CN110639589B - Carbon nitride material with one-dimensional nano structure and preparation method and application thereof - Google Patents

Carbon nitride material with one-dimensional nano structure and preparation method and application thereof Download PDF

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CN110639589B
CN110639589B CN201910963092.6A CN201910963092A CN110639589B CN 110639589 B CN110639589 B CN 110639589B CN 201910963092 A CN201910963092 A CN 201910963092A CN 110639589 B CN110639589 B CN 110639589B
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tubular
nitrogen
carbon nitride
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左士祥
姚超
王灿
吴凤芹
刘文杰
李霞章
严向玉
毛辉麾
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Changzhou Nano Materials S&t Co ltd
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Abstract

The invention belongs to the field of preparation of nano functional materials, and particularly relates to a carbon nitride material with a one-dimensional nano structure, a preparation method and application thereof, wherein natural tubular clay is taken as a template, added into a closed container, and vacuumized until the vacuum degree is kept; then injecting ethanol dispersion liquid rich in carbon and nitrogen raw materials into the closed container to enable the surface and the inner diameter of the tubular clay mineral to be filled with the carbon and nitrogen raw materials, drying and calcining the tubular clay mineral, and removing the template to obtain the carbon nitride material with the core-shell nano structure; or filling the inner diameter of the tubular clay mineral with a raw material rich in carbon and nitrogen, cleaning to remove the raw material on the surface of the tubular clay mineral, and calcining to obtain the clay mineral with the inside diameter of g-C3N4And (3) removing the tubular clay template by using acid to obtain the carbon nitride material with the rod-like nano structure. Finally preparing one-dimensional nano g-C3N4The material shows excellent photocatalytic performance as a photocatalytic desulfurizer.

Description

Carbon nitride material with one-dimensional nano structure and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of nano functional materials, and particularly relates to a method for preparing a carbon nitride material with a one-dimensional nano structure by taking natural tubular silicate clay as a template.
Background
Graphite phase carbon nitride (g-C)3N4) Is a novel visible light response non-metal base photocatalytic material, and compared with the traditional metal oxide catalyst, g-C3N4Has the advantages of simple preparation process, no metal element, excellent thermal and chemical stability and the like, and is widely used in the field of catalysis. In general, g-C3N4The morphology of (A) has a great influence on the photocatalytic performance of the photocatalyst. In particular, one-dimensional nanostructured g-C3N4Is beneficial to photo-generated electrons in g-C3N4The axial movement in the nano-wire effectively promotes the separation of photo-generated electrons and holes, thereby improving the photo-response area and the photo-absorption rate, providing an effective path for the transmission of the photo-generated electrons to a target object, and being beneficial to the improvement of the photocatalytic performance.
At present, the preparation method and the structure of graphite phase carbon nitride are researched more, wherein g-C3N4The mesoporous structure, the hollow structure and the sheet structure are main research hotspots, such as: CN201811640311.9 a g-C3N4Preparation method of ultrathin nanosheet and CN201910141462.8 hollow tubular g-C3N4Photocatalyst, preparation method and application thereof. In the existing rod-like g-C3N4In the preparation method, the size of the rod-shaped carbon nitride is difficult to control to be in a nanometer level, the thickness of the rod-shaped carbon nitride is not uniform, and the rod-shaped carbon nitride is disordered in distribution, so that the application of the rod-shaped carbon nitride is seriously influenced. Preparation of core-shells g-C is not currently relevant3N4And report and application of preparing nano-rod-shaped carbon nitride by a template method.
g-C3N4The photocatalyst has wide application in the aspects of hydrogen production by photolysis of water, degradation of organic pollutants and the likeWide application prospect. But with respect to g-C3N4The application of photocatalysis in gasoline is less. In the preparation of the catalyst, the catalyst is required to be in g-C3N4The composite catalyst is obtained by doping metal or nonmetal active components, and then is used for photocatalyst degradation, so that the process is complex and the cost is high.
Therefore, how to prepare one-dimensional g-C with simple process and low cost3N4The material gasoline desulfurization photocatalysis becomes a research hotspot.
Disclosure of Invention
The invention provides a method for preparing g-C with a one-dimensional nano structure by taking natural tubular clay as a template3N4A method of making a material.
The first purpose is to provide a one-dimensional core-shell nano carbon nitride material: using natural tubular silicate clay as template, filling the surface and inner diameter of tubular clay mineral with raw material rich in carbon and nitrogen, drying, calcining to obtain tubular clay with g-C in outer surface and pipe diameter3N4And (3) removing the tubular clay template to obtain the carbon nitride material with the core-shell nano structure.
The second purpose is to provide carbon nitride with a one-dimensional rod-like structure: using natural tubular silicate clay as template, filling the inner diameter of tubular clay mineral with raw material rich in carbon and nitrogen, cleaning to remove raw material on the outer surface of tube, calcining to obtain clay with the tube diameter containing g-C3N4And (3) removing the tubular clay template by using acid to obtain the carbon nitride material with the rod-like nano structure.
In order to achieve the purpose, the method adopts the following specific preparation steps:
nanorod-like g-C3N4The preparation steps are as follows:
1. adding the tubular clay mineral into a closed container, vacuumizing the closed container to a vacuum degree of-0.1 to-0.05 MPa, and keeping the vacuum state of the system for 20 to 40 minutes; then injecting ethanol dispersion liquid rich in carbon and nitrogen raw materials into the closed container; finally, recovering the system to a standard atmospheric pressure state, maintaining the state for 30-60 minutes (at the moment, the pipeline is filled with the raw material rich in carbon and nitrogen), filtering and washing to remove the raw material containing carbon and nitrogen on the outer surface of the pipe (the pipeline is filled with the raw material rich in carbon and nitrogen), and then drying at the system temperature of 40-60 ℃ to obtain a tubular clay/raw material compound containing carbon and nitrogen;
further, the tubular clay mineral is one of halloysite or imogolite, and the inner pipe diameter is 5-20 nm;
the raw material rich in carbon and nitrogen is dicyandiamide or melamine;
the mass ratio of the raw material rich in carbon and nitrogen to the tubular clay mineral is 2-4: 1;
the ethanol dispersion liquid rich in carbon and nitrogen raw materials is 20-30% by weight. ,
2. the tubular clay/carbon and nitrogen containing raw material compound obtained in the step 1 is placed at the temperature of 450-600 ℃ for pyrolysis for 2-4 hours to obtain tubular clay/g-C3N4Composite material, then tubular clay/g-C3N4Adding the composite material into an acid solution, standing for 6-12 hours, filtering, washing until the pH value of filtrate is 6-7, and drying to obtain the g-C3N4And (4) nanorods.
Further, the acidic solution in the step 2 is one of hydrogen fluoride or ammonium bifluoride, and the mass percentage concentration is 10-20%.
g-C of core-shell nanostructures3N4The preparation method comprises the following steps:
1. adding the tubular clay mineral into a closed container, vacuumizing the closed container to a vacuum degree of-0.1 to-0.05 MPa, and keeping the vacuum state of the system for 20 to 40 minutes; then injecting ethanol dispersion liquid rich in carbon and nitrogen raw materials into the closed container; finally, recovering the system to a standard atmospheric pressure state and maintaining the state for 30-60 minutes, and drying the obtained dispersion liquid at the system temperature of 40-60 ℃ to obtain a tubular clay/carbon-nitrogen-containing raw material compound;
the tubular clay mineral in the step 1 is one of halloysite or imogolite, and the inner pipe diameter is 5-20 nm; the raw material rich in carbon and nitrogen is one of dicyandiamide or melamine; the mass ratio of the carbon-nitrogen-rich raw material to the tubular clay mineral is 2-4: 1; the ethanol dispersion liquid rich in carbon and nitrogen raw materials accounts for 20-30% by weight.
2. The tubular clay/carbon-nitrogen-containing raw material compound obtained in the step 1 is put into the temperature of 450-600 ℃ for pyrolysis for 2-4 hours to prepare tubular clay/g-C3N4Composite material, then tubular clay/g-C3N4Adding the composite material into an acid solution, standing for 6-12 hours, filtering, washing until the pH value of filtrate is 6-7, and drying to obtain the g-C with the core-shell structure3N4A material.
Further, the acidic solution in the step 2 is one of hydrogen fluoride or ammonium bifluoride, and the mass percentage concentration is 10-20%.
The invention has the beneficial effects that:
1. the invention firstly uses tubular clay as a template to respectively synthesize one-dimensional g-C with a rod-shaped structure and a core-shell structure3N4The material has the following specific principle: firstly, in the process of vacuumizing, air in the clay pipe is discharged and is in a negative pressure state; then, in the process of recovering the standard atmospheric pressure, the ethanol dispersion liquid rich in the carbon and nitrogen raw materials is pressed into the clay pipe due to the action of the pressure difference; finally, in the drying process, ethanol is heated to be rapidly volatilized, and raw materials rich in carbon and nitrogen can be attached to the inside and the outside of the tube respectively. On the one hand, under high temperature, raw materials rich in carbon and nitrogen in and out of the clay pipe can be pyrolyzed to form g-C3N4. Removing the tubular clay template to obtain the rod-shaped g-C with a core-shell structure3N4So that the material has high porosity, large specific surface area and high light trapping rate, and the traditional g-C is obviously improved3N4The photocatalytic performance of the material is improved by the material,
on the other hand, a simple rod-like g-C is also provided3N4The material is prepared through the steps of using tubular clay template, removing carbon and nitrogen rich material from the outside of the pipe, high temperature pyrolysis and removing tubular clay to obtain rod-shaped g-C3N4The material has a rod-like size in a nanometer level, has a large specific surface area and shows an excellent photocatalytic effect.
2. The invention has the advantages of cheap and easily obtained raw materials and simple synthesis process, and the rod-shaped g-C is obtained after the tubular clay template is removed3N4The core and the shell of the material form a gap (see figure 1), have a domain-limited catalytic effect and show excellent photocatalytic performance.
Drawings
FIG. 1 shows g-C of one-dimensional core-shell structure prepared by the present invention3N4Process scheme diagrams.
Detailed Description
Example 1
1. Adding 1.0 kg of halloysite into a closed container, vacuumizing the closed container to the vacuum degree of-0.1 MPa, and keeping the vacuum state of the system for 20 minutes; then, 10.0 kg of ethanol dispersion of melamine with the mass percentage of 20% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 30 minutes, filtration and washing are carried out until the filtrate is neutral so as to remove carbon and nitrogen containing raw materials on the outer surface of the tube, and then the mixture is dried under the condition that the system temperature is 40 ℃ so as to obtain the halloysite/melamine compound;
2. putting the halloysite/melamine compound obtained in the step 1 into a temperature condition of 450 ℃ for pyrolysis for 4 hours to obtain halloysite/g-C3N4Compounding the composite material, and adding halloysite/g-C3N4Adding the composite material into a hydrogen fluoride solution with the mass percentage concentration of 10%, statically soaking for 6 hours, filtering, washing until the pH value of filtrate is 6.0, and drying to obtain the one-dimensional nano rod-shaped g-C3N4A material.
Example 2
1. Adding 1.5 kg of imogolite into a closed container, vacuumizing the closed container until the vacuum degree is-0.05 MPa, and keeping the vacuum state of the system for 40 minutes; then, 20.0 kg of ethanol dispersion of dicyandiamide with the mass percentage of 30% is injected into the closed container; finally, recovering the system to a standard atmospheric pressure state and maintaining for 60 minutes, filtering and washing until the filtrate is neutral to remove carbon and nitrogen-containing raw materials on the outer surface of the tube, and then drying at the system temperature of 60 ℃ to obtain the imogolite/dicyandiamide compound;
2. subjecting the imogolite/dicyandiamide compound obtained in the step 1 to pyrolysis at the temperature of 600 ℃ for 2 hours to obtain imogolite/g-C3N4Compounding the raw materials, and adding imogolite per g-C3N4Adding the composite material into an ammonium bifluoride solution with the mass percentage concentration of 20%, statically soaking for 12 hours, filtering, washing until the pH value of filtrate is 7, and drying to obtain the g-C with the one-dimensional nanorod structure3N4A material.
Example 3
1. Adding 1.0 kg of imogolite into a closed container, vacuumizing the closed container until the vacuum degree is-0.05 MPa, and keeping the vacuum state of the system for 30 minutes; then 12.0 kg of 25% by mass of an ethanol dispersion of melamine was injected into the closed container; finally, recovering the system to a standard atmospheric pressure state and maintaining for 45 minutes, filtering and washing until filtrate is neutral to remove carbon and nitrogen-containing raw materials on the outer surface of the tube, and then drying at the system temperature of 50 ℃ to obtain the imogolite/melamine compound;
2. subjecting the imogolite/melamine compound obtained in the step 1 to pyrolysis at the temperature of 525 ℃ for 3 hours to obtain imogolite/g-C3N4Compounding the material, and then adding imogolite per g-C3N4Adding the composite material into 15 mass percent ammonium bifluoride solution, statically soaking for 9 hours, filtering, washing until the pH value of filtrate is 6.5, and drying to obtain the g-C with the one-dimensional nanorod structure3N4A material.
Example 4
1. Adding 1.0 kg of halloysite into a closed container, vacuumizing the closed container to-0.1 MPa, and keeping the vacuum state of the system for 35 minutes; then, 14.0 kg of an ethanol dispersion of dicyandiamide with the mass percentage of 25% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 50 minutes, filtration and washing are carried out until the filtrate is neutral so as to remove carbon and nitrogen containing raw materials on the outer surface of the tube, and then the mixture is dried under the condition that the system temperature is 55 ℃ so as to obtain the halloysite/dicyandiamide compound;
2. putting the halloysite/dicyandiamide compound obtained in the step 1 into a temperature of 550 ℃ for pyrolysis for 3.5 hours to obtain halloysite/g-C3N4Compounding the composite material, and adding halloysite/g-C3N4Adding the composite material into a hydrogen fluoride solution with the mass percentage concentration of 10%, statically soaking for 10 hours, filtering, washing until the pH value of filtrate is 6.0, and drying to obtain the g-C with the one-dimensional nanorod structure3N4A material.
Example 5
1. Adding 1.0 kg of halloysite into a closed container, vacuumizing the closed container to the vacuum degree of-0.1 MPa, and keeping the vacuum state of the system for 20 minutes; then, 10.0 kg of ethanol dispersion liquid of melamine with the mass percentage of 20 percent is injected into the closed container; finally, the system is restored to the state of standard atmospheric pressure and maintained for 30 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 40 ℃, so that the halloysite/melamine compound is obtained;
2. putting the halloysite/melamine compound obtained in the step 1 into a temperature condition of 450 ℃ for pyrolysis for 4 hours to obtain halloysite/g-C3N4Compounding the composite material, and adding halloysite/g-C3N4Adding the composite material into a hydrogen fluoride solution with the mass percentage concentration of 10%, statically soaking for 6 hours, filtering, washing until the pH value of filtrate is 6.0, and drying to obtain the g-C with the one-dimensional core-shell structure3N4A material.
Example 6
1. Adding 1.5 kg of imogolite into a closed container, vacuumizing the closed container until the vacuum degree is-0.05 MPa, and keeping the vacuum state of the system for 40 minutes; then 20.0 kg of dicyandiamide ethanol dispersion liquid with the mass percentage of 30% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 60 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 60 ℃, so that the imogolite/dicyandiamide compound is obtained;
2. subjecting the imogolite/dicyandiamide compound obtained in the step 1 to pyrolysis at the temperature of 600 ℃ for 2 hours to obtain imogolite/g-C3N4Compounding the raw materials, and adding imogolite per g-C3N4Adding the composite material into an ammonium bifluoride solution with the mass percentage concentration of 20%, statically soaking for 12 hours, filtering, washing until the pH value of the filtrate is 7, and drying to obtain the g-C with the one-dimensional core-shell structure3N4A material.
Example 7
1. Adding 1.0 kg of imogolite into a closed container, vacuumizing the closed container until the vacuum degree is-0.05 MPa, and keeping the vacuum state of the system for 30 minutes; then 12.0 kg of 25% by mass of an ethanol dispersion of melamine was injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 45 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 50 ℃, so that the imogolite/melamine compound is obtained;
2. subjecting the imogolite/melamine compound obtained in the step 1 to pyrolysis at the temperature of 525 ℃ for 3 hours to obtain imogolite/g-C3N4Compounding the raw materials, and adding imogolite per g-C3N4Adding the composite material into 15 mass percent ammonium bifluoride solution, statically soaking for 9 hours, filtering, washing until the pH value of filtrate is 6.5, and drying to obtain the g-C with the one-dimensional core-shell structure3N4A material.
Example 8
1. Adding 1.0 kg of halloysite into a closed container, vacuumizing the closed container to-0.1 MPa, and keeping the vacuum state of the system for 35 minutes; then, 14.0 kg of an ethanol dispersion of dicyandiamide with the mass percentage of 25% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 50 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 55 ℃, so that the halloysite/dicyandiamide compound is obtained;
2. putting the halloysite/dicyandiamide compound obtained in the step 1 into a temperature of 550 ℃ for pyrolysis for 3.5 hours to obtain halloysite/g-C3N4Compounding the composite material, and adding halloysite/g-C3N4The composite material is added with 10 percent of fluorine by mass percentageStatically soaking in hydrogen hydride solution for 10 hours, filtering, washing until the pH value of the filtrate is 6.0, and drying to obtain the g-C with the one-dimensional core-shell structure3N4A material.
Comparative example 1
In comparative example 1, the tubular clay template removal process of example 8 was omitted, and other process conditions were unchanged, and the specific operation steps were as follows:
1. adding 1.0 kg of halloysite into a closed container, vacuumizing the closed container to-0.1 MPa, and keeping the vacuum state of the system for 35 minutes; then, 14.0 kg of an ethanol dispersion of dicyandiamide with the mass percentage of 25% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 50 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 55 ℃, so that the halloysite/dicyandiamide compound is obtained;
2. the halloysite/dicyandiamide compound obtained in the step 1 is put at the temperature of 550 ℃ for pyrolysis for 3.5 hours to obtain halloysite/g-C3N4A composite material.
Comparative example 2
In comparative example 2, the hollow tubular halloysite in example 8 was replaced with a solid rod-like attapulgite, and other process conditions were unchanged, and the specific operation steps were as follows:
1. adding 1.0 kg of attapulgite into a closed container, vacuumizing the closed container to-0.1 MPa, and keeping the vacuum state of the system for 35 minutes; then, 14.0 kg of an ethanol dispersion of dicyandiamide with the mass percentage of 25% is injected into the closed container; finally, the system is restored to the standard atmospheric pressure state and maintained for 50 minutes, and the obtained dispersion liquid is directly dried under the condition that the system temperature is 55 ℃, so that the attapulgite/dicyandiamide compound is obtained;
2. the attapulgite/dicyandiamide compound obtained in the step 1 is put at the temperature of 550 ℃ for pyrolysis for 3.5 hours to prepare attapulgite/g-C3N4Compounding the composite material with attapulgite in a ratio of g to C3N4Adding the composite material into a hydrogen fluoride solution with the mass percentage concentration of 10%, statically soaking for 10 hours, filtering and washing until the mixture is completely soakedThe pH value of the filtrate is 6.0, and the g-C with the one-dimensional tubular structure is obtained after drying3N4A material.
Comparative example 3
In comparative example 3, the preparation of example 8 was carried out without using the vacuum pumping method, and other process conditions were not changed, and the specific operation steps were as follows:
1. adding 1.0 kg of halloysite into a closed container, and injecting 14.0 kg of an ethanol dispersion of dicyandiamide with the mass percentage of 25% into the closed container; stirring and mixing for 50 minutes, and directly drying the obtained dispersion liquid at the system temperature of 55 ℃ to obtain a halloysite/dicyandiamide compound;
2. putting the halloysite/dicyandiamide compound obtained in the step 1 into a temperature of 550 ℃ for pyrolysis for 3.5 hours to obtain halloysite/g-C3N4Compounding the composite material, and adding halloysite/g-C3N4Adding the composite material into a hydrogen fluoride solution with the mass percentage concentration of 10%, statically soaking for 10 hours, filtering, washing until the pH value of the filtrate is 6.0, and drying to obtain the one-dimensional g-C3N4A material.
Evaluation of photocatalytic desulfurization Performance
The materials obtained in the examples and the comparative examples are used as desulfurization catalysts for photocatalytic desulfurization, and the catalytic performance of the materials is comprehensively evaluated. The specific scheme is as follows:
preparing simulated gasoline: the raw materials are normal octane and benzothiophene, and the sulfur content is 236 ppm. The desulfurization experiment is normal temperature desulfurization, specifically, 0.5 g of desulfurization catalyst is put into a conical flask, 25 ml (17.5 g) of simulated gasoline with the sulfur content of 236ppm is added, and 4-5 drops of H are dropped2O2Stirring for 30-120 min under the irradiation of mercury lamp (300W). Adding 25 ml of N-N-Dimethylformamide (DMF), continuously stirring for 5 minutes, standing for layering, separating out an oil phase, measuring the sulfur content and calculating the desulfurization rate. The test uses an RPP-2000S type fluorescence sulfur determinator to determine the sulfur content in gasoline, and the results are shown in Table 1.
The desulfurization rate calculation method comprises the following steps: the desulfurization rate is (1-the sulfur content of the desulfurized gasoline/the sulfur content of the gasoline in the raw oil) multiplied by 100 percent
TABLE 1
Time Desulfurization rate of 30 minutes Desulfurization rate in 60 minutes Desulfurization rate of 90 minutes Desulfurization rate in 120 minutes
Example 1 23.6％ 45.9％ 68.4％ 79.6％
Example 2 21.7％ 48.2％ 70.3％ 78.3％
Example 3 22.1％ 47.7％ 70.5％ 80.7％
Example 4 23.5％ 48.4％ 71.1％ 80.8％
Example 5 27.6％ 51.8％ 72.7％ 83.3％
Example 6 25.7％ 50.6％ 72.4％ 84.7％
Example 7 26.1％ 52.9％ 73.2％ 85.2％
Example 8 28.5％ 57.7％ 78.6％ 86.3％
Comparative example 1 16.5％ 27.1％ 37.8％ 57.4％
Comparative example 2 20.3％ 34.9％ 47.5％ 65.8％
Comparative example 3 20.6％ 35.8％ 51.0％ 67.6％

Claims (4)

1. The application of the carbon nitride material with the one-dimensional nano structure as a photocatalyst in photocatalytic desulfurization is characterized in that: the carbon nitride material with the one-dimensional nano structure comprises the following specific preparation steps:
(1) adding tubular silicate clay into a closed container, vacuumizing the closed container until the vacuum degree is-0.1 to-0.05 MPa, and keeping the vacuum state of the system for 20 to 40 minutes;
(2) then injecting ethanol dispersion liquid rich in carbon and nitrogen raw materials into the closed container, and finally recovering the system to a standard atmospheric pressure state and maintaining for 30-60 minutes to obtain dispersion liquid;
(3) directly drying the dispersion liquid obtained in the step (2) at the temperature of 40-60 ℃ to obtain a tubular clay/carbon and nitrogen containing raw material compound;
(4) pyrolyzing the tubular clay/carbon-nitrogen-containing raw material compound in the step (3) at the high temperature of 450-600 ℃ for 2-4 hours to obtain tubular clay/g-C3N4Compounding the material, and then adding tubular clay/g-C3N4Adding the composite material into an acid solution, standing for 6-12 hours, filtering, washing and drying to obtain a carbon nitride material with a one-dimensional core-shell nano structure;
the photocatalytic desulfurization step comprises: adding carbon nitride material with one-dimensional core-shell nano structure into a container, adding gasoline, and dripping H2O2Stirring for 30-120 min under the irradiation of mercury lamp, adding N, N-dimethylformamide, stirring, standing for layering, and separating oil phase.
2. The use of the one-dimensional nanostructured carbon nitride material according to claim 1 as a photocatalyst in photocatalytic desulfurization, characterized in that: the tubular silicate clay is halloysite or imogolite, and the inner pipe diameter is 5-20 nm; the raw material rich in carbon and nitrogen is dicyandiamide or melamine; the ethanol dispersion liquid rich in the carbon and nitrogen raw material is 20-30% by weight.
3. The use of the one-dimensional nanostructured carbon nitride material according to claim 1 as a photocatalyst in photocatalytic desulfurization, characterized in that: the mass ratio of the carbon-nitrogen-rich raw material to the tubular silicate clay is 2-4: 1.
4. The use of the one-dimensional nanostructured carbon nitride material according to claim 1 as a photocatalyst in photocatalytic desulfurization, wherein: the acidic solution in the step (4) is one of a hydrogen fluoride solution or an ammonium bifluoride solution, and the mass percentage concentration is 10% -20%.
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