CN115814837B - Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst - Google Patents
Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229960002180 tetracycline Drugs 0.000 description 5
- 229930101283 tetracycline Natural products 0.000 description 5
- 235000019364 tetracycline Nutrition 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005540 biological transmission 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
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000008987 corocalm Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen ion Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst, belongs to the technical field of photocatalyst, can solve the existing Bi 2 O 2 [BO 2 (OH)]The photo-catalytic material has the defects of high photo-generated electron recombination rate and light absorption range only in the ultraviolet light range, and the invention leads Bi (NO 3 ) 3 ·5H 2 Ultrasonic mixing O with ethanol to obtain bismuth nitrate solution, BCN and K 2 B 4 O 7 ·4H 2 Adding O into ethanol, ultrasonically mixing, then dripping bismuth nitrate solution, fully stirring, transferring into a reaction kettle, and reacting in a constant-temperature oven at 120-200 ℃ for 12-36 hours. Naturally cooling to room temperature, filtering, washing and drying the obtained product to obtain hollow flower-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]A photocatalyst. The method is simple and low in cost.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]A photocatalyst.
Background
Due to the large emission of contaminants such as dyes, antibiotics, phenols, pesticides, etc., many efforts have been made in water treatment such as reverse osmosis, filtration, adsorption, precipitation, chemical and biological treatment, etc. However, these methods cannot thoroughly decompose the organic substances in the wastewater. In recent years, photocatalysis has been favored as a green technology, which oxidizes organic pollutants to CO 2 、H 2 O or small molecules, and does not cause secondary pollution. Most of the currently reported photocatalysts have the defects of low efficiency, high cost, high toxicity and the like. Among various photocatalysts, bismuth-based photocatalysts have received attention because of their low toxicity, good stability, special electronic structure and abundant reserves. In addition, bi 2 O 2 [BO 2 (OH)]The photocatalyst is mostly similar to Bi 2 O 2 CO 3 The layered crystal structure, the medium band gap and the strong oxidizing ability are favorable for improving the photocatalytic performance, and the novel macroscopic polarization photocatalyst is a promising novel macroscopic polarization photocatalyst.
Preparation of layered photocatalyst Bi by Rui Zhang et al (CrystEngComm, 16 (2014) 4931) 2 O 2 [BO 2 (OH)]The nanoplatelets have an internal polar field enhanced photocatalysis,but the photo-generated electron recombination rate of a single photocatalyst is fast, and the catalytic activity is reduced fast; halogenation of Shuguan Li et al (Applied Surface Science,582 (2022) 152407) by halogen ion solution soaking method, I - Grafting Bi 2 O 2 [BO 2 (OH)]The nano-sheet expands the light absorption range and remarkably improves the degradation performance of BPA, but only has reaction to ultraviolet rays and can not fully utilize solar energy, and the Bi/OVs co-modified Bi is prepared by a hydrothermal method and a chemical deposition method by Xi Zhou et al (Journal of Hazardous Materials,436 (2022) 129271) 2 O 2 [BO 2 (OH)]Covalent rings (surface cations- & gtplasma metal- & gtanions) formed by charge alternation and oxygen vacancies can remarkably improve the charge separation efficiency and the yield of active oxygen, but the catalyst has single morphology and insufficient reactive surface.
Disclosure of Invention
The invention aims at the existing Bi 2 O 2 [BO 2 (OH)]The photo-generated electrons in the photo-catalytic material have the defects of high recombination rate and light absorption range only in the ultraviolet light range, and the photo-generated electrons have the advantages of simple operation, controllable preparation of morphology, acceleration of carrier separation of photo-excited charges, suppression of carrier recombination and widening of the light absorption range 2 O 2 [BO 2 (OH)]A preparation method of a photocatalyst.
The invention adopts the following technical scheme:
hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]The preparation method of the photocatalyst comprises the following steps:
in a first step, bi (NO 3 ) 3 ·5H 2 Ultrasonic mixing O and ethanol to obtain bismuth nitrate solution;
second, BCN and K are combined 2 B 4 O 7 ·4H 2 Adding O into ethanol, ultrasonically mixing, then dripping bismuth nitrate solution, fully stirring, transferring into a reaction kettle, and reacting in a constant-temperature oven at 120-200 ℃ for 12-36 hours;
thirdly, after the reaction is finished, naturally cooling to room temperature, and carrying out suction filtration and washing on the obtained productWashing and drying to obtain hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]A photocatalyst.
Further, the Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to ethanol is 1:16-1:8.
Further, the Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to ethanol is 1:12.
Further, in the second step, the BCN, K 2 B 4 O 7 ·4H 2 The mass ratio of O to ethanol is 0.01:1:12-0.05:1:12.
Further, the BCN, K 2 B 4 O 7 ·4H 2 The mass ratio of O to ethanol is 0.025:1:12.
Further, the reaction temperature in the second step was 160℃and the reaction time was 24 hours.
Further, the drying temperature in the third step is 60 ℃ and the drying time is 24 hours.
The beneficial effects of the invention are as follows:
the method is simple and low in cost, and the hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi is prepared through in-situ hydrothermal reaction 2 O 2 [BO 2 (OH)]The photocatalyst has the advantages that the prepared material is uniform in appearance, stable in structure and large in specific surface area, and the special Z-shaped heterojunction structure can rapidly perform photocatalytic degradation on Methylene Blue (MB) and Tetracycline (TC) under the irradiation of visible light.
Drawings
FIG. 1 is an X-ray powder diffraction spectrum of the sample prepared in example 1.
Fig. 2 is an SEM image of the sample prepared in example 1.
Fig. 3 is a TEM image of the sample prepared in example 1.
FIG. 4 is an HR-TEM image of the sample prepared in example 1.
Fig. 5 is an SEM image of the sample prepared in comparative example 1.
Fig. 6 is an SEM image of BCN.
Fig. 7 is an SEM image of the sample prepared in example 2.
Fig. 8 is an SEM image of the sample prepared in example 3.
FIG. 9 is BCN nanoplatelets, bi 2 O 2 [BO 2 (OH)]Hollow flower ball, BCN/Bi prepared in example 1 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 2 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 3 2 O 2 [BO 2 (OH)]And degrading MB under the photocatalysis of visible light irradiation.
FIG. 10 is BCN nanoplatelets, bi 2 O 2 [BO 2 (OH)]Hollow flower ball, BCN/Bi prepared in example 1 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 2 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 3 2 O 2 [BO 2 (OH)]Photocatalytic degradation of TC under visible light irradiation.
Detailed Description
The invention will be further described with reference to specific examples.
The BCN nanoplatelets used in the following examples were prepared according to the following method: 1.24 g of H 3 BO 3 Mixing with 10 g urea, grinding into fine powder in an agate mortar, and transferring into a corundum crucible with a cover. Subsequently, the crucible is placed in a tube furnace together with the reagents, in N 2 In the atmosphere, the heating rate is controlled to be 2.5 ℃/min, the mixture is heated to 550 ℃ and kept at the temperature for 3 hours, and the mixture is naturally cooled to obtain the product B doped g-C 3 N 4 （BCN）。
Example 1
0.73g Bi(NO 3 ) 3 ·5H 2 Adding O into 10 mL ethanol, and performing ultrasonic treatment for 30 min to obtain bismuth nitrate solution. 50 Adding BCN mg into 30 mL ethanol, ultrasonic treating for 30 min, and adding 2 g K 2 B 4 O 7 ·4H 2 O was stirred for 30 min. And finally, dropwise adding the bismuth nitrate solution, and continuously stirring for 30 min. The mixture was placed in a reaction kettle and reacted at 160℃for 24h. After the reaction is finished, naturally cooling, filtering and washing, and drying 24h in a constant temperature drying oven at 60 ℃ to obtain the hollow flower-spherical Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]。
The inventors used an X-ray diffractometer, a cold field emission scanning electron microscope, and a field emission transmission electron microscope to characterize the beige powder obtained in example 1, and the results are shown in FIGS. 1 to 4. As can be seen from XRD results of FIG. 1, the sample was BCN/Bi 2 O 2 [BO 2 (OH)]. As can be seen from fig. 2 and 3, the morphology features a hollow open flower-like structure with a diameter of about 2 μm assembled in nano-sheets. Bi can be detected in the high resolution TEM of FIG. 4 2 O 2 [BO 2 (OH)]The characteristic lattice fringes of the (130) crystal face and the (002) crystal face of the BCN respectively, and a distinct crystal face interface area exists between the two phases, which indicates that the composite BCN/Bi 2 O 2 [BO 2 (OH)]And a heterojunction is successfully formed.
Comparative example 1
0.73g Bi(NO 3 ) 3 ·5H 2 Adding O into 10 mL ethanol, and performing ultrasonic treatment for 30 min to obtain bismuth nitrate solution. 2 g K 2 B 4 O 7 ·4H 2 Adding O into 30 mL ethanol, stirring for 30 min to obtain potassium borate solution, dripping bismuth nitrate solution into the potassium borate solution, and stirring for 30 min. Finally, the mixed solution is put into a reaction kettle to react at 160 ℃ for 24h. After the reaction is finished, naturally cooling, filtering and washing, and drying 24h in a constant temperature drying oven at 60 ℃ to obtain a sample Bi 2 O 2 [BO 2 (OH)]Hollow flower ball.
Example 2
0.73g Bi(NO 3 ) 3 ·5H 2 Adding O into 10 mL ethanol, and performing ultrasonic treatment for 30 min to obtain bismuth nitrate solution. 20 Adding BCN mg into 30 mL ethanol, ultrasonic treating for 30 min, and adding 2 g K 2 B 4 O 7 ·4H 2 O was stirred for 30 min. And finally, dropwise adding the bismuth nitrate solution, and continuously stirring for 30 min. The mixture was placed in a reaction kettle and reacted at 160℃for 24h. After the reaction is finished, naturally cooling, filtering and washing, and drying 24h in a constant temperature drying oven at 60 ℃ to obtain the hollow flower-spherical Z-shaped heterojunction 20 BCN/Bi 2 O 2 [BO 2 (OH)]。
Example 3
0.73g Bi(NO 3 ) 3 ·5H 2 Adding O into 10 mL ethanol, and performing ultrasonic treatment for 30 min to obtain bismuth nitrate solution. 100 Adding BCN mg into 30 mL ethanol, ultrasonic treating for 30 min, and adding 2 g K 2 B 4 O 7 ·4H 2 O was stirred for 30 min. And finally, dropwise adding the bismuth nitrate solution, and continuously stirring for 30 min. The mixture was placed in a reaction kettle and reacted at 160℃for 24h. After the reaction is finished, naturally cooling, filtering and washing, and drying 24h in a constant temperature drying oven at 60 ℃ to obtain the hollow flower-spherical Z-shaped heterojunction 100 BCN/Bi 2 O 2 [BO 2 (OH)]。
In order to prove the beneficial effects of the invention, the inventor takes MB and TC as research objects, and respectively adds the BCN nanosheets and Bi 2 O 2 [BO 2 (OH)]Hollow flower ball, BCN/Bi prepared in example 1 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 2 2 O 2 [BO 2 (OH)]BCN/Bi prepared in example 3 2 O 2 [BO 2 (OH)]Degradation experiments were performed under irradiation of visible light, and the results are shown in fig. 9 and 10. The results show that: BCN/Bi prepared in example 1 of the present invention 2 O 2 [BO 2 (OH)]The photocatalytic degradation performance of the heterojunction catalyst is more excellent than that of a single sample and a composite heterojunction material prepared in other proportions. Due to the Z-type heterojunction BCN/Bi formed under the optimal proportion 2 O 2 [BO 2 (OH)]The BCN/BOBH photocatalyst has a wider light absorption range, improves the light utilization rate, simultaneously retains a stronger redox capability, effectively promotes charge separation and transfer, remarkably enhances the BCN/BOBH photocatalytic activity of the embodiment 1, and effectively and photo-catalytically degrades methylene blue and tetracycline.
Claims (7)
1. Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the preparation method of the photocatalyst comprises the following steps:
in a first step, bi (NO 3 ) 3 ·5H 2 Ultrasonic mixing O and ethanol to obtain bismuth nitrate solution;
second step, willBCN and K 2 B 4 O 7 ·4H 2 Adding O into ethanol, ultrasonically mixing, then dripping bismuth nitrate solution, fully stirring, transferring into a reaction kettle, and reacting in a constant-temperature oven at 120-200 ℃ for 12-36 hours; the BCN is B doped g-C 3 N 4 ；
Thirdly, after the reaction is finished, naturally cooling to room temperature, and carrying out suction filtration, washing and drying on the obtained product to obtain the hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]A photocatalyst.
2. A hollow flower-ball-shaped Z-heterojunction BCN/Bi as claimed in claim 1 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: in the first step the Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to ethanol is 1:16-1:8.
3. A hollow flower-ball-shaped Z-heterojunction BCN/Bi as claimed in claim 2 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the Bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to ethanol is 1:12.
4. A hollow flower-ball-shaped Z-heterojunction BCN/Bi as claimed in claim 1 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the second step is to blend the B with g-C 3 N 4 、K 2 B 4 O 7 ·4H 2 The mass ratio of O to ethanol is 0.01:1:12-0.05:1:12.
5. A hollow flower-ball-shaped Z-heterojunction BCN/Bi as claimed in claim 4 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the B is doped with g-C 3 N 4 、K 2 B 4 O 7 ·4H 2 The mass ratio of O to ethanol is 0.025:1:12.
6. A hollow flower ball shape according to claim 1Z-type heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the reaction temperature in the second step is 160 ℃, and the reaction time is 24 hours.
7. A hollow flower-ball-shaped Z-heterojunction BCN/Bi as claimed in claim 1 2 O 2 [BO 2 (OH)]The photocatalyst is characterized in that: the drying temperature in the third step is 60 ℃, and the drying time is 24 hours.
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