CN103819667B - Method for preparing secondarily-doped polyaniline nanofiber material through total liquid phase method - Google Patents
Method for preparing secondarily-doped polyaniline nanofiber material through total liquid phase method Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 55
- 239000002121 nanofiber Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007791 liquid phase Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 4
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229920001002 functional polymer Polymers 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明涉及了二次掺杂聚苯胺纳米纤维的制备的一种新方法。本发明采用全液相法制备了粗细均匀，形貌良好的聚苯胺纳米纤维。该发明利用聚苯胺具有可逆的掺杂及解掺杂特性，改进以往二次掺杂过程中的洗涤、干燥、研磨等步骤合成了形貌良好的二次掺杂聚苯胺纳米纤维。该发明方法简单易行，重复率好，合成所需原料廉价易得并且合成的聚苯胺纳米纤维的产率高、电导率高、溶解性能良好，适合大规模的工业生产。该发明具有良好的应用前景，所得产物可应用于化学传感器、超级电容器、金属防腐以及功能高分子复合材料等领域。
The invention relates to a new method for preparing secondary doped polyaniline nanofibers. The invention adopts the whole liquid phase method to prepare polyaniline nanofibers with uniform thickness and good shape. The invention utilizes the reversible doping and dedoping properties of polyaniline, and improves the previous steps of washing, drying, and grinding in the secondary doping process to synthesize secondary doped polyaniline nanofibers with good morphology. The inventive method is simple and easy to implement, has good repetition rate, cheap and easy-to-obtain raw materials required for synthesis, and the synthesized polyaniline nanofiber has high yield, high electrical conductivity and good solubility, and is suitable for large-scale industrial production. The invention has good application prospects, and the obtained product can be applied to fields such as chemical sensors, supercapacitors, metal anticorrosion, and functional polymer composite materials.
Description
技术领域：本发明涉及二次掺杂聚苯胺纳米纤维制备的一种新方法Technical field: the present invention relates to a new method for the preparation of secondary doped polyaniline nanofibers
背景技术Background technique
导电聚合物的电导率覆盖面广，跨越了绝缘体-半导体-金属导体的宽广范围，是目前任何种类的材料都无法相媲美的。此外，导电聚合物还具有完全可逆的氧化还原特性及掺杂解掺杂特性，且伴随着可逆的光学、电学及磁学性能的变化。在众多导电聚合物材料中，聚苯胺因原料易得、制备过程简单、易于得到不同形貌的纳米级产物，并且其掺杂及解掺杂过程可逆、导电性能良好、电化学性质稳定和环境稳定性好等一系列的优点，成为目前最受关注的导电聚合物之一。纳米结构的聚苯胺由于同时具有纳米结构材料和导电聚合物的独特性质，在分子器件、催化、分离、药物释放、能量存储、微波吸收和传感器等领域均有潜在的用途。The conductivity of conductive polymers covers a wide range, spanning a wide range of insulator-semiconductor-metal conductors, which is unmatched by any type of material at present. In addition, conductive polymers also have fully reversible redox characteristics and doping and dedoping characteristics, accompanied by reversible changes in optical, electrical and magnetic properties. Among many conductive polymer materials, polyaniline is easy to obtain raw materials, simple preparation process, easy to obtain nanoscale products with different shapes, and its doping and dedoping process is reversible, good electrical conductivity, stable electrochemical properties and environmental protection. With a series of advantages such as good stability, it has become one of the most concerned conductive polymers at present. Nanostructured polyaniline has potential applications in the fields of molecular devices, catalysis, separation, drug release, energy storage, microwave absorption, and sensors due to the unique properties of both nanostructured materials and conductive polymers.
由于聚苯胺纳米结构的性质特殊，应用潜能巨大，其制备方法也引起了人们的广泛兴趣。目前，研究工作者开发了各种各样的方法用于制备纳米结构的聚苯胺。传统的化学氧化聚合法(Huang J,Kaner R B.A general chemical route to polyanilinenanofibers[J].Journal of the American Chemical Society,2004,126(3):851-855.)、界面聚合法（HuangJ,VirjiS,Weiller B H,et al.Polyaniline nanofibers:facilesynthesis and chemical sensors[J].Journal of the American Chemical Society,2003,125(2):314-315.）、模板法（Wang C W,Wang Z,Li M K,Li H L.Well-alignedpolyaniline nano-fibril array membrane and its field emission property[J].Chem.Phys.Lett.,2001,341:431-434.）等都可以用于制备纳米结构聚苯胺。但是值得注意的是，考虑到大规模生产聚苯胺的可行性和实际性，上述的方法都存在一定的缺陷。通过传统化学氧化法制备的纳米结构聚苯胺的可加工性能较差；界面聚合法虽然能够形成形貌良好的聚苯胺纳米纤维，但由于需要引入有机溶剂，这些有机溶剂会对人类的健康和生存环境产生严重的危害；模板法的后处理过程复杂，且聚合产物的形貌、尺寸可控性差，产率低。Due to the special properties of polyaniline nanostructures and their great application potential, their preparation methods have also aroused widespread interest. Currently, researchers have developed various methods for preparing nanostructured polyaniline. Traditional chemical oxidation polymerization (Huang J, Kaner R B.A general chemical route to polyaniline nanofibers [J]. Journal of the American Chemical Society, 2004, 126 (3): 851-855.), interfacial polymerization (HuangJ, VirjiS, Weiller B H, et al.Polyaniline nanofibers:facilesynthesis and chemical sensors[J].Journal of the American Chemical Society,2003,125(2):314-315.), template method (Wang C W, Wang Z, Li M K, Li H L. Well-aligned polyaniline nano-fibril array membrane and its field emission property [J]. Chem. Phys. Lett., 2001, 341: 431-434.) etc. can be used to prepare nanostructured polyaniline. But it is worth noting that, considering the feasibility and practicality of large-scale production of polyaniline, the above-mentioned methods all have certain defects. The processability of nanostructured polyaniline prepared by traditional chemical oxidation method is poor; although interfacial polymerization method can form polyaniline nanofibers with good shape, but due to the need to introduce organic solvents, these organic solvents will affect human health and survival. Serious harm to the environment; the post-treatment process of the template method is complicated, and the morphology and size of the polymerization product are poorly controllable and the yield is low.
最近也有相关研究开始讨论利用聚苯胺掺杂及解掺杂的可逆性对聚苯胺进行二次掺杂（王刚,刘维锦.二次掺杂聚苯胺的防腐蚀性能[J].腐蚀与防护,2009,30(008):555-557.）。二次掺杂是通过在特定体系中先制备得到最佳形貌的聚苯胺纳米结构，再利用其可逆的掺杂及解掺杂特性，二次掺杂上具有特殊功能的官能团，开发出同时拥有最佳的纳米结构和功能化应用官能团的新型聚苯胺纳米材料。但其中间步骤（如洗涤、干燥、研磨等）造成了资源浪费以及能量损失，使得生成的二次掺杂聚苯胺并没有达到预期的良好性能。因此，为了更好地适应对聚苯胺材料的需求，提供更能迎合可持续发展战略的纳米结构的制备新方法，对于可大规模生产聚苯胺纳米结构的制备方法的研究迫在眉睫。Recently, related research has begun to discuss the secondary doping of polyaniline by using the reversibility of polyaniline doping and dedoping (Wang Gang, Liu Weijin. Anticorrosion performance of secondary doped polyaniline[J]. Corrosion and Protection, 2009 , 30(008):555-557.). The secondary doping is to prepare the polyaniline nanostructure with the best shape in a specific system, and then use its reversible doping and dedoping characteristics to secondary dope with functional groups with special functions to develop a simultaneous Novel polyaniline nanomaterials with optimal nanostructure and functional groups for functional applications. However, the intermediate steps (such as washing, drying, grinding, etc.) cause resource waste and energy loss, so that the secondary doped polyaniline does not achieve the expected good performance. Therefore, in order to better meet the demand for polyaniline materials and provide new methods for preparing nanostructures that can better meet the sustainable development strategy, research on preparation methods for large-scale production of polyaniline nanostructures is imminent.
发明内容Contents of the invention
本发明的目的在于扩展聚苯胺纳米纤维的制备方法，提供一种更能迎合可持续发展战略的聚苯胺纳米纤维的制备新方法。本发明根据现有方法的技术不足，提供了一种更能迎合市场需求，经济有效，简单易行，重复性好且适用于大规模生产的二次掺杂聚苯胺纳米纤维的制备方法。The purpose of the present invention is to expand the preparation method of polyaniline nanofibers, and provide a new preparation method of polyaniline nanofibers that can better meet the strategy of sustainable development. Based on the technical deficiencies of the existing methods, the present invention provides a preparation method for secondary doped polyaniline nanofibers that can better meet market demands, is economical, effective, simple, easy to implement, good in repeatability and suitable for large-scale production.
本发明提供的聚苯胺纳米纤维的制备方法，包括如下步骤：The preparation method of the polyaniline nanofiber provided by the invention comprises the steps:
全液相法制备二次掺杂聚苯胺纳米纤维的特征在于所有反应在一个溶液中完成，苯胺和 氧化剂分别溶于第一无机酸中，迅速混合，充分反应，然后加入氨水还原成本征态的聚苯胺。最后加入第二无机酸溶液于本征态聚苯胺溶液中，反应完全后，将产物分离出来即得纳米纤维聚苯胺。The whole liquid phase method to prepare secondary doped polyaniline nanofibers is characterized in that all reactions are completed in one solution, aniline and oxidant are respectively dissolved in the first inorganic acid, mixed rapidly, fully reacted, and then added ammonia water to reduce the original state polyaniline. Finally, the second inorganic acid solution is added to the intrinsic polyaniline solution. After the reaction is complete, the product is separated to obtain nanofiber polyaniline.
其中，第一酸与第二酸相同或者不同。Wherein, the first acid is the same or different from the second acid.
其中，第一酸的浓度为0.01-4mol/l。Wherein, the concentration of the first acid is 0.01-4 mol/l.
其中，反应在0-80℃。Wherein, the reaction is at 0-80°C.
其中，反应时苯胺和氧化剂的摩尔比为0.01-5。推荐使用苯胺和氧化剂的摩尔比为0.8:1。Wherein, the molar ratio of aniline and oxidant is 0.01-5 during the reaction. The recommended molar ratio of aniline to oxidizing agent is 0.8:1.
其中，充分反应的时间为0.01-48h。Wherein, the time for full reaction is 0.01-48h.
其中，加入氨水还原成本征态的聚苯胺的反应时间为0.01-48h。Wherein, the reaction time of adding ammonia water to reduce the polyaniline in its original state is 0.01-48h.
其中，加入第二酸使得溶液的pH值小于7以便充分反应。Wherein, the second acid is added so that the pH value of the solution is less than 7 so as to fully react.
其中，反应完全的时间为0.01-48h。Wherein, the time for complete reaction is 0.01-48h.
其中，产物分离出来的方法，推荐使用：将所得产物经过滤，去离子水、乙醇清洗至中性，然后放入真空干燥箱中干燥即得聚苯胺纳米纤维。Among them, the method for separating the product is recommended: the obtained product is filtered, washed with deionized water and ethanol until neutral, and then placed in a vacuum drying oven to dry to obtain polyaniline nanofibers.
本发明提供的全液相法二次掺杂聚苯胺纳米纤维的制备方法与现有技术的区别在于：制备工艺简单，重复率高，纤维形貌可控性强，可适用于大规模工业生产。The difference between the preparation method of secondary doped polyaniline nanofibers provided by the present invention and the prior art is that the preparation process is simple, the repetition rate is high, the fiber shape is highly controllable, and it can be applied to large-scale industrial production .
1、本发明所需的装置简单，具有简单经济，操作方便，稳定可靠等优点。1. The device required by the present invention is simple, and has the advantages of being simple and economical, convenient to operate, stable and reliable.
2、本发明不同于传统方法，氧化剂种类、比例，酸浓度等对合成聚苯胺形貌，产率等影响重大。本发明可以首先在适合的掺杂酸环境中获得高质量的掺杂纳米纤维，再利用聚苯胺的掺杂解掺杂特性对其进行二次掺杂，可获得形貌可控的聚苯胺的纳米纤维。2. The present invention is different from the traditional method. The type, ratio, and acid concentration of the oxidant have a great influence on the morphology and yield of the synthesized polyaniline. The present invention can first obtain high-quality doped nanofibers in a suitable doping acid environment, and then use the doping and dedoping characteristics of polyaniline to perform secondary doping to obtain polyaniline with controllable morphology. Nanofibers.
3、本发明所有的反应均在一个溶液中进行，与传统的分步二次掺杂不同，省去了中间环节抽滤洗涤、干燥、研磨等工艺操作，节省了时间，大大提高了合成聚苯胺纳米纤维的效率及产率，同时减少了资源浪费。3. All the reactions of the present invention are carried out in one solution, which is different from the traditional step-by-step secondary doping, which saves the intermediate links such as suction filtration washing, drying, grinding, etc., saves time, and greatly improves the synthetic polymerization process. The efficiency and yield of aniline nanofibers are improved, while reducing the waste of resources.
本发明利用全液相法二次掺杂合成了形貌良好的聚苯胺纳米纤维(由扫描电镜图证实)，所得产物的产率可达145.95%，溶解率最高可达64.3%，电导率最高达到3.33S/cm。因此本方法是一种简单有效的制备聚苯胺纳米纤维的方法，其操作简单易行，适合大规模工业化生产。In the present invention, polyaniline nanofibers with good morphology (confirmed by scanning electron microscopy) are synthesized by secondary doping by the full liquid phase method, and the yield of the obtained product can reach 145.95%, the highest dissolution rate can reach 64.3%, and the highest electrical conductivity Reach 3.33S/cm. Therefore, the method is a simple and effective method for preparing polyaniline nanofibers, the operation is simple and easy, and it is suitable for large-scale industrial production.
附图说明Description of drawings
图1、硫酸一次掺杂聚苯胺纳米纤维的扫描电镜图Figure 1. Scanning electron microscope image of polyaniline nanofibers doped with sulfuric acid once
图2、全液相法硫酸二次掺杂合成聚苯胺纳米纤维的扫描电镜图及红外光谱图（第一酸硫酸，第二酸硫酸）Figure 2. Scanning electron microscope and infrared spectrum of polyaniline nanofibers synthesized by secondary doping with sulfuric acid in full liquid phase (first acid sulfuric acid, second acid sulfuric acid)
图3、全液相法磷酸二次掺杂合成聚苯胺纳米纤维的扫描电镜图及红外光谱图（第一酸硫酸，第二酸磷酸）Figure 3. Scanning electron microscope and infrared spectrum of polyaniline nanofibers synthesized by secondary doping of phosphoric acid in the all-liquid phase method (first acid sulfuric acid, second acid phosphoric acid)
图4、全液相法复合酸二次掺杂合成聚苯胺纳米纤维的扫描电镜图及红外光谱图（第一酸硫酸，第二酸复合酸）Figure 4. Scanning electron microscope and infrared spectrum of polyaniline nanofibers synthesized by secondary doping with compound acid in full liquid phase (first acid sulfuric acid, second acid compound acid)
具体实施方式detailed description
本发明用以下实例来进一步说明本发明的技术特征，但本发明的保护范围并不仅限于以下实例。The present invention further illustrates technical characterictic of the present invention with following example, but protection scope of the present invention is not limited to following example.
实施例1Example 1
室温下，取苯胺（ANI）与氧化剂（APS）的摩尔比为0.8:1。分别将0.73ml苯胺和2.28g过硫酸铵溶于20ml，1mol/l的硫酸溶液中，再将两份溶液迅速混合，搅拌至溶液呈墨绿色。静置反应24h。再向该溶液中加入150ml，1mol/l的氨水搅拌反应1h，然后加入200ml，1mol/l硫酸溶液，静置反应24h，用去离子水和乙醇清洗至中性，60℃真空干燥24h，得到全液相法H2SO4-H2SO4二次掺杂聚苯胺纳米纤维。At room temperature, the molar ratio of aniline (ANI) to oxidant (APS) was 0.8:1. Dissolve 0.73ml of aniline and 2.28g of ammonium persulfate in 20ml of 1mol/l sulfuric acid solution respectively, then quickly mix the two solutions and stir until the solution turns dark green. Stand for reaction for 24h. Then add 150ml, 1mol/l ammonia water to the solution and stir for 1h, then add 200ml, 1mol/l sulfuric acid solution, let stand for reaction for 24h, wash with deionized water and ethanol until neutral, and vacuum dry at 60°C for 24h to obtain Secondary doping of polyaniline nanofibers with H 2 SO 4 -H 2 SO 4 in full liquid phase.
实施例2Example 2
室温下，取苯胺（ANI）与氧化剂（APS）的摩尔比为0.8:1。分别将0.73ml苯胺和2.28g过硫酸铵溶于20ml，1mol/l的硫酸溶液中，再将两份溶液迅速混合，搅拌至溶液呈墨绿色。静置反应24h。再向该溶液中加入150ml，1mol/l的氨水搅拌反应1h，然后加入200ml，1mol/l磷酸溶液，静置反应24h，用去离子水和乙醇清洗至中性，60℃真空干燥24h，得到全液相法H2SO4-H3PO4二次掺杂聚苯胺纳米纤维。At room temperature, the molar ratio of aniline (ANI) to oxidant (APS) was 0.8:1. Dissolve 0.73ml of aniline and 2.28g of ammonium persulfate in 20ml of 1mol/l sulfuric acid solution respectively, then quickly mix the two solutions and stir until the solution turns dark green. Stand for reaction for 24h. Then add 150ml, 1mol/l ammonia water to the solution and stir for 1h, then add 200ml, 1mol/l phosphoric acid solution, let stand for reaction for 24h, wash with deionized water and ethanol until neutral, and vacuum dry at 60°C for 24h to obtain Secondary doping of polyaniline nanofibers with H 2 SO 4 -H 3 PO 4 in full liquid phase.
实施例3Example 3
室温下，取苯胺（ANI）与氧化剂（APS）的摩尔比为0.8:1。分别将0.73ml苯胺和2.28g过硫酸铵溶于20ml，1mol/l的硫酸溶液中，再将两份溶液迅速混合，搅拌至溶液呈墨绿色。静置反应24h。再向该溶液中加入150ml，1mol/l的氨水搅拌反应1h，然后加入200ml，1mol/l硫酸与对甲苯磺酸的复合酸溶液，静置反应24h，用去离子水和乙醇清洗至中性，60℃真空干燥24h，得到全液相法H2SO4-复合酸二次掺杂聚苯胺纳米纤维。At room temperature, the molar ratio of aniline (ANI) to oxidant (APS) was 0.8:1. Dissolve 0.73ml of aniline and 2.28g of ammonium persulfate in 20ml of 1mol/l sulfuric acid solution respectively, then quickly mix the two solutions and stir until the solution turns dark green. Stand for reaction for 24h. Then add 150ml, 1mol/l ammonia water to the solution and stir for 1h, then add 200ml, 1mol/l compound acid solution of sulfuric acid and p-toluenesulfonic acid, leave to react for 24h, wash with deionized water and ethanol until neutral , dried in vacuum at 60° C. for 24 hours to obtain polyaniline nanofibers secondarily doped with H 2 SO 4 -complex acid in the full liquid phase.
实施例4Example 4
室温下，取苯胺（ANI）与氧化剂（APS）的摩尔比为0.8:1。分别将0.73ml苯胺和2.28g过硫酸铵溶于20ml，1mol/l的高氯酸溶液中，再将两份溶液迅速混合，搅拌至溶液呈墨绿色。静置反应24h。再向该溶液中加入150ml，1mol/l的氨水搅拌反应1h，然后加入200ml，1mol/l磷酸溶液，静置反应24h，用去离子水和乙醇清洗至中性，60℃真空干燥24h，得到全液相法HClO4-H3PO4二次掺杂聚苯胺纳米纤维。At room temperature, the molar ratio of aniline (ANI) to oxidant (APS) was 0.8:1. Dissolve 0.73ml of aniline and 2.28g of ammonium persulfate in 20ml of 1mol/l perchloric acid solution respectively, then quickly mix the two solutions and stir until the solution is dark green. Stand for reaction for 24h. Then add 150ml, 1mol/l ammonia water to the solution and stir for 1h, then add 200ml, 1mol/l phosphoric acid solution, let stand for reaction for 24h, wash with deionized water and ethanol until neutral, and vacuum dry at 60°C for 24h to obtain Secondary doping of polyaniline nanofibers with HClO 4 -H 3 PO 4 in full liquid phase.
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