CN107383872B - Polypyromellitic-acyl p-phenylenediamine/carbon cloth material and preparation method and application thereof - Google Patents
Polypyromellitic-acyl p-phenylenediamine/carbon cloth material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polybenzoxazole p-phenylenediamine/carbon cloth material and a preparation method and application thereof. The polybenzoylmethane-p-phenylenediamine/carbon cloth material is formed by uniformly coating a polybenzoylmethane-p-phenylenediamine nanosheet on a carbon cloth fiber. The preparation method is obtained by a two-step method, and specifically comprises the following steps: firstly, pretreating the carbon cloth by using acid, namely functionalizing the surface of the carbon cloth fiber by using polar groups; and secondly, coating and growing a poly (tetramethylbenzene sulfonyl) p-phenylenediamine nanosheet on the surface of the carbon cloth fiber by adopting a solution polymerization method and a high-temperature reaction. The material of the invention effectively improves the selectivity of the electro-catalysis ammonia synthesis, obviously improves the ammonia yield and the Faraday efficiency by means of the porous structures of the nano-sheets and the carbon cloth fiber and the characteristic of the poly (tetramethyleneterephthalamide) for inhibiting the hydrogen evolution reaction, and provides a good method for solving the efficiency problem of the electro-catalysis ammonia synthesis at present. The material has the characteristics of low raw material price, stable structure, high efficiency and the like, and the preparation method has the advantages of low energy consumption, simple method, easy operation and the like.
Description
Technical Field
The invention relates to the field of electrochemical ammonia synthesis and utilization, in particular to a polybenzoylp-phenylenediamine/carbon cloth material and a preparation method and application thereof.
Background
The ammonia is used as a new hydrogen energy carrier, has the advantages of cleanness, high efficiency, storage and transportation and the like, and is one of the most ideal pollution-free green energy sources in the future. In liquid ammonia, the mass fraction of hydrogen has been proven to be 17%, which is much higher than 12.5% in methanol, so the development and utilization of ammonia are of great significance for relieving the energy crisis caused by the exhaustion of petrochemical energy. In view of the fact that ammonia gas has been difficult to meet the strong demand in the chemical industry, the development of a more inexpensive and feasible method for synthesizing ammonia has received a great deal of attention from various countries. However, the traditional ammonia synthesis method takes hydrogen and nitrogen as raw materials and is carried out under the conditions of 100-200 atmospheric pressure and 500-600 DEG CThe load type Fe is catalyzed to obtain ammonia gas, huge conventional energy is consumed, the production cost is too high, and the popularization and the application of the load type Fe are greatly limited. In recent years, many researchers develop imagination, and research on the catalytic system suffering from the imagination from different angles is carried out, and development of a new catalytic system is expected to reduce energy consumption of synthetic ammonia. Among these, in particular the biological nitrogen fixation mechanism (N)2+6H++nMg-ATP+6e-(enzyme) → 2NH3+ nMg-ADP + nPi) revealed the possibility of electrochemical ammonia production. The electrochemical ammonia production is an electro-catalysis technology which takes water and nitrogen as raw materials, the process is environment-friendly, no pollution is brought to the environment, the synthesis system has simple structure and low investment, can be applied in small scale and developed in large scale, and is one of the technologies with the greatest prospect in the ammonia synthesis field. However, the electrochemical ammonia production technology is still in the preliminary research stage, the research system mostly adopts expensive catalyst materials, and the dominant hydrogen evolution competition reaction causes that only very low ammonia production current efficiency (less than 1%) is obtained.
The poly (tetramethyloyl-p-phenylenediamine) is one of polyimide polymers and one of important chemical plastics. In the past, they have been commonly used as structural skeleton materials due to their good mechanical toughness and thermal stability. However, its inherent insulating properties make it less desirable for researchers in the field of electrochemical material applications. Recent studies have shown that its insulating properties can be improved by introducing a conductive carbon group, and that it can also exhibit reversible redox behavior as an electrode material. In the electrochemical process, the poly (pyromellitic dianhydride) can generate reversible enolization conjugated structure change due to the adjacent aromatic ring and carbonyl structure of the poly (pyromellitic dianhydride) polymer. It is noted that, in the negative potential, the reduction reaction of the poly (tetramethylethylenediamine) can effectively inhibit the hydrogen evolution reaction. It is well known that a key problem faced by electrochemical ammonia synthesis technology is that the prevailing hydrogen evolution competing reaction results in faradaic inefficiencies in the electrosynthesis of ammonia. The characteristic of the polybenzoylp-phenylenediamine material for inhibiting the hydrogen evolution reaction can be used as an advantage to improve the efficiency of the electrochemical ammonia synthesis. Therefore, the designed and synthesized porous poly (pyromellitic dianhydride) p-phenylenediamine nanosheet is expected to effectively improve the selectivity of electrocatalytic ammonia synthesis by combining the characteristic of inhibiting the hydrogen evolution reaction, so that the ammonia yield and the Faraday efficiency are improved, and a method for providing reference is provided for solving the problem of low efficiency of electrocatalytic ammonia synthesis at present. In addition, the catalytic material has the characteristics of low price, stable structure, high efficiency and the like, and the preparation method has the advantages of low energy consumption, simple method, easy operation and the like, and is expected to be produced in large scale. The materials and the method designed by the invention lay a solid theoretical and practical foundation for realizing high-selectivity electrochemical ammonia synthesis.
Disclosure of Invention
One of the purposes of the invention is to provide a poly (pyromellitic dianhydride)/carbon cloth material.
The second purpose of the invention is to provide a preparation method of the poly (pyromellitic dianhydride)/carbon cloth material. In order to overcome the problem that the preparation of the electrochemical ammonia synthesis material in the prior art is only limited to the preparation of a powder sample, a simple method for directly growing a porous high polymer material on a conductive carrier is provided, so that an electrode and an active material are integrated, and an additional electrode preparation procedure is avoided.
The invention also aims to provide the oriented functionalization application of the poly (pyromellitic dianhydride)/carbon cloth material, namely the application in electrocatalytic ammonia synthesis.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a polybenzoylp-phenylenediamine/carbon cloth material comprises the following steps:
(1) pretreatment of carbon cloth: soaking the carbon cloth in a concentrated nitric acid solution to obtain carbon cloth fibers with functionalized surface polar groups;
(2) adding the carbon cloth pretreated in the step (1) into the early-stage reaction liquid, stirring and mixing uniformly, and heating the solution to start reaction; the early-stage reaction liquid consists of the following components: pyromellitic dianhydride, p-chlorophenol, dimethylformamide and p-phenylenediamine;
(3) and after the reaction is finished, naturally cooling to room temperature, taking out the carbon cloth, washing, drying, then carrying out heat treatment in an argon atmosphere, and then washing to obtain the polybenzoylteramethylenediamine/carbon cloth material.
Preferably, in the step (1), the carbon cloth is a commercial carbon fiber cloth.
Preferably, in the step (1), the concentrated nitric acid solution is commercial concentrated nitric acid, and the mass fraction of the concentrated nitric acid solution is 65%.
Preferably, in the step (1), the soaking time is 12-48 h.
Preferably, in the step (2), the early-stage reaction liquid is composed of 7-10 g of pyromellitic dianhydride, 10-13 g of p-chlorophenol, 100-150 mL of dimethylformamide and 0.5-1.5 mL of p-phenylenediamine.
Preferably, in the step (2), the reaction temperature is 150-250 ℃, and the reaction time is 3-6 h.
Preferably, in the step (3), the heat treatment is divided into two temperature control procedures, wherein the first procedure is a temperature raising procedure, the temperature is raised from room temperature to 350-400 ℃, and the temperature raising time is 2-3 hours; the second stage is a constant temperature process, and the temperature is maintained at 350-400 ℃ for 2-3 h.
Preferably, in the step (3), the washing is fully cleaning by using ethanol and distilled water.
The polybenzoxazole p-phenylenediamine/carbon cloth material prepared by the preparation method has the advantage that the outer layer of the surface of the carbon cloth fiber is coated and grown with the polybenzoxazole p-phenylenediamine nanosheet.
The application of the above-mentioned pyromellitic acyl p-phenylenediamine/carbon cloth material in electrocatalytic ammonia synthesis.
The poly (pyromellitic dianhydride)/carbon cloth material is used as an electro-catalytic ammonia synthesis material, solves the problem of few active sites of a powder polymer stacking structure, and provides a simple method for directly growing a porous polymer material on a conductive carrier, thereby improving the specific surface area of an electrode.
The carbon cloth fiber surface with good electrochemical synthetic ammonia performance provided by the invention is coated with a growth polybenzoxazole p-phenylenediamine nanosheet material, which is abbreviated as: the poly (pyromellitic dianhydride)/carbon cloth material is characterized in that a reticular poly (pyromellitic dianhydride) nanosheet is wrapped on the surface of a carbon cloth fiber. The material has the characteristic of inhibiting hydrogen evolution reaction and has high-efficiency electrochemical ammonia synthesis performance.
The shape of the reticular lamina is regulated and controlled by setting the components of the precursor solution for synthesizing the poly (tetramethylenetetracyl-p-phenylenediamine) and the synthesis time and temperature thereof, so that the reticular lamina grows orderly and controllably; the selective electrochemical synthesis of ammonia is further achieved by setting the ability to suitably inhibit the hydrogen evolution reaction of the polybenzoylp-phenylenediamine material.
Compared with the prior art, the invention has the following beneficial effects:
(1) most of the high molecular polymer materials discovered at present are stacked structures, and the nano-sheet structure is difficult to prepare, so that the application of the high molecular polymer materials in the electrochemical field is limited. According to the invention, the poly (pyromellitic dianhydride) nano sheet with a porous net shape is coated on the surface of the carbon cloth fiber, so that the specific surface area of the electrode material is increased, and the reaction sites on the surface of the electrode are greatly increased.
(2) The polybenzoylmethane-p-phenylenediamine/carbon cloth material of the invention has unique property of inhibiting hydrogen evolution reaction, is beneficial to the expression of selective electrochemical synthesis ammonia reaction, and provides a good method for solving the problem of electrochemical ammonia synthesis efficiency.
(3) The preparation method of the poly (pyromellitic dianhydride)/carbon cloth material has the advantages of low energy consumption, simple method, easy operation and the like, and is expected to be produced in large scale.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of the PPTA/carbon cloth material obtained in example 1;
FIG. 2 is an infrared spectrum (FT-IR) of a polytetramethylene terephthalamide/carbon cloth material obtained in example 1;
FIG. 3 is a Cyclic Voltammogram (CV) of the polytetramethylenebisamide/carbon cloth material obtained in example 1;
FIG. 4 is a graph showing the Faraday efficiency of the synthesized ammonia at different potentials for the PPTA/carbon cloth material obtained in example 1;
FIG. 5 is a graph showing the rate of ammonia synthesis at different potentials for the polybenzoylp-phenylenediamine/carbon cloth material obtained in example 1;
FIG. 6 is a Scanning Electron Microscope (SEM) of the PPTA/carbon cloth material obtained in example 2;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the PPTA/carbon cloth material obtained in example 3.
Detailed Description
The following describes a specific embodiment of the present invention with reference to the examples and the drawings, but the present invention is not limited thereto.
Example 1
The synthesis of the polybenzoylp-phenylenediamine/carbon cloth material is realized by a solution reaction method, and specifically comprises the following steps:
(1) pretreatment of carbon cloth: placing carbon fiber cloth (3cm x 2cm) in a concentrated nitric acid solution (65 wt%) to soak for 12h at normal temperature, then sequentially and respectively ultrasonically cleaning in absolute ethyl alcohol and deionized water for 10min, and then soaking in absolute ethyl alcohol for later use;
(2) placing the carbon fiber pretreated in the step (1) in a round-bottom flask filled with the early-stage reaction liquid, stirring and mixing uniformly, and heating the solution to react for 3 hours at 150 ℃; the early-stage reaction liquid consists of the following components: 7g of pyromellitic dianhydride, 10g of p-chlorophenol, 100mL of dimethylformamide and 0.5mL of p-phenylenediamine;
(3) after the reaction is finished, naturally cooling to room temperature, taking out the pyromellitic dianhydride/carbon cloth, repeatedly cleaning the pyromellitic dianhydride/carbon cloth by using ethanol and deionized water, drying, then placing the pyromellitic dianhydride/carbon cloth in a crucible, and carrying out heat treatment in an argon atmosphere, namely controlling the temperature by two stages of programs, wherein the first stage is heating program calcination, the temperature is raised from room temperature (25 ℃) to 350 ℃, and the heating time is 2 hours; the second stage is a constant temperature program, maintained at 350 ℃ for 2 h. And cooling to room temperature after heat treatment, repeatedly washing the obtained sample by using ethanol and deionized water, and airing at room temperature to obtain the poly (tetramethylacyl-p-phenylenediamine)/carbon cloth material.
Performance test: the phase of the polybenzoylp-phenylenediamine/carbon cloth material prepared in this example was characterized, and the results are shown in fig. 1. Scanning Electron Microscope (SEM) images (fig. 1) show that reticular pyromellitic paraphenylene diamine nanosheets grow uniformly and regularly on carbon cloth fibers. The polybenzoylp-phenylenediamine/carbon cloth material was subjected to elemental valence bond analysis by infrared spectroscopy (FT-IR). Figure 2 demonstrates that C ═ O and C — N characteristic bonds are present in pyromellitic para-phenylenediamine. In the aspect of performance test, the prepared poly-pyromellitic-acyl p-phenylenediamine/carbon cloth material is used as a cathode to carry out performance test of hydrogen evolution reaction inhibition and electrochemical synthesis of ammonia. As can be seen from FIG. 3, the polybenzoylp-phenylenediamine/carbon cloth material has a unique property of inhibiting hydrogen evolution reaction, and the hydrogen evolution overpotential is very large. In the electrochemical ammonia synthesis test (see fig. 4, fig. 5), the faraday efficiency of the poly (tetramethyloyl-p-phenylenediamine)/carbon cloth material at a potential of-0.5V (vs. rhe) and a test temperature of 25 ℃ is 1.87%, which is higher than most currently reported values of faraday efficiency (< 1%). From the analysis of the results, the selectivity of the electrochemical synthesis ammonia reaction of the pyromellitic-acyl p-phenylenediamine/carbon cloth material is obviously improved, which is mainly due to the characteristic of inhibiting the hydrogen evolution reaction of the pyromellitic-acyl p-phenylenediamine, so that the pyromellitic-acyl p-phenylenediamine has wider potential selection advantage in the electrochemical synthesis ammonia reaction application. In conclusion, the polybenzoxazole p-phenylenediamine/carbon cloth material prepared by the embodiment shows better selectivity of the electrochemical synthesis of ammonia, and has great prospect in the field of the electrochemical synthesis of ammonia.
The pyromellitic dianhydride/carbon cloth material prepared by the embodiment is used, the influence on the ammonia-producing process drawing efficiency and the ammonia-producing process drawing rate of the pyromellitic dianhydride/carbon cloth material is researched by regulating and controlling different test potentials, and the relation is shown in table 1.
TABLE 1
The pyromellitic dianhydride/carbon cloth material prepared by the embodiment has the influence on the ammonia-producing process drawing efficiency and the ammonia-producing process drawing rate of the pyromellitic dianhydride/carbon cloth material by regulating and controlling different test temperatures, and the relationship is shown in table 2.
TABLE 2
Example 2
The synthesis of the polybenzoylp-phenylenediamine/carbon cloth material is realized by a solution reaction method, and specifically comprises the following steps:
(1) pretreatment of carbon cloth: placing carbon fiber cloth (3cm x 2cm) in a concentrated nitric acid solution (65 wt%) to soak for 36h at normal temperature, then sequentially and respectively ultrasonically cleaning in absolute ethyl alcohol and deionized water for 10min, and then soaking in absolute ethyl alcohol for later use;
(2) placing the carbon fiber pretreated in the step (1) in a round-bottom flask filled with the early-stage reaction liquid, stirring and mixing uniformly, and heating the solution to react for 4.5 hours at 200 ℃; the early-stage reaction liquid consists of the following components: 8.5g pyromellitic dianhydride, 11.5g p-chlorophenol, 125mL dimethylformamide and 1.0mL p-phenylenediamine;
(3) after the reaction is finished, naturally cooling to room temperature, taking out the pyromellitic dianhydride/carbon cloth, repeatedly cleaning the pyromellitic dianhydride/carbon cloth by using ethanol and deionized water, drying, then placing the pyromellitic dianhydride/carbon cloth in a crucible, and carrying out heat treatment in an argon atmosphere, namely controlling the temperature by two stages of programs, wherein the first stage is heating program calcination, the temperature is raised from room temperature (25 ℃) to 375 ℃, and the heating time is 2.5 hours; the second stage is a constant temperature program, maintained at 375 ℃ for 2.5 h. And cooling to room temperature after heat treatment, repeatedly washing the obtained sample by using ethanol and deionized water, and airing at room temperature to obtain the poly (tetramethylacyl-p-phenylenediamine)/carbon cloth material.
Performance test: the morphology of the pyromellitic dianhydride/carbon cloth material prepared in this example was characterized, and the results are shown in fig. 6. Similar to example 1, Scanning Electron Microscope (SEM) images (fig. 6) show uniform and regular growth of reticulated pyromellitic paraphenylene diamine nanoplates on carbon cloth fibers.
The pyromellitic dianhydride/carbon cloth material prepared in this example was used to study the influence on the ammonia-producing process drawing efficiency and rate of the pyromellitic dianhydride/carbon cloth material by adjusting and controlling different test potentials, and the relationship is shown in table 3.
TABLE 3
The pyromellitic dianhydride/carbon cloth material prepared by the embodiment has the influence on the ammonia-producing process drawing efficiency and the ammonia-producing process drawing rate of the pyromellitic dianhydride/carbon cloth material by regulating and controlling different test temperatures, and the relationship is shown in table 4.
TABLE 4
Example 3
The synthesis of the polybenzoylp-phenylenediamine/carbon cloth material is realized by a solution reaction method, and specifically comprises the following steps:
(1) pretreatment of carbon cloth: placing carbon fiber cloth (3cm x 2cm) in a concentrated nitric acid solution (65 wt%) to soak for 48h at normal temperature, then sequentially and respectively ultrasonically cleaning in absolute ethyl alcohol and deionized water for 10min, and then soaking in absolute ethyl alcohol for later use;
(2) placing the carbon fiber pretreated in the step (1) in a round-bottom flask filled with the early-stage reaction liquid, stirring and mixing uniformly, and heating the solution to react for 6 hours at 250 ℃; the early-stage reaction liquid consists of the following components: 10g of pyromellitic dianhydride, 13g of p-chlorophenol, 150mL of dimethylformamide and 1.5mL of p-phenylenediamine;
(3) after the reaction is finished, naturally cooling to room temperature, taking out the pyromellitic dianhydride/carbon cloth, repeatedly cleaning the pyromellitic dianhydride/carbon cloth by using ethanol and deionized water, drying, then placing the pyromellitic dianhydride/carbon cloth in a crucible, and carrying out heat treatment in an argon atmosphere, namely controlling the temperature by two stages of programs, wherein the first stage is heating program calcination, the temperature is raised from room temperature (25 ℃) to 400 ℃, and the heating time is 3 hours; the second stage is a constant temperature program, maintained at 400 ℃ for 3 h. And cooling to room temperature after heat treatment, repeatedly washing the obtained sample by using ethanol and deionized water, and airing at room temperature to obtain the poly (tetramethylacyl-p-phenylenediamine)/carbon cloth material.
Performance test: the morphology of the pyromellitic dianhydride/carbon cloth material prepared in this example was characterized, and the results are shown in fig. 7. Similar to examples 1 and 2, Scanning Electron Microscope (SEM) images (fig. 7) show that reticular pyromellitic acyl p-phenylenediamine nanosheets grow uniformly and regularly on carbon cloth fibers.
The pyromellitic dianhydride/carbon cloth material prepared in this example was used to study the influence on the ammonia-producing process drawing efficiency and rate of the pyromellitic dianhydride/carbon cloth material by adjusting and controlling different test potentials, and the relationship is shown in table 5.
TABLE 5
The pyromellitic dianhydride/carbon cloth material prepared by the embodiment has the influence on the ammonia-producing process drawing efficiency and the ammonia-producing process drawing rate of the pyromellitic dianhydride/carbon cloth material by regulating and controlling different test temperatures, and the relationship is shown in table 6.
TABLE 6
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the polybenzoylp-phenylenediamine/carbon cloth material is characterized by comprising the following steps:
(1) pretreatment of carbon cloth: soaking the carbon cloth in a concentrated nitric acid solution to obtain carbon cloth fibers with functionalized surface polar groups;
(2) adding the carbon cloth pretreated in the step (1) into the early-stage reaction liquid, stirring and mixing uniformly, and heating the solution to start reaction; the early-stage reaction liquid consists of the following components: pyromellitic dianhydride, p-chlorophenol, dimethylformamide and p-phenylenediamine;
(3) after the reaction is finished, naturally cooling to room temperature, taking out the carbon cloth, washing, drying, then carrying out heat treatment in an argon atmosphere, and then washing to obtain the polybenzoylteramethylenediamine/carbon cloth material;
in the step (2), the reaction temperature is 150-250 ℃, and the reaction time is 3-6 h.
2. The production method according to claim 1, wherein in the step (1), the carbon cloth is a carbon fiber cloth.
3. The method according to claim 1, wherein in the step (1), the concentrated nitric acid solution is a commercially available concentrated nitric acid with a mass fraction of 65%.
4. The preparation method according to claim 1, wherein in the step (1), the soaking time is 12-48 h.
5. The method according to claim 1, wherein in the step (2), the early-stage reaction solution comprises 7 to 10g of pyromellitic dianhydride, 10 to 13g of p-chlorophenol, 100 to 150mL of dimethylformamide, and 0.5 to 1.5mL of p-phenylenediamine.
6. The preparation method according to claim 1, wherein in the step (3), the heat treatment is divided into two temperature control procedures, wherein the first procedure is a temperature raising procedure, the temperature is raised from room temperature to 350-400 ℃, and the temperature raising time is 2-3 h; the second stage is a constant temperature process, and the temperature is maintained at 350-400 ℃ for 2-3 h.
7. The method according to claim 1, wherein in the step (3), the washing is performed by washing with ethanol and distilled water.
8. A polybenzoylp-phenylenediamine/carbon cloth material produced by the production process as claimed in any one of claims 1 to 7.
9. Use of a pyromellitic para-phenylenediamine/carbon cloth material according to claim 8 in electrocatalytic ammonia synthesis.
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| CN104103812B (en) * | 2014-07-21 | 2016-08-24 | 国家纳米科学中心 | A kind of composite and flexible electrode material and its production and use |
| CN104987717A (en) * | 2015-07-01 | 2015-10-21 | 南京工业大学 | Polyimide-based material with super capacitance characteristics and preparation method |
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