CN116589754A - High-loading nano-structure polyaniline composite material and preparation method thereof - Google Patents
High-loading nano-structure polyaniline composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000011068 loading method Methods 0.000 title claims abstract description 40
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 40
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 108090000790 Enzymes Proteins 0.000 claims description 17
- 102000004190 Enzymes Human genes 0.000 claims description 17
- 229940088598 enzyme Drugs 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 11
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 108010059892 Cellulase Proteins 0.000 claims description 7
- 229940106157 cellulase Drugs 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 239000007974 sodium acetate buffer Substances 0.000 claims description 5
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000011232 storage material Substances 0.000 abstract description 4
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 abstract 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 abstract 1
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- 229940068041 phytic acid Drugs 0.000 abstract 1
- 235000002949 phytic acid Nutrition 0.000 abstract 1
- 239000000467 phytic acid Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
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- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of a high-load nano-structure polyaniline composite material, which comprises the steps of using pulp fibers as a substrate, using phytic acid as a doping agent, using alizarin red S as a regulating agent, dispersing pulp fibers and aniline monomers in a solution dissolved with the doping agent and the regulating agent, then dropwise adding an oxidant into the mixed dispersion liquid, coating nano-structure polyaniline on the surface of the pulp fibers through an in-situ oxidative polymerization process, and finally filtering, washing and drying to obtain the high-load nano-structure polyaniline composite material. The polyaniline composite material with the high-loading nano-structure obtained by the preparation method has the characteristics of high active material loading, excellent electrochemical performance and the like; the invention has simple process, high utilization rate of raw materials, no need of complex equipment and suitability for large-scale industrial production; the raw material pulp fiber used in the invention has wide sources, is degradable and renewable; the cost is low, the environment is protected, and the method is green and safe, and has important significance for environmental protection and promotion of development of flexible energy storage materials.
Description
Technical Field
The invention relates to the technical field of polyaniline composite materials, in particular to a high-loading nano-structure polyaniline composite material and a preparation method thereof.
Background
The conductive polymer, such as polyaniline, polypyrrole, etc., is a novel high molecular functional material, and can realize the specific conductive function by self conductivity or doping other materials. Among these conductive polymers, polyaniline is of great interest due to low cost, simple preparation and unique doping behavior. Meanwhile, polyaniline also has higher theoretical specific capacitance, and has wide application prospect in the energy storage field. As an energy storage material, polyaniline can undergo reversible oxidation-reduction reactions of n-type, p-type doping and dedoping when charged and discharged, so that charges are stored in polymer chains, thereby generating faraday capacitances. The phase change of the electrode material is basically unchanged in the whole charge and discharge process, so that the energy storage of the electrode material has better reversibility. In addition, polyaniline is the most studied intrinsic conductive polymer, because it has excellent electrochemical and optical properties, is easy to synthesize, and has the characteristics of higher working voltage, good plasticity and the like. When polyaniline is in a half-oxidation half-reduction state, the molecular structure is a benzene-quinone alternating structure which can be changed into a conductor through proton acid doping, and the polyaniline is in an emerald middle oxidation state, and the conductivity of the polyaniline is maximum at the moment. However, polyaniline has the disadvantages of incapability of forming films and poor mechanical processability, is difficult to directly apply, and can only be compounded with other materials to obtain sheet-like or film-like materials.
Pulp fiber is the most common material in pulp and paper industry, has the advantages of wide sources, low cost, machinability and the like, and is an excellent base material. The pulp fiber is used as a substrate material for loading polyaniline, so that the mechanical processing property of the polyaniline can be improved, the low-cost high-performance energy storage material can be prepared, the application field of the polyaniline is enlarged, and the industrialized application of the polyaniline is promoted.
At present, the polyaniline is loaded on pulp fibers by an in-situ polymerization method, so that the paper porosity can be completely maintained, and the polyaniline is uniformly distributed on the surface and inside of the paper. However, in the in-situ polymerization process, the deposition amount of polyaniline on pulp fibers is limited, and it is difficult to obtain high-loading polyaniline composite materials. Research shows that increasing the addition of reactants such as aniline monomer and oxidant can increase the loading of polyaniline. However, the cost is increased, the difficulty of wastewater treatment is increased, and the polyaniline in the prepared composite material also has serious agglomeration phenomenon, so that the overall performance of the composite material is reduced.
Because it is necessary to propose a new high-loading nano-structured polyaniline composite material and a preparation method thereof, the above problems are solved.
Disclosure of Invention
The invention aims to solve the technical problems that in the in-situ polymerization process, the deposition amount of polyaniline on pulp fibers is limited, and a high-loading polyaniline composite material is difficult to obtain, and provides a high-loading nano-structure polyaniline composite material and a preparation method thereof.
The preparation method of the high-loading nano-structure polyaniline composite material comprises the following steps: enzyme pretreatment is carried out on paper pulp fibers, sulfosalicylic acid is taken as a doping agent, ammonium persulfate is taken as an oxidant, alizarin red S is taken as a morphology regulator, and the high-loading nano-structure polyaniline composite material is prepared through an in-situ polymerization process.
The preparation method specifically comprises the following steps:
step one, preprocessing pulp fibers:
placing pulp fibers in a sealed bag at room temperature; adding cellulase solution, rapidly adding acetic acid-sodium acetate buffer solution with pH of 4.8, kneading for 1-2min to disperse fiber uniformly, sealing the sealed bag, and standing in water bath for a period of time; taking out, washing impurities with ethanol, and obtaining the rapid enzyme pretreatment pulp fiber;
further, the oven dry mass of the pulp was 0.5g; the dosage of the cellulase solution is 0.05-0.3mL, and the concentration is 3.5EGU/mL; the buffer was used in an amount of 50mL. The water bath temperature is 10-50deg.C, and the standing time is 1-20min.
Step two, preparing a high-load nano-structure polyaniline composite material:
placing the rapid enzyme pretreated pulp fiber in a round bottom flask and placing in an ice water bath; adding sulfosalicylic acid and alizarin red S solution into the flask, and mechanically stirring for 20min; adding aniline monomer, and continuing stirring for 30min; then dropwise adding ammonium persulfate solution, and continuously stirring for a period of time under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
Further, the dosage of the sulfosalicylic acid is 100mL, and the concentration is 0.1-0.8mol/L; the dosage of alizarin red S is 50mL, and the concentration is 0.1-0.8mol/L; the dosage of the aniline monomer is 0.1-1mL; the dosage of ammonium persulfate is 50mL, and the concentration is 1-10mmol/L. Stirring in ice water bath for 1-6h.
The principle of the invention is as follows:
in order to improve the loading capacity of polyaniline in the polyaniline composite material, the invention activates the reactive group on the surface of paper pulp by carrying out rapid enzyme pretreatment on paper base fiber, improves the specific surface area of the paper pulp fiber, provides more active sites for the deposition of polyaniline, promotes the efficient in-situ deposition of polyaniline on the paper pulp fiber, and further achieves the aim of improving the loading capacity of polyaniline.
Meanwhile, alizarin red S is introduced as a morphology regulator, and the microstructure of the high-loading polyaniline is regulated and controlled. On the one hand, alizarin red S contains sulfonic groups, can be used as a doping agent to enter polyaniline polymer chains, has larger steric hindrance of anthraquinone groups, can prevent polyaniline chains from approaching each other, and reduces aggregation among polyaniline particles; on the other hand, the alizarin red S contains hydroxyl, so that the hydrophilicity of the polymer chain can be endowed, the dispersion performance of the alizarin red S in the water phase is improved, and the agglomeration among particles is reduced. The microcosmic morphology of polyaniline is regulated and controlled by alizarin red S, so that the agglomeration of high-load polyaniline is avoided, and the polyaniline is promoted to form a nano structure. Finally, the high-loading nano-structure polyaniline composite material is obtained through rapid enzyme pretreatment and alizarin red S doping regulation.
The implementation of the invention has the following beneficial effects:
the invention discloses a preparation method of a polyaniline composite material with a high-loading nano-structure, which has the advantages of simple process, high raw material utilization rate, no need of complex equipment and suitability for large-scale industrial production;
the raw material pulp fiber used in the invention has wide sources, is degradable and renewable;
the high-loading nano-structure polyaniline composite material prepared by the invention has low cost, is green and safe, and has important significance for environmental protection and promotion of development of flexible energy storage materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the high loading nanostructured polyaniline composite material prepared in example 3;
FIG. 2 is a scanning electron microscope image of the high loading nanostructured polyaniline composite material produced in example 4;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Placing 0.5g of pulp fiber in a round bottom flask and placing in an ice water bath; 100mL of sulfosalicylic acid with the concentration of 0.1mol/L and 50mL of alizarin red S solution with the concentration of 0.1mol/L are added into a flask and mechanically stirred for 20min; adding 0.5mL of aniline monomer, and continuously stirring for 30min; then dropwise adding ammonium persulfate solution, wherein the dosage of ammonium persulfate is 50mL, the concentration is 1mmol/L, and stirring is continued for 1h under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
Example 2
Placing 0.5g pulp fiber in a sealed bag at room temperature; adding 0.1mL of cellulase solution with concentration of 3.5EGU/mL, rapidly adding 50mL of acetic acid-sodium acetate buffer solution with pH of 4.8, kneading for 2min to uniformly disperse fibers, sealing the sealing bag, and standing in water bath at 50deg.C for 5min; taking out, washing impurities with ethanol, and obtaining the rapid enzyme pretreatment pulp fiber;
placing the rapid enzyme pretreated pulp fiber in a round bottom flask and placing in an ice water bath; 100mL of sulfosalicylic acid with the concentration of 0.1mol/L and 50mL of alizarin red S solution with the concentration of 0.1mol/L are added into a flask and mechanically stirred for 20min; adding 0.5mL of aniline monomer, and continuously stirring for 30min; then dropwise adding ammonium persulfate solution, wherein the dosage of ammonium persulfate is 50mL, the concentration is 1mmol/L, and stirring is continued for 1h under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
Example 3
Placing 0.5g pulp fiber in a sealed bag at room temperature; adding 0.1mL of cellulase solution with concentration of 3.5EGU/mL, rapidly adding 50mL of acetic acid-sodium acetate buffer solution with pH of 4.8, kneading for 2min to uniformly disperse fibers, sealing the sealing bag, and standing in water bath at 50deg.C for 10min; taking out, washing impurities with ethanol, and obtaining the rapid enzyme pretreatment pulp fiber;
placing the rapid enzyme pretreated pulp fiber in a round bottom flask and placing in an ice water bath; 100mL of sulfosalicylic acid with the concentration of 0.1mol/L and 50mL of alizarin red S solution with the concentration of 0.1mol/L are added into a flask and mechanically stirred for 20min; adding 0.5mL of aniline monomer, and continuously stirring for 30min; then dropwise adding ammonium persulfate solution, wherein the dosage of ammonium persulfate is 50mL, the concentration is 1mmol/L, and stirring is continued for 1h under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
Example 4
Placing 0.5g pulp fiber in a sealed bag at room temperature; adding 0.1mL of cellulase solution with concentration of 3.5EGU/mL, rapidly adding 50mL of acetic acid-sodium acetate buffer solution with pH of 4.8, kneading for 2min to uniformly disperse fibers, sealing the sealing bag, and standing in water bath at 50deg.C for 10min; taking out, washing impurities with ethanol, and obtaining the rapid enzyme pretreatment pulp fiber;
placing the rapid enzyme pretreated pulp fiber in a round bottom flask and placing in an ice water bath; 100mL sulfosalicylic acid with the concentration of 0.1mol/L is added into a flask and is mechanically stirred for 20min; adding 0.5mL of aniline monomer, and continuously stirring for 30min; then dropwise adding ammonium persulfate solution, wherein the dosage of ammonium persulfate is 50mL, the concentration is 1mmol/L, and stirring is continued for 1h under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
The experimental results for examples 1-4 are shown in the following table:
table 1 experimental parameters and results comparison table for examples 1-4
As can be seen from table 1, examples 2-4 after pretreatment of pulp fibers with fast enzymes have significantly improved loadings and significantly reduced resistivity compared to example 1 without pretreatment. Whereas examples 2 and 3 with alizarin red S added have lower resistivity than example 4 without alizarin red S added. That is to say: the rapid enzyme pretreatment of the pulp fiber can obviously improve the loading capacity of polyaniline, and simultaneously reduce the resistivity of the composite material, while the influence of the enzyme pretreatment time on the polyaniline loading capacity and the resistivity of the composite material is less obvious; the addition of alizarin red S can reduce the resistivity of the material, which may be related to the microstructure changes of polyaniline.
Carrying out electron microscope characterization on the high-loading nano-structure polyaniline composite material obtained in the examples 3 and 4, please refer to fig. 1-2, fig. 1 is a scanning electron microscope picture of the high-loading nano-structure polyaniline composite material prepared in the example 3; fig. 2 is a scanning electron microscope image of the high loading nanostructured polyaniline composite material prepared in example 4.
As can be seen from the scanning electron microscope pictures, the polyaniline in the sample 3 shows a better dispersion state, the nano-particles have smaller size and a porous structure, the polyaniline agglomeration phenomenon in the sample 4 is obvious, and the porous structure is basically absent. Therefore, the addition of alizarin red S is also beneficial to reducing the size of polyaniline particles in the composite material and reducing the agglomeration phenomenon.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The preparation method of the high-loading nano-structure polyaniline composite material is characterized by comprising the following steps of: enzyme pretreatment is carried out on paper pulp fibers, sulfosalicylic acid is taken as a doping agent, ammonium persulfate is taken as an oxidant, alizarin red S is taken as a morphology regulator, and the high-loading nano-structure polyaniline composite material is prepared through an in-situ polymerization process.
2. The method for preparing the high-loading nano-structured polyaniline composite material according to claim 1, comprising the following steps:
step one, preprocessing pulp fibers:
placing pulp fibers in a sealed bag at room temperature; adding cellulase solution, rapidly adding acetic acid-sodium acetate buffer solution with pH of 4.8, kneading for 1-2min to disperse fiber uniformly, sealing the sealed bag, and standing in water bath for a period of time; taking out, washing impurities with ethanol, and obtaining the rapid enzyme pretreatment pulp fiber;
step two, preparing a high-load nano-structure polyaniline composite material:
placing the rapid enzyme pretreated pulp fiber in a round bottom flask and placing in an ice water bath; adding sulfosalicylic acid and alizarin red S solution into the flask, and mechanically stirring for 20min; adding aniline monomer, and continuing stirring for 30min; then dropwise adding ammonium persulfate solution, and continuously stirring for a period of time under the ice water bath condition; filtering and washing after the reaction is finished until the filtrate becomes colorless to remove impurities; the obtained composite material is subjected to suction filtration, squeezing and drying to obtain the polyaniline composite material with the high-loading nano-structure.
3. The method of preparing a high loading nanostructured polyaniline composite according to claim 2, wherein the oven dry mass of the pulp in step one is 0.5g; the dosage of the cellulase solution is 0.05-0.3mL, and the concentration is 3.5EGU/mL; the buffer was used in an amount of 50mL.
4. The method for preparing a high-loading nano-structured polyaniline composite material according to claim 3, wherein the water bath temperature in the first step is 10-50 ℃ and the standing time is 1-20min.
5. The method for preparing the high-loading nano-structure polyaniline composite material according to claim 3, wherein the sulfosalicylic acid in the second step is used in an amount of 100mL and the concentration is 0.1-0.8mol/L; the dosage of alizarin red S is 50mL, and the concentration is 0.1-0.8mol/L; the dosage of the aniline monomer is 0.1-1mL; the dosage of ammonium persulfate is 50mL, and the concentration is 1-10mmol/L.
6. The method for preparing a high-loading nano-structured polyaniline composite according to claim 5, wherein the stirring time in the ice-water bath in the second step is 1-6h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102212210A (en) * | 2011-04-29 | 2011-10-12 | 南京理工大学 | Method for preparing polyaniline-coated bacteria cellulose nano conductive composite by in-situ polymerization |
| CN109180978A (en) * | 2018-10-10 | 2019-01-11 | 华南理工大学 | A kind of polyaniline/cellulose conductive composite film and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212210A (en) * | 2011-04-29 | 2011-10-12 | 南京理工大学 | Method for preparing polyaniline-coated bacteria cellulose nano conductive composite by in-situ polymerization |
| CN109180978A (en) * | 2018-10-10 | 2019-01-11 | 华南理工大学 | A kind of polyaniline/cellulose conductive composite film and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| CHANG ZY等: "Design and fabrication of high performance supercapacitor with cellulosic paper electrode and plant-derived redox active molecules", CARBOHYDRATE POLYMERS, vol. 244, 24 May 2020 (2020-05-24), pages 116442, XP086182049, DOI: 10.1016/j.carbpol.2020.116442 * |
| 常紫阳: "导电聚合物/纤维素纤维柔性电极材料的制备及储能性能研究", 中国博士学位论文全文数据库工程科技Ⅰ辑, no. 01, 15 January 2021 (2021-01-15), pages 020 - 146 * |
| 杨刚 等: "茜素红S掺杂聚苯胺/纤维素纸基电极材料的制备及性能研究", 中国造纸, vol. 42, no. 12, 25 December 2023 (2023-12-25), pages 15 - 23 * |
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