CN110683538A - Preparation method of nitrogen-phosphorus co-doped graded porous carbon material - Google Patents
Preparation method of nitrogen-phosphorus co-doped graded porous carbon material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-phosphorus co-doped hierarchical porous carbon material, which is used for solving the technical problem of poor practicability of the existing preparation method of the hierarchical porous carbon material. The technical scheme is that the polyamino molecular water solution is added with polyphosphoric acid under the conditions of low temperature and stirring for reaction to obtain the amino polyphosphate. Under the high-temperature condition, the amino polyphosphate realizes pore-forming through an in-situ self-activation process. The nitrogen-phosphorus co-doped hierarchical porous carbon can be directly obtained under the high-temperature condition by taking the amino polyphosphate as a carbon, nitrogen and phosphorus source. Because the polyamino molecules provide C, N sources, the polyphosphoric acid provides P sources, and the polyamino is easy to react with the polyphosphoric acid in a crosslinking way at low temperature to obtain the amino polyphosphate precursor. And (3) under the atmosphere of high-temperature inert gas, performing pore-forming on phosphoric acid molecules through an in-situ self-activation process to obtain the carbon material with high specific surface area and rich pore structure. The method does not need to introduce additional pore-forming agent or activating agent, has simple operation steps, no post-treatment process and good practicability.
Description
Technical Field
The invention relates to a preparation method of a hierarchical porous carbon material, in particular to a preparation method of a nitrogen-phosphorus co-doped hierarchical porous carbon material.
Background
The hierarchical porous carbon is a carbon material with macropores (the aperture is more than 50nm), mesopores (the aperture is less than 2nm and less than 50nm) and micropores (the aperture is less than 2nm), has large specific surface area, can integrate the advantages of different pore structures in the electrochemical reaction process, realizes the full infiltration of electrolyte on an electrode material, accelerates the transfer of electrolyte ions and shortens a charge transmission path. By doping the heteroatoms, the electrochemical performance of the carbon material can be further optimized, and the application of the carbon material in the energy field is expanded; thereby making up the defect of low device performance when the traditional carbon material is used as an electrode. The preparation of the hierarchical porous carbon mainly depends on two approaches of pore forming by chemical reagents and template agents at present:
document 1 "Ducheng, Chenjian, etc. Preparation of Nitrogen and sulfur co-doped hierarchical porous carbon from rape seed ash-performance super capacitor electrode [ J ] by rape pollen for high-performance super capacitor Nitrogen and sulfur co-doped hierarchical porous carbon]Electrochemical reports electrochimica acta.2019,311: 72-82' disclose a preparation method of a nitrogen and sulfur co-doped hierarchical porous carbon material. The method uses ZnCl2FeCl is used as template agent to realize pore-forming3To promote graphitization with a catalyst: 2g of rape pollen and 6g of ZnCl2、16gFeCl3And adding 10mL of deionized water into the mixture, stirring for 12h, freeze-drying, reacting at high temperature under Ar atmosphere, washing the product with a corrosive reagent HCl, repeatedly washing with deionized water until the aqueous solution is neutral, and drying the sample to obtain the hierarchical porous carbon.
Document 2, "chinese patent application publication No. CN 109354004A" discloses a method for preparing a hierarchical porous carbon material. The method comprises the steps of firstly ultrasonically cleaning fish scales for more than half an hour, then soaking the fish scales in a strong acid solution for more than 12 hours (to remove calcium), and then cleaning the fish scales with deionized water, drying and pre-carbonizing the fish scales at a low temperature. And adding the pre-carbonized sample into a nitrogen-containing reagent, carrying out hydrothermal reaction at 160-110 ℃ to obtain a nitrogen-doped sample, adding KOH into the solution, stirring and evaporating to dryness, drying and grinding the obtained viscous solid, and calcining and carbonizing the viscous solid under inert protective gas. And finally, further grinding the carbonized sample, washing with hydrochloric acid, washing with deionized water to neutrality, and drying to obtain the graded porous carbon material.
However, the hierarchical porous carbon obtained by the above two methods usually has only micropores and mesopores, and is not favorable for the infiltration of the electrolyte to the electrode material due to the lack of a macroporous structure. Meanwhile, in both preparation methods, a strong corrosive chemical reagent is needed, and complicated post-treatment is carried out, so that the defects of dangerous operation, difficulty in large-scale preparation and low efficiency exist in material preparation, and the commercialization process of the material is seriously influenced.
Disclosure of Invention
In order to overcome the defect that the existing preparation method of the hierarchical porous carbon material is poor in practicability, the invention provides a preparation method of a nitrogen-phosphorus co-doped hierarchical porous carbon material. In the method, polyamino molecular water solution is added with polyphosphoric acid under the conditions of low temperature and stirring for reaction, the obtained product is washed with deionized water for multiple times, and after drying, the amino polyphosphate is obtained. Under the high-temperature condition, the amino polyphosphate realizes pore-forming through the in-situ self-activation process, thereby avoiding the use of corrosive pore-forming agents. Meanwhile, the nitrogen-phosphorus co-doped hierarchical porous carbon can be directly obtained by taking the amino polyphosphate as a carbon, nitrogen and phosphorus source under the high-temperature condition without any post-treatment. Because the polyamino molecules provide C, N sources, the polyphosphoric acid provides P sources, and the polyamino is easy to react with the polyphosphoric acid in a crosslinking way at low temperature to obtain the amino polyphosphate precursor. And (3) under the atmosphere of high-temperature inert gas, performing pore-forming on phosphoric acid molecules through an in-situ self-activation process to obtain the carbon material with high specific surface area and rich pore structure. The method does not need to introduce additional pore-forming agent or activating agent, has simple operation steps and no post-treatment process, greatly simplifies the process flow, and has low cost, easy scale production and good practicability.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a nitrogen-phosphorus co-doped hierarchical porous carbon material is characterized by comprising the following steps:
step one, adding acid containing phosphoric acid groups into the polyamino molecular water solution at the temperature of 50-100 ℃ under the stirring condition, and reacting for 1-5 hours. Wherein the molar ratio of the polyamino molecules to the phosphoric acid group-containing acid is 1: 0.5-1: 2.
And step two, washing the product obtained in the step one with deionized water for multiple times, and drying in a constant-temperature oven at 50-90 ℃ for 6-12 hours.
And step three, calcining the product obtained in the step two for 1-6 hours at 700-900 ℃ in an inert atmosphere to obtain the nitrogen-phosphorus co-doped hierarchical porous carbon material.
The polyamino molecules are any one of p-phenylenediamine, tetra-amino nickel phthalocyanine, tetra-amino iron phthalocyanine, tetra-amino copper phthalocyanine, melamine or organic polyamine compounds.
The phosphoric acid group-containing acid is any one of phytic acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid or polyphosphoric acid.
The invention has the beneficial effects that: in the method, polyamino molecular water solution is added with polyphosphoric acid under the conditions of low temperature and stirring for reaction, the obtained product is washed with deionized water for multiple times, and after drying, the amino polyphosphate is obtained. Under the high-temperature condition, the amino polyphosphate realizes pore-forming through the in-situ self-activation process, thereby avoiding the use of corrosive pore-forming agents. Meanwhile, the nitrogen-phosphorus co-doped hierarchical porous carbon can be directly obtained by taking the amino polyphosphate as a carbon, nitrogen and phosphorus source under the high-temperature condition without any post-treatment. Because the polyamino molecules provide C, N sources, the polyphosphoric acid provides P sources, and the polyamino is easy to react with the polyphosphoric acid in a crosslinking way at low temperature to obtain the amino polyphosphate precursor. And (3) under the atmosphere of high-temperature inert gas, performing pore-forming on phosphoric acid molecules through an in-situ self-activation process to obtain the carbon material with high specific surface area and rich pore structure. The method does not need to introduce additional pore-forming agent or activating agent, has simple operation steps and no post-treatment process, greatly simplifies the process flow, and has low cost, easy scale production and good practicability.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Drawings
Fig. 1 is an SEM image of a nitrogen and phosphorus co-doped graded porous carbon material prepared in example 1 of the present invention.
Fig. 2 is a partially enlarged view of fig. 1.
Fig. 3 is a pore size distribution diagram of the nitrogen and phosphorus co-doped hierarchical porous carbon material prepared in example 1 of the method of the present invention.
Fig. 4 is an XPS chart of the nitrogen and phosphorus co-doped graded porous carbon material prepared in example 1 of the present invention.
Detailed Description
The following examples refer to fig. 1-4.
Example 1
Step one, weighing 4.32g of p-phenylenediamine to disperse in 400mL of deionized water, adding 5mL of polyphosphoric acid under the condition of stirring at 80 ℃, and reacting for 2 hours.
And step two, washing the product obtained in the step one with deionized water for multiple times, and drying in a constant-temperature oven at 90 ℃ for 6 hours to obtain the amino polyphosphate.
And step three, placing the amino polyphosphate obtained in the step two in a tubular furnace, heating to 900 ℃ in an argon atmosphere, and preserving heat for 1 hour to obtain nitrogen and phosphorus co-doped hierarchical porous carbon.
As can be seen from fig. 1 and 2, the nitrogen-phosphorus co-doped hierarchical porous carbon material prepared in this embodiment is rich in a hierarchical porous structure.
As can be seen from fig. 3, the nitrogen-phosphorus co-doped hierarchical porous carbon material prepared in this embodiment has obvious structures of micropores (D <2nm), mesopores (2nm < D <50nm), and macropores (D >50 nm).
As can be seen from fig. 4, the nitrogen-phosphorus co-doped hierarchical porous carbon material prepared in this embodiment contains three elements, namely nitrogen, phosphorus and carbon, which indicates that the nitrogen-phosphorus co-doped carbon material is obtained in this embodiment.
Example 2.
Step one, weighing 25g of tetraaminophthalocyanine nickel, dispersing in 400mL of deionized water, adding 5mL of polyphosphoric acid under the stirring condition at 50 ℃, and reacting for 5 hours.
And step two, washing the product obtained in the step one with deionized water for multiple times, and drying in a constant-temperature oven at 50 ℃ for 12 hours to obtain the amino polyphosphate.
And step three, placing the amino polyphosphate obtained in the step two in a tubular furnace, heating to 700 ℃ in an argon atmosphere, and preserving heat for 6 hours to obtain nitrogen and phosphorus co-doped hierarchical porous carbon.
Example 3.
Step one, weighing 4.32g of p-phenylenediamine to disperse in 400mL of deionized water, adding 5mL of metaphosphoric acid under the stirring condition at 100 ℃, and reacting for 1 hour.
And step two, washing the product obtained in the step one with deionized water for multiple times, and drying in a constant-temperature oven at 70 ℃ for 9 hours to obtain the amino polyphosphate.
And step three, placing the amino polyphosphate obtained in the step two in a tubular furnace, heating to 800 ℃ in an argon atmosphere, and preserving heat for 4 hours to obtain nitrogen and phosphorus co-doped hierarchical porous carbon.
In the above-described embodiment, the polyamino molecules may be any of iron tetraaminophthalocyanine, copper tetraaminophthalocyanine, melamine, or organic polyamine compounds, in addition to p-phenylenediamine and nickel tetraaminophthalocyanine.
The phosphoric acid group-containing acid in the above examples may be any of phytic acid, phosphoric acid and pyrophosphoric acid, in addition to metaphosphoric acid and polyphosphoric acid.
Claims (3)
1. A preparation method of a nitrogen-phosphorus co-doped hierarchical porous carbon material is characterized by comprising the following steps:
firstly, adding an acid containing a phosphoric acid group into a polyamino molecular water solution at the temperature of 50-100 ℃ under the stirring condition, and reacting for 1-5 hours; wherein the molar ratio of the polyamino molecules to the phosphoric acid group-containing acid is 1: 0.5-1: 2;
step two, washing the product obtained in the step one by deionized water for multiple times, and drying in a constant-temperature oven at 50-90 ℃ for 6-12 hours;
and step three, calcining the product obtained in the step two for 1-6 hours at 700-900 ℃ in an inert atmosphere to obtain the nitrogen-phosphorus co-doped hierarchical porous carbon material.
2. The preparation method of the nitrogen-phosphorus-codoped hierarchical porous carbon material according to claim 1, characterized in that: the polyamino molecule is any one of p-phenylenediamine, tetra-amino nickel phthalocyanine, tetra-amino iron phthalocyanine, tetra-amino copper phthalocyanine, melamine or organic polyamine compounds.
3. The preparation method of the nitrogen-phosphorus-codoped hierarchical porous carbon material according to claim 1, characterized in that: the phosphoric acid group-containing acid is any one of phytic acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid or polyphosphoric acid.
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| CN112838215A (en) * | 2021-03-04 | 2021-05-25 | 桂林电子科技大学 | Three-dimensional porous carbon nanosheet-sulfur material and preparation method and application thereof |
| CN113845097A (en) * | 2021-09-13 | 2021-12-28 | 西北工业大学 | Universal preparation method of nitrogen-phosphorus co-doped carbon-loaded transition metal phosphide |
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