CN114150397B - Tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber and preparation method thereof - Google Patents
Tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber and preparation method thereof Download PDFInfo
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- CN114150397B CN114150397B CN202111410119.2A CN202111410119A CN114150397B CN 114150397 B CN114150397 B CN 114150397B CN 202111410119 A CN202111410119 A CN 202111410119A CN 114150397 B CN114150397 B CN 114150397B
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
A tetra-beta-carboxylic acid-based metal phthalocyanine polypyrrole binary nanofiber and a preparation method thereof. The morphology modulation methods for polypyrrole nanostructures are typically soft template and hard template methods. The synthesis of the soft template generally requires a surfactant or a polymer stabilizer to guide pyrrole monomers to polymerize orderly in a solution, and the method is simple and effective, and the soft template can be cleaned by a proper solvent after the reaction is finished. However, the product synthesized by the method has low shape controllability, and the relatively expensive soft template has certain defects in mass production and is easy to cause environmental pollution. The invention is prepared from 0.21% of tetra-beta-sodium carboxylate metal phthalocyanine salt, 1.36% of pyrrole monomer, 26.42% of isopropanol, 67.39% of deionized water and 4.62% of ammonium persulfate by mass percent. The invention is used for gas sensing materials.
Description
Technical Field
The invention belongs to the technical field of polypyrrole morphology regulation and control, and particularly relates to a preparation method of tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber.
Background
The conductive polymer is easily combined with specific gas molecules due to its special functional group and conjugated structure, and has a gas sensing property that can normally operate at room temperature to exhibit no custom. In recent years, the unique redox properties between polypyrrole and ammonia gas have attracted considerable attention in the field of gas sensing among many conductive polymers, however, such single materials also have problems such as: low sensitivity, poor selectivity, slow recovery, short life, etc.
In order to overcome the disadvantages of single polypyrrole and enhance its gas sensing capability, it is an effective strategy to improve the random microscopic morphology of polypyrrole. The effective surface area and the porosity of the polypyrrole are increased by adjusting the microscopic morphology of the polypyrrole, so that gas molecules are contacted with active sites to a greater extent, and the gas sensing performance of the polypyrrole nano material is improved.
The morphology modulation methods for polypyrrole nanostructures are typically soft template and hard template methods. The synthesis of the soft template generally requires a surfactant or a polymer stabilizer to guide pyrrole monomers to polymerize orderly in a solution, and the method is simple and effective, and the soft template can be cleaned by a proper solvent after the reaction is finished. However, the product synthesized by the method has low shape controllability, and the relatively expensive soft template has certain defects in mass production and is easy to cause environmental pollution. The hard template is usually a material with a specific nanostructure chosen as a carrier, allowing the pyrrole monomer to polymerize on its surface. Synthesis using the hard template method requires a relatively demanding post-processing procedure to eliminate the hard template, which is complex and time consuming. Therefore, the object of the present invention is to provide a substance which can regulate and control the polymerization morphology of pyrrole and has gas-sensitive activity so as to enhance the gas sensing performance of the material.
Disclosure of Invention
The invention aims to provide the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber with controllable morphology, wherein tetra-beta-carboxylic acid sodium metal phthalocyanine salt in the synthetic raw material is used as a pyrrole polymerization hard template, and the gas sensing performance of the composite material is enhanced by utilizing the cooperative optimization between the tetra-beta-carboxylic acid metal phthalocyanine and the polypyrrole binary nanofiber.
The above object is achieved by the following technical scheme:
a tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber is prepared from raw materials of 0.05-0.79% of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36-2.56% of pyrrole monomer, 24.81-26.5% of isopropanol, 63.18-67.46% of deionized water and 4.60-8.72% of ammonium persulfate by mass percent.
The tetra-beta-carboxylic acid-based metal phthalocyanine polypyrrole binary nanofiber is prepared from raw materials of 0.21% of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36% of pyrrole monomer, 26.42% of isopropanol, 67.39% of deionized water and 4.62% of ammonium persulfate by mass percent.
The center metal of the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber is cobalt, nickel, zinc, manganese, iron or copper.
The preparation method of the tetra-beta-carboxylic acid-based metal phthalocyanine poly/pyrrole binary nanofiber is characterized in that the tetra-beta-carboxylic acid sodium metal phthalocyanine salt is used as a hard template to polymerize polypyrrole in situ, and the preparation method comprises the following steps: preparing a solution A taking isopropanol as a solvent and a freshly distilled pyrrole monomer as a solute;
solution B taking deionized water as a solvent, and tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate as solutes;
and (3) mixing and stirring the solution A, B under the ice water bath condition for reaction for 4-8 hours to obtain a black product, filtering the black product, sequentially soaking and washing the black product with absolute ethyl alcohol and deionized water, and drying the filtrate after the filtrate is colorless to obtain the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber product.
The preparation method of the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber comprises the step of preparing a solution A and a solution B in a volume ratio of 1:2.
The preparation method of the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber comprises the step of carrying out ice water bath at a reaction temperature of 0-5 ℃.
The preparation method of the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber is characterized in that the drying temperature is 60-80 ℃.
The beneficial effects are that:
1. the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber provided by the invention has the advantages that because coordination metal at the center of the tetra-beta-carboxylic acid metal phthalocyanine is used as an active site for adsorbing oxygen, the formed adsorption oxygen is easy to combine with ammonia gas to generate electrons; on the other hand, polypyrrole has unique chemical structure and is easy to undergo oxidation-reduction reaction with ammonia gas and electron transfer. This allows the composite to have a fast response recovery capability and high sensitivity at room temperature. The four-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber prepared by the method has excellent gas sensing performance due to the synergistic advantage of the two and the unique nanofiber structure, so that the four-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber has great utilization value in the field of detection of toxic and harmful gases.
2. The diameter of the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber provided by the invention can be controlled by changing the ratio of pyrrole monomer to tetra-beta-sodium carboxylate metal phthalocyanine salt.
3. The tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber provided by the invention has excellent sensing performance in the aspect of gas-sensitive response to ammonia gas, and the response sensitivity of the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber greatly exceeds that of a single polypyrrole and tetra-beta-carboxylic acid-based metal phthalocyanine gas-sensitive material, so that the rapid response recovery capability and the high-efficiency sensitivity are still maintained on the basis.
4. The preparation method provided by the invention is easy to operate, and the preparation of the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber can be completed only by one step of reaction. And the post-treatment is simple, the template is not required to be removed additionally, the product can be purified only by washing with deionized water and ethanol, the purity is high, the yield is high, the appearance is uniform, and the diameter of the product is controllable. The preparation method has the advantages of low cost, green and pollution-free performance and simple operation.
Description of the drawings:
FIG. 1 is an electron micrograph of a cobalt tetra- β -carboxylate phthalocyanine/polypyrrole binary nanofiber prepared in example 1 of the present embodiment;
wherein: a is a Scanning Electron Microscope (SEM) photograph, and B is a partial enlarged view thereof; c is a Transmission Electron Microscope (TEM) photograph, and D is an enlarged view thereof;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of three nanofibers obtained from pyrrole monomer and sodium phthalocyanine cobalt tetra-beta-carboxylate in accordance with the mass ratio as a variable in example 2;
wherein: the mass ratio A is 3.5:1, B is 7.0:1, and C is 14.0:1;
FIG. 3 is a graph showing the morphology contrast of the cobalt tetra-beta-carboxylate phthalocyanine/polypyrrole binary nanofiber prepared at different temperatures in example 3 of the specific embodiment;
wherein: panel A is at ambient temperature (25 ℃); panel B is (0-5 ℃);
FIG. 4 is an ultraviolet-visible absorption spectrum of tetra- β -carboxylmethylphthalocyanine cobalt, monopyrrole, and tetra- β -carboxylmethylphthalocyanine cobalt/polypyrrole binary nanofiber in N-N dimethylformamide in example 1 of the present embodiment;
FIG. 5 is an infrared spectrum of tetra- β -carboxylmethyl cobalt phthalocyanine, monopyrrole, and tetra- β -carboxylmethyl cobalt phthalocyanine/polypyrrole binary nanofibers of example 1;
FIG. 6 is a full spectrum of XPS and fine spectra of internal C1 s and N1 s for tetra-beta-carboxylmethylphthalocyanine cobalt, mono-polypyrrole, and tetra-beta-carboxylmethylphthalocyanine cobalt/polypyrrole binary nanofibers of example 2;
FIG. 7 is a graph showing the gas-sensitive properties of the cobalt tetra-beta-carboxylate phthalocyanine/polypyrrole binary nanofiber prepared in example 2 of the present embodiment with respect to ammonia gas with different concentration gradients;
wherein: FIG. A is a response recovery graph; panel B is a graph of response versus recovery time.
The specific embodiment is as follows:
example 1:
a tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber, which is prepared from raw materials of 0.05 to 0.79 percent of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36 to 2.56 percent of pyrrole monomer, 24.81 to 26.5 percent of isopropanol, 63.18 to 67.46 percent of deionized water and 4.60 to 8.72 percent of ammonium persulfate by mass percent;
the preparation method of the tetra-beta-carboxylic acid cobalt phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. And (3) placing 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine cobalt in deionized water under 67.39% ice water bath condition, and adding 4.62% Ammonium Persulfate (APS) as solution B after the tetra-beta-carboxylic acid sodium phthalocyanine cobalt is fully dissolved.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The preparation method of tetra-beta-sodium phthalocyanine cobalt carboxylate in the embodiment 1 comprises the following steps:
(1) 34.52% of crushed trimellitic anhydride, 10.68% of cobalt chloride hexahydrate, 53.95% of urea and 0.86% of ammonium molybdate are transferred into a three-necked flask according to mass percent, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido cobalt phthalocyanine.
(2) Taking 2.26% of tetra-beta-amido cobalt phthalocyanine powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine cobalt carboxylate.
Example 2:
the influence of the change of the dosage of pyrrole monomer and tetra-beta-carboxylic acid group cobalt phthalocyanine on the microscopic morphology of the tetra-beta-carboxylic acid group metal phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) Three parts of 1.36% freshly distilled Py monomer are respectively placed in 26.36%, 26.42% and 26.45% isopropanol solution under ice water bath condition (0-5 ℃) according to mass percentage to be recorded as group A; 0.42%, 0.21% and 0.11% of sodium tetra- β -carboxylate cobalt phthalocyanine are dissolved in deionized water under the conditions of 67.25%, 67.39% and 67.46% ice water bath, respectively, and after the sodium tetra- β -carboxylate cobalt phthalocyanine is sufficiently dissolved, 4..60%, 4.61% and 4.62% Ammonium Persulfate (APS) are added, respectively, as group B.
(2) And after the group A is fully stirred and the solute in the group B is fully dissolved, maintaining the ice-water bath condition, and sequentially dripping the three solutions in the group B into the three solutions in the group A for reaction for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The obtained product is observed to have microscopic morphology by a scanning electron microscope, and the three dosage proportions are found to show a uniform three-dimensional network nanofiber structure, and the average diameter of the nanofiber is gradually increased along with the reduction of the dosage of the sodium tetra-beta-carboxylate cobalt phthalocyanine.
TABLE 1 influence of variation of the mass ratio of pyrrole monomer to sodium tetra- β -carboxylate cobalt phthalocyanine on the average diameter of nanofibers
| Mass ratio of pyrrole monomer to cobalt tetra-beta-carboxylate phthalocyanine | Average diameter of nanofiber |
| 3.5:1 | 83 nm |
| 7.0:1 | 130 nm |
| 14.0:1 | 145 nm |
From table 1, it is known that the diameter of the nanofiber can be controlled by changing the mass ratio of pyrrole monomer to sodium tetra- β -carboxylate cobalt phthalocyanine.
Example 3:
the influence on the microscopic morphology of the cobalt tetra-beta-carboxylic phthalocyanine/polypyrrole binary nanofiber at low temperature (0-5 ℃) and room temperature (25 ℃) comprises the following steps:
(1) Two parts of 1.36% freshly distilled Py monomer were taken in mass ratio, one part was placed in 26.42% isopropanol at room temperature (25 ℃) in ice water bath conditions (0-5 ℃) and the other part was placed in 26.42% isopropanol at room temperature (25 ℃), denoted as solutions A1 and A2, respectively. Two parts of 0.21% sodium tetra-beta-carboxylate cobalt phthalocyanine were taken, one part was placed in deionized water under 67.39% ice water bath conditions, and the other part was placed in 67.39% room temperature deionized water, noted as solutions B1 and B2, respectively. To solutions B1 and B2, 4.61% Ammonium Persulfate (APS) was added after the cobalt tetra-beta-carboxylate sodium phthalocyanine was sufficiently dissolved.
(2) After the solutions A1 and A2 are fully stirred and the solutes in the solutions B1 and B2 are fully dissolved, the solution B1 is added into the solution A1 under the condition of ice-water bath, and the reaction is carried out for 8 hours. Solution B2 was added to solution A2 at room temperature and reacted for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The microscopic morphology of the product obtained by taking the temperature as a variable is observed by a scanning electron microscope, and compared with the tetra-beta-carboxylic acid cobalt phthalocyanine/polypyrrole binary nanofiber prepared at room temperature, the nanofiber obtained at low temperature has better dispersibility, more uniformity and longer length.
Example 4:
the preparation method of the tetra-beta-carboxylic acid zinc phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine zinc is placed in deionized water under the condition of 67.39% ice water bath, and after the tetra-beta-carboxylic acid sodium phthalocyanine zinc is fully dissolved, 4.61% Ammonium Persulfate (APS) is added as solution B.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The preparation method of tetra-beta-sodium phthalocyanine zinc carboxylate described in the present example 4 comprises the following steps:
(1) 36.34% of crushed trimellitic anhydride, 6.44% of anhydrous zinc chloride, 56.75% of urea and 0.47% of ammonium molybdate are transferred into a three-necked flask according to mass percent, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido zinc phthalocyanine.
(2) Taking 2.26% of tetra-beta-amido zinc phthalocyanine powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine zinc carboxylate.
Example 5:
the preparation method of the tetra-beta-sodium carboxylate phthalocyanine iron/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. And (3) placing 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine iron in deionized water under 67.39% ice water bath condition, and adding 4.61% Ammonium Persulfate (APS) as solution B after the tetra-beta-carboxylic acid sodium phthalocyanine iron is fully dissolved.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The method for preparing tetra-beta-sodium carboxylate iron phthalocyanine described in the present example 5 comprises the steps of:
(1) 35.90% of crushed trimellitic anhydride, 7.57% of anhydrous ferric chloride, 56.06% of urea and 4.67% of ammonium molybdate are transferred into a three-necked flask according to mass percent, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido iron phthalocyanine.
(2) Taking 2.26% of tetra-beta-amido phthalocyanine iron powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain tetra-beta-sodium carboxylate phthalocyanine iron.
Example 6:
the preparation method of the tetra-beta-sodium phthalocyanine nickel/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. And (3) placing 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine nickel in deionized water under 67.39% ice water bath condition, and adding 4.62% Ammonium Persulfate (APS) as solution B after the tetra-beta-carboxylic acid sodium phthalocyanine nickel is fully dissolved.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The preparation method of tetra-beta-sodium phthalocyanine nickel carboxylate in the embodiment 6 comprises the following steps:
(1) 34.68% of crushed trimellitic anhydride, 10.71% of nickel chloride hexahydrate, 54.16% of urea and 0.45% of ammonium molybdate are transferred into a three-necked flask according to mass percent, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido nickel phthalocyanine.
(2) Taking 2.26% of tetra-beta-amido phthalocyanine nickel powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain tetra-beta-sodium phthalocyanine nickel carboxylate.
Example 7:
the preparation method of the tetra-beta-sodium carboxylate copper phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine copper is placed in deionized water under the condition of 67.39% ice water bath, and after the tetra-beta-carboxylic acid group phthalocyanine copper is fully dissolved, 4.62% Ammonium Persulfate (APS) is added as a solution B.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The preparation method of tetra-beta-sodium phthalocyanine copper carboxylate described in the present example 7 comprises the following steps:
(1) 35.77% of crushed trimellitic anhydride, 7.91% of cupric chloride dihydrate, 55.86% of urea and 0.47% of ammonium molybdate are transferred into a three-necked flask according to mass percent, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido copper phthalocyanine.
(2) Taking 2.26% of tetra-beta-amido copper phthalocyanine powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine copper carboxylate.
Example 8:
the preparation method of the tetra-beta-sodium phthalocyanine manganese/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by mass of freshly distilled Py monomer was taken and placed in isopropanol at a content of 26.42% in an ice-water bath (0-5 ℃) and recorded as solution A. And (3) placing 0.21% of tetra-beta-carboxylic acid sodium phthalocyanine manganese in deionized water under 67.39% ice water bath condition, and adding 4.62% Ammonium Persulfate (APS) as solution B after the tetra-beta-carboxylic acid group phthalocyanine manganese is fully dissolved.
(2) After the solution A is fully stirred and the solute in the solution B is fully dissolved, the solution B is dropwise added into the solution A under the ice-water bath condition, and the reaction is carried out for 8 hours. After the reaction is finished, a black product is obtained and filtered, and is soaked and washed by absolute ethyl alcohol and deionized water in sequence, and the filtrate is dried at 60 ℃ after being colorless, and the product is collected.
The preparation method of the tetra-beta-sodium phthalocyanine manganese carboxylate in the embodiment 8 comprises the following steps:
(1) 35.31% of crushed trimellitic anhydride, 9.08% of tetrahydrate manganese chloride, 55.15% of urea and 0.46% of ammonium molybdate are transferred into a three-necked flask according to mass percentage, and after mechanical stirring for 1 hour in an oil bath at 160 ℃, the temperature is raised to 230 ℃ and heated for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and after washing the solid powder with boiling water until the filtrate was colorless, it was washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido phthalocyanine manganese.
(2) Taking 2.26% of tetra-beta-amido manganese phthalocyanine powder according to the mass percentage, adding 97.74% of NaOH (2 mol/L) solution into a round-bottom flask, fully mixing, refluxing and heating at 100 ℃ until no ammonia gas is released or ammonia gas smell is small, stopping heating, filtering and collecting an upper filter cake, washing for a plurality of times by using absolute methanol and acetone, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine manganese carboxylate.
The uv-visible absorption spectrum of the tetra- β -carboxylate cobalt phthalocyanine/polypyrrole binary nanofiber obtained in this example 1 (the solvent is N-N dimethylformamide), and it can be seen from fig. 4 that there is a distinct characteristic peak of Q band (686 nm) and B band (349 nm) of tetra- β -carboxylate cobalt phthalocyanine/polypyrrole binary nanofiber in the spectrum compared to single polypyrrole. There is a red shift of 18 nm for both peaks compared to the tetra- β -carboxylic acid based metal cobalt phthalocyanine. These all indicate successful preparation of the-beta-sodium phthalocyanine cobalt/polypyrrole binary nanofiber.
The infrared spectrum of the tetra- β -carboxyphthalocyanine cobalt/polypyrrole binary nanofiber obtained in this example 1 is shown in fig. 5, and a new peak 1710 cm-1 (c=o) derived from the tetra- β -carboxyphthalocyanine cobalt appears in the infrared spectrum of the tetra- β -carboxyphthalocyanine cobalt/polypyrrole binary nanofiber as compared with polypyrrole, and a slight red shift (6 cm-1) occurs. The absorption peaks of the tetra-beta-carboxylic acid cobalt phthalocyanine/polypyrrole binary nanofiber are about 1556 and 1467c m-1, which are assigned to symmetrical and antisymmetric stretching modes of the pyrrole ring. At the same time, the absorption peaks at 1191, 1049, 922 and 794, cm-1, respectively, indicate the doped and polymerized states of polypyrrole. This further illustrates the successful preparation of tetra- β -carboxyphtalocyanine cobalt/polypyrrole binary nanofibers.
The XPS full spectrum and the fine spectrum of the tetra-beta-carboxylic acid group cobalt phthalocyanine/polypyrrole binary nanofiber obtained in the example 1 are shown in fig. 7, and obvious Co characteristic peaks are obviously observed on the spectral lines of the tetra-beta-carboxylic acid group cobalt phthalocyanine/polypyrrole binary nanofiber in the full spectrum. In addition, in the fine spectrum, C1 s and N1 s of polypyrrole can be decomposed into six gaussian peaks, located at 283.71 (sp 2C), 284.82 (sp 3C), 286.21 (-cn+), 287.54 (-c=n+), 399.45 (-NH-) and 400.17eV (-nh+), respectively. When cobalt tetra- β -carboxylate is bound to polypyrrole, there is no peak in the cobalt tetra- β -carboxylate/polypyrrole binary nanofiber corresponding to 285.74 eV (C-OH) of cobalt tetra- β -carboxylate because cobalt tetra- β -carboxylate interacts with PPy in an ionic fashion in aqueous solution, the C1 s peak of cobalt tetra- β -carboxylate is in 288.51 eV (c=o) red shifted to 289.62 eV, indicating that the-COO-group is doped into polypyrrole by electrostatic action (insert (a) in fig. 3). In addition, the peaks of 283.58 (sp 2C) and 286.2 eV (C-N) for the cobalt tetra- β -carboxylate phthalocyanine/polypyrrole binary nanofibers correspond to 283.71 eV and 286.21 eV, respectively, in polypyrrole. In comparison to the N1 s spectrum of the tetra- β -carboxyphtalocyanine cobalt/polypyrrole binary nanofiber, the peak positions of 400.03 eV (-nh++) and 399.48eV (-NH-) were shifted with respect to polypyrrole due to the intervention of the tetra- β -carboxyphtalocyanine cobalt, and there was a characteristic peak derived from the tetra- β -carboxyphtalocyanine cobalt (397.63 eV) (inset (b) in fig. 3). All these evidence further indicate that tetra- β -carboxyphtalocyanine cobalt/polypyrrole binary nanofibers were successfully prepared based on acid-base interactions.
Taking 0.06% of tetra-beta-carboxylic cobalt phthalocyanine/polypyrrole binary nanofiber obtained in the example 1 according to the mass percentage, adding the nano-fiber into 99.94% of absolute ethyl alcohol, absorbing a proper amount of dispersed liquid by a micro-injector after the nano-fiber is uniformly dispersed, coating the dispersed liquid on the surface of an interdigital electrode, and putting the well-dripped interdigital electrode into a 60 ℃ oven to dry the solvent, thus successfully preparing the test electrode. The static ammonia gas detection is carried out at room temperature within the range of 50 ppb-500 ppm, and the test result shows that the binary nanofiber has excellent ammonia gas sensitivity (50 ppm, 49.32%), can stably maintain more than 200 s at each concentration, and has rapid response (50 ppm,8.1 s) and natural recovery capability (50 ppm,370.8 s).
The water-soluble metal phthalocyanine salt (sodium tetra-beta-carboxylate metal phthalocyanine salt) obtained by adjusting the substituent is a hard template, a proper amount of the water-soluble metal phthalocyanine salt is introduced into polypyrrole, and the acid-base protonation action of the water-soluble metal phthalocyanine salt and the sodium tetra-beta-carboxylate metal phthalocyanine salt is utilized to orderly change the microscopic morphology of the polypyrrole, regulate and control the diameter of the nanofiber material, so that the sensing capability of the nanofiber material on gas is improved. The product is prepared from pyrrole monomer, tetra-beta-sodium carboxylate metal phthalocyanine salt, deionized water, isopropanol and ammonium persulfate. The method comprises the steps of mixing and stirring pyrrole monomers respectively dissolved in isopropanol, tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate dissolved in deionized water at low temperature under the ice water bath condition, filtering, washing and drying to obtain a target product. The product of the invention has controllable size, uniform appearance and excellent gas-sensitive performance; the method has the characteristics of simple and convenient operation, low cost, simple synthesis equipment, no toxicity, no harm and environmental protection.
Example 9:
the tetra- β -carboxylic acid based metal phthalocyanine polypyrrole binary nanofiber as described in example 1 wherein the central metal of the tetra- β -sodium metal phthalocyanine salt is cobalt, nickel, zinc, manganese, iron or copper.
Example 10:
according to the preparation method of the tetra-beta-carboxylic acid-based metal phthalocyanine polypyrrole binary nanofiber in the embodiment 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or the preparation method, the drying temperature is 60-80 ℃.
Claims (6)
1. A tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber is characterized in that: the binary nanofiber is prepared from raw materials of 0.05-0.79% of tetra-beta-sodium carboxylate metal phthalocyanine salt, 1.36-2.56% of pyrrole monomer, 24.81-26.5% of isopropanol, 63.18-67.46% of deionized water and 4.60-8.72% of ammonium persulfate by mass percent;
the central metal of the tetra-beta-sodium carboxylate metal phthalocyanine salt is cobalt, nickel, zinc, manganese, iron or copper;
the tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber is prepared by in-situ polymerization of polypyrrole by taking tetra-beta-carboxylic acid sodium metal phthalocyanine salt as a hard template, and is prepared by the following method: preparing a solution A taking isopropanol as a solvent and a freshly distilled pyrrole monomer as a solute;
solution B taking deionized water as a solvent, and tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate as solutes;
and (3) mixing and stirring the solution A, B under the ice water bath condition for reaction for 4-8 hours to obtain a black product, filtering the black product, sequentially soaking and washing the black product with absolute ethyl alcohol and deionized water, and drying the filtrate after the filtrate is colorless to obtain the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber product.
2. The tetra- β -carboxylic acid based metal phthalocyanine/polypyrrole binary nanofiber as claimed in claim 1, characterized in that: the binary nanofiber is prepared from raw materials of 0.21% of tetra-beta-sodium carboxylate metal phthalocyanine salt, 1.36% of pyrrole monomer, 26.42% of isopropanol, 67.39% of deionized water and 4.62% of ammonium persulfate by mass percent.
3. A method for preparing tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofibers according to any one of claims 1 to 2, characterized in that: the polypyrrole is prepared by in-situ polymerization of a rigid template by using tetra-beta-sodium carboxylate metal phthalocyanine salt, and the method comprises the following steps of: preparing a solution A taking isopropanol as a solvent and a freshly distilled pyrrole monomer as a solute;
solution B taking deionized water as a solvent, and tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate as solutes;
and (3) mixing and stirring the solution A, B under the ice water bath condition for reaction for 4-8 hours to obtain a black product, filtering the black product, sequentially soaking and washing the black product with absolute ethyl alcohol and deionized water, and drying the filtrate after the filtrate is colorless to obtain the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber product.
4. A method for preparing tetra- β -carboxylic acid based metal phthalocyanine/polypyrrole binary nanofibers according to claim 3, wherein: the volume ratio of the solution A to the solution B is 1:2.
5. The method for preparing tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber as claimed in claim 4, wherein the method comprises the following steps: the reaction temperature of the ice water bath condition is 0-5 ℃.
6. The method for preparing tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber as claimed in claim 5, wherein the method comprises the following steps: the drying temperature is 60-80 ℃.
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| WO2008114607A1 (en) * | 2007-03-22 | 2008-09-25 | Shinshu University | Water-soluble metal phthalocyanine complex, sensor element, sensor using the sensor element, and method for production of sensor element |
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| WO2008114607A1 (en) * | 2007-03-22 | 2008-09-25 | Shinshu University | Water-soluble metal phthalocyanine complex, sensor element, sensor using the sensor element, and method for production of sensor element |
| CN107057059A (en) * | 2017-02-14 | 2017-08-18 | 黑龙江大学 | A kind of four β carboxyls metal phthalocyanines/polyaniline composite conducting nanotube and its preparation method and application |
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