CN114150397A - Tetra-beta-carboxylic acid base metal phthalocyanine/polypyrrole binary nanofiber and preparation method thereof - Google Patents
Tetra-beta-carboxylic acid base metal phthalocyanine/polypyrrole binary nanofiber and preparation method thereof Download PDFInfo
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- 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
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Abstract
A tetra-beta-carboxylic acid base metal phthalocyanine polypyrrole binary nanofiber and a preparation method thereof. The morphology tuning methods for polypyrrole nanostructures are typically soft and hard template methods. The synthesis of the soft template usually needs some surfactants or polymer stabilizers to guide pyrrole monomers to orderly polymerize in solution, the method is simple and effective, and the soft template can be cleaned by using a proper solvent after the reaction is finished. However, the product synthesized by the method has low shape controllability, and the expensive soft template has certain disadvantages in large-scale production and is easy to cause environmental pollution. The invention is prepared by 0.21 percent of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36 percent of pyrrole monomer, 26.42 percent of isopropanol, 67.39 percent of deionized water and 4.62 percent of ammonium persulfate according to mass percentage. 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 easy to combine with specific gas molecules due to the special functional group and the conjugated structure of the conductive polymer, and has the property of normally working at room temperature so as to show unusual gas sensing performance. In recent years, among many conductive polymers, the unique redox property between polypyrrole and ammonia gas has attracted a great deal of attention in the field of gas sensing, however, such single materials also have some problems, such as: low sensitivity, poor selectivity, slow recovery, short lifetime, etc.
In order to overcome the defects of single polypyrrole and enhance the gas sensing capability of the single polypyrrole, the improvement of the irregular micro-morphology of the polypyrrole is an effective strategy. The effective surface area and porosity of the polypyrrole can be increased by adjusting the micro-morphology of the polypyrrole, so that gas molecules can be contacted with active sites to a greater extent, and the gas sensing performance of the polypyrrole nano material can be improved.
The morphology tuning methods for polypyrrole nanostructures are typically soft and hard template methods. The synthesis of the soft template usually needs some surfactants or polymer stabilizers to guide pyrrole monomers to orderly polymerize in solution, the method is simple and effective, and the soft template can be cleaned by using a proper solvent after the reaction is finished. However, the product synthesized by the method has low shape controllability, and the expensive soft template has certain disadvantages in large-scale production and is easy to cause environmental pollution. The hard template method is generally to select a material with a specific nano structure as a carrier, and to polymerize pyrrole monomers on the surface of the carrier. Synthesis using the hard template method requires a more demanding post-treatment process to eliminate the hard template, which is complex and time consuming. Therefore, the problem that a substance which can regulate the polymerization morphology of pyrrole and has gas-sensitive activity so as to enhance the gas sensing performance of the material is needed to be broken through is sought.
Disclosure of Invention
The invention aims to provide a morphology-controllable tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber, wherein tetra-beta-carboxylic acid sodium metal phthalocyanine salt in synthetic raw materials is used as a pyrrole polymerization hard template, and the gas sensing performance of a composite material is enhanced by utilizing the synergistic optimization between the tetra-beta-carboxylic acid sodium metal phthalocyanine salt and the pyrrole polymerization hard template.
The above purpose is realized by the following technical scheme:
the binary nanofiber is prepared from 0.05-0.79 mass percent of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36-2.56 mass percent of pyrrole monomer, 24.81-26.5 mass percent of isopropanol, 63.18-67.46 mass percent of deionized water and 4.60-8.72 mass percent of ammonium persulfate.
The binary nanofiber is prepared from 0.21 mass percent of sodium metal phthalocyanine tetra-beta-carboxylate, 1.36 mass percent of pyrrole monomer, 26.42 mass percent of isopropanol, 67.39 mass percent of deionized water and 4.62 mass percent of ammonium persulfate.
The tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber has the advantages that the central metal of the tetra-beta-carboxylic acid sodium metal phthalocyanine salt is cobalt, nickel, zinc, manganese, iron or copper.
The preparation method of the tetra-beta-carboxylic acid-based metal phthalocyanine poly/pyrrole binary nanofiber comprises the following steps of taking tetra-beta-carboxylic acid sodium metal phthalocyanine as a hard template to polymerize polypyrrole in situ, and preparing the polypyrrole into the nanofiber by the following method: preparing a solution A with isopropanol as a solvent and a freshly distilled pyrrole monomer as a solute;
a solution B with deionized water as a solvent and tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate as solutes;
and 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 by using 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.
According to the preparation method of the tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofiber, the volume ratio of the solution A to the solution B is 1: 2.
The preparation method of the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber is characterized in that the reaction temperature under the ice-water bath condition is 0-5 ℃.
The preparation method of the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber has the drying temperature of 60-80 ℃.
Has the advantages that:
1. according to the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber provided by the invention, because the coordinated metal at the center of the tetra-beta-carboxylic acid-based metal phthalocyanine is used as an active site for adsorbing oxygen, the formed adsorbed oxygen is easy to combine with ammonia gas to generate electrons; on the other hand, the unique chemical structure of polypyrrole is easy to generate oxidation-reduction reaction with ammonia gas and generate electron transfer. This makes the composite material possess fast response restoring capacity and high sensitivity performance at room temperature. The two have synergistic advantages and a unique nanofiber structure, so that the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber prepared by the method has excellent gas sensing performance, and 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 monomers to sodium tetra-beta-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, the response sensitivity of the fiber greatly exceeds that of a single polypyrrole and tetra-beta-carboxylic acid based metal phthalocyanine gas-sensitive material, and on the basis, the fast response recovery capability and high-efficiency sensitivity are still maintained.
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 by only one step of reaction. And the post-treatment is simple, a template does not need 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, no pollution and simple operation.
Description of the drawings:
fig. 1 is an electron microscope photograph of the tetra- β -cobalt phthalocyanine carboxylate/polypyrrole binary nanofiber prepared in embodiment 1;
wherein: a is a Scanning Electron Microscope (SEM) picture, 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 types of nanofibers obtained by using a mass ratio of pyrrole monomers to sodium tetra- β -carboxylate phthalocyanine cobalt in embodiment example 2 as a variable;
wherein: the mass ratio of A to B is 3.5:1, B to C is 7.0:1 and C to C is 14.0: 1;
FIG. 3 is a graph showing a comparison of the morphology of binary cobalt tetra- β -carboxylate phthalocyanine/polypyrrole nanofibers prepared at different temperatures in example 3;
wherein: panel A shows normal temperature (25 deg.C); panel B is (0-5 ℃);
fig. 4 is an ultraviolet-visible absorption spectrum of cobalt tetra- β -carboxylate phthalocyanine, polypyrrole alone, and binary cobalt tetra- β -carboxylate phthalocyanine/polypyrrole nanofibers in N-N dimethylformamide in embodiment 1;
FIG. 5 is an IR spectrum of Co-tetra- β -carboxylate, single polypyrrole and Co-tetra- β -carboxylate/polypyrrole nanofibers of example 1;
fig. 6 is an XPS survey of cobalt tetra- β -carboxylate, single polypyrrole and cobalt tetra- β -carboxylate/polypyrrole binary nanofibers and internal C1 s and N1 s fine spectra in embodiment 2;
fig. 7 is a gas-sensitive performance diagram of the tetra- β -cobalt phthalocyanine carboxylate/polypyrrole binary nanofiber prepared in embodiment 2 for ammonia gas with different concentration gradients;
wherein: graph a is a response recovery graph; graph B is a response versus recovery time graph.
The specific implementation mode is as follows:
example 1:
the tetra-beta-carboxylic acid-based metal phthalocyanine/polypyrrole binary nanofiber is prepared from 0.05-0.79 mass percent of tetra-beta-carboxylic acid sodium metal phthalocyanine salt, 1.36-2.56 mass percent of pyrrole monomer, 24.81-26.5 mass percent of isopropanol, 63.18-67.46 mass percent of deionized water and 4.60-8.72 mass percent of ammonium persulfate;
the preparation method of the tetra-beta-carboxylic acid group cobalt phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium cobalt phthalocyanine is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.62 percent of Ammonium Persulfate (APS) is added as a solution B after the tetra-beta-carboxylic acid cobalt phthalocyanine is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The preparation method of cobalt tetra- β -carboxylate phthalocyanine described in this embodiment 1 includes the following steps:
(1) 34.52 percent of ground trimellitic anhydride, 10.68 percent of cobalt chloride hexahydrate, 53.95 percent of urea and 0.86 percent of ammonium molybdate are taken according to the mass percentage and transferred into a three-neck flask, and after mechanical stirring is carried out 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 the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido cobalt phthalocyanine.
(2) Taking 2.26 percent of tetra-beta-amido phthalocyanine cobalt powder according to the mass percent, adding 97.74 percent of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-sodium carboxylate phthalocyanine cobalt.
Example 2:
the influence of the change of the dosage of pyrrole monomer and cobalt tetra-beta-carboxylate phthalocyanine on the microscopic morphology of the tetra-beta-carboxylate metal phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) taking three parts of 1.36% of freshly distilled Py monomer according to mass percent, and respectively placing the three parts into 26.36%, 26.42% and 26.45% of isopropanol solution under the ice-water bath condition (0-5 ℃) to be marked as a group A; 0.42%, 0.21% and 0.11% of cobalt tetra- β -carboxylate phthalocyanine were dissolved in deionized water in 67.25%, 67.39% and 67.46% ice-water bath conditions, and 4..60%, 4.61% and 4.62% of Ammonium Persulfate (APS) were added as group B after cobalt tetra- β -carboxylate phthalocyanine was sufficiently dissolved.
(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, dropwise adding the three solutions in the group B into the three solutions in the group A in sequence, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
Observing the microscopic morphology of the obtained product by using a scanning electron microscope, and finding that the three dosage proportions show a uniform three-dimensional reticular nano-fiber structure, and the average diameter of the nano-fiber can be gradually increased along with the reduction of the dosage of the tetra-beta-sodium carboxylate phthalocyanine cobalt.
TABLE 1 influence of variation of the mass ratio of pyrrole monomers to sodium tetra-beta-carboxylate cobalt phthalocyanine on the average diameter of the nanofibers
| Mass ratio of pyrrole monomer to cobalt tetra-beta-carboxylphthalocyanine | Average diameter of nanofiber |
| 3.5:1 | 83 nm |
| 7.0:1 | 130 nm |
| 14.0:1 | 145 nm |
As shown in table 1, the diameter of the nanofiber can be controlled by changing the mass ratio of the pyrrole monomer to the sodium tetra- β -carboxylate phthalocyanine cobalt.
Example 3:
the influence on the micro-morphology of the tetra-beta-carboxylic acid group cobalt phthalocyanine/polypyrrole binary nanofiber at low temperature (0-5 ℃) and room temperature (25 ℃) comprises the following steps:
(1) two portions of 1.36% freshly distilled Py monomer were taken in mass ratio, one portion was placed in 26.42% isopropanol at ice-water bath conditions (0-5 deg.C) and the other portion was placed in 26.42% isopropanol at room temperature (25 deg.C) and labeled as solutions A1 and A2, respectively. Two portions of 0.21% cobalt tetra- β -carboxylate phthalocyanine, one portion placed in 67.39% deionized water in an ice-water bath, and the other portion placed in 67.39% deionized water at room temperature, were labeled as solutions B1 and B2, respectively. 4.61% Ammonium Persulfate (APS) was added to solutions B1 and B2 after the cobalt tetra- β -carboxylate phthalocyanine was sufficiently dissolved.
(2) And after the solutions A1 and A2 are fully stirred and the solutes in the solutions B1 and B2 are fully dissolved, keeping the ice-water bath condition, adding the solution B1 into the solution A1, and reacting for 8 hours. The solution B2 was added to the solution A2 at room temperature and reacted for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The microscopic morphology of the product obtained by taking the temperature as a variable is observed by a scanning electron microscope, and the nano-fiber obtained at low temperature has better dispersibility, more uniformity and longer length compared with the tetra-beta-cobalt phthalocyanine carboxylate/polypyrrole binary nano-fiber prepared at room temperature.
Example 4:
the preparation method of the tetra-beta-carboxylic acid group cyanine zinc/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium phthalocyanine zinc is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.61 percent of Ammonium Persulfate (APS) is added as a solution B after the tetra-beta-carboxylic acid sodium phthalocyanine zinc is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The preparation method of tetra-beta-carboxylic acid sodium phthalocyanine zinc described in the embodiment 4 comprises the following steps:
(1) 36.34% by mass of ground trimellitic anhydride, 6.44% by mass of anhydrous zinc chloride, 56.75% by mass of urea and 0.47% by mass of ammonium molybdate were transferred to a three-necked flask, mechanically stirred in an oil bath at 160 ℃ for 1 hour, and then heated to 230 ℃ for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido zinc phthalocyanine.
(2) Taking 2.26 percent of tetra-beta-amido zinc phthalocyanine powder according to the mass percent, adding 97.74 percent of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or the ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine zinc carboxylate.
Example 5:
the preparation method of the tetra-beta-sodium phthalocyanine iron/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium iron phthalocyanine is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.61 percent of Ammonium Persulfate (APS) is added as a solution B after the tetra-beta-carboxylic acid iron phthalocyanine is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The method for preparing tetra-beta-carboxylic acid sodium iron phthalocyanine described in this example 5 comprises the following steps:
(1) 35.90% by mass of ground trimellitic anhydride, 7.57% by mass of anhydrous ferric chloride, 56.06% by mass of urea, and 4.67% by mass of ammonium molybdate were transferred to a three-necked flask, mechanically stirred in an oil bath at 160 ℃ for 1 hour, and then heated to 230 ℃ for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido phthalocyanine iron.
(2) Taking 2.26 percent of tetra-beta-amido iron phthalocyanine powder according to the mass percent, adding 97.74 percent of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or the ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine iron carboxylate.
Example 6:
the preparation method of the tetra-beta-sodium phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium phthalocyanine nickel is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.62 percent of Ammonium Persulfate (APS) is added as a solution B after the tetra-beta-carboxylic acid sodium phthalocyanine nickel is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The method for preparing tetra-beta-carboxylic acid sodium phthalocyanine nickel described in this example 6 includes the following steps:
(1) 34.68% by mass of ground trimellitic anhydride, 10.71% by mass of nickel chloride hexahydrate, 54.16% by mass of urea and 0.45% by mass of ammonium molybdate were transferred to a three-necked flask, mechanically stirred in an oil bath at 160 ℃ for 1 hour, and then heated to 230 ℃ for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido phthalocyanine nickel.
(2) Taking 2.26 percent of tetra-beta-amido phthalocyanine nickel powder according to the mass percentage, adding 97.74 percent of NaOH (2 mol/L) solution into a round-bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or the ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-carboxylic acid sodium phthalocyanine nickel.
Example 7:
the preparation method of the tetra-beta-sodium phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium copper phthalocyanine is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.62 percent of Ammonium Persulfate (APS) is added to be used as a solution B after the tetra-beta-carboxylic acid copper phthalocyanine is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The method for preparing copper tetra- β -carboxylate sodium phthalocyanine as described in this example 7, includes the following steps:
(1) 35.77% by weight of ground trimellitic anhydride, 7.91% by weight of copper chloride dihydrate, 55.86% by weight of urea and 0.47% by weight of ammonium molybdate were transferred to a three-necked flask, mechanically stirred in an oil bath at 160 ℃ for 1 hour, and then heated to 230 ℃ for 7 hours. After the reaction was stopped and cooled to room temperature, the product was crushed, and the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido copper phthalocyanine.
(2) Taking 2.26 percent of tetra-beta-amido copper phthalocyanine powder according to the mass percent, adding 97.74 percent of NaOH (2 mol/L) solution into a round bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or the ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine copper carboxylate.
Example 8:
the preparation method of the tetra-beta-sodium carboxylate manganese phthalocyanine/polypyrrole binary nanofiber comprises the following steps:
(1) 1.36% by weight of freshly distilled Py monomer was taken in isopropanol 26.42% in ice-water bath (0-5 ℃ C.) and recorded as solution A. 0.21 percent of tetra-beta-carboxylic acid sodium phthalocyanine manganese is put into deionized water under the condition of 67.39 percent of ice-water bath, and 4.62 percent of Ammonium Persulfate (APS) is added as a solution B after the tetra-beta-carboxylic acid sodium phthalocyanine manganese is fully dissolved.
(2) And after the solution A is fully stirred and the solute in the solution B is fully dissolved, maintaining the ice-water bath condition, dropwise adding the solution B into the solution A, and reacting for 8 hours. After the reaction is finished, filtering the obtained black product, sequentially soaking and washing the black product by absolute ethyl alcohol and deionized water, drying the black product at the temperature of 60 ℃ after the filtrate is colorless, and collecting the product.
The method for preparing tetra-beta-carboxylic acid sodium phthalocyanine manganese described in this example 8 includes the following steps:
(1) 35.31 percent of ground trimellitic anhydride, 9.08 percent of manganese chloride tetrahydrate, 55.15 percent of urea and 0.46 percent of ammonium molybdate are taken according to the mass percentage and transferred into a three-neck flask, and after mechanical stirring is carried out 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 the solid powder was washed with boiling water until the filtrate was colorless, and then washed with methanol and acetone several times. Drying at 70 ℃ to obtain the product tetra-beta-amido manganese phthalocyanine.
(2) Taking 2.26 percent of tetra-beta-amido manganese phthalocyanine powder according to the mass percent, adding 97.74 percent of NaOH (2 mol/L) solution into a round-bottom flask, fully mixing, heating under reflux at 100 ℃ until no ammonia gas is released or the ammonia smell is small, stopping heating, filtering, collecting an upper filter cake, washing with anhydrous methanol and acetone for multiple times, and drying at 70 ℃ to obtain the tetra-beta-sodium phthalocyanine carboxylate.
In the ultraviolet-visible absorption spectrum (solvent is N-N dimethylformamide) of the binary cobalt tetra- β -carboxylate/polypyrrole nanofiber obtained in this example 1, as can be seen from fig. 4, compared with a single polypyrrole, a spectrum of the binary cobalt tetra- β -carboxylate/polypyrrole nanofiber has a clear characteristic peak in a Q band (686 nm) of cobalt tetra- β -carboxylate and a characteristic peak in a B band (349 nm). There was a 18 nm red shift of both peaks compared to cobalt tetra- β -carboxylate. These all indicate the successful preparation of the-beta-sodium carboxylate cobalt phthalocyanine/polypyrrole binary nanofiber.
The ir spectrum of the binary tetra-beta-cobalt phthalocyanine carboxylate/polypyrrole nanofiber obtained in this example 1 is shown in fig. 5, and compared with polypyrrole, a new peak 1710 cm "1 (C = O) derived from the cobalt tetra-beta-phthalocyanine carboxylate appears in the ir spectrum of the binary tetra-beta-cobalt phthalocyanine carboxylate/polypyrrole nanofiber, and a slight red shift (6 cm" 1) occurs. In addition, the absorption peak of the tetra-beta-carboxylic phthalocyanine cobalt/polypyrrole binary nano-fiber of about 1556 and 1467c m-1 belongs to the symmetric and anti-symmetric stretching modes of the pyrrole ring. Meanwhile, the absorption peaks at 1191, 1049, 922 and 794 cm-1 respectively indicate the doping and polymerization states of polypyrrole. This further illustrates the successful preparation of tetra-beta-cobalt phthalocyanine carboxylate/polypyrrole binary nanofibers.
The XPS full spectrum and the fine spectrum of the binary cobalt tetra- β -carboxyphthalocyanine/polypyrrole nanofiber obtained in example 1 are shown in fig. 7, and a Co characteristic peak is clearly observed in the full spectrum on the spectrum line of the binary cobalt tetra- β -carboxyphthalocyanine/polypyrrole nanofiber. In addition, in the fine spectrum, the polypyrrole C1 s and N1 s 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 +). When cobalt tetra- β -carboxylate phthalocyanine was combined with polypyrrole, no peak corresponding to 285.74 eV (C-OH) of cobalt tetra- β -carboxylate phthalocyanine was present in the binary nanofibers of cobalt tetra- β -carboxylate/polypyrrole due to ionic interaction of cobalt tetra- β -carboxylate with PPy in aqueous solution, with the cobalt tetra- β -carboxylate C1 s peak at 288.51 eV (C = O) red-shifted to 289.62 eV, indicating that the-COO-group was doped into polypyrrole by electrostatic interaction (inset (a) in fig. 3). In addition, the peak values of 283.58 (sp 2C) and 286.2 eV (C-N) of the cobalt tetra- β -carboxylate phthalocyanine/polypyrrole binary nanofibers correspond to 283.71 eV and 286.21 eV in polypyrrole, respectively. Compared with the N1 s spectrum of the binary nano-fiber of the tetra-beta-cobalt carboxylate/polypyrrole, the peak positions of 400.03 eV (-NH + -) and 399.48 eV (-NH-) are shifted relative to polypyrrole due to the intervention of the cobalt tetra-beta-cobalt carboxylate, and a characteristic peak derived from the cobalt tetra-beta-cobalt carboxylate (397.63 eV) exists (fig. 3, inset (b)). All these evidences further indicate that the cobalt tetra- β -carboxylate phthalocyanine/polypyrrole binary nanofibers were successfully prepared based on acid-base interactions.
0.06% of the cobalt tetra-beta-carboxylate phthalocyanine/polypyrrole binary nanofiber obtained in the example 1 is added into 99.94% of absolute ethyl alcohol according to the mass percentage, after uniform ultrasonic dispersion, a micro-injector is used for sucking a proper amount of dispersed liquid drops to be coated on the surface of the interdigital electrode, and the coated interdigital electrode is placed in an oven at 60 ℃ to dry a solvent, so that the test electrode is successfully prepared. The binary nanofiber has excellent ammonia gas sensitivity (50 ppm, 49.32%), can stably keep more than 200 s at each concentration, and has quick response (50 ppm, 8.1 s) and natural recovery capability (50 ppm, 370.8 s).
The water-soluble metal phthalocyanine salt (tetra-beta-sodium carboxylate metal phthalocyanine salt) obtained by adjusting the substituent group is taken as a hard template, is properly introduced into the polypyrrole, and utilizes the acid-base protonation of the metal phthalocyanine salt and the acid-base protonation of the metal phthalocyanine salt to orderly change the microscopic morphology of the polypyrrole and adjust and control the diameter of the nanofiber material so as to improve the gas sensing capability of the nanofiber material. 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, sodium tetra-beta-carboxylate metal phthalocyanine salt and ammonium persulfate dissolved in deionized water at a low temperature under the condition of ice-water bath, 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 friendliness.
Example 9:
the bi-nanofiber of tetra-beta-metal carboxylate phthalocyanine polypyrrole according to example 1, wherein the central metal of the sodium metal phthalocyanine tetra-beta-carboxylate is cobalt, nickel, zinc, manganese, iron or copper.
Example 10:
the method for preparing the bi-component nanofiber of tetra-beta-metal carboxylate phthalocyanine polypyrrole according to example 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein the drying temperature is 60-80 ℃.
Claims (7)
1. A tetra-beta-carboxylic acid base metal phthalocyanine/polypyrrole binary nanofiber is characterized in that: the binary nanofiber is prepared from 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.
2. The tetra-beta-metal carboxylate phthalocyanine polypyrrole binary nanofiber as claimed in claim 1, wherein: the binary nanofiber is prepared from 0.21 mass percent of tetra-beta-sodium carboxylate metal phthalocyanine salt, 1.36 mass percent of pyrrole monomer, 26.42 mass percent of isopropanol, 67.39 mass percent of deionized water and 4.62 mass percent of ammonium persulfate.
3. The tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofiber as claimed in claim 1 or 2, wherein: the central metal of the tetra-beta-sodium carboxylate metal phthalocyanine salt is cobalt, nickel, zinc, manganese, iron or copper.
4. A method for preparing tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofibers according to any of claims 1 to 3, which is characterized by: the polypyrrole film is prepared by in-situ polymerizing polypyrrole by taking tetra-beta-sodium carboxylate metal phthalocyanine salt as a hard template by the following method: preparing a solution A with isopropanol as a solvent and a freshly distilled pyrrole monomer as a solute;
a solution B with deionized water as a solvent and tetra-beta-sodium carboxylate metal phthalocyanine salt and ammonium persulfate as solutes;
and 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 by using 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.
5. The method for preparing tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofibers according to claim 4, wherein the method comprises the following steps: the volume ratio of the solution A to the solution B is 1: 2.
6. The method for preparing tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofibers according to claim 4 or 5, wherein the method comprises the following steps: the reaction temperature of the ice-water bath condition is 0-5 ℃.
7. The method for preparing tetra-beta-metal carboxylate phthalocyanine/polypyrrole binary nanofibers according to claim 4 or 5, wherein the method comprises the following steps: the drying temperature is 60-80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107561129A (en) * | 2017-07-04 | 2018-01-09 | 上海工程技术大学 | A kind of hetero-junctions gas sensor of Inorganic whisker structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107561129A (en) * | 2017-07-04 | 2018-01-09 | 上海工程技术大学 | A kind of hetero-junctions gas sensor of Inorganic whisker structure |
Non-Patent Citations (1)
| Title |
|---|
| ZIHUI LYU等: "The enhanced capacitance performance of the modified polypyrrole with the mixture of carbon nanomaterials", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, pages 380 * |
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