CN111036274A - Modified BiVO4Preparation method of nanosheet - Google Patents
Modified BiVO4Preparation method of nanosheet Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 12
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910020700 Na3VO4 Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
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- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
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- 239000004202 carbamide Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
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- 239000000969 carrier Substances 0.000 abstract description 3
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- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000000707 layer-by-layer assembly Methods 0.000 description 1
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- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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Abstract
The invention relates to the field of semiconductor materials, and aims to provide a modified BiVO4A preparation method of the nano-sheet. The method comprises the following steps: mixing Na3VO4Solution is dripped into BiCl3In the solution, BiVO is prepared through hydrothermal reaction4Nanosheets; firing the nitrogen-containing precursor to obtain g-C3N4Treating the granules with mixed acid solution, soaking, washing and dispersing to obtain g-C3N4An aqueous dispersion of nanoparticles; then dropwise adding the mixture to BiVO4In the suspension, the solid product obtained by ultrasonic and stirring is filtered, washed, dried and ground to obtain the modified BiVO4Nanosheets. The invention can realize g-C3N4Nanoparticles at normal temperatureBiVO4The firm loading of the surface of the nanosheet avoids the problems of particle agglomeration, grain growth and the like which are possibly caused by the traditional high-temperature calcination compounding. The surface dispersion type nano heterojunction is constructed, the phenomenon of interface mismatch caused by different crystal structures is effectively avoided, and the generation of photon-generated carriers in BiVO is promoted4And g-C3N4The photocatalytic quantum efficiency is improved by the migration and separation between the two.
Description
Technical Field
The invention relates to the field of semiconductor materials, in particular to a modified BiVO4A preparation method of the nano-sheet.
Background
The semiconductor photocatalytic material has wide application prospect in the field of energy environmental protection, and the first report of TiO in 19722After water is decomposed by photocatalysis, development and application of photocatalysis materials are widely concerned by people. However, TiO2The forbidden band is wider (3.0-3.2eV), only 3% -5% of ultraviolet light energy in sunlight can be utilized, and visible light accounting for about 45% of the sunlight energy is less utilized. Therefore, visible light-responsive photocatalytic materials are currently being studied.
Bismuth vanadate (BiVO)4) The semiconductor is a narrow-bandgap semiconductor, has better response characteristic to visible light, but still has the problem that photo-generated electrons and holes are easy to recombine, and further improvement of the catalytic performance of the semiconductor is restricted. Methods such as transition metal doping, rare earth element doping, noble metal deposition, non-metal ion doping, semiconductor heterojunction construction and the like have been developed to improve the photocatalytic activity. The semiconductor heterojunction is constructed to inhibit the recombination of photon-generated electron-hole pairs through the migration of photon-generated carriers in the heterojunction.
In recent years, graphite-like carbon nitride (g-C)3N4) Great attention has been paid to the excellent visible light response characteristics (2.7eV) and low cost. Due to g-C3N4And BiVO4Matching energy band structure by g-C3N4And BiVO4The semiconductor heterojunction is constructed byPromote BiVO4An effective method of photocatalytic activity. However, currently g-C3N4/BiVO4The composite material is mostly in the form of lamellar or micron-scale g-C3N4And BiVO4The recombination between the larger-sized particles leads to the reduction of the contact surface between the heterogeneous particles on the one hand and the g-C3N4And BiVO4The phenomenon of interface mismatching caused by different crystal structures is more obvious, thereby greatly reducing the g-C3N4And BiVO4Uniformity and effectiveness of compounding.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and provides a modified BiVO4A preparation method of the nano-sheet.
In order to solve the technical problem, the solution of the invention is as follows:
provides a modified BiVO4The preparation method of the nanosheet comprises the following steps:
(1) weighing a certain amount of BiCl3And surfactant, sequentially adding into ethylene glycol, and stirring for 40min to obtain BiCl3A solution; weighing and reacting with BiCl3Equal amount of Na3VO4Dissolving the powder in water, stirring, and dripping BiCl3Stirring the solution for 40 min; pouring the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction, and naturally cooling to room temperature; filtering the obtained precipitate, cleaning and drying to obtain BiVO4Nanosheets;
wherein, BiCl3And a surfactant in a ratio of 7:1 to 1: 1; BiCl3The concentration of the solution is 10-30 g/L; the hydrothermal reaction temperature is 120-160 ℃, and the time is 3-12 h;
(2) loading nitrogen-containing precursor into crucible, covering, placing into muffle furnace, heating to 600 deg.C, and treating for 3 hr to obtain g-C3N4Particles; g to C3N4Dispersing the particles in mixed acid solution of concentrated nitric acid and concentrated sulfuric acid, stirring for 1-4h under constant temperature water bath condition, and pouring 50 times volume of deionized waterDiluting in the sub-water; standing for 5-10h, filtering the obtained precipitate, washing with deionized water and ethanol to neutrality, dispersing the precipitate into methanol water solution, and stirring at 60 deg.C in water bath for 20 h; centrifuging, washing, and dispersing in deionized water to obtain g-C with solid content of 0.1%3N4An aqueous dispersion of nanoparticles;
wherein g-C3N4The solid content of the particles in the mixed acid solution is 5-20%; the temperature of the water bath is 60-80 ℃;
(3) BiVO prepared in the step (1)4Dispersing the nano-sheets into water, carrying out ultrasonic treatment for 30min, and stirring for 30min to obtain BiVO4A suspension; g-C prepared in the step (2)3N4Ultrasonic treating the nanoparticle water dispersion for 30min, stirring for 30min, and then dropwise adding into BiVO4In suspension; mixing and ultrasonically stirring for 0.5-2 h, and then stirring for 12-24 h; the obtained solid product is filtered, washed, dried and ground to obtain the product g-C3N4Nanoparticle modified BiVO4Nanosheets;
wherein, the dosage of the suspension and the dispersion liquid is controlled to ensure that the solid content in the mixed liquid is 0.1 to 1 percent and g-C3N4And BiVO4The mass ratio of (A) to (B) is 1: 100-1: 1.
In the invention, the surfactant used in the step (1) is at least one of polyoxyethylene octylphenol ether, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide.
In the invention, the mixed solution of water and ethanol with the volume ratio of 7:3 is used for washing the sediment in the step (1), and the washing is repeated for 5 times; the drying refers to drying in an oven at 80 ℃.
In the invention, the filling ratio in the high-pressure reaction kettle in the step (1) is 60-90%.
In the invention, the nitrogen-containing precursor in the step (2) is a mixture of urea and at least one of melamine, dicyandiamide and cyanamide.
In the invention, in the step (2), the temperature rise rate of the muffle furnace is controlled to be 3 ℃/min.
In the invention, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid solution in the step (2) is 1:3-3: 1.
The realization principle of the invention is as follows:
the invention adopts a surfactant to BiVO4Controlling the morphology to obtain a two-dimensional nanosheet with a large specific surface area; the ammonia gas generated by decomposing the urea in the composite nitrogen-containing precursor is used as a gas template to improve the g-C prepared3N4Porosity of the particles to facilitate penetration of strong acid to g-C3N4The inside of the particles is rapidly etched to obtain g-C with uniform size3N4A nanoparticle; refluxing with methanol on g-C3N4A large number of defects on the surface of the nano-particles are properly repaired, so that the adverse effect of excessive defects on the photocatalytic performance is reduced to the greatest extent while the subsequent load binding capacity of the nano-particles is ensured; promoting positively charged g-C by adopting a method of combining electrostatic self-assembly with unsaturated dangling bond3N4The nano particles are firmly loaded on the negatively charged BiVO4And (3) the surface of the nanosheet.
Compared with the prior art, the invention has the technical effects that:
1. to achieve g-C3N4Nano particles at room temperature in BiVO4The firm loading of the surface of the nanosheet avoids the problems of particle agglomeration, grain growth and the like which are possibly caused by the traditional high-temperature calcination compounding.
2. Through the reaction in BiVO4g-C loaded on nanosheet surface3N4The nano particles construct a surface dispersed nano heterojunction and effectively avoid g-C3N4And BiVO4Interface mismatching phenomenon caused by different crystal structures promotes photon-generated carriers in BiVO4And g-C3N4The photocatalytic quantum efficiency is improved by the migration and separation between the two.
Drawings
FIG. 1 shows g-C obtained in example 33N4Nanoparticle modified BiVO4Scanning electron microscope photographs of the nanosheets.
FIG. 2 shows g-C obtained in example 33N4Modification of nanoparticlesSexual BiVO4Nanosheet, g-C prepared by conventional method3N4Block-modified BiVO4Nanosheet, single BiVO4The nano-sheet has a photocatalytic degradation curve for rhodamine B dye.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific embodiments below:
modified BiVO4The preparation method of the nanosheet comprises the following steps:
(1) weighing BiCl according to the mass ratio of 7:1 to 1:13And a surfactant, which are sequentially added into ethylene glycol and fully stirred for 40min to obtain BiCl with the concentration of 10-30 g/L3A solution; the surfactant is at least one of polyoxyethylene octylphenol ether, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide.
Weighing and reacting with BiCl3Equal amount of Na3VO4Dissolving the powder in water, stirring, and dripping BiCl3Stirring the solution for 40 min; pouring the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the filling ratio is 60-90%; controlling the hydrothermal reaction temperature to be 120-160 ℃ and the time to be 3-12 h; naturally cooling to room temperature after the reaction is finished, filtering the obtained precipitate, washing the precipitate by using a mixed solution of water and ethanol with a volume ratio of 7:3, and repeatedly washing for 5 times; then putting the mixture into a drying oven to be dried at the temperature of 80 ℃ to obtain BiVO4Nanosheets;
(2) loading nitrogen-containing precursor (mixture of urea and at least one of melamine, dicyandiamide and cyanamide) into crucible, covering, placing into muffle furnace, heating to 600 deg.C at heating rate of 3 deg.C/min, and treating for 3 hr to obtain g-C3N4Particles; g to C3N4Dispersing the particles in a mixed acid solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:3-3:1, g-C3N4The solid content of the particles in the mixed acid solution is 5-20%; stirring for 1-4h at 60-80 deg.C in thermostatic water bath, and diluting with 50 times volume of deionized water; standing for 5-10 hr, filtering the obtained precipitate, washing with deionized water and ethanol to neutralityThen dispersing the precipitate into a methanol water solution, and stirring for 20 hours under the condition of water bath at the temperature of 60 ℃; centrifuging, washing, and dispersing in deionized water to obtain g-C with solid content of 0.1%3N4An aqueous dispersion of nanoparticles;
(3) BiVO prepared in the step (1)4Dispersing the nano-sheets into water, carrying out ultrasonic treatment for 30min, and stirring for 30min to obtain BiVO4A suspension; g-C prepared in the step (2)3N4Ultrasonic treating the nanoparticle water dispersion for 30min, stirring for 30min, and then dropwise adding into BiVO4In suspension; the dosage of the suspension and the dispersion liquid is controlled to ensure that the solid content in the mixed liquid is 0.1 to 1 percent and g-C3N4And BiVO4The mass ratio of (A) to (B) is 1: 100-1: 1. Mixing and ultrasonically stirring for 0.5-2 h, and then stirring for 12-24 h; the obtained solid product is filtered, washed, dried and ground to obtain the product g-C3N4Nanoparticle modified BiVO4Nanosheets.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Respectively successfully prepare modified BiVO through 8 examples4The experimental data for the preparation of the nanoplatelets, in each example, are given in table 1 below.
Table 1 data table of examples
Finally, it should also be noted that the above list is only a specific implementation example of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. Modified BiVO4The preparation method of the nanosheet is characterized by comprising the following steps:
(1) weighing a certain amount of BiCl3And surfactant, sequentially adding into ethylene glycol, and stirring for 40min to obtain BiCl3A solution; weighing and reacting with BiCl3Equal amount of Na3VO4Dissolving the powder in water, stirring, and dripping BiCl3Stirring the solution for 40 min; pouring the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction, and naturally cooling to room temperature; filtering the obtained precipitate, cleaning and drying to obtain BiVO4Nanosheets;
wherein, BiCl3And a surfactant in a ratio of 7:1 to 1: 1; BiCl3The concentration of the solution is 10-30 g/L; the hydrothermal reaction temperature is 120-160 ℃, and the time is 3-12 h;
(2) loading nitrogen-containing precursor into crucible, covering, placing into muffle furnace, heating to 600 deg.C, and treating for 3 hr to obtain g-C3N4Particles; g to C3N4Dispersing the particles in mixed acid liquid of concentrated nitric acid and concentrated sulfuric acid, stirring for 1-4h under the condition of constant-temperature water bath, and pouring into deionized water with 50 times of volume for dilution; standing for 5-10h, filtering the obtained precipitate, washing with deionized water and ethanol to neutrality, dispersing the precipitate into methanol water solution, and stirring at 60 deg.C in water bath for 20 h; centrifuging, washing, and dispersing in deionized water to obtain g-C with solid content of 0.1%3N4An aqueous dispersion of nanoparticles;
wherein g-C3N4The solid content of the particles in the mixed acid solution is 5-20%; the temperature of the water bath is 60-80 ℃;
(3) BiVO prepared in the step (1)4Dispersing the nano-sheets into water, carrying out ultrasonic treatment for 30min, and stirring for 30min to obtain BiVO4A suspension; g-C prepared in the step (2)3N4Ultrasonic treating the nanoparticle water dispersion for 30min, stirring for 30min, and then dropwise adding into BiVO4In suspension; mixing and ultrasonically stirring for 0.5-2 h, and then stirring for 12-24 h; the solid product obtainedFiltering, washing, drying and grinding to obtain the product g-C3N4Nanoparticle modified BiVO4Nanosheets;
wherein, the dosage of the suspension and the dispersion liquid is controlled to ensure that the solid content in the mixed liquid is 0.1 to 1 percent and g-C3N4And BiVO4The mass ratio of (A) to (B) is 1: 100-1: 1.
2. The method according to claim 1, wherein the surfactant used in step (1) is at least one of polyoxyethylene octylphenol ether, polyvinylpyrrolidone, and cetyltrimethylammonium bromide.
3. The method according to claim 1, wherein the precipitate is washed in step (1) with a mixed solution of water and ethanol at a volume ratio of 7:3, and the washing is repeated 5 times; the drying refers to drying in an oven at 80 ℃.
4. The method according to claim 1, wherein the filling ratio in the high-pressure reaction tank in the step (1) is 60 to 90%.
5. The method according to claim 1, wherein the nitrogen-containing precursor in step (2) is a mixture of urea and at least one of melamine, dicyandiamide and dicyandiamide.
6. The method according to claim 1, wherein the temperature rise rate of the muffle furnace in the step (2) is controlled to be 3 ℃/min.
7. The method according to claim 1, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid solution in the step (2) is 1:3 to 3: 1.
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