CN111318298B - P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst and preparation method and application thereof - Google Patents
P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst as well as a preparation method and application thereof, belonging to the technical field of photocatalysis. The invention provides a preparation method of a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst, which comprises the following steps: mixing porous g-C3N4Mixing a photocatalyst and sodium dihydrogen phosphate to obtain a raw material mixture; sintering the raw material mixture in an air atmosphere to obtain a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst; the sintering temperature is 290-310 ℃, and the time is 0.8-1.2 h. The preparation method of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst provided by the invention is simple and easy to operate, and the phosphorus source sodium dihydrogen phosphate is cheap and easy to obtain, has low cost and no pollution, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst and a preparation method and application thereof.
Background
With the exhaustion of energy and the growing deterioration of the environment, it is increasingly important to find alternative clean energy. Graphite phase carbon nitride (g-C)3N4) As a novel non-metal semiconductor material, the material has the advantages of rich source, simple synthesis process, low price, no toxicity, no pollution and the like, and has relatively small band gap and stable optical property, so that the material can be used in the field of photochemical production of hydrogenHas wide application. But due to pure g-C3N4The photocatalytic activity of the material is not high, the specific surface area is small, and photo-generated electron-hole pairs are easy to recombine, so that the material is limited in visible light photocatalytic application. Therefore, to increase g-C3N4The photocatalytic activity of the photocatalyst is researched, such as the doping of metal and nonmetal to improve the activity; or g-C3N4The nano sheet is made into a porous nano sheet, so that the specific surface area of the nano sheet is increased, and the activity is improved; however, the preparation method is complex in preparation process, expensive in cost and not suitable for industrial application.
Disclosure of Invention
The invention aims to provide a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst, which comprises the following steps:
mixing porous g-C3N4Mixing a photocatalyst and sodium dihydrogen phosphate to obtain a raw material mixture;
sintering the raw material mixture in an air atmosphere to obtain a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst; the sintering temperature is 290-310 ℃, and the time is 0.8-1.2 h.
Preferably, the porous g-C3N4The mass ratio of the photocatalyst to the sodium dihydrogen phosphate is 1: 0.05-0.3.
Preferably, the porous g-C3N4The photocatalyst is mixed with sodium dihydrogen phosphate by mixing the porous g-C3N4Mixing the photocatalyst, sodium dihydrogen phosphate and ethanol, and stirring at 70-80 DEG CAnd (5) drying.
Preferably, the porous g-C3N4The mass-volume ratio of the photocatalyst to the ethanol is 1g: 180-220 mL.
Preferably, the heating rate of heating to the temperature required by sintering the raw material mixture is 4-6 ℃/min.
Preferably, the porous g-C3N4The preparation method of the photocatalyst comprises the following steps:
g to C3N4Sintering the photocatalyst at 480-520 ℃ for 1.8-2.2 h under the protective atmosphere to obtain porous g-C3N4A photocatalyst.
Preferably, the temperature is raised to the g-C3N4The temperature rise rate of the temperature required by sintering of the photocatalyst is 4-6 ℃/min.
The invention also provides the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst prepared by the preparation method in the technical scheme.
The invention also provides the application of the P-doped hollow porous worm-like graphite phase carbon nitride photocatalyst in the technical scheme in hydrogen production by photocatalytic water.
Preferably, the application of the above technical solution includes the following steps:
mixing the P-doped hollow porous worm-shaped graphite-phase carbon nitride photocatalyst, chloroplatinic acid, triethanolamine and water, and carrying out photocatalytic hydrogen production with water under the irradiation of visible light.
The invention provides a preparation method of a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst, which comprises the following steps: mixing porous g-C3N4Mixing the photocatalyst and sodium dihydrogen phosphate to obtain a raw material mixture; sintering the raw material mixture in an air atmosphere to obtain a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst; the sintering temperature is 290-310 ℃, and the time is 0.8-1.2 h. The preparation method of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst provided by the invention is simple and easy to operate, and the phosphorus source sodium dihydrogen phosphate is cheap and easy to obtain, the cost is low, and the sintering process is pollution-freeDyeing and being suitable for large-scale production.
In addition, the preparation method provided by the invention can effectively improve the porous g-C3N4The surface area of the photocatalyst is large, the catalyst forms a hollow porous worm-shaped structure due to P doping, the structure shortens the distance of photo-generated electron holes to migrate to the surface to generate a photocatalytic reaction, recombination of the electron holes is reduced, the porous structure provides more reaction active sites for the catalyst reaction, and the catalytic performance of the catalyst is obviously improved.
Drawings
FIG. 1 is an XRD pattern of CN and CNCP-15 obtained in example 1;
FIG. 2 is an SEM photograph of CN, CNC and CNCP-15 obtained in example 1;
FIG. 3 is a TEM image of CN, CNC and CNCP-15 obtained in example 1;
FIG. 4 is a UV-VIS absorption spectrum of CN, CNC and CNCP-15 obtained in example 1;
FIG. 5 is a graph showing the BET test results of CN, CNC and CNCP-15 obtained in example 1;
FIG. 6 is an XPS spectrum of CN and CNCP-15 obtained in example 1;
FIG. 7 is a graph showing the results of the photocatalytic hydrogen production performance tests of CN, CNC and CNCP-15 obtained in example 1;
FIG. 8 is a hydrogen production test chart of CN obtained in example 1 and P-doped hollow porous vermicular graphite phase carbon nitride photocatalysts obtained in examples 1-5;
FIG. 9 is a graph showing the results of the cycle stability test of CN and CNCP-15 obtained in example 1.
Detailed Description
The invention provides a preparation method of a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst, which comprises the following steps:
mixing porous g-C3N4Mixing a photocatalyst and sodium dihydrogen phosphate to obtain a raw material mixture;
sintering the raw material mixture in an air atmosphere to obtain a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst; the sintering temperature is 290-310 ℃, and the time is 0.8-1.2 h.
The invention firstly prepares the porous g-C3N4The photocatalyst is mixed with sodium dihydrogen phosphate to obtain a raw material mixture.
The porous g-C of the present invention3N4The source of the photocatalyst is not particularly limited, and commercially available products or porous g-C as disclosed in the prior art are used3N4Porous g-C prepared by preparation method of photocatalyst3N4The photocatalyst may be any one. In the examples of the present invention, the porous g-C3N4The preparation method of the photocatalyst preferably comprises the following steps:
g to C3N4Sintering the photocatalyst at 480-520 ℃ for 1.8-2.2 h under the protective atmosphere to obtain porous g-C3N4A photocatalyst.
The invention is directed to said g-C3N4The source of the photocatalyst is not particularly limited, and commercially available products or g-C disclosed in the prior art are used3N4The preparation method of the photocatalyst can be used for preparing the photocatalyst, and in the embodiment of the invention, the g-C3N4The preparation method of the photocatalyst preferably comprises the following steps:
sintering urea at 480-520 ℃ for 1.8-2.2 h in air atmosphere to obtain g-C3N4A photocatalyst.
In the invention, the sintering temperature of the urea is preferably 500 ℃, and the sintering time is preferably 2 h; the heating rate of heating to the temperature required by sintering the urea is preferably 8-12 ℃/min, and more preferably 10 ℃/min.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an inert gas atmosphere.
In the present invention, the g-C3N4The sintering temperature of the photocatalyst is more preferably 500 ℃, and the sintering is carried outThe junction time is more preferably 2 h.
In the present invention, the temperature is raised to the g-C3N4The heating rate of the temperature required for sintering the photocatalyst is preferably 4-6 ℃/min, and more preferably 5 ℃/min.
In the present invention, the porous g-C3N4The mass ratio of the photocatalyst to the sodium dihydrogen phosphate is preferably 1: 0.05-0.3, more preferably 1: 0.1-0.2, and most preferably 1: 0.15.
The porous g-C of the present invention3N4The method for mixing the photocatalyst and sodium dihydrogen phosphate is not particularly limited, and a raw material mixture which is uniformly mixed may be obtained. In the examples of the present invention, the porous g-C3N4The method for mixing the photocatalyst and the sodium dihydrogen phosphate is preferably that the porous g-C is mixed3N4Mixing the photocatalyst, sodium dihydrogen phosphate and ethanol, and stirring at 70-80 ℃ until the mixture is dry. In the present invention, the stirring to dryness method prevents the porous g-C3N4The catalyst and sodium dihydrogen phosphate precipitate in layers in ethanol, resulting in a heterogeneous feedstock mixture.
In the present invention, the porous g-C3N4The mass-volume ratio of the photocatalyst to the ethanol is preferably 1g: 180-220 mL, and more preferably 1g:200 mL; the ethanol is preferably anhydrous ethanol.
After the raw material mixture is obtained, the raw material mixture is sintered in the air atmosphere to obtain the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst.
In the invention, the sintering temperature of the raw material mixture is 290-310 ℃, and preferably 300 ℃; the time is 0.8-1.2 h, preferably 1 h. In the present invention, sodium dihydrogen phosphate is supported on porous g-C in the raw material mixture3N4The sodium dihydrogen phosphate is decomposed on the surface of the photocatalyst in the sintering process to generate sodium metaphosphate and water, and the volume is sharply shrunk to ensure that the porous g-C3N4The layered structure of the photocatalyst curls along with the volume change of the sodium dihydrogen phosphate to form a hollow porous worm-like structure, and part of sodium metaphosphate is doped into the porous g-C3N4In a photocatalyst.
In the invention, the heating rate of heating to the temperature required for sintering the raw material mixture is preferably 4-6 ℃/min, and more preferably 5 ℃/min. In the present invention, the temperature increase rate is mild, and sodium dihydrogen phosphate in the sample can be sufficiently decomposed.
After sintering is finished, the sintered product is preferably washed and dried sequentially to obtain the P-doped hollow porous wormlike graphite-phase carbon nitride photocatalyst. In the invention, the water washing can remove undoped sodium metaphosphate attached to the surface of the catalyst in the sintered product.
The invention also provides the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst prepared by the preparation method in the technical scheme.
The invention also provides the application of the P-doped hollow porous worm-like graphite phase carbon nitride photocatalyst in the technical scheme in hydrogen production by photocatalytic water.
In the present invention, the application preferably comprises the steps of:
mixing the P-doped hollow porous worm-shaped graphite-phase carbon nitride photocatalyst, chloroplatinic acid, triethanolamine and water, and carrying out photocatalytic hydrogen production with water under the irradiation of visible light.
In the invention, the mass-to-volume ratio of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst to chloroplatinic acid is preferably 1g: 75-85 mL, and more preferably 1g:80 mL; the mass-to-volume ratio of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst to triethanolamine is preferably 1g: 150-170 mL, and more preferably 1g:160 mL; the mass ratio of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst to water is preferably 1: 1300-1400, and more preferably 1: 1360.
In the invention, chloroplatinic acid is used as a cocatalyst to improve the activity of a main catalyst (P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst); triethanolamine, as a sacrificial agent, is oxidized to release electrons, which further participate in the water splitting reaction.
The following examples are provided to illustrate the preparation and application of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst provided by the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Heating 10g of urea to 500 ℃ at a heating rate of 10 ℃/min in air atmosphere, and sintering for 2h to obtain g-C3N4A photocatalyst (denoted as CN);
(2) 1g of g-C obtained in step (1)3N4Heating the photocatalyst to 500 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and sintering for 2h to obtain porous g-C3N4Photocatalyst (noted CNC);
(3) 0.2g of the porous g-C obtained in step (2)3N4Mixing photocatalyst, 0.03g sodium dihydrogen phosphate and 20mL anhydrous ethanol, stirring in 75 deg.C water bath to dry to obtain porous g-C3N4Photocatalyst-sodium dihydrogen phosphate mixture;
(4) mixing the porous g-C3N4And (3) heating the photocatalyst-sodium dihydrogen phosphate mixture to 300 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and sintering for 1h to obtain the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst (marked as CNCP-15).
Example 2
A P-doped hollow porous vermicular graphite phase carbonitride photocatalyst was prepared as in example 1, except that the amount of sodium dihydrogen phosphate was 0.01g, and the resulting P-doped hollow porous vermicular graphite phase carbonitride photocatalyst, designated CNCP-5.
Example 3
A P-doped hollow porous vermicular graphite phase carbonitride photocatalyst was prepared as in example 1, except that the amount of sodium dihydrogen phosphate was 0.02g, and the resulting P-doped hollow porous vermicular graphite phase carbonitride photocatalyst, designated CNCP-10.
Example 4
A P-doped hollow porous vermicular graphite phase carbonitride photocatalyst was prepared as in example 1, except that the amount of sodium dihydrogen phosphate was 0.04g, and the resulting P-doped hollow porous vermicular graphite phase carbonitride photocatalyst, designated CNCP-20.
Example 5
A P-doped hollow porous vermicular graphite phase carbonitride photocatalyst was prepared as in example 1, except that the amount of sodium dihydrogen phosphate was 0.06g, and the resulting P-doped hollow porous vermicular graphite phase carbonitride photocatalyst, designated CNCP-30.
The CN obtained in the step (1) of the example 1 and the CNCP-15 obtained in the step (4) were subjected to X-ray diffraction, and the XRD curves are shown in FIG. 1. As can be seen from FIG. 1, the P-modified sample (i.e., CNCP-15) still had the original g-C3N4Respectively at 13.1 DEG and 27.2 DEG, respectively corresponding to g-C3N4Due to in-plane structural stacking and interlayer stacking of aromatic segments, similar characteristic peaks indicate that the P-modified sample is still g-C3N4. However, the diffraction peak intensity at 27.2 ℃ was slightly reduced, indicating that the g-C after the incorporation of sodium dihydrogen phosphate3N4Break up the good periodic structure of the structure. XRD characterization was performed on the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst obtained in examples 2-5, and the results were similar.
SEM images of CN, CNC and CNCP-15 obtained in example 1 were tested, and the results are shown in FIG. 2, wherein a is CN, b is CNC, and c is CNCP-15. As can be seen from fig. 2, the morphology of CN is regular lamellar structure (as shown in a in fig. 2), after sintering in nitrogen atmosphere, the morphology of CN is still lamellar structure (as shown in b in fig. 2), and after doping sodium dihydrogen phosphate, the morphology of the sample becomes irregular hollow porous worm-like structure (as shown in c in fig. 2), which indicates that the hollow porous worm-like structure is caused by the introduction of sodium dihydrogen phosphate. SEM characterization of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst obtained in examples 2-5 was similar to that of the CNCP-15 obtained in example 1.
TEM images of CN, CNC and CNCP-15 obtained in example 1 were tested, and the results are shown in FIG. 3, in which a is CN, b is CNC, and c is CNCP-15. As can be seen from FIG. 3, CN is a layered structure, and only a small number of pores (shown as a in FIG. 3) are present; while a large number of pores exist in the CNC (as shown in b of fig. 3), and the pore structure of the CNCP-15 is not much different from that of the CNC (as shown in c of fig. 3), it can be known in connection with fig. 2 that CN becomes a porous structure after being sintered in a nitrogen atmosphere, and then the CNC becomes a hollow porous worm-like structure through modification of P. TEM characterization of the P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst obtained in examples 2-5 was similar to that of CNCP-15 obtained in example 1.
The ultraviolet-visible light absorption spectrograms of CN, CNC and CNCP-15 are tested, the results are shown in FIG. 4, the forbidden bandwidths of CN, CNC and CNCP-15 are calculated, the results are sequentially 2.786eV, 2.767eV and 2.786eV, the forbidden bandwidth of CNCP-15 is the same as that of CN, and the doping of P does not reduce the forbidden bandwidth of graphite-phase carbon nitride.
The specific surface areas of CN, CNC and CNCP-15 were measured by BET, and the results are shown in FIG. 5, in which the specific surface areas of CN, CNC and CNCP-15 were 39.29m2/g、48.51m2G and 51.36m2And g, indicating that the doping of P improves the specific surface area of the catalyst.
The XPS spectra of CN and CNCP-15 in example 1 were tested and the results are shown in FIG. 6, wherein a is the XPS survey spectrum of CN and CNCP-15 and b is the high resolution XPS spectrum of CNCP-15. As can be seen from fig. 6, the full spectrum does not have the peak of P, but only the peaks of C, N and O, and the high resolution graph clearly shows that P exists in the sample, and the peak of P may correspond to P ═ O bond, so that it can be analyzed, and the peak of P that is not seen in the full spectrum may be undetected due to the small content of P, and it is presumed that the doping form of P is sodium metaphosphate.
Testing the hydrogen performance of the photocatalytic water:
the photocatalytic water hydrogen production performance of CN, CNC, CNCP-15, CNCP-5, CNCP-10, CNCP-20 and CNCP-30 is tested by the following specific test method:
(1) adding 0.05g of catalyst to be detected, 4mL of chloroplatinic acid, 8mL of triethanolamine and 68mL of deionized water into a three-necked bottle, and then carrying out ultrasonic treatment for 10min to obtain a mixed solution;
(2) introducing nitrogen into the three-mouth bottle for 30min, removing air in the bottle, and sealing the three-mouth bottle; a 300W xenon lamp is used as a light source, the photocurrent is adjusted to be 15mA, and the light intensity center is adjusted to be irradiated on the three-mouth bottle;
(3) and (3) starting timing during illumination, extracting 0.2mL of gas in the three-mouth bottle every 1h for the sample, performing gas chromatography analysis to test the hydrogen yield, and recording the hydrogen yield within 5h of reaction.
The test results of CN, CNC and CNCP-15 are shown in FIG. 7, and it can be seen from FIG. 7 that the hydrogen production of CNC is greater than CN, the hydrogen production of CNCP-15 is the largest, and the hydrogen production at 5h is 10.985mmol/g, the hydrogen production of CN is 1.440mmol/g, and the hydrogen production of CNCP-15 is 7.6 times that of CN relative to CN, which indicates that CNCP-15 has more excellent photocatalytic water hydrogen production performance.
The test results of CNCP-5, CNCP-10, CNCP-20, and CNCP-30 are shown in FIG. 8, and for comparison, the test results of CN and CNCP-15 are shown in FIG. 8. As can be seen from FIG. 8, the catalytic activity of the P-doped hollow porous wormlike graphite phase carbon nitride photocatalyst is higher than that of g-C3N4Photocatalyst, and the catalytic activity of CNCP-15 is optimal.
The cycling stability of CN and CNCP-15 was tested: the hydrogen production of the catalyst in 5h of photocatalytic reaction is recorded according to the test method for the hydrogen production performance of photocatalytic water, and recorded as a cycle, then the photocatalyst is taken out, the test is repeated, and the hydrogen production of 4 consecutive cycles is recorded, and the result is shown in fig. 9. As can be seen from FIG. 9, the hydrogen production of CNCP-15 did not decrease significantly with increasing cycle number, while the hydrogen production of CN decreased gradually with increasing cycle number, indicating that P-modified g-C having a hollow porous worm-like structure3N4The photocatalyst (namely CNCP-15) has better cycle stability performance and can reduce the cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst is characterized by comprising the following steps:
mixing porous g-C3N4Mixing a photocatalyst and sodium dihydrogen phosphate to obtain a raw material mixture; the porous g-C3N4The mass ratio of the photocatalyst to the sodium dihydrogen phosphate is 1: 0.05-0.3;
sintering the raw material mixture in an air atmosphere to obtain a P-doped hollow porous vermicular graphite phase carbon nitride photocatalyst; the sintering temperature is 290-310 ℃, and the time is 0.8-1.2 h.
2. The method of claim 1, wherein the porous g-C is3N4The photocatalyst is mixed with sodium dihydrogen phosphate by mixing the porous g-C3N4Mixing the photocatalyst, sodium dihydrogen phosphate and ethanol, and stirring at 70-80 ℃ until the mixture is dry.
3. The method of claim 2, wherein the porous g-C is3N4The mass-volume ratio of the photocatalyst to the ethanol is 1g: 180-220 mL.
4. The method according to claim 1, wherein a temperature rise rate of raising the temperature to a temperature required for sintering the raw material mixture is 4 to 6 ℃/min.
5. The method of claim 1, wherein the porous g-C is3N4The preparation method of the photocatalyst comprises the following steps:
g to C3N4Sintering the photocatalyst at 480-520 ℃ for 1.8-2.2 h under the protective atmosphere to obtain porous g-C3N4A photocatalyst.
6. The method according to claim 5, wherein the temperature is raised to the g-C3N4Sintering station of photocatalystThe temperature rise rate required is 4-6 ℃/min.
7. The P-doped hollow porous wormlike graphite-phase carbon nitride photocatalyst obtained by the preparation method of any one of claims 1 to 6.
8. The use of the P-doped hollow porous worm-like graphite phase carbon nitride photocatalyst of claim 7 in photocatalytic aqueous hydrogen production.
9. Use according to claim 8, characterized in that it comprises the following steps:
mixing the P-doped hollow porous worm-shaped graphite-phase carbon nitride photocatalyst, chloroplatinic acid, triethanolamine and water, and carrying out photocatalytic hydrogen production with water under the irradiation of visible light.
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