CN112499603A - Novel graphite-like phase carbon nitride photocatalytic material and preparation method and application thereof - Google Patents

Novel graphite-like phase carbon nitride photocatalytic material and preparation method and application thereof Download PDF

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CN112499603A
CN112499603A CN201910872397.6A CN201910872397A CN112499603A CN 112499603 A CN112499603 A CN 112499603A CN 201910872397 A CN201910872397 A CN 201910872397A CN 112499603 A CN112499603 A CN 112499603A
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carbon nitride
graphite
photocatalytic material
phase carbon
temperature
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杨国强
王艳龙
赵智胜
张洋
罗坤
李宝忠
史开元
张李
苏磊
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Institute of Chemistry CAS
Yanshan University
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Yanshan University
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Abstract

The invention provides a graphite-like phase carbon nitride photocatalytic material and a preparation method and application thereof, wherein the method comprises the following steps: conventional carbon nitride (g-C)3N4) And keeping the reaction solution at high temperature and high pressure for a certain time to obtain the graphite-like phase carbon nitride photocatalytic material. The light absorption edge of the prepared novel graphite-like phase carbon nitride photocatalytic material is prolonged to 650 nanometers, and the novel graphite-like phase carbon nitride photocatalytic material has high photocatalytic hydrogen production activity. The conventional carbon nitride material is first treated by a cubic press at a high temperature and a high pressure within an industrially achievable rangeThe production process is simple and easy to control, and is suitable for large-scale production. And the high-voltage field and the photocatalysis field are connected, so that a foundation is laid for the mutual promotion and coordinated development of two disciplines, and a certain demonstration effect is played.

Description

Novel graphite-like phase carbon nitride photocatalytic material and preparation method and application thereof
Technical Field
The invention belongs to the field of high-pressure material synthesis and photocatalytic materials, and particularly relates to a novel graphite-like phase carbon nitride photocatalytic material and a preparation method and application thereof.
Background
With the rapid development of society, the energy consumed by human beings is increasing day by day, the non-renewable fossil energy in nature is gradually exhausted, and the requirement of the human beings on clean renewable energy is also increasing. Clean renewable energy sources, represented by solar energy, are being gradually applied to various fields of social life. However, direct use of sunlight causes a decrease in efficiency and an increase in cost due to its disadvantages such as dispersibility, low density, and instability. Therefore, the conversion of solar energy into hydrogen energy with high energy density, cleanness, no pollution and convenient storage and transportation is an urgent need. In the research of hydrogen energy, the method for preparing hydrogen by decomposing water by using photocatalyst is the most prominent, and the method has low cost and equipmentThe device is simple and environment-friendly, and the like, and is concerned about. Traditional photocatalysts generally contain metals, even noble metals, and most of the photocatalysts only respond in an ultraviolet region, so that the traditional photocatalysts are not suitable for large-scale use. In recent years, non-metallic graphite phase carbon nitride (g-C)3N4) The photocatalyst is easily prepared, has good stability, can be used in a visible light area and the like, quickly becomes a focus of much attention of researchers, and has wide application in the aspects of hydrogen preparation by photolysis of water, photodegradation of organic pollutants, reduction of carbon dioxide and the like. However, the carbon nitride material prepared by the traditional method still has the problems of absorption only in the short wave of the visible light region, easy recombination of electron holes, poor conductivity and the like, and the development and application of the carbon nitride material are greatly limited.
Around the above-mentioned technical problems, researchers have taken many approaches to improve the hydrogen-generating capability of photocatalytic materials. For example, increasing the specific surface area, decreasing the band gap, increasing the charge mobility, decreasing the charge carrier recombination rate, etc.
Disclosure of Invention
The invention aims to provide a novel graphite-like phase carbon nitride photocatalytic material and a preparation method and application thereof. Compared with the conventional carbon nitride material, the obtained novel graphite-like phase carbon nitride material has the advantages that the range of absorption wavelength is enlarged, the electron-hole separation efficiency is enhanced, the conductivity is increased, the utilization rate of sunlight is improved, the efficient hydrogen production performance by photocatalytic water decomposition is shown, the hydrogen production by photocatalytic water decomposition in a long wave range can be realized, and the hydrogen production efficiency is obviously improved.
High pressure is an important extreme condition and, together with temperature and composition, constitutes three completely independent physical parameters in the study of material systems. Generally, under high pressure conditions, the material changes its optical, thermal, electrical, etc. properties. The inventor of the application researches and discovers that high voltage generally changes the band gap and the conductivity of a semiconductor, and brings new possibility for developing new materials. Currently, in the preparation and modification research of photocatalyst materials, most researchers mainly focus on the important role of temperature in the modification of photocatalyst materials. The invention firstly applies high pressure means to modify the photocatalytic material represented by carbon nitride under high temperature and high pressure conditions to synthesize a new material with high photocatalytic hydrogen production performance. The graphite-like phase carbon nitride photocatalytic material has excellent catalytic effect, and provides a new idea and method for synthesis and development of other photocatalysts.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a graphite-like phase carbon nitride photocatalytic material comprises the following steps:
conventional carbon nitride (g-C)3N4) And keeping the reaction solution at high temperature and high pressure for a certain time to obtain the graphite-like phase carbon nitride photocatalytic material.
According to the present invention, the conventional carbon nitride is conventional carbon nitride (g-C) known in the art3N4) Which has a graphite phase structure, more precisely, a Melon structure, and the conventional carbon nitride has an interlayer spacing of 0.326 nm, a unit cell parameter gamma of 90 °, and a layer stacking arrangement of the Melon structure, which may be prepared by at least one of a solid phase reaction method, a solvothermal method, a chemical deposition method, and a thermal polymerization method.
According to the invention, the conventional carbon nitride is prepared by melamine through a thermal polymerization method, and then the conventional carbon nitride is treated at high temperature and high pressure to obtain the graphite-like phase carbon nitride photocatalytic material.
According to the invention, the method comprises the following steps:
(1) carrying out thermal polymerization reaction in a muffle furnace by taking melamine as a precursor to obtain conventional carbon nitride;
(2) and (2) performing high-temperature high-pressure treatment on the conventional carbon nitride obtained in the step (1) in a cubic press to obtain the graphite-like phase carbon nitride photocatalytic material.
According to the present invention, the melamine is a conventional melamine known in the art, which is either commercially available or may be prepared.
According to the invention, the rate of temperature rise of the thermal polymerization is 1-10 ℃/min, for example 5 ℃/min; the temperature of the thermal polymerization reaction is 500-700 ℃, for example 600 ℃; the thermal polymerization reaction time is 2 to 4 hours, for example, 3 hours. The thermal polymerization is carried out in air.
According to the invention, the temperature of the high-temperature high-pressure treatment in step (2) is 100 ℃ to 900 ℃, preferably 100 ℃ to 700 ℃, for example 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃; the pressure of the high-temperature high-pressure treatment is more than 0 GPa and less than or equal to 7GPa, preferably 1-6GPa, such as 1GPa, 2GPa, 3GPa, 4GPa, 5GPa and 6 GPa; the time for the high temperature and high pressure treatment is 0.5 to 5 hours, preferably 0.5 to 2 hours, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours.
According to the invention, the cubic press is used for producing a high-temperature and high-pressure environment, and the cubic press can be a German Woorerite LPQ6-2400 cubic press.
According to the invention, the method further comprises the steps of:
(3) and (3) crushing and grinding the graphite-like phase carbon nitride photocatalytic material prepared in the step (2).
According to the invention, the particle size of the crushed and ground graphite-like phase carbon nitride photocatalytic material is 0.1-20 microns.
According to the invention, the crystal structure of the conventional carbon nitride photocatalytic material is changed after high-temperature and high-pressure treatment, so that the graphite-like phase carbon nitride photocatalytic material is formed, specifically, after high-temperature and high-pressure treatment, dislocation exists between layers due to interlayer sliding, a newly-stacked Melon-like structure is formed, and the unit cell parameter gamma is reduced from 90 degrees to 70-90 degrees and does not contain 90 degrees; the interlayer spacing is reduced from 0.326 nm to 0.300-0.326 nm without 0.326 nm, a more compact graphite-like phase crystal structure is formed, and because nanocrystals appear in the material, the crystallinity is improved, the crystal structure is more compact, the capability of absorbing light is enhanced, particularly, the absorption band of the material is red-shifted and is prolonged to about 650 nm, photo-generated carriers can be rapidly generated, separated and transferred, and the photocatalytic activity of the material is further improved.
The invention also provides the graphite-like phase carbon nitride photocatalytic material prepared by the method.
According to the invention, the graphite-like phase carbon nitride photocatalytic material contains nano-crystals, and preferably, the size of the nano-crystals is 5-65 nanometers.
According to the invention, the interlayer spacing of the graphite-like phase carbon nitride photocatalytic material is 0.300-0.326 nm, and 0.326 nm is not included. The unit cell parameter gamma of the graphite-like phase carbon nitride photocatalytic material is 70-90 degrees, and 90 degrees is not included.
According to the invention, the layer stacking arrangement of the graphite-like phase carbon nitride photocatalytic material is a re-stacked Melon-like structure.
The invention also provides a graphite-like phase carbon nitride photocatalytic material, which contains nano-crystals, wherein the size of the nano-crystals is preferably 5-65 nm.
Specifically, the interlayer spacing of the graphite-like phase carbon nitride photocatalytic material is 0.300-0.326 nm, and 0.326 nm is not included. The unit cell parameter gamma of the graphite-like phase carbon nitride photocatalytic material is 70-90 degrees, and 90 degrees is not included. The layer stacking arrangement mode of the graphite-like phase carbon nitride photocatalytic material is a re-stacked Melon-like structure.
The invention also provides the application of the graphite-like carbon nitride photocatalytic material, which is used for preparing hydrogen by photocatalytic decomposition of water.
According to the invention, the hydrogen production efficiency of the graphite-like phase carbon nitride photocatalytic material under the illumination with the wavelength of more than 420 nanometers is about 8 times that of the conventional carbon nitride photocatalytic material (the intermediate product prepared in the step (1)).
According to the invention, the hydrogen production efficiency of the graphite-like phase carbon nitride photocatalytic material under the illumination with the wavelength of more than 490 nanometers is about 100 times that of the conventional carbon nitride photocatalytic material (the intermediate product prepared in the step (1).
The invention has the beneficial effects that:
the invention provides a graphite-like phase carbon nitride photocatalytic material and a preparation method and application thereof, wherein the method comprises the following steps: conventional carbon nitride (g-C)3N4) Maintaining at high temperature and high pressure for a certain time to obtain graphite-like phaseA carbon nitride photocatalytic material. The photo-absorption edge of the prepared graphite-like phase carbon nitride photocatalytic material is prolonged to 650 nanometers, and the prepared graphite-like phase carbon nitride photocatalytic material has high photocatalytic hydrogen production activity. The conventional carbon nitride material is subjected to high-temperature and high-pressure treatment by using the cubic press for the first time, the pressure is within an industrially reachable range, the whole production process is simple, the control is easy, and the method is suitable for large-scale production. And the high-voltage field and the photocatalysis field are connected, so that a foundation is laid for the mutual promotion and coordinated development of two disciplines, and a certain demonstration effect is played.
Drawings
FIG. 1 is an optical photograph of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in examples 3, 5, and 8.
FIG. 2 is a transmission electron micrograph of the novel graphite-like carbon nitride photocatalytic material obtained in example 5.
Fig. 3 is a powder X-ray diffraction pattern of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5.
Fig. 4 shows the uv-vis diffuse reflection absorption spectra of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5.
FIG. 5 is a graph showing the steady state fluorescence emission spectra of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5.
FIG. 6 is a Fourier transform infrared spectrum of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5.
FIG. 7 is a graph showing the comparison of the activities of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 in photocatalytic decomposition of water under irradiation of a xenon lamp having a wavelength of 420 nm or more.
FIG. 8 is a graph showing the comparison of the activities of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 in photocatalytic decomposition of water under irradiation of a xenon lamp having a wavelength of 490 nm or more.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The melamine used in the examples described below was purchased from Ankangi chemistry.
Example 1
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
Example 2
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. Putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 200 ℃ and 1GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 3
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. And (3) putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 550 ℃ and 1GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 4
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. And (3) putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 600 ℃ and 1GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 5
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. Putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 650 ℃ and 1GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 6
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. And (3) putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 650 ℃ and 3GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 7
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The conventional carbon nitride material is put into a cubic press to be processed at high temperature and high pressure. And (3) putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 650 ℃ and 6GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Example 8
The melamine is heated in a muffle furnace and polymerized into the conventional carbon nitride material. Specifically, the method comprises the following steps:
approximately 26 grams of melamine in each crucible was heated gradually in a muffle furnace at a rate of 5 deg.C/min. Heated to 550 ℃ and held at temperature for 2 hours. And then cooling along with the furnace to obtain the conventional carbon nitride material.
The above conventional carbon nitride material is treated at high temperature and high pressure in a cubic press. Putting a certain amount of prepared conventional carbon nitride material into a pressure cavity of a cubic press, gradually heating and pressurizing to 700 ℃ and 1GPa, and preserving heat for 0.5 hour. Then the temperature is reduced and the pressure is relieved to normal temperature and normal pressure, and the novel graphite-like phase carbon nitride material is obtained.
Performance testing
FIG. 1 is an optical photograph of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in examples 3, 5, and 8. As can be seen from the figure, the color of the novel graphite-like carbon nitride photocatalytic material gradually becomes darker along with the increase of the temperature and the pressure, which indicates that the material is more sensitive to light, and can absorb light with long wavelength in particular. Specifically, the color of the sample of example 1 shown in fig. 1 was light yellow, the color of the sample of example 3 was bright yellow, the color of the sample of example 5 was yellow brown, and the color of the sample of example 8 was black.
FIG. 2 is a transmission electron micrograph of the novel graphite-like carbon nitride photocatalytic material obtained in example 5, from which it can be seen that nanocrystals appeared in the novel graphite-like carbon nitride photocatalytic material obtained in example 5, the nanocrystal size was between 5 nm and 65 nm.
Fig. 3 is a powder X-ray diffraction pattern of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5. It can be seen from the figure that, in the novel graphite-like phase carbon nitride material obtained in example 5 after the high-temperature and high-pressure treatment, multiple new peaks appear between 15 degrees and 25 degrees of the diffraction angle, and the main peak (the peak between 25 degrees and 30 degrees of the diffraction angle) moves towards a high angle, so that the analysis can show that the crystal structure of the material changes, molecules in a layer are re-stacked, the interlayer spacing is reduced from the original 0.326 nm to 0.319 nm, and a more compact crystal structure is formed.
Fig. 4 shows the uv-vis diffuse reflection absorption spectra of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5. It can be seen that the absorption band of the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 is red-shifted to about 650 nm relative to the conventional carbon nitride photocatalytic material obtained in example 1.
FIG. 5 is a graph showing the steady state fluorescence emission spectra of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5. The fluorescence intensity of the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 is remarkably reduced compared with that of the conventional carbon nitride photocatalytic material obtained in example 1, which indicates that the photoelectron flow is increased and the recombination probability of electron holes is reduced.
FIG. 6 is a Fourier transform infrared spectrum of the conventional carbon nitride photocatalytic material obtained in example 1 (solid line) and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 (short-dashed line). 800cm in the figure-1And 1200--1The signal peaks in the interval correspond to the respiratory vibration and the stretching vibration of the heptazine ring (3-s-triazine ring), respectively, and the fact that the structure with the heptazine ring as a unit still exists is shown.
FIG. 7 is a graph showing the comparison of the activities of the conventional carbon nitride photocatalytic material obtained in example 1 and the novel graphite-like phase carbon nitride photocatalytic material obtained in example 5 in photocatalytic decomposition of water under irradiation of a xenon lamp having a wavelength of 420 nm or more.
The testing process comprises the following steps: 10 mg of the conventional carbon nitride photocatalytic material obtained in example 1 or the novel graphite-like carbon nitride photocatalytic material obtained in example 5 and a chloroplatinic acid solution (Pt loading of 2.5 wt.%) were charged into a 20mL reactor of 25 vol.% triethanolamine aqueous solution, and hydrogen gas was produced under the illumination of a xenon lamp (equipped with a cutoff piece having a wavelength of greater than 420 nm). From the graph, it can be found that under the irradiation of xenon lamp with the wavelength of more than 420 nm, the hydrogen production rate of the novel graphite-like carbon nitride photocatalytic material obtained in the example 5 is 1832.49 μmol/h/g catalyst, which is 8 times of the hydrogen production rate (229.69 μmol/h/g catalyst) of the conventional carbon nitride photocatalytic material obtained in the example 1.
FIG. 8 is a graph comparing the activity of the conventional carbon nitride photocatalytic material obtained in example 1 and the activity of the novel graphite-like carbon nitride photocatalytic material obtained in example 5 in photocatalytic decomposition of water under irradiation of a xenon lamp having a wavelength of 490 nm or more.
The testing process comprises the following steps: 10 mg of the conventional carbon nitride photocatalytic material obtained in example 1 or the novel graphite-like carbon nitride photocatalytic material obtained in example 5 and a chloroplatinic acid solution (Pt loading of 2.5 wt.%) were charged into a 20mL reactor of 25 vol.% triethanolamine aqueous solution, and hydrogen gas was produced under illumination with a xenon lamp (equipped with a cutoff piece having a wavelength of more than 490 nm). From the graph, it can be found that under the illumination of xenon lamp with the wavelength of more than 490 nanometers, the hydrogen production rate of the novel graphite-like carbon nitride photocatalytic material obtained in the example 5 is 482.50 micromoles/hour/gram of catalyst, which is 100 times of the hydrogen production rate (4.89 micromoles/hour/gram of catalyst) of the conventional carbon nitride photocatalytic material obtained in the example 1.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. 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 preparation method of a graphite-like phase carbon nitride photocatalytic material comprises the following steps:
conventional carbon nitride (g-C)3N4) And keeping the reaction solution at high temperature and high pressure for a certain time to obtain the graphite-like phase carbon nitride photocatalytic material.
2. The method of claim 1, wherein the conventional carbon nitride has an interlayer spacing of 0.326 nm and a unit cell parameter γ of 90 °, and is prepared by at least one of a solid-phase reaction method, a solvothermal method, a chemical deposition method, and a thermal polymerization method.
Preferably, the melamine is prepared into conventional carbon nitride by a thermal polymerization method, and the conventional carbon nitride is kept for a certain time at high temperature and high pressure to obtain the graphite-like phase carbon nitride photocatalytic material.
3. The method according to any of claims 1-2, wherein the method comprises in particular the steps of:
(1) carrying out thermal polymerization reaction in a muffle furnace by taking melamine as a precursor to obtain conventional carbon nitride;
(2) and (2) performing high-temperature high-pressure treatment on the conventional carbon nitride obtained in the step (1) in a cubic press to obtain the graphite-like phase carbon nitride photocatalytic material.
4. The process according to any one of claims 1-3, wherein the thermal polymerization has a temperature rise rate of 1-10 ℃/min, such as 5 ℃/min; the temperature of the thermal polymerization reaction is 500-700 ℃, for example 600 ℃; the thermal polymerization reaction time is 2 to 4 hours, for example, 3 hours. The thermal polymerization is carried out in air.
5. The method according to any one of claims 1 to 4, wherein the temperature of the high temperature and high pressure treatment is 100 ℃ to 900 ℃, preferably 100 ℃ to 700 ℃; the pressure of the high-temperature high-pressure treatment is more than 0 and less than or equal to 7GPa, preferably 1-6 GPa; the time for the high-temperature high-pressure treatment is 0.5 to 5 hours, preferably 0.5 to 2 hours.
6. The method according to any one of claims 1-5, wherein the method further comprises the steps of:
(3) and (3) crushing and grinding the graphite-like phase carbon nitride photocatalytic material prepared in the step (2).
Preferably, the particle size of the crushed and ground graphite-like phase carbon nitride photocatalytic material is 0.1-20 microns.
7. The graphite-like phase carbon nitride photocatalytic material prepared by the method of any one of claims 1 to 6.
8. The material of claim 7, wherein the graphite-like phase carbon nitride photocatalytic material contains nanocrystals.
Preferably, the nanocrystal size is from 5 nanometers to 65 nanometers;
preferably, the interlayer spacing of the graphite-like phase carbon nitride photocatalytic material is 0.300-0.326 nanometers and does not contain 0.326 nanometers;
preferably, the unit cell parameter gamma of the graphite-like phase carbon nitride photocatalytic material is 70-90 degrees, and does not contain 90 degrees.
9. A graphite-like phase carbon nitride photocatalytic material, wherein the graphite-like phase carbon nitride photocatalytic material contains nanocrystals,
preferably, the nanocrystal size is from 5 nanometers to 65 nanometers;
preferably, the interlayer spacing of the graphite-like phase carbon nitride photocatalytic material is 0.300-0.326 nanometers and does not contain 0.326 nanometers;
preferably, the unit cell parameter gamma of the graphite-like phase carbon nitride photocatalytic material is 70-90 degrees, and does not contain 90 degrees.
10. Use of the graphite-like phase carbon nitride photocatalytic material according to any one of claims 7 to 9 for photocatalytic decomposition of water to produce hydrogen.
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