nm respectively.

Claims (10)

1. a preparation method of phthalocyanine nanomaterial, is characterized in that, comprises: S1) mixing phthalocyanine and/or phthalocyanine compound with water, and performing ultrasonic treatment to obtain a phthalocyanine suspension; S2) subjecting the phthalocyanine suspension to laser irradiation treatment, and centrifuging and drying to obtain phthalocyanine nanomaterials. 2. The preparation method according to claim 1, characterized in that, the mass ratio of the phthalocyanine and/or phthalocyanine compound to water is (0.01-10):(0.1-100). 3. The preparation method according to claim 1, characterized in that the ultrasonic treatment time in the step S1) is 1-30 min. 4. The preparation method according to claim 1, characterized in that the power of the ultrasound in the step S1) is 1-100W. 5 . The preparation method according to claim 1 , wherein the power of the laser in the laser irradiation treatment in the step S2) is 0.01-10W. 6 . The preparation method according to claim 1 , characterized in that, the laser irradiation treatment time in the step S2) is 1-1000 min. 7. The preparation method according to claim 1, characterized in that, the wavelength of the laser in the laser irradiation treatment in the step S2) is 193-1064 nm. 8. The preparation method according to claim 1, characterized in that, in the step S2), the speed of centrifugation is 100-50000 rpm; the time of centrifugation is 1-60 min. 9. The preparation method according to claim 1, characterized in that, the drying temperature in the step S2) is 80°C-180°C; the drying time is 1-24h. 10. The nano-phthalocyanine material prepared according to any one of claims 1-9, characterized in that, the nano-phthalocyanine material is spherical; and the nano-phthalocyanine material has a diameter of 20-500 nm.