CN110002414B - Preparation method of porous carbon nitride nanotube - Google Patents
Preparation method of porous carbon nitride nanotube Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B01J35/40—
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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
Abstract
The invention discloses a preparation method of a porous carbon nitride nanotube, which comprises the following steps: using nitrogen-rich organic matter as raw material, carrying out phosphoric acid acidification hydrothermal treatment to obtain supramolecular precursor dispersed in the mixed solution, washing and drying the supramolecular precursor mixed solution, putting the supramolecular precursor mixed solution into an aluminum oxide crucible with a cover, putting the crucible in the central position of a muffle furnace chamber, and carrying out high-temperature treatment to obtain the porous carbon nitride nanotube. The diameter of the nanotube is about 3-8 μm, and many micropores are distributed on the surface. Compared with bulk graphite phase carbon nitride, the porous tubular structure can effectively increase the specific surface area, provide more catalytic active sites, facilitate the rapid separation of photon-generated carriers and improve the utilization rate of visible light. The porous carbon nitride nanotube shows excellent photocatalytic performance under the condition of visible light irradiation. The raw materials related by the method are low in price and simple in experimental operation, and the method can be applied to large-scale actual production and preparation of the porous carbon nitride nanotube with excellent photocatalytic performance.
Description
Technical Field
The invention belongs to the technical field of preparation of graphite-phase carbon nitride, and particularly relates to a preparation method of a porous carbon nitride nanotube for a high-efficiency photocatalyst.
Background
With the development of industrialization and urbanization, the problems of environmental pollution, energy crisis and the like are increasingly prominent. How to effectively utilize the green resource of solar energy to solve the environmental and energy problems has become a hotspot of the present society. The development of semiconductor photocatalytic technology has brought new hopes for the solution of the above problems. Graphite phase carbon nitride is used as a polymer semiconductor material without metal components, and has wide application prospects in the fields of photocatalysis, biological imaging, sensors and the like by virtue of stable physical and chemical properties, unique energy band structure, good biocompatibility and photocatalytic activity.
At present, the main methods for synthesizing carbon nitride include solvothermal methods, electrochemical deposition methods, magnetron sputtering methods, thermal polycondensation methods, and the like. The solvothermal method has the advantages of relatively mild synthesis conditions, low loss of nitrogen and the like. However, the crystallinity of the obtained graphite phase carbon nitride is generally poor, and some toxic organic solvents are usually involved in the reaction process, so that the method is harmful to the environment and laboratory staff. The electrochemical deposition method is generally used for preparing a carbon nitride film or coating, and the obtained carbon nitride film is generally polycrystalline or amorphous and is not suitable for preparing carbon nitride powder. The magnetron sputtering method is also a method for preparing a carbon nitride film, but the product is generally in a polycrystalline coexisting state, and the method has high requirements on the purity of the target material and the reaction gas. The thermal polycondensation method is a common method for preparing graphite-phase carbon nitride, and has the advantages of direct reaction process, simplicity, low cost, no environmental pollution and the like. However, most of products obtained by thermal polycondensation of nitrogen-rich organic matters are bulk graphite phase carbon nitride, and the defects of low surface area, few catalytic active sites, high recombination rate of photon-generated carriers and the like seriously limit the photocatalytic performance of the products. Therefore, in order to improve the photocatalytic performance of graphite-phase carbon nitride, researchers have proposed various improvements such as element doping, compounding with other semiconductors, precious metal surface deposition, fuel sensitization, and obtaining two-dimensional carbon nitride nanosheets by exfoliating the phase carbon nitride. Although the above modification method can improve the photocatalytic performance to some extent, the improvement effect is generally limited. In addition, the above experimental process is generally complicated to operate, the use of some metal salts causes problems of environmental pollution and the like, and the addition of expensive noble metals severely limits the large-scale practical application thereof.
It is well known that the microstructure of graphite phase carbon nitride plays a crucial role in the photocatalytic reaction process. For example, the photocatalytic performance of graphite-phase carbon nitride with micro-morphology structures such as nanospheres, nanotubes, nanobelts, nanorods and the like is obviously improved compared with bulk graphite-phase carbon nitride. Relevant researches show that the carbon nitride with the porous tubular structure has a potential huge application prospect in the field of photocatalysis. Due to the special one-dimensional porous tubular structure, photon-generated carriers can be rapidly separated along the radial dimension direction of the photon-generated carriers; meanwhile, light can be reflected for multiple times in the tube, so that the utilization rate of visible light is improved. In addition, the porous tubular structure contributes to the increase of the specific surface area and provides more catalytically active sites, and the structural advantages contribute to the improvement of the photocatalytic performance.
The method for preparing carbon nitride nanotubes is mainly a template method, for example, Wangxinchen at Fuzhou university, et al, prepares carbon nitride nanotubes by using cyanamide precursor and silica nanotubes as templates (image science and photochemistry 2015, 33 (5): 417-. However, the experiment is complicated in operation and long in period, and due to the introduction of the template in the reaction process, the template needs to be removed by using toxic and corrosive reagents such as ammonium bifluoride after the reaction is finished, so that the method is not environment-friendly.
The molecular self-assembly technology is a method which is developed in recent years and is widely applied to the micro-morphology regulation of nano materials. Raw material molecules are polymerized into a supramolecular precursor under the action of a hydrogen bond, and the obtained supramolecular precursor generally has a specific microstructure due to the directionality and the saturation of the hydrogen bond. The products obtained by directly heat treating supramolecular precursors generally also have a corresponding morphology. At present, scientists have prepared carbon nitride nanotubes by molecular self-assembly methods. Such as those of the people in the China Shaoxing academy of Queenshan Innovation, Nanjing university, China Shaoxing, a method for preparing self-assembled carbon nitride nanotubes and nanotubes prepared by the method, publication No. CN102616757A, by a self-assembly method. However, the carbon nitride nanotubes obtained by the general molecular self-assembly method have no porous structure, and further improvement of the photocatalytic performance is affected.
Disclosure of Invention
The invention aims to solve the problems that: aiming at the application requirements in the fields of photocatalytic degradation of organic pollutants, hydrogen production by photocatalytic water splitting, biological imaging and the like, a simple and effective method is provided for preparing the porous carbon nitride nanotube with excellent photocatalytic activity.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a porous carbon nitride nanotube is characterized by comprising the following preparation processes: the preparation method comprises the steps of taking nitrogen-rich organic powder as a raw material, carrying out phosphoric acid acidification and hydrothermal treatment to obtain a supramolecular precursor dispersed in a mixed solution, washing and drying the supramolecular precursor mixed solution, putting the supramolecular precursor mixed solution into an aluminum oxide crucible with a cover, then putting the crucible into the center of a muffle furnace chamber, and carrying out high-temperature treatment to obtain the porous carbon nitride nanotube.
Further, the nitrogen-rich organic matter is one or more of melamine, dicyandiamide, thiourea, cyanamide and cyanuric acid.
Further, the phosphoric acid acidification process is to add 1-3 g of nitrogen-rich organic powder into 60mL of phosphoric acid solution with the concentration of 0.25-1.0 mol/L, and stir for 10min to obtain uniformly dispersed mixed liquid.
Further, the hydrothermal treatment process comprises the steps of transferring the uniformly stirred mixed solution into a 100mL high-temperature reaction kettle, carrying out hydrothermal treatment for 4-8 h at 160-180 ℃, and naturally cooling to room temperature to obtain the supramolecular precursor dispersed in the mixed solution.
Further, the washing and drying process of the supramolecular precursor mixed solution comprises the steps of washing the supramolecular precursor mixed solution for multiple times by using deionized water until the pH value of the mixed solution after the last washing is neutral, and drying the mixed solution at the temperature of 60 ℃ to obtain the supramolecular precursor.
Further, the high-temperature treatment process comprises the steps of placing the supermolecule precursor in a muffle furnace, heating to 520-550 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, naturally cooling to room temperature, and collecting the obtained light yellow product to obtain the porous carbon nitride nanotube.
The porous carbon nitride nanotube prepared by the method is used for preparing a photocatalyst, and can be particularly used as a high-efficiency photocatalyst to be applied to the field of photodegradation of organic pollutants.
The beneficial effects of adopting the above technical scheme are as follows:
(1) the raw materials are only low-cost melamine and phosphoric acid, and expensive or environmentally harmful reagents such as organic solvents or protective gases are not used.
(2) The experimental process is simple and easy to operate.
(3) The product is pure, no catalyst, template, substrate and the like are introduced in the synthesis process, the content of impurities is greatly reduced, and the influence of impurity components on the structure and the property of the target product is favorably reduced.
(4) The product porous carbon nitride nanotube has excellent and stable photocatalytic performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product obtained in example 1.
FIG. 2 is a scanning electron micrograph of the product obtained in example 1.
FIG. 3 is a graph comparing the effect of photocatalytic degradation of organic pollutant rhodamine B of the porous carbon nitride nanotube and bulk carbon nitride obtained in example 1.
Detailed Description
The method for preparing the porous carbon nitride nanotube according to the present invention is further described in detail by the following specific examples.
Comparative example 1 preparation of carbon nitride nanotubes by template method
The main method for preparing carbon nitride nanotubes is a template method, for example, chinese patent, publication No. CN107986247A (a method for preparing graphite phase carbon nitride nanotubes), in which alumina having a pore diameter in the range of 10 to 200nm is used as a template, the alumina template is placed above a precursor, the precursor is deposited in alumina pores through a low-temperature reaction stage (100 to 200 ℃), the precursor is pyrolyzed in the alumina pores through a high-temperature reaction, and the alumina template is removed by acid treatment to obtain the final carbon nitride nanotubes. In the preparation process, due to the introduction of the alumina template, the subsequent template removing process is complicated, and the template can not be completely removed completely, so that impurity ions are introduced into a final product. And the reaction is as long as 10 hours in only a low-temperature stage, which is also a non-negligible factor.
In addition, chinese patent publication No. CN105217584A (a method for preparing carbon nitride nanotubes) discloses hydrolyzing tetraethoxysilane in situ in an alkaline alcohol solution to obtain silica spheres, and using the silica spheres as a template to synthesize carbon nitride nanotubes. The method has complicated operation steps and is not easy to control. The hydrolysis process is harsh, and the size and the micro-morphology of the silicon dioxide spheres are directly influenced if the hydrolysis process is improperly controlled, so that the micro-morphology of the product is influenced. And in the subsequent template removing process, extremely toxic and corrosive hydrofluoric acid is used and is harmful to the environment, so that the large-scale practical application of the template is limited.
Comparative example 2 preparation of carbon nitride nanotubes by Freeze-drying method
Chinese patent, publication No. CN105883732A (a carbon nitride nanotube and its preparation method) first prepares urea and sodium bicarbonate into a homogeneous solution according to a certain proportion, and then freezes the solution at-20 to-80 ℃ for more than 24h to obtain a white block solid. And (2) quickly transferring the white massive solid into a true pore freeze drying chamber, obtaining white with the true pore degree not more than the upper value, freeze-drying the white massive solid for more than 20 hours at the freezing temperature not more than the freezing temperature to obtain a white massive object, calcining the white massive object in a nitrogen atmosphere furnace to obtain a light yellow powder sample, finally placing the light yellow powder sample in impurity-free water, standing for more than 12 hours, dialyzing for about 1-3 days, and drying to obtain the carbon nitride nanotube. Although the method can prepare the carbon nitride nanotube, the operation is complicated, and the experimental conditions are harsh, so that the requirement on equipment is high. In addition, the whole experiment period is too long, and the production efficiency is seriously influenced.
Comparative example 3 preparation of carbon nitride nanotubes by self-Assembly method
Chinese patent CN102616757A (a method for preparing self-assembled carbon nitride nanotubes and nanotubes prepared by the method), which comprises dissolving melamine in ethylene glycol to form a saturated solution, adding 0.12mol/L nitric acid solution to obtain a large amount of white precipitate, collecting the white precipitate, washing with ethanol, drying, and heating to obtain carbon nitride nanotubes. However, this method requires the use of various raw materials and organic reagents in the process of preparing the carbon nitride nanotubes, the precipitation rate of the white precipitate is difficult to control, and the solubility of melamine in ethylene glycol is low at normal temperature, which is not favorable for the mass production of carbon nitride nanotubes. In addition, the carbon nitride nanotubes obtained by the general molecular self-assembly method do not have a porous structure, and further improvement of the photocatalytic performance is limited.
Example 1
Putting 1g of melamine into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine at 160 ℃ for 4h, naturally cooling the melamine to room temperature to obtain a supramolecular precursor dispersed in the mixed solution, washing the supramolecular precursor mixed solution for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying the mixed solution at 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
And performing structural and morphological characterization on the obtained powder product by using an X-ray diffraction spectrum, a scanning electron microscope, a transmission electron microscope and the like, and confirming that the product is graphite-phase carbon nitride with porous tubular shape and is pure.
FIG. 1 is an X-ray diffraction pattern of the obtained product, in which a (100) diffraction peak appears at the left and right positions of FIG. 13.1, and corresponds to a structure of a heptazine ring unit in which carbon nitride is repeated in the same plane, which can also be understood as the distance between adjacent N holes in the repeating triazine unit. A distinct (002) diffraction peak appears at the 27.4-th separation position, which is a characteristic peak of interlayer stacking of aromatic substances, and proves that the product is carbon nitride with a graphite-like laminated structure.
FIG. 2 is a scanning electron micrograph of the resulting product, in which it can be seen that the synthesized product is substantially a porous carbon nitride nanotube, the length is 3-8 products, the diameter is mostly about 500nm, and the morphology is uniform.
FIG. 3 is a graph showing the degradation rate of the product porous carbon nitride nanotube and bulk-phase carbon nitride to rhodamine B, which is an organic pollutant, under the irradiation of visible light, and it can be clearly seen that the photocatalytic degradation efficiency of the porous carbon nitride nanotube to rhodamine B is obviously superior to that of bulk-phase carbon nitride.
Example 2
Putting 1g of melamine into 60mL of phosphoric acid solution with the concentration of 0.5mol/L, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine for 4h at 160 ℃, and naturally cooling the melamine to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 3
Putting 1g of melamine into 60mL of 1.0mol/L phosphoric acid solution, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine at 170 ℃ for 4h, and naturally cooling the melamine to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 520 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 4
Putting 1g of melamine into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine for 8h at 180 ℃, and naturally cooling the melamine to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 5
Putting 2g of melamine into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine for 4h at 160 ℃, and naturally cooling the melamine to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 520 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 6
Putting 3g of melamine into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the melamine, then transferring the melamine into a 100mL high-temperature reaction kettle, heating the melamine for 6h at 170 ℃, and naturally cooling the melamine to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 7
1g of dicyandiamide is put into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirred for 10min to be uniformly dispersed, then transferred into a 100mL high-temperature reaction kettle and heated at 160 ℃ for 4h, and naturally cooled to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 8
1g of thiourea is put into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirred for 10min to be uniformly dispersed, then transferred into a 100mL high-temperature reaction kettle and heated at 160 ℃ for 4h, and naturally cooled to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 9
Putting 1g of cyanamide into 60mL of phosphoric acid solution with the concentration of 0.5mol/L, stirring for 10min to uniformly disperse the cyanamide, then transferring the cyanamide into a 100mL high-temperature reaction kettle, heating the cyanamide at 180 ℃ for 4h, and naturally cooling the cyanamide to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 10
Putting 3g of cyanuric acid into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the cyanuric acid, then transferring the cyanuric acid into a 100mL high-temperature reaction kettle, heating the cyanuric acid at 160 ℃ for 6h, and naturally cooling the cyanuric acid to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 11
Putting 1g of melamine and 1g of cyanuric acid into 60mL of phosphoric acid solution with the concentration of 0.25mol/L, stirring for 10min to uniformly disperse the melamine and cyanuric acid, then transferring the melamine and cyanuric acid into a 100mL high-temperature reaction kettle, heating the melamine and cyanuric acid at 180 ℃ for 4h, and naturally cooling the melamine and cyanuric acid to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
Example 12
1g of dicyandiamide and 2g of thiourea are put into 60mL of phosphoric acid solution with the concentration of 1.0mol/L, stirred for 10min to be uniformly dispersed, then transferred into a 100mL high-temperature reaction kettle and heated at 160 ℃ for 8h, and naturally cooled to room temperature; performing suction filtration and collection to obtain a supramolecular precursor, washing the supramolecular precursor for multiple times by using deionized water until the pH value of the mixed solution at the last time is neutral, and then drying at the temperature of 60 ℃; and (3) putting the dried supermolecule precursor into an alumina crucible with a cover, placing the crucible at the center of a muffle furnace chamber, slowly heating to 550 ℃ at the heating speed of 3 ℃/min, preserving the temperature for 4 hours, and naturally cooling to room temperature to obtain the porous carbon nitride nanotube.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (1)
1. A preparation method of porous carbon nitride nanotubes is characterized in that the preparation process comprises the following steps: taking nitrogen-rich organic matters as raw materials, carrying out phosphoric acid acidification hydrothermal treatment to obtain a supramolecular precursor dispersed in a mixed solution, washing and drying the supramolecular precursor mixed solution, putting the supramolecular precursor mixed solution into an aluminum oxide crucible with a cover, then putting the crucible into the center of a muffle furnace chamber, and carrying out high-temperature treatment to obtain a porous carbon nitride nanotube;
the nitrogen-rich organic matter is one or more of melamine, dicyandiamide, thiourea, cyanamide and cyanuric acid;
the phosphoric acid acidification process is to add 1-3 g of nitrogen-rich organic powder into 60mL of phosphoric acid solution with the concentration of 0.25-1.0 mol/L and stir for 10min to obtain uniformly dispersed mixed liquid;
the hydrothermal treatment process comprises the steps of transferring the uniformly stirred mixed solution into a 100mL high-temperature reaction kettle, carrying out hydrothermal treatment for 4-8 h at 160-180 ℃, and then naturally cooling to room temperature to obtain a supramolecular precursor dispersed in the mixed solution;
the washing and drying process of the supramolecular precursor mixed solution comprises the steps of washing the supramolecular precursor mixed solution for multiple times by using deionized water until the p H value of the mixed solution after the last washing is neutral, and drying the mixed solution at the temperature of 60 ℃ to obtain the supramolecular precursor;
and the high-temperature treatment is to place the supramolecular precursor in a muffle furnace, heat the supramolecular precursor to 520-550 ℃ at a heating rate of 3 ℃/min, keep the temperature for 4h, naturally cool the supramolecular precursor to room temperature, and collect the obtained light yellow product to obtain the porous carbon nitride nanotube serving as the photocatalyst.
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