CN109499494B - A kind of polypyrrole/UiO-66 composite aerogel and preparation method thereof - Google Patents
A kind of polypyrrole/UiO-66 composite aerogel and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种聚吡咯/UiO‑66复合气凝胶，首先利用多巴胺的自聚合特性对聚吡咯气凝胶进行改性，然后将改性后的聚吡咯气凝胶置于UiO‑66的前驱体溶液中进行晶化反应，得聚吡咯/UiO‑66复合气凝胶。本发明利用聚多巴胺的氨基与羟基以及聚吡咯气凝胶的多孔结构有效吸附锆离子，实现聚吡咯与UiO‑66的充分复合，既可改善UiO‑66导电性较差的缺点，又可有效提升聚吡咯的电化学循环稳定性，同时可实现将聚吡咯的赝电容与UiO‑66的双电层电容相结合；且涉及的制备方法简单，反应条件温和，并可控制复合气凝胶的组分含量，适用于超级电容器等领域。The invention discloses a polypyrrole/UiO-66 composite aerogel. Firstly, the self-polymerization property of dopamine is used to modify the polypyrrole aerogel, and then the modified polypyrrole aerogel is placed in UiO-66 The crystallization reaction is carried out in the precursor solution of , and the polypyrrole/UiO-66 composite aerogel is obtained. The present invention utilizes the amino group and hydroxyl group of polydopamine and the porous structure of polypyrrole aerogel to effectively adsorb zirconium ions, and realizes full compounding of polypyrrole and UiO-66, which can not only improve the disadvantage of poor conductivity of UiO-66, but also effectively The electrochemical cycle stability of polypyrrole is improved, and the pseudocapacitance of polypyrrole can be combined with the electric double layer capacitance of UiO-66; the preparation method involved is simple, the reaction conditions are mild, and the composite aerogel can be controlled. component content, suitable for supercapacitors and other fields.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to polypyrrole/UiO-66 composite aerogel and a preparation method thereof.
Background
The conductive polymer materials such as polyaniline, polypyrrole, polythiophene and the like are easily available in raw materials and simple in synthesis process. The conductive polymer has a unique polymer chain conjugated structure, can perform reversible redox reaction under different voltages, and has better specific capacity and specific energy than carbon materials. However, in the long-time charge and discharge process of the conductive polymer material, the volume of the conductive polymer material is greatly expanded and contracted, so that the specific capacitance of the conductive polymer material is greatly reduced, and the electrochemical stability is weakened.
In recent years, the metal organic framework compound has a skeleton structure material with a periodic structure, which is assembled by taking an organic ligand as a connector and a metal ion as a node through a coordination bond, has the advantages of a multi-layer porous structure, high specific surface area and the like, and has potential application prospects in the fields of gas adsorption separation, fluorescence, catalysis and the like. Heqin and the like (applied to chemical 2014,43, 311-315) report that UiO-66 is loaded on the surface of a semiconductor material, and then conductive polyaniline is prepared by an in-situ polymerization method to obtain the polyaniline/UiO-66/semiconductor composite material. Wang et al (j.am. chem. soc.2015,137,4920-4923) reported that a flexible solid-state supercapacitor was constructed by coating a synthesized metal-organic framework compound on carbon cloth and electrochemically polymerizing aniline monomer. However, the metal organic framework compound is difficult to be uniformly dispersed in the solvent, and the effective compounding of the metal organic framework compound and the conductive polymer material is limited. And previous work has only studied the compounding of a conductive polymer with a metal-organic framework compound in a particulate state or on a two-dimensional substrate.
Disclosure of Invention
The invention mainly aims to provide a polypyrrole/UiO-66 composite aerogel and a preparation method thereof aiming at the defects in the prior art; polypyrrole aerogel is modified through self-polymerization of dopamine, zirconium ions are effectively adsorbed by utilizing amino groups and hydroxyl groups of the polypyrrole aerogel and a porous structure of the polypyrrole aerogel, sufficient combination of polypyrrole and UiO-66 is effectively realized, the obtained polypyrrole/UiO-66 composite aerogel can show excellent electrochemical performance and circulation stability, and the related preparation method is simple and easy to control, and is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
polypyrrole/UiO-66 composite aerogel is prepared by soaking polypyrrole aerogel in dopamine solution for polymerization modification, and then placing the modified polypyrrole aerogel in precursor solution of UiO-66 for crystallization reaction.
In the scheme, the precursor solution of the UiO-66 is an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid.
The preparation method of the polypyrrole/UiO-66 composite aerogel comprises the following steps:
1) soaking polypyrrole aerogel in a dopamine solution, adjusting the pH value of the obtained mixed solution to 8-9, and performing polymerization modification on the polypyrrole aerogel;
2) placing the modified polypyrrole aerogel in a precursor solution of UiO-66, and heating for crystallization reaction;
3) washing and drying the product obtained in the step 2) to obtain the polypyrrole/UiO-66 composite aerogel.
In the scheme, the concentration of the dopamine in the dopamine solution is 3-5 mg/mL.
In the scheme, the polymerization modification temperature in the step 1) is room temperature, and the time is 18-24 h.
In the scheme, the crystallization reaction temperature is 100-120 ℃, and the time is 10-20 h.
In the above scheme, the precursor solution of UiO-66 is an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, and after the modified polypyrrole aerogel is added thereto, the obtained mixed system comprises the following components in parts by weight: 3-6 parts of modified polypyrrole aerogel, 3-6 parts of zirconium chloride, 8-20 parts of terephthalic acid and 100-250 parts of N, N-dimethylformamide.
In the scheme, the drying temperature in the step 3) is 80-90 ℃, and the time is 24-36 h.
Compared with the prior art, the invention has the beneficial effects that:
1) the preparation method provided by the invention is simple, the reaction conditions are mild, and the component content of the composite aerogel can be regulated and controlled;
2) polypyrrole aerogel is modified through self-polymerization of dopamine, and zirconium ions are effectively adsorbed by utilizing amino and hydroxyl groups of the polydopamine and a porous structure of the polypyrrole aerogel, so that sufficient compounding of polypyrrole and UiO-66 is effectively realized;
3) the porous structure of the obtained polypyrrole/UiO-66 composite aerogel is beneficial to migration in and out of electrolyte, and the combination of the polypyrrole aerogel and the UiO-66 can improve the defect of poor conductivity of the UiO-66, combine the pseudocapacitance of the polypyrrole with the double electric layer capacitance of the UiO-66 and effectively improve the electrochemical cycle stability of the polypyrrole; in addition, the composite material obtained by the invention is suitable for the fields of supercapacitors and the like.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the polypyrrole aerogel used was prepared according to literature reports, and the polypyrrole aerogel was prepared by self-assembly, lyophilization, and other steps (see Synthetic Metals 2016, 218, 50-55).
Example 1
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in a dopamine solution with the concentration of 3mg/mL, adjusting the pH value to 8.0 by using a Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 18 hours at room temperature);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 100 ℃, and carrying out heat preservation reaction for 12 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 3 parts of modified polypyrrole aerogel, 3 parts of zirconium chloride, 9 parts of terephthalic acid and 110 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 90 ℃ for 24h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 95.1% after 1000 times of charge and discharge cycles at a current density of 1A/g.
Example 2
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in a dopamine solution with the concentration of 4mg/mL, adjusting the pH value to 8.5 by using a Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 20 hours at room temperature);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 110 ℃, and carrying out heat preservation reaction for 15 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 5 parts of modified polypyrrole aerogel, 4 parts of zirconium chloride, 15 parts of terephthalic acid and 150 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 80 ℃ for 28h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 95.8% after 1000 times of charge and discharge cycles at a current density of 1A/g.
Example 3
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in a dopamine solution with the concentration of 3mg/mL, adjusting the pH value to 8.0 by using a Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 22 hours at room temperature);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 120 ℃, and carrying out heat preservation reaction for 20 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 6 parts of modified polypyrrole aerogel, 6 parts of zirconium chloride, 18 parts of terephthalic acid and 230 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 85 ℃ for 36h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 94.7% after 1000 times of charge and discharge cycles at a current density of 1A/g.
Example 4
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in a dopamine solution with the concentration of 5mg/mL, adjusting the pH value to 9.0 by using a Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 24 hours at room temperature);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 110 ℃, and carrying out heat preservation reaction for 18 h; wherein in the obtained reaction system, the components are as follows according to parts by weight: 3 parts of modified polypyrrole aerogel, 3 parts of zirconium chloride, 10 parts of terephthalic acid and 140 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 90 ℃ for 32h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 94.9% after 1000 times of charge and discharge cycles at a current density of 1A/g.
Example 5
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in a dopamine solution with the concentration of 4mg/mL, adjusting the pH value to 8.0 by using a Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 20 hours at room temperature);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 105 ℃, and carrying out heat preservation reaction for 16 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 4 parts of modified polypyrrole aerogel, 6 parts of zirconium chloride, 18 parts of terephthalic acid and 200 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 80 ℃ for 36h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 94.2% after 1000 times of charge and discharge cycles at a current density of 1A/g.
Example 6
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) soaking polypyrrole aerogel in dopamine solution with the concentration of 3.5mg/mL, adjusting the pH value to 8.5 by using Tris buffer solution, and modifying the polypyrrole aerogel (room temperature reaction for 22 h);
2) putting the polypyrrole aerogel modified in the step 1) into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 100 ℃, and carrying out heat preservation reaction for 12 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 3 parts of modified polypyrrole aerogel, 6 parts of zirconium chloride, 20 parts of terephthalic acid and 240 parts of N, N-dimethylformamide;
3) washing the reaction product obtained in the step 2) with methanol, and drying at 90 ℃ for 32h to obtain the polypyrrole/UiO-66 composite aerogel.
Electrochemical detection is carried out on the polypyrrole/UiO-66 composite aerogel obtained in the embodiment, and the capacitance retention rate is 93.8% after 1000 times of charge and discharge cycles at the current density of 1A/g.
Comparative example 1
The preparation method of the modified polypyrrole aerogel comprises the following steps:
soaking polypyrrole aerogel in dopamine solution with the concentration of 3.5mg/mL, adjusting the pH value to 8.5 by using Tris buffer solution, and modifying the polypyrrole aerogel (reacting for 22 hours at room temperature) to obtain modified polypyrrole aerogel;
the modified polypyrrole aerogel obtained in the comparative example is subjected to electrochemical detection, and the capacitance retention rate is only 53.8% after 1000 times of cyclic charge and discharge at the current density of 1A/g.
Comparative example 2
A polypyrrole/UiO-66 composite aerogel, its preparation method includes the following steps:
1) putting the polypyrrole aerogel into an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, heating to 100 ℃, and carrying out heat preservation reaction for 12 hours; wherein in the obtained reaction system, the components are as follows according to parts by weight: 3 parts of modified polypyrrole aerogel, 10 parts of zirconium chloride, 20 parts of terephthalic acid and 240 parts of N, N-dimethylformamide;
2) washing the reaction product obtained in the step 1) with methanol, and drying at 90 ℃ for 32h to obtain the polypyrrole/UiO-66 composite aerogel.
The polypyrrole/UiO-66 composite aerogel obtained in the embodiment is subjected to electrochemical detection, and the capacitance retention rate is 83.4% after 1000 times of charge and discharge cycles at a current density of 1A/g.
The invention can be realized by all the listed raw materials, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials; the examples are not to be construed as limiting the scope of the invention. The upper and lower limit values and interval values of the process parameters can realize the invention, and the embodiments are not listed.
Claims (8)
1. polypyrrole/UiO-66 composite aerogel is prepared by soaking polypyrrole aerogel in dopamine solution, adjusting the pH value of the obtained mixed solution to 8-9, carrying out polymerization modification on the polypyrrole aerogel, and then placing the modified polypyrrole aerogel in a precursor solution of UiO-66 for crystallization reaction to obtain polypyrrole/UiO-66 composite aerogel;
the polymerization modification temperature is room temperature.
2. The polypyrrole/UiO-66 composite aerogel according to claim 1, wherein the precursor solution of UiO-66 is a solution of N, N-dimethylformamide containing zirconium chloride and terephthalic acid.
3. A method for preparing polypyrrole/UiO-66 composite aerogel described in claim 1 or 2, which comprises the following steps:
1) soaking polypyrrole aerogel in a dopamine solution, adjusting the pH value of the obtained mixed solution to 8-9, and performing polymerization modification on the polypyrrole aerogel;
2) placing the modified polypyrrole aerogel in a precursor solution of UiO-66, and heating for crystallization reaction;
3) washing and drying the product obtained in the step 2) to obtain the polypyrrole/UiO-66 composite aerogel.
4. The preparation method according to claim 3, wherein the concentration of dopamine in the dopamine solution is 3-5 mg/mL.
5. The preparation method according to claim 3, wherein the polymerization modification temperature in the step 1) is room temperature, and the time is 18-24 h.
6. The preparation method according to claim 3, wherein the crystallization reaction temperature is 100-120 ℃ and the time is 10-20 h.
7. The preparation method according to claim 3, wherein the precursor solution of UiO-66 is an N, N-dimethylformamide solution containing zirconium chloride and terephthalic acid, and after the modified polypyrrole aerogel is added, the obtained mixed system comprises the following components in parts by weight: 3-6 parts of modified polypyrrole aerogel, 3-6 parts of zirconium chloride, 8-20 parts of terephthalic acid and 100-250 parts of N, N-dimethylformamide.
8. The preparation method according to claim 3, wherein the drying temperature in the step 3) is 80-90 ℃ and the drying time is 24-36 h.
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