CN114618586A - Porous carbon nitride ultrathin film material, preparation and application thereof - Google Patents

Porous carbon nitride ultrathin film material, preparation and application thereof Download PDF

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CN114618586A
CN114618586A CN202210336526.1A CN202210336526A CN114618586A CN 114618586 A CN114618586 A CN 114618586A CN 202210336526 A CN202210336526 A CN 202210336526A CN 114618586 A CN114618586 A CN 114618586A
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carbon nitride
porous carbon
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韩庆
吴崇备
余冠行
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Beijing Institute of Technology BIT
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Abstract

The invention relates to a porous carbon nitride ultrathin membrane material, and preparation and application thereof, and belongs to the technical field of carbon nitride materials. The membrane material is prepared by using CCl containing carbon nitride and adipoyl chloride4The solution and NaOH aqueous solution containing hexamethylene diamine are formed into a film on a latticed supporting substrate, the film can be formed on one side of the latticed supporting substrate, the film can be formed on the two sides of the latticed supporting substrate, and a single layer or multiple layers can be formed on the surface of the latticed supporting substrate. The membrane material has a porous fold structure, is good in stability, can be quickly recovered after catalytic reaction, and is convenient to reuse; the preparation method is simple and easy to operate, and technological parameters can be regulated and controlledThe photocatalytic performance of the membrane material has good application prospect in the aspect of photocatalytic hydrogen production.

Description

Porous carbon nitride ultrathin film material, preparation and application thereof
Technical Field
The invention relates to a porous carbon nitride ultrathin membrane material, and preparation and application thereof, and belongs to the technical field of carbon nitride materials.
Background
With the development of human society science and technology, the energy problem is more and more concerned by people. Traditional fossil energy is energy mainly developed and utilized by people at present, but the reserves of the energy are limited, and the energy is difficult to regenerate after being developed and utilized; meanwhile, the use of these energy sources is accompanied by the generation of waste materials having an influence on the environment, resulting in problems of environmental pollution, greenhouse effect, and the like. Hydrogen energy has been studied and utilized as an environmentally friendly and recyclable green energy source. However, the conventional electrolysis method has high energy consumption, and the value of hydrogen generation cannot offset the energy consumption, so that the conventional electrolysis method is not an economical and practical method. Therefore, the use of "inexhaustible" sunlight to decompose water to produce hydrogen is an effective and environmentally friendly approach.
The carbon nitride material is used as a two-dimensional material without metal components, has low cost, excellent chemical stability, proper oxidation-reduction energy band position and good adjustability of an electronic structure, and is widely applied to the fields of photocatalytic water decomposition hydrogen production, solar energy conversion, pollutant degradation and the like. However, most of the research on hydrogen production by photocatalytic water decomposition is carried out based on carbon nitride powder materials, and the system has the problems of small experimental scale, difficulty in recycling after reaction and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a porous carbon nitride ultrathin membrane material, and preparation and application thereof.
The purpose of the invention is realized by the following technical scheme.
A porous carbon nitride ultrathin film material is prepared from CCl containing carbon nitride and adipoyl chloride4The solution and NaOH aqueous solution containing hexamethylene diamine are formed into a film on a latticed supporting substrate.
Preferably, CCl containing carbon nitride and adipoyl chloride4The molar ratio of adipoyl chloride in the solution to hexamethylenediamine in the hexamethylenediamine-containing NaOH aqueous solution is (0.5-6) to 1, more preferably (0.8-1.5): 1.
preferably, CCl containing carbon nitride and adipoyl chloride4The concentration of carbon nitride in the solution is 2 mg/mL-13 mg/mL, more preferably 5 mg/mL-10 mg/mL.
Preferably, CCl containing carbon nitride and adipoyl chloride4In solution, adipoyl chloride and CCl4The volume ratio of (0.2-3) to (1); in the NaOH aqueous solution containing hexamethylenediamine, the concentration of hexamethylenediamine is 0.02-0.63 mg/mL, and the concentration of NaOH is 3mg/mL～20mg/mL。
Preferably, the mesh number of the latticed support substrate is 10-40 meshes.
The film material may be formed on one surface of the lattice-shaped support substrate or on both surfaces of the lattice-shaped support substrate, and a single-layer or multi-layer (including two or more layers, the same applies hereinafter) film may be formed on the surface of the lattice-shaped support substrate, and preferably a single-layer film is formed on each surface of the lattice-shaped support substrate.
The preparation method of the porous carbon nitride ultrathin film material comprises the following steps:
adding carbon nitride powder and adipoyl chloride liquid into CCl4Uniformly mixing the solution A and the liquid A to obtain a solution A;
dissolving a hexamethylene diamine solid in a NaOH aqueous solution, and uniformly mixing to obtain a solution B;
dipping one surface of the latticed support substrate with the solution B, then dipping the surface with the solution A to form a layer of membranous product on the surface, and drying at the temperature of not higher than 80 ℃ to form a single-layer porous carbon nitride ultrathin membrane material on one surface of the latticed support substrate;
or according to the sequence of dipping the solution B and then dipping the solution A, alternately dipping the solution B and the solution A on one surface of the latticed support substrate in sequence to form a multi-layer membranous product on the surface, wherein after the solution B and the solution A are dipped once, the multi-layer membranous product is dried at the temperature of not higher than 80 ℃ (namely the multi-layer porous carbon nitride ultrathin membrane material is formed on one surface of the latticed support substrate;
or dipping one surface of the latticed support substrate with the solution B and the solution A in sequence to form a film-shaped product on one surface, and then drying at the temperature of not higher than 80 ℃; sequentially dipping the other surface of the latticed support substrate with the solution B and the solution A in sequence to form a layer of membranous product on the other surface, and drying at the temperature of not higher than 80 ℃, namely forming single-layer porous carbon nitride ultrathin membrane materials on the two surfaces of the latticed support substrate respectively;
or according to the sequence of dipping the solution B first and then dipping the solution A, dipping the solution B and the solution A alternately on one surface of the latticed support substrate in sequence, and forming a multi-layer film-shaped product on one surface; and then alternately dipping the solution B and the solution A on the other surface of the latticed support substrate in sequence to form a multilayer film-shaped product on the other surface, wherein after the solution B and the solution A are dipped once, the multilayer film-shaped product is dried at the temperature of not higher than 80 ℃, namely, a multilayer porous carbon nitride ultrathin film material is respectively formed on the two surfaces of the latticed support substrate.
The porous carbon nitride ultrathin membrane material disclosed by the invention is applied to the aspect of photocatalytic hydrogen production. Wherein, when the photocatalyst is used for photocatalytic hydrogen production, the surface of the membrane material is preferably loaded with 0.025mg/cm2～0.05mg/cm2And (3) Pt of (1).
Has the advantages that:
(1) the membrane material is formed in a liquid polymerization mode, mainly through directly forming a membrane through amino and halogen groups at the tail end of a precursor, and is free from doping of other impurities, so that an ultrathin membrane is easily formed; the membrane material has a porous fold structure, is good in stability, can be quickly recovered after catalytic reaction, is convenient to reuse, and has a good application prospect in the aspect of photocatalytic hydrogen production.
(2) The carbon nitride in the film material is a main active substance, the photocatalytic performance is gradually increased along with the increase of the introduced mass of the carbon nitride, but the photocatalytic performance is reduced due to the fact that the introduced carbon nitride is too large, mainly because the excessive carbon nitride can cause the agglomeration of the active substance and is not beneficial to the photocatalytic reaction. Therefore, the performance of photocatalytic hydrogen production can be optimized by regulating and controlling the content of carbon nitride in the membrane material.
(3) In the preparation of the membrane material, the proportion of the hexamethylene diamine and the adipoyl chloride is a main factor influencing the photocatalytic hydrogen production, and the proportion influences the quality of carbon nitride loaded on the membrane material so as to influence the photocatalytic performance, so that the proportion of the hexamethylene diamine and the adipoyl chloride needs to be reasonably regulated and controlled to obtain good photocatalytic performance.
(4) In the preparation of the membrane material, when the mesh number of the latticed supporting substrate is too large, carbon nitride active substances are agglomerated due to the surface tension of liquid, so that the number of active sites in the photocatalysis process is influenced, and the performance of preparing hydrogen by photocatalysis is reduced. Therefore, the performance of photocatalytic hydrogen production can be optimized by selecting proper mesh number in the preparation process of the membrane material.
(5) The volume of hydrogen generated by photocatalysis of the double-sided membrane material prepared by the invention is slightly increased but not multiplied compared with that of a single-layer membrane material, which shows that the number of the membrane surfaces is not an important factor influencing the generation of hydrogen by photocatalysis. The main reason is that the illumination position is the front side of the membrane material, the front side membrane is the main active surface for generating hydrogen through photocatalysis, and light reaches the back side membrane after passing through the front side membrane, so that the penetrating power of the light is weakened, the light absorption capacity of the back side membrane is reduced, and the direct reason is that the back side membrane cannot rapidly generate hydrogen.
(6) The preparation method of the membrane material is simple and rapid, can regulate and control the size of the membrane material by controlling the size of the latticed support substrate, and is a method which can be widely applied and prepared in a large scale.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the porous carbon nitride ultrathin film material prepared in example 1.
FIG. 2 is a schematic diagram of the porous carbon nitride ultrathin film material prepared in example 1.
FIG. 3 is a scanning electron microscope image of the porous carbon nitride ultrathin film material prepared in example 1 after being applied with photocatalysis.
FIG. 4 is a nuclear magnetic spectrum comparison chart of the carbon nitride powder, the solution A and the single layer film material 1 in example 1; wherein a is carbon nitride powder, b is solution A, and c is single-layer film material 1.
FIG. 5 is a comparison graph of photocatalytic hydrogen production performance of the single-layer film materials prepared in examples 1 to 4 and comparative examples 1 to 2.
FIG. 6 is a histogram comparing photocatalytic hydrogen production performance of the single-layer film materials prepared in examples 1 to 4 and comparative examples 1 to 2.
Fig. 7 is a graph comparing the photocatalytic hydrogen production performance of the single layer membrane material 4 prepared in example 4 and the three layer membrane material prepared in example 5.
Fig. 8 is a graph comparing the photocatalytic hydrogen production performance of the single-layer membrane material 1 prepared in example 1 and the double-sided membrane material 1 prepared in example 6.
Fig. 9 is a scanning electron microscope photograph of a single-layered thin film material containing no carbon nitride prepared in comparative example 2.
Fig. 10 is a comparison graph of photocatalytic hydrogen production performance of the single-layer membrane materials prepared in example 1 and examples 7 to 8.
Fig. 11 is a comparative graph of photocatalytic hydrogen production performance of the double-sided film materials prepared in examples 6 and 9 to 11.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples:
scanning Electron Microscope (SEM): the Japanese Electron JSM-7001F;
a photocatalytic detection system: a 6A photocatalytic system of Peking Pofely photocatalysis;
light source model: beijing Pofilly 300W Xe lamp;
gas Chromatograph (GC): shanghai Tianmei GC-7900;
solid nuclear magnetic spectrometer: JNM-ECZ600R solid-state NMR spectrometer.
Example 1
150mg of carbon nitride powder and 5mL of adipoyl chloride liquid were added to 15mL of CCl4Uniformly mixing the solution A and the solution B to obtain a solution A;
dissolving 2.5mg of hexamethylenediamine solid in 20mL of NaOH aqueous solution with the concentration of 10mg/mL, and uniformly mixing to obtain a solution B;
taking a 40-mesh titanium net as a supporting substrate, firstly slightly dipping one surface of the titanium net in the solution B to cover one surface of the titanium net with the solution B, then dipping the surface of the titanium net dipped in the solution B in the solution A, then taking out the solution A, forming a film-shaped product on the surface of the titanium net, and drying the film-shaped product at 50 ℃ to form a single-layer porous carbon nitride ultrathin film material, namely a single-layer film material 1.
The prepared single-layer membrane material 1 is subjected to morphology characterization, and as can be seen from fig. 1, the carbon nitride material is uniformly loaded on the surface of the membrane, and presents two-dimensional layered morphology arrangement without obvious agglomeration. In addition, as can be seen from FIG. 2, the prepared macroscopic carbon nitride film material has a side length of 30cm and an area of 900cm2The surface is uniform, and no obvious wrinkles or breakage are caused.
The prepared single-layer membrane material 1 is subjected to photocatalytic application and then subjected to morphology characterization, and as can be seen from fig. 3, the recovered carbon nitride membrane material also presents a two-dimensional layered arrangement form, and does not drop obviously, which indicates that the carbon nitride membrane material has stable support.
The nuclear magnetic spectrum test is performed on the carbon nitride powder, the solution a and the single-layer film material 1, and it can be seen from the nuclear magnetic spectrum in fig. 4 that: the line a in the left nuclear magnetic spectrum is the C spectrum of the pure carbon nitride material, and the chemical shift of carbon element in heptazine structural unit is obvious in 150 ppm-175 ppm; the line b in the left nuclear magnetic spectrum is C spectrum solid nuclear magnetism of a reaction intermediate (namely solution A) of adipoyl chloride and carbon nitride, the right structural formula b shows that the amino at the end position of the carbon nitride and the halogen group of the adipoyl chloride are subjected to polymerization reaction, and the chemical shift of carbon element in a heptazine unit at the position of 150 ppm-175 ppm can be obviously seen in the line b, which indicates that the carbon nitride structure cannot be damaged due to the polymerization reaction; the line c in the left nuclear magnetic spectrum is the carbon spectrum solid nuclear magnetic of the carbon nitride film material, and the chemical shift of carbon element in heptazine unit at the position of 150 ppm-175 ppm can be clearly observed, which indicates that the carbon nitride film material not only maintains the framework structure of carbon nitride, but also successfully polymerizes with the film material.
Example 2
On the basis of the embodiment 1, only the mass of the carbon nitride powder in the embodiment 1 is changed from 150mg to 200mg, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 2, is formed on one surface of the titanium mesh.
Example 3
On the basis of the embodiment 1, only the mass of the carbon nitride powder in the embodiment 1 is modified from 150mg to 100mg, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 3, is formed on one surface of the titanium mesh.
Example 4
On the basis of the embodiment 1, only the mass of the carbon nitride powder in the embodiment 1 is modified from 150mg to 50mg, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 4, is formed on one surface of the titanium mesh.
Example 5
By adopting the solution A and the solution B prepared in the embodiment 4, according to the sequence of dipping the solution B and then dipping the solution A, one surface of a 40-mesh titanium net is alternately dipped with the solution B and the solution A in sequence, the dipping times of the solution B and the solution A are 3 times, wherein after the solution B and the solution A are dipped once, the solution B and the solution A are dried at 50 ℃, and correspondingly, three layers of porous carbon nitride ultrathin film materials, namely three layers of film materials, are formed on one surface of the titanium net.
Example 6
By adopting the solution A and the solution B prepared in the embodiment 1, firstly, one surface of a 40-mesh titanium net is sequentially dipped with the solution B and the solution A in sequence and dried at 50 ℃, and then a film-shaped product is formed on one surface; and sequentially dipping the other surface of the titanium net in the solution B and the solution A in sequence, and drying at 50 ℃, so that a film-shaped product is formed on the other surface, namely, a single-layer porous carbon nitride ultrathin film material, namely a double-sided film material 1 is formed on the two surfaces of the titanium net respectively.
Example 7
On the basis of the embodiment 1, only the mass of the adipoyl chloride in the embodiment 1 is modified from 5mL to 10mL, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 5, is formed on one surface of the titanium net.
Example 8
On the basis of the embodiment 1, only the mass of the adipoyl chloride in the embodiment 1 is changed from 5mL to 2.5mL, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 6, is formed on one surface of the titanium net.
Example 9
On the basis of the embodiment 6, only the titanium mesh with 40 meshes in the embodiment 6 is modified into the titanium mesh with 30 meshes, other steps and conditions are not changed, and correspondingly, single-layer porous carbon nitride ultrathin film materials, namely the double-sided film material 2, are respectively formed on two surfaces of the titanium mesh.
Example 10
On the basis of the embodiment 6, only the titanium mesh with 40 meshes in the embodiment 6 is modified into the titanium mesh with 20 meshes, other steps and conditions are not changed, and correspondingly, single-layer porous carbon nitride ultrathin film materials, namely, the double-sided film material 3, are respectively formed on two surfaces of the titanium mesh.
Example 11
On the basis of the embodiment 6, only the titanium mesh with 40 meshes in the embodiment 6 is modified into the titanium mesh with 10 meshes, other steps and conditions are not changed, and correspondingly, single-layer porous carbon nitride ultrathin film materials, namely the double-sided film material 4, are respectively formed on two surfaces of the titanium mesh.
Comparative example 1
On the basis of the embodiment 1, only the mass of the carbon nitride powder in the embodiment 1 is modified from 150mg to 10mg, other steps and conditions are not changed, and correspondingly, a single-layer porous carbon nitride ultrathin film material, which is abbreviated as a single-layer film material 7, is formed on one surface of the titanium mesh.
Comparative example 2
On the basis of the embodiment 1, only the mass of the carbon nitride powder in the embodiment 1 is modified from 150mg to 0mg, and other steps and conditions are not changed, accordingly, a single-layer film material, which is abbreviated as a single-layer film material 8, is formed on one surface of the titanium mesh.
The prepared single-layer membrane material 8 is subjected to morphology characterization, and as can be seen from fig. 9, the membrane material surface without the carbon nitride load has no obvious two-dimensional layered structure and wrinkles, and presents a smooth surface structure except for a part of micro pore structures.
Respectively placing the titanium nets containing the single-layer film materials prepared in the examples 1-4 and the comparative examples 1-2 in a reactor of a photocatalytic detection system, and adding 90mL of deionized water and 10mL of methanol to ensure that the single-layer film materials are fully contacted with liquid; chloroplatinic acid was added to the reactor with stirring to provide a Pt loading of 0.025mg/cm on the monolayer film material2And then the reactor is vacuumized to 2.0kPa and is continuously stirred (a titanium net is supported at the middle lower part of the reactor, the surface of the titanium net is parallel to the bottom surface of the reactor but is not contacted with the bottom surface of the reactor), a gas chromatograph is started to perform online test under illumination, and the automatic sampling test is performed every 1h, and the test results are shown in fig. 5 and 6. From the test results of fig. 5 and fig. 6, it can be seen that the volume of hydrogen generated by photocatalysis gradually increases with the increasing load mass of carbon nitride, the maximum value of hydrogen generated by photocatalysis (maximum value of 1.067mL/h) is reached when the load mass of carbon nitride reaches 150mg, and the volume of hydrogen generated by photocatalysis begins to decrease with the increasing load mass of carbon nitride to 200mg, and a significant volcano diagram trend is presented.
According to the conditions for testing photocatalytic hydrogen production of the single-layer film material, the photocatalytic hydrogen production performance of the three-layer film material prepared in example 5 is tested, and as can be seen from the test result in fig. 7, the volume of the photocatalytic hydrogen production of the single-layer film material 4 and the three-layer film material has no linear relationship with the number of film layers, which indicates that the number of film layers is not an important factor influencing the photocatalytic hydrogen production.
According to the conditions for testing the photocatalytic hydrogen production of the single-layer membrane material, the photocatalytic hydrogen production performance of the double-sided membrane material 1 prepared in example 6 is tested, and as can be seen from the test result in fig. 8, the volume of hydrogen produced by photocatalysis of the double-sided membrane material 1 is slightly increased but not increased by times compared with that of the single-layer membrane material 1, which indicates that the number of the membrane surfaces is not an important factor influencing the photocatalytic hydrogen production.
According to the conditions for testing photocatalytic hydrogen production of the single-layer membrane material, the photocatalytic hydrogen production performance tests are respectively carried out on the single-layer membrane material 5 and the single-layer membrane material 6 prepared in the embodiments 7 to 8, and as can be seen from the test result of fig. 10, the ratio of hexamethylene diamine to adipoyl chloride is a main factor influencing photocatalytic hydrogen production. When the ratio of hexamethylene diamine to adipoyl chloride is 1:1, the performance of photocatalytic hydrogen production reaches the maximum, and the quality of carbon nitride supported by a membrane material is affected by too high or too low ratio, so that the photocatalytic performance is reduced.
According to the conditions for testing the photocatalytic hydrogen production of the single-layer film material, the photocatalytic hydrogen production performance test is respectively carried out on the double-sided film materials 2 to 4 prepared in the embodiments 9 to 11, and as can be seen from the test result of fig. 11, the mesh number of the supporting net is a main factor influencing the photocatalytic hydrogen production, and when the mesh number is too large, the carbon nitride active substances are agglomerated due to the surface tension of the liquid, so that the number of active sites in the photocatalytic process is influenced, and the performance of the photocatalytic hydrogen production is reduced.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A porous carbon nitride ultrathin film material is characterized in that: the membrane material is prepared by using CCl containing carbon nitride and adipoyl chloride4The solution and NaOH aqueous solution containing hexamethylene diamine are formed into a film on a latticed supporting substrate.
2. The porous carbon nitride ultrathin film material of claim 1, characterized in that: CCl containing carbon nitride and adipoyl chloride4The molar ratio of adipoyl chloride in the solution to hexamethylenediamine in the hexamethylenediamine-containing NaOH aqueous solution is (0.5-6): 1.
3. The porous carbon nitride ultrathin film material of claim 1, characterized in that: CCl containing carbon nitride and adipoyl chloride4The concentration of carbon nitride in the solution was 2mg/mL～13mg/mL。
4. The porous carbon nitride ultrathin film material of claim 1, characterized in that: the mesh number of the latticed supporting substrate is 10-40 meshes.
5. The porous carbon nitride ultrathin film material of claim 1, characterized in that: CCl containing carbon nitride and adipoyl chloride4The molar ratio of the adipoyl chloride in the solution to the hexamethylene diamine in the NaOH aqueous solution containing the hexamethylene diamine is (0.5-6) to 1; CCl containing carbon nitride and adipoyl chloride4In the solution, the concentration of the carbon nitride is 2 mg/mL-13 mg/mL; the mesh number of the latticed supporting substrate is 10-40 meshes.
6. The porous carbon nitride ultrathin film material of claim 1, characterized in that: CCl containing carbon nitride and adipoyl chloride4The molar ratio of the adipoyl chloride in the solution to the hexamethylenediamine in the hexamethylenediamine-containing NaOH aqueous solution is (0.8-1.5): 1; CCl containing carbon nitride and adipoyl chloride4In the solution, the concentration of the carbon nitride is 5 mg/mL-10 mg/mL; the mesh number of the latticed supporting substrate is 10-40 meshes.
7. The porous carbon nitride ultrathin film material according to any one of claims 1 to 6, characterized in that: CCl containing carbon nitride and adipoyl chloride4In solution, adipoyl chloride with CCl4The volume ratio of (0.2-3) to (1); the concentration of hexamethylenediamine in the aqueous solution of NaOH containing hexamethylenediamine is 0.02-0.63 mg/mL, and the concentration of NaOH is 3-20 mg/mL.
8. The porous carbon nitride ultrathin film material according to any one of claims 1 to 6, characterized in that: the membrane material forms a membrane on both sides of a latticed support substrate and forms a single-layer membrane on each surface.
9. A method for preparing a porous carbon nitride ultrathin film material as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps of,
adding carbon nitride powder and adipoyl chloride liquid into CCl4Uniformly mixing the solution A and the solution B to obtain a solution A;
dissolving a hexamethylene diamine solid in a NaOH aqueous solution, and uniformly mixing to obtain a solution B;
dipping one surface of the latticed support substrate with the solution B, then dipping the surface with the solution A to form a layer of membranous product on the surface, and drying at the temperature of not higher than 80 ℃ to form a single-layer porous carbon nitride ultrathin membrane material on one surface of the latticed support substrate;
or according to the sequence of dipping the solution B and then dipping the solution A, alternately dipping the solution B and the solution A on one surface of the latticed support substrate in sequence to form a multi-layer membranous product on the surface, wherein after the solution B and the solution A are dipped once, the multi-layer membranous product is dried at the temperature of not higher than 80 ℃, namely a multi-layer porous carbon nitride ultrathin membrane material is formed on one surface of the latticed support substrate;
or dipping one surface of the latticed support substrate with the solution B and the solution A in sequence to form a film-shaped product on one surface, and then drying at the temperature of not higher than 80 ℃; sequentially dipping the solution B and the solution A on the other surface of the latticed support substrate in sequence to form a layer of membranous product on the other surface, and drying at the temperature of not higher than 80 ℃, namely forming a single-layer porous carbon nitride ultrathin membrane material on the two surfaces of the latticed support substrate respectively;
or according to the sequence of dipping the solution B first and then dipping the solution A, dipping the solution B and the solution A alternately on one surface of the latticed support substrate in sequence, and forming a multi-layer film-shaped product on one surface; and then alternately dipping the solution B and the solution A on the other surface of the latticed support substrate in sequence to form a multilayer film-shaped product on the other surface, wherein after the solution B and the solution A are dipped once, the multilayer film-shaped product is dried at the temperature of not higher than 80 ℃, namely, a multilayer porous carbon nitride ultrathin film material is respectively formed on the two surfaces of the latticed support substrate.
10. Use of the porous carbon nitride ultrathin membrane material as claimed in any one of claims 1 to 6 in the aspect of photocatalytic hydrogen production.
CN202210336526.1A 2022-03-31 2022-03-31 Porous carbon nitride ultrathin film material, preparation and application thereof Pending CN114618586A (en)

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