CN115920931B - BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof - Google Patents
BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN115920931B CN115920931B CN202211457607.3A CN202211457607A CN115920931B CN 115920931 B CN115920931 B CN 115920931B CN 202211457607 A CN202211457607 A CN 202211457607A CN 115920931 B CN115920931 B CN 115920931B
- Authority
- CN
- China
- Prior art keywords
- biobr
- photocatalyst
- heterojunction
- solution
- bio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004098 Tetracycline Substances 0.000 claims abstract description 30
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 30
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 30
- 229960002180 tetracycline Drugs 0.000 claims abstract description 25
- 229930101283 tetracycline Natural products 0.000 claims abstract description 25
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 14
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 11
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 11
- 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 claims abstract description 11
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 11
- 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 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 98
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 49
- 230000015556 catabolic process Effects 0.000 claims description 42
- 238000006731 degradation reaction Methods 0.000 claims description 42
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 230000001105 regulatory effect Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 12
- 239000000975 dye Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 83
- 238000003756 stirring Methods 0.000 description 41
- 239000000843 powder Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000000227 grinding Methods 0.000 description 21
- 238000011049 filling Methods 0.000 description 20
- 239000013049 sediment Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 15
- 230000005684 electric field Effects 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229940040944 tetracyclines Drugs 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 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 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 2
- 229940039790 sodium oxalate Drugs 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- -1 bromine compound Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008684 selective degradation Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a BiOBr/Bi 4O5Br2 heterojunction photocatalyst, and a preparation method and application thereof, and the preparation method comprises the following steps: the preparation method of the invention needs short time, forms the BiOBr/Bi 4O5Br2 Z heterojunction containing oxygen vacancies, enhances the visible light absorption range and strength, degrades antibiotics such as tetracycline and ciprofloxacin and organic dyes such as rhodamine B, methylene orange and methylene blue under visible light irradiation, can store holes and electrons, and can degrade organic pollutants under the condition of dim light, thereby realizing all-weather catalysis.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a BiOBr/Bi 4O5Br2 heterojunction photocatalyst, a preparation method and application thereof.
Background
The antibiotics are widely used, drug resistance is easy to occur, and after the antibiotics such as tetracycline, ciprofloxacin and the like enter human bodies, the antibiotics are difficult to be absorbed by intestines and stomach, and about 75% of antibiotics are discharged into sewage in the form of parent compounds. As a potential environmental ecological hazard source, the method for eliminating antibiotics in water is an effective mode, and the antibiotics in water environment can be removed without secondary pollution through photocatalysis degradation of the antibiotics by the photocatalyst. Conventional photocatalysts require continuous light irradiation (during the daytime) to drive a series of redox reactions, and when light irradiation is limited (during the nighttime), the generation and separation of photogenerated carriers are stopped, so that the generation of active species is stopped, and the catalytic activity is immediately lost, thus limiting practical use.
Br - in BiOBr forms [ Br 2]2- layer, bi and O link to each other through strong covalent bond and form [ Bi 2O2]2+ layer, [ Br 2]2- layer and [ Bi 2O2]2+ layer in the crystal link to each other through Van der Waals' force, arrange alternately, because positive and negative charge layer is arranged alternately, make photogenerated electron and hole migrate to different directions in the crystal under the effect of electric field force, have inhibited the recombination of photogenerated electron and hole, the photon quantum efficiency is improved, thus has strengthened the photocatalytic activity. However, the original two-dimensional tetragonal phase BiOBr still has the problems of limited photoresponsivity, easy recombination of photocarriers and the like.
The valence band of Bi xOyBrz is mainly composed of the hybridized orbitals of O2 p and Br 4p, and the conduction band is composed of the orbitals of Bi 6p, so that the band gap energy (E g) is reduced by increasing the Bi content in the Bi xOyBrz material to shift the edges of CB and VB upwards, and stronger visible light absorption and reduction capability are obtained. However, the single Bi xOyBrz photocatalyst still has the problems of easy electron-hole recombination, higher reduction potential and the like.
The prior art discloses a heterojunction of BiOBr/Bi 4O5Br2, a document CN108262050B discloses a two-dimensional composite visible light catalyst, a preparation method and application thereof, and the method comprises the steps of taking bismuth nitrate as a bismuth source, adjusting the pH value of a solution, then adding a surfactant cetyl trimethyl ammonium bromide as a bromine source and a coating agent to control the morphology, and preparing the two-dimensional BiOBr-Bi 4O5Br2 composite visible light catalyst, wherein the defect cannot be formed in the BiOBr-Bi 4O5Br2 due to the fact that the morphology is controlled by using an organic surfactant, so that the BiOBr-Bi 4O5Br2 composite visible light catalyst is a type II heterojunction. Document CN108187699a discloses a bisx-Bi 4O5X2 heterojunction, a method for preparing the same and applications thereof, wherein bismuth nitrate, one or more of bismuth oxalate and bismuth oxide containing Bi 3+, a salt of X - or an aqueous solution containing an acid of X - and glucose are subjected to a heating reaction; calcining the hydrothermal reaction product at 400-500 ℃ to prepare a BiOX-Bi 4O5X2 heterojunction, and treating at high temperature to ensure that the defect of the heterojunction cannot exist; literature 201910898187.4 discloses a preparation method of a Bi 4O5Br2/BiOBr composite photocatalyst for oilfield wastewater treatment, and discloses that glycerol solution containing a bromine compound is dropwise added into glycerol solution containing a bismuth compound, uniformly stirred, and subjected to hydrothermal reaction at 140-180 ℃ for 14-18 hours to obtain a precursor; distilled water is added into the precursor, and the hydrolysis reaction is carried out for 21-26 hours under the water bath condition of 40-70 ℃ to obtain the Bi 4O5Br2/BiOBr composite photocatalyst, and the Bi 4O5Br2/BiOBr is formed through hydrothermal and hydrolysis methods, so that the long-time hydrolysis reaction is carried out, and the time period for forming the heterojunction is long. The application of the catalyst is to degrade pollutants under visible light, so that the service time and the scene of the catalyst are limited, and the catalyst can be degraded only by continuous strong light.
Disclosure of Invention
The invention aims to provide a BiOBr/Bi 4O5Br2 heterojunction photocatalyst, a preparation method and application thereof, wherein the preparation method needs short time, and the formed BiOBr/Bi 4O5Br2 Z heterojunction containing oxygen vacancies can degrade organic matters under dim light and illumination conditions, so that all-weather catalysis is realized.
The invention is realized by the following technical scheme:
The preparation method of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst comprises the following steps:
Step 1, dissolving Bi (NO 3)3·5H2 O and NaBr into water to obtain a mixed solution;
Step 2, regulating the pH value of the mixed solution to 3-9 by using alkali solution to obtain precursor solution;
and step 3, carrying out hydrothermal reaction on the precursor solution, and washing and drying the obtained precipitate to obtain the BiOBr/Bi 4O5Br2 heterojunction photocatalyst.
Preferably, in step 1, the molar ratio of Bi (NO 3)3·5H2 O to NaBr) is (0.5-1.5): 0.5-1.5.
Preferably, in step 1, the concentrations of Bi (NO 3)3·5H2 O and NaBr) in the mixed solution are (0.0125-0.05) mol.L -1、(0.0125-0.05)mol·L-1, respectively.
Preferably, in step 2, the alkaline solution is NaOH solution.
Preferably, in the step 3, the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 8-20h.
Preferably, in step 3, the washing is performed with deionized water and absolute ethanol, respectively.
The BiOBr/Bi 4O5Br2 heterojunction photocatalyst obtained by the preparation method is characterized in that BiOBr and Bi 4O5Br2 coexist in the BiOBr/Bi 4O5Br2 heterojunction photocatalyst, a Z-type heterojunction is formed between BiOBr and Bi 4O5Br2, and contains oxygen vacancies, bi 4O5Br2 stores h + and BiOBr stores e -.
The BiOBr/Bi 4O5Br2 heterojunction photocatalyst is applied to the catalytic degradation of organic matters under the condition of dim light or illumination, so that all-weather catalysis is realized.
Preferably, the illumination condition is visible light.
Preferably, the organic matter is an antibiotic or an organic dye.
Preferably, the antibiotic is tetracycline or ciprofloxacin, and the organic dye is rhodamine B, methylene orange or methylene blue.
Compared with the prior art, the invention has the following beneficial effects:
According to the preparation method, bismuth nitrate is used as a bismuth source, inorganic salt NaBr is used as a bromine source, a surfactant is not added, the pH of the mixed solution is regulated, bismuth nitrate is controlled to hydrolyze to form BiO + polymer ions, and the BiOBr/Bi 4O5Br2 Z heterojunction containing oxygen vacancies is prepared through one-time hydrothermal reaction, so that the reaction time is short. The invention utilizes the change of Bi (NO 3)3·5H2 O hydrolyzed in precursor solutions with different pH values, forms BiOBr [ ((BiO) 2)·((BiO)3)·(BiO)4]Br7(OH)5 micelle) in BiOBr crystal nucleus, saturates and crystallizes in the hydrothermal reaction process to form BiOBr/Bi 4O5Br2 crystal, forms an interface electric field with [ ((BiO) 2)·((BiO)3)·(BiO)4]9+) in a colloidal particle solid-liquid interface BiOBr due to the existence of a diffusion double electric layer, forms OVs in a hydrothermal anoxic environment, and electrons bound by the BiOBr migrate to Bi 4O5Br2 under the action of the interface electric field, so that the Bi 3+ concentration of the BiOBr in the BiOBr/Bi 4O5Br2 is increased, the Bi +(3-x) concentration of the Bi 4O5Br2 is increased, the BiOBr/Bi 4O5Br2 Z heterojunction photocatalyst containing oxygen vacancies is formed, and the Bi 4O5Br2 stores h + and the BiOBr stores e - under the condition of retaining the original high redox capability, the BiOBr/Bi 4O5Br2 Z heterojunction containing oxygen vacancies prepared by the method enhances the visible light absorption range and strength, degrades antibiotics such as tetracycline, ciprofloxacin and the like and organic dyes such as rhodamine B, methylene orange, methylene blue and the like under the irradiation of visible light, obviously improves the photocatalytic performance, enhances the selective degradation of the tetracycline, and has simple and efficient method.
Realize all-weather catalysis "
Compared with pure-phase BiOBr and Bi 4O5Br2, the BiOBr/Bi 4O5Br2 heterojunction photocatalyst has the advantages that the oxygen vacancy concentration is increased, the combination energy is shifted rightwards, an interface electric field of Bi 4O5Br2 pointing to BiOBr is formed, under visible light irradiation, both BiOBr and Bi 4O5Br2 can be excited to generate electrons and holes, the electrons and the holes are respectively migrated to own conduction bands and valence bands, under the action of the interface electric field of BiOBr and Bi 4O5Br2, the electrons on the BiOBr conduction band are compounded with the holes on the Bi 4O5Br2 valence band, the photogenerated electrons reserved on the conduction band of Bi 4O5Br2 keep stronger reduction capability, the photogenerated electrons can react with O 2 to generate O 2 -, the holes on the VB of BiOBr react with water to generate OH, and the high carrier separation efficiency and the stronger redox capability of the BiOBr/Bi 4O5Br2 photocatalyst are realized. Therefore, the invention forms a Z-type heterojunction with the BiOBr and the Bi 4O5Br2, the band gap energy of the Bi 4O5Br2 is lower than that of the BiOBr (about 2.74 eV) photocatalyst, the absorption range of visible light of the heterojunction is enlarged, the oxidation-reduction capability is improved, the antibiotics and the organic dye can be degraded under dark and visible light irradiation, and the invention can be used for the application of a method for treating water pollution by photocatalysis.
Drawings
FIG. 1 is an XRD pattern of the photocatalyst prepared in comparative example 1, examples 1 to 3, comparative examples 2 and 3 according to the present invention.
Fig. 2 is an SEM image of the photocatalyst prepared in comparative example 1 of the present invention.
Fig. 3 is an SEM image of the photocatalyst prepared in example 2 of the present invention.
Fig. 4 is an SEM image of the photocatalyst prepared in comparative example 2 of the present invention.
FIG. 5 is a high resolution O1s XPS spectrum of the photocatalyst prepared in comparative example 1, example 2 and comparative example 2 of the present invention.
Fig. 6 is a high resolution Bi 4f XPS spectrum of the photocatalyst prepared in comparative example 1, example 2 and comparative example 2 of the present invention.
FIG. 7 is a Raman diagram of the photocatalyst prepared in comparative example 1, examples 1-3 and comparative example 2 of the present invention.
FIG. 8 is a graph of photocurrent i-t under irradiation of visible light for the photocatalysts prepared in comparative example 1, example 2 and comparative example 2 according to the present invention.
FIG. 9 is a graph showing the removal of tetracycline by the photocatalyst prepared in comparative example 1, examples 1-3, comparative examples 2, 3 according to the present invention under irradiation of visible light.
FIG. 10 shows apparent rate constants of degradation of tetracycline under irradiation of visible light of photocatalyst powders prepared in comparative example 1, examples 1 to 3, comparative examples 2 and 3 of the present invention.
FIG. 11 is a graph showing the removal of ciprofloxacin by the photocatalyst prepared in comparative example 1, examples 1 to 3, comparative examples 2 and 3 under irradiation of visible light.
FIG. 12 shows apparent rate constants of degradation of ciprofloxacin under irradiation of visible light of the photocatalyst powders prepared in comparative example 1, examples 1 to 3, and comparative examples 2 and 3 according to the present invention.
FIG. 13 shows the degradation rates of rhodamine B, methylene orange and methylene blue by the photocatalyst powder prepared in example 2 of the present invention under irradiation of visible light.
FIG. 14 is a graph showing the detection of active species of tetracycline degradation in visible light by the photocatalyst prepared in example 2 of the present invention.
FIG. 15 is a graph showing the ultraviolet-visible diffuse reflectance spectrum of the photocatalyst powders prepared in comparative example 1, examples 1 to 3, comparative examples 2 and 3 of the present invention.
FIG. 16 is a graph showing band gaps of the photocatalysts of comparative examples 1 and 2.
FIG. 17 is an XPS VB graph of the photocatalyst of comparative example 1 of the present invention.
FIG. 18 is an XPS VB graph of the photocatalyst of comparative example 2 of the present invention.
FIG. 19 is a graph of the photocatalytic mechanism of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst prepared according to the present invention under visible light.
FIG. 20 shows the removal curves of tetracycline in dark light for the photocatalysts prepared in comparative examples 1, 1-3 and comparative examples 2 and 3 according to the present invention.
FIG. 21 shows apparent rate constants of the photocatalysts prepared in comparative examples 1, 1-3 and comparative examples 2 and 3 for tetracycline degradation in dark light.
FIG. 22 is a graph showing TOC removal of tetracycline degradation in dark light for the photocatalyst prepared in example 2 of the present invention.
FIG. 23 is a graph showing the removal of ciprofloxacin by the photocatalyst prepared in comparative example 1, examples 1 to 3, comparative examples 2 and 3 under dark light.
FIG. 24 shows apparent rate constants of degradation of ciprofloxacin under dim light for the photocatalysts prepared in comparative example 1, examples 1 to 3, and comparative examples 2 and 3 according to the present invention.
FIG. 25 is a graph showing TOC removal rate of ciprofloxacin degraded by the photocatalyst prepared in example 2 of the present invention under dark light.
FIG. 26 shows the degradation rates of rhodamine B, methylene orange and methylene blue by the photocatalyst powder prepared in example 2 of the present invention under the dark light.
FIG. 27 is a graph showing the detection of active species of tetracycline degradation in dark light by the photocatalyst prepared in example 2 of the present invention.
FIG. 28 is a graph of the photocatalytic mechanism of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst prepared according to the present invention under dim light.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The preparation method of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst comprises the following steps:
Step1, dissolving a certain amount of Bi (NO 3)3·5H2 O and NaBr into water, and stirring to obtain a mixed solution;
step 2, regulating the pH value of the mixed solution to be 3-9 by using a NaOH solution, and then stirring to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution, and washing, drying and grinding the obtained precipitate to obtain the BiOBr/Bi 4O5Br2 heterojunction.
In the step 1, the concentration of Bi (NO 3)3·5H2 O and NaBr) in the mixed solution is (0.0125-0.05) mol.L -1、(0.0125-0.05)mol·L-1.Bi(NO3)3·5H2 O and the molar ratio of NaBr is (0.5-1.5).
In step 2, the concentration of the NaOH solution is 1mol L -1.
The temperature of the hydrothermal reaction in the step 3 is 120-200 ℃, and the hydrothermal reaction time is 8-20h; the washing is to wash with deionized water and absolute ethanol respectively.
In the BiOBr/Bi 4O5Br2 heterojunction photocatalyst, two phases of BiOBr and Bi 4O5Br2 coexist, and a Z-type heterojunction is formed between BiOBr and Bi 4O5Br2; biOBr belongs to tetragonal phase, and the space point group is P4/nmm (129); bi 4O5Br2 belongs to monoclinic phase, and the space point group is P21 (4).
The BiOBr/Bi 4O5Br2 heterojunction photocatalyst can degrade antibiotics and organic dyes under dark light and visible light. The antibiotics are tetracycline or ciprofloxacin, and the organic dye is rhodamine B, methylene orange, methylene blue, and the like.
Comparative example 1
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
And 2, carrying out hydrothermal reaction on the mixed solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr powder.
Comparative example 2
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
Step 2, adjusting the pH=12 of the mixed solution by using 1mol L -1 of NaOH solution, and stirring for 30min to obtain a precursor solution;
And 3, placing the precursor solution in a hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting the precipitate in the reaction solution sequentially, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain Bi 4O5Br2 powder.
Comparative example 3
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, adjusting the pH=14 of the mixed solution by using 1mol L -1 of NaOH solution, and stirring for 30min to obtain a precursor solution;
And 3, placing the precursor solution in a hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting the precipitate in the reaction solution sequentially, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain Bi 2O3 powder.
Example 1
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
Step 2, regulating the pH=3 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, placing the precursor solution in a hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting the precipitate in the reaction solution sequentially, and respectively performing 3 times of washing, drying and grinding by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 2
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 3
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=9 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 4
Step 1, dissolving 0.5mmol of Bi (NO 3)3·5H2 O and 0.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 5
Step 1, dissolving 1.5mmol of Bi (NO 3)3·5H2 O and 1.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 6
Step 1, dissolving 2mmol of Bi (NO 3)3·5H2 O and 2mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 7
Step 1, dissolving 0.5mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
Step 2, regulating the pH=6 of the mixed solution by using a 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 8
Step 1, dissolving 0.5mmol of Bi (NO 3)3·5H2 O and 1.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 9
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 0.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 10
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 11
Step 1, dissolving 1.5mmol of Bi (NO 3)3·5H2 O and 0.5mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 12
Step 1, dissolving 1.5mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 13
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 120 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 14
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 12 hours at 200 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 15
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
and 3, carrying out hydrothermal reaction on the precursor solution for 8 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 16
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 16 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
Example 17
Step 1, dissolving 1mmol of Bi (NO 3)3·5H2 O and 1mmol of NaBr into 40mL of water, and stirring for 30min to obtain a mixed solution;
step 2, regulating the pH=6 of the mixed solution by using 1mol L -1 NaOH solution, and then stirring for 30min to obtain a precursor solution;
And 3, carrying out hydrothermal reaction on the precursor solution for 20 hours at 160 ℃ with the filling rate of 80%, and finally collecting sediment in the reaction solution in sequence, and respectively washing, drying and grinding for 3 times by using deionized water and absolute ethyl alcohol to obtain the BiOBr/Bi 4O5Br2 heterojunction.
FIG. 1 shows XRD patterns of photocatalysts prepared in comparative examples 1, 1-3 and 2 and 3, respectively, in which a corresponds to examples 1 and b-d and examples 1-3, e and f correspond to powders prepared in examples 2 and 3, respectively. Examples 1-3 present (001), (102) and (110) crystal plane diffraction peaks corresponding to the tetragonal phase of BiOBr (JCPDS No. 09-0393) at 10.9 °, 31.7 and 32.22 °, the space point group being P4/nmm (129); the corresponding monoclinic phase Bi 4O5Br2 (JCPDS No. 37-0699) appears at 29.55 degrees, 29.70 degrees, 31.67 degrees and 31.81 degrees, the diffraction peaks of (11-3), (41-1), (402), (020) crystal faces are the space point group P21 (4), and when the pH is less than 3, biOBr is prepared, namely, comparative example 1; the preparation at ph=3-9 is BiOBr/Bi 4O5Br2, and as pH increases, bi 4O5Br2 content gradually increases, and at ph=12, only Bi 4O5Br2 phase appears, i.e. comparative example 2; the (220), (013) and (123) crystal plane diffraction peaks of cubic phase Bi 2O3 (JCPDS No. 74-1375) appear at 29.072 °, 32.594 ° and 38.784 ° at ph=14, i.e. comparative example 3, indicating that hydrothermal preparation yields cubic phase Bi 2O3, comparative example 3, at precursor ph=14.
Bi (NO 3)3·5H2 O is dissolved in water, hydrolyzed to form BiO +, equation (1) reacted, naBr hydrolyzed to Br - and Na +, equation (2) reacted, biO + formed a BiO-cr colloidal particle with Br -, equation (3) reacted, and hydrothermal formed a BiO-cr crystal of comparative example 1; when the pH value of the precursor solution is adjusted to 3-9, some BiO + and Br - form BiOBr crystal nuclei rapidly in aqueous solution, other BiO + gradually forms dimer ions (BiO) 2 2+, trimer ions (BiO) 3 3+ and tetramer ions (BiO) 4 4+, equations (3) to (6) react, the ions are adsorbed on the surface of the BiOBr crystal nuclei to form adsorption layers, biOBr [ (BiO)) 2(BiO)3(BiO)4]9+ colloidal particles, equation (7) and the colloidal particles are positively charged, then Br - and OH - in the solution are adsorbed to form a diffusion double layer, a micelle BiOBr [ (BiO) 2)·((BiO)3)·(BiO)4]Br7(OH)5, equation (8) is formed in a hydrothermal reaction system to form saturated crystals, the micelle forms BiOBr/Bi 4O5Br2 crystals, an electric field is formed between BiOBr and [ (BiO) 2)·((BiO)3)·(BiO)4]9+ due to diffusion exists at a colloidal particle solid-liquid interface, the direction points to BiOBr, when pH=12, biO + is polymerized to form tetramer (BiOBr) and BiOBr/BiOBr) crystals (BiO) 4332 are fully saturated in a hydrothermal reaction system (BiO) 4332, equation (10); at ph=14, biO + forms amorphous BiOOH with OH @, (BiO) 2 2+、(BiO)3 3+、(BiO)4 4+ also forms amorphous BiOOH with OH @, equations (11) - (14) react, and hydrothermal forms cubic phase crystal Bi 2O3, equation (15).
Bi(NO3)3+H2O＝BiONO3+2H++NO3- (1)
NaBr+H2O＝Br-+Na+ (2)
BiO++Br-＝BiOBr (3)
BiO++BiO+＝(BiO)2 2+ (4)
(BiO)2 2++BiO+＝(BiO)3 3+ (5)
(BiO)3 3++BiO+＝(BiO)4 4+ (6)
[(BiO)2]2++[(BiO)3]3++[(BiO)4]4++BiOBr＝
BiOBr[((BiO)2)·((BiO)3)·(BiO)4]9+ (7)
BiOBr[((BiO)2)·((BiO)3)·(BiO)4]9++Br-+OH-+H2O＝
BiOBr[((BiO)2)·((BiO)3)·(BiO)4]9+(Br)7(OH)5 (8)
BiOBr[((BiO)2)·((BiO)3)·(BiO)4]9+(Br)7(OH)5++H2O＝BiOBr/
Bi4O5Br2 (9)
(BiO)4 4++2Br-+H2O＝(BiO)4(Br)2(OH)2＝Bi4O5Br2 (10)
BiO++OH-＝BiOOH (11)
(BiO)2 2++2OH-＝(BiO)2(OH)2＝2BiOOH (12)
(BiO)3 3++3OH-＝(BiO)3(OH)3＝3BiOOH (13)
(BiO)4 4++4OH-＝(BiO)4(OH)4＝4BiOOH (14)
2BiO++2OH-＝2BiOOH＝Bi2O3+H2O (15)
Fig. 2, 3, and 4 are SEM images of the photocatalysts prepared in comparative example 1, example 2, and comparative example 2. Fig. 2 shows a pure phase BiOBr as a flower-like insert, but with thicker layers. Fig. 3 shows that the bilbr/Bi 4O5Br2 heterojunction nanoplatelets thin and the individual nanoplatelets become smaller in area, the specific surface area increases, and the increase in pH promotes nucleation of the bilcr, resulting in a decrease in grain size, possibly due to the differentiated nucleation process of the bilcr. When ph=12, i.e. becomes pure phase Bi 4O5Br2, the individual nanoplatelets decrease in area and are thinner, exhibiting a more loose structure, as shown in fig. 4.
FIG. 5 is a high resolution O1s XPS spectrum of the photocatalyst prepared in comparative example 1, example 2 and comparative example 2 of the present invention. Wherein a, c, e represent the BiOBr, biOBr/Bi 4O5Br2 and Bi 4O5Br2 photocatalysts synthesized according to comparative example 1, example 2 and comparative example 2, respectively. The pure phase BiOBr O1s spectra can be fitted to two peaks corresponding to oxygen vacancies, [ lattice oxygen atoms of Bi 2O2]2+ layer, ] at 532.42eV, 530.26eV, respectively, with an oxygen vacancy concentration of about 10.44%. The pure phase Bi 4O5Br2 O1s spectra can be fitted to two peaks corresponding to oxygen vacancies at 532.25eV, 529.63eV, respectively, [ lattice oxygen atoms of Bi 2O2]2+ layer, ] with an oxygen vacancy concentration of about 3.84%. The BiOBr/Bi 4O5Br2 O1s spectra can be fitted to two peaks, corresponding to oxygen vacancies at 531.17eV, 528.73eV, [ lattice oxygen atoms of Bi 2O2]2+ layer, ] with an oxygen vacancy concentration of about 14.46%, with an increase in oxygen vacancy concentration and shift in binding energy to the right compared to the pure phase of BiOBr and Bi 4O5Br2, demonstrating an increase in charge density of Bi 4O5Br2 O in BiOBr/Bi 4O5Br2.
Fig. 6 is a high resolution Bi 4f XPS spectrum of the photocatalyst prepared in comparative example 1, example 2 and comparative example 2 of the present invention. The pure phase BiOBr shows two strong peaks at about 164eV and about 158eV, which respectively belong to Bi 4f 7/2 and Bi 4f 5/2, and after fitting, the two peaks can be divided into eV and eV, eV and 156.90eV 4 binding energies, the eV and the eV are respectively attributed to Bi concentration about 63.03%, the low binding energy at the eV and the eV is attributed to low-charge Bi ions in the compound (Bi concentration about 36.97 percent in the BiOBr/Bi heterojunction, the peaks of 162.03 and eV are attributed to Bi concentration about 60.93 percent, and the peak of 155.29eV is attributed to Bi concentration about%, the binding energy is shifted rightwards and the concentration is increased, and the fact that the interface interaction between BiOBr/Bi causes the change of the chemical environment is proved to be respectively classified into eV and eV (Bi), the eV and the eV (Bi concentration about 29.72 percent when the BiOBr/Bi is formed, the diffusion double electric double layer exists, the interface between the BiOBr and the oxygen deficiency (BiO) forms an interface, the oxygen deficiency environment is formed in the thermal equilibrium condition, and the thermal energy of the Bir/Bir is increased until the two-level-of the oxygen-poor environment is reached.
FIG. 7 is a Raman diagram of the photocatalysts prepared in comparative example 1, examples 1-3 and comparative example 2 of the present invention, wherein a corresponds to the powder prepared in comparative example 1, b-d corresponds to examples 1-3, and e-f corresponds to comparative example 2-3. The strong raman peak at 114cm -1 of the pure phase bio-ir is due to the Bi-O stretching mode inside a 1g, the raman peak at 161.681cm -1 is due to the Bi-O stretching mode inside E g, and the E g and B 1g bands generated by the movement of oxygen atoms around 367cm -1 are very weak, not obvious, in relation to the compressive movement of the [ Bi 2O2]2+ layer and the dihalide [ Br 2]2- layer ]. As the pH is increased, the characteristic peak of A 1g at 110cm -1 gradually decreases and shifts to the right, the characteristic peak of E g at 156cm -1 gradually increases and shifts to the left, and both vibration peaks are related to the [ Bi 2O2]2+ layer and the [ Br 2]2- layer ], which are caused by different crystal structures of BiOBr and Bi 4O5Br2, which shows that the structure of BiOBr changes, and a BiOBr/Bi 4O5Br2 heterojunction is generated, consistent with the XRD result.
FIG. 8 is a graph of photocurrent i-t of the photocatalyst prepared in comparative example 1, example 2 and comparative example 2 under irradiation of visible light, in which a corresponds to comparative example 1, c corresponds to example 2, e corresponds to the powder prepared in comparative example 2. Fig. 8 shows that all samples had photocurrent responses under visible light, indicating that they both generated photo-generated charge under illumination and photo-generated electrons could migrate directionally. The photo-current of the BiOBr/Bi 4O5Br2 photocatalyst is significantly enhanced compared to the pure phase sample, which suggests that its photo-current separation rate and mobility are maximized.
FIG. 9 is a graph showing the degradation curves of the photocatalyst powder prepared in comparative examples 1, 1-3 and comparative examples 2-3 on tetracyclines with concentration of 20mg.L -1 under irradiation of visible light, and FIG. 10 is the corresponding apparent rate constants, wherein the degradation curves and apparent rate constants of the powder prepared in comparative examples 1, b-d and e-f on tetracyclines prepared in comparative examples 1-3 and 2-3 are shown, the degradation efficiencies of 0.5g of pure phase BiOBr, pure phase Bi 4O5Br2, pure phase Bi 2O3 and BiOBr/Bi 4O5Br2 prepared in examples 1-3 on tetracyclines are 28.26%, 12.29%, 12.56%, 50.69%, 69.48% and 58.51% respectively, the degradation activities of the heterojunction of a and b-d on tetracyclines under irradiation of visible light are obviously higher than those of Bir, bi 4O5Br2 and Bi 2O3, and the degradation efficiencies of the BiOBr/Bi 4O5Br2 prepared in example 2 on tetracyclines can reach the corresponding apparent rates of -1 min.
FIG. 11 is a graph showing the degradation curves of the photocatalytic powder prepared in comparative examples 1, 1-3 and comparative examples 2-3 on ciprofloxacin with the concentration of 10 mg.L -1 under the irradiation of visible light, and FIG. 12 is the corresponding apparent rate constants, wherein the degradation curves and apparent rate constants of the powder prepared in comparative examples 1-3 and e-f corresponding to comparative examples 1-3 and 2-3 are shown in the graph, respectively, the degradation activities of 0.5g of pure phase BiOBr, pure phase Bi 4O5Br2, pure phase Bi 2O3 and BiOBr/Bi 4O5Br2 prepared in examples 1-3 on ciprofloxacin under the irradiation of visible light are 23.15%, 33.68%, 17.24%, 45.83%, 72.47% and 66.23% respectively, the corresponding apparent rate constants are respectively, the degradation activities of the heterojunction prepared in comparative examples 1-b-d on ciprofloxacin under the irradiation of visible light are obviously higher than those of pure phase BiOBr, bi 4O5Br2 and Bi 2O3, and BiOBr/Bi 3525 can reach the degradation constants of -1 min for BiOBr/Bi 4O5Br2 prepared in the example.
FIG. 13 shows the degradation rates of 0.5g of the photocatalyst powder prepared in example 2 of the present invention on 10 mg.L -1 rhodamine B, 10 mg.L -1 methylene orange and 10 mg.L -1 methylene blue under irradiation of visible light, the degradation rate of the BiOBr/Bi 4O5Br2 photocatalyst on rhodamine B is 67.32%, the degradation rate on methylene orange is 67.39% and the degradation rate on methylene blue is 60.22%, and it can be seen that the prepared BiOBr/Bi 4O5Br2 photocatalyst also has good degradation ability on dye.
FIG. 14 is a graph showing the capturing of visible light on tetracycline degrading active species by the photocatalyst powder prepared in example 2 of the present invention, wherein benzoquinone is added as an O 2 - free radical scavenger, sodium oxalate is added as an h + scavenger, tert-butanol is added as an OH scavenger, the photodegradation reaction is inhibited to different degrees, and the contribution of the active species to the removal of tetracycline is in turn O 2 ->h+ OH.
FIG. 15 is a graph showing the ultraviolet-visible diffuse reflectance spectra of the photocatalyst powders prepared in comparative example 1, examples 1-3, comparative examples 2 and 3, in which a corresponds to the powder prepared in comparative example 1-3, b-d corresponds to the powder prepared in comparative example 2-3. The absorption range of the pure phase BiOBr in the visible light region is smaller, the absorption edge is 437.29nm, and the absorption edge of the pure phase Bi 4O5Br2 is 472.63nm. The BiOBr/Bi 4O5Br2 heterojunction photocatalyst has red shift in the visible light absorption range, the absorption edge red shifts to 480.12nm, and the absorption intensity of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst on visible light is enhanced.
FIG. 16 is a graph showing band gaps of the photocatalysts of comparative examples 1 and 2. In the figure, a and e correspond to the BiOBr and Bi 4O5Br2 photocatalyst powders prepared in comparative examples 1 and 2, respectively. The bandgap of BiOBr is 2.68eV and that of Bi 4O5Br2 is 2.25eV. Fig. 17 and 18 are band gap diagrams of the photocatalysts of comparative examples 1 and 2 of the present invention. The valence band position of BiOBr is +2.59eV, and the valence band position of Bi 4O5Br2 is +1.49eV. The conduction bands for BiOBr and Bi 4O5Br2 are-0.09 eV and-0.76 eV, respectively, according to equation E CB＝EVB-Eg. Under illumination, biOBr and Bi 4O5Br2 valence band electrons are excited into the conduction band, leaving corresponding holes in the valence band. If the Bi 4O5Br2 conduction band electron migrates to the conduction band of the Bi obr, the Bi obr valence band hole migrates to the valence band of Bi 4O5Br2, forming a conventional type II heterojunction, but this is not in agreement with the active species results. Thus, a Z-type heterojunction is formed between Bi 4O5Br2 and BiOBr.
FIG. 19 is a graph of the photocatalytic mechanism of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst prepared according to the present invention under visible light. In the preparation process of the photocatalyst, an interface electric field of Bi 4O5Br2 pointing to BiOBr is formed due to the existence of a diffusion double layer. Under the irradiation of visible light, biOBr and Bi 4O5Br2 can be excited to generate electrons and holes, the electrons and the holes are respectively migrated to the conduction band and valence band of the BiOBr and Bi 4O5Br2, under the action of an interface electric field of the BiOBr and Bi 4O5Br2, the electrons on the BiOBr conduction band are combined with holes on the Bi 4O5Br2 valence band, the photo-generated electrons reserved on the conduction band of Bi 4O5Br2 have strong reducing capability and can react with dissolved O 2 in solution to generate O 2 -, and the photo-generated holes reserved on the valence band of the BiOBr react with water to generate OH with strong oxidizing capability, so that the high carrier separation efficiency and the strong redox capability of the BiOBr/Bi 4O5Br2 photocatalyst are realized.
FIG. 20 is a graph showing the removal curves of tetracycline at a concentration of 20mg.L -1 under dark light for the photocatalysts prepared in comparative examples 1, 1-3 and comparative examples 2 and 3, and FIG. 21 is a graph showing the respective apparent rate constants, wherein the powder prepared in comparative examples 1, b-d and 2-3 shows the degradation curves and the apparent rate constants of tetracycline. As can be seen from the graph, after 50min of dark light, the degradation efficiency of 0.5g of pure phase BiOBr, pure phase Bi 4O5Br2, pure phase Bi 2O3 and BiOBr/Bi 4O5Br2 prepared in examples 1-3 on tetracycline is respectively 32.93%, 40.52%, 24.35%, 57.12%, 63.44% and 47.69%, the corresponding apparent rate constants are respectively that the degradation activity of 0.00867min-1、0.01175min-1、0.00569min-1、0.02024min-1、0.02351min-1、0.01565min-1.BiOBr/Bi4O5Br2 heterojunction on tetracycline under dark light is obviously higher than that of BiOBr, bi 4O5Br2 and Bi 2O3, wherein the degradation efficiency of BiOBr/Bi 4O5Br2 photocatalyst prepared in example 2 on tetracycline can reach 63.44%, and the corresponding apparent rate constant is 0.02351min -1. FIG. 22 is a graph showing TOC removal of tetracycline at a concentration of 40 mg.L -1 under dark light for the photocatalyst prepared in example 2 of the present invention. The mineralization capacity of the BiOBr/Bi 4O5Br2 photocatalyst is further verified through TOC test, after 50min of dark light, the TOC removal rate of the BiOBr/Bi 4O5Br2 photocatalyst to 40mg/L tetracycline can reach 28.86%, and the BiOBr/Bi 4O5Br2 photocatalyst has higher mineralization capacity under the dark light.
FIG. 23 is a graph showing the degradation curves of the photocatalytic powder prepared in comparative examples 1, 1-3 and comparative examples 2-3 for ciprofloxacin with concentration of 10mg.L -1 in the dark, and FIG. 24 is the corresponding apparent rate constants, wherein the degradation curves and apparent rate constants of the powder prepared in comparative examples 1-3 and e-f corresponding to comparative examples 1-3 for a corresponding to comparative examples 1-b-d are respectively higher than those of the powder prepared in comparative examples 2-3 for ciprofloxacin, and the degradation efficiencies of 0.5g of pure phase BiOBr, pure phase Bi 4O5Br2, pure phase Bi 2O3 and BiOBr/Bi 4O5Br2 prepared in examples 1-3 for ciprofloxacin are respectively 56.42%, 45.69%, 26.14%, 63.56%, 75.95% and 60.37% for a corresponding apparent rate constant are respectively 0.04218min-1、0.02805min-1、0.0147min-1、0.0499min-1、0.0729min-1、0.04487min-1.BiOBr/Bi4O5Br2 heterojunction, and the degradation activities of the powder prepared in dark for ciprofloxacin are obviously higher than those of pure phase BiOBr, 4O5Br2 and Bi 2O3, wherein the degradation efficiency of BiOBr/Bi 4O5Br2 prepared in example 2 for the dark is respectively equal to 56.42%, and the apparent rate of the catalyst is equal to 0729.689. FIG. 25 is a graph showing TOC removal of ciprofloxacin at a concentration of 20 mg.L -1 under dark light by the photocatalyst prepared in example 2 of the present invention. The mineralization capacity of the BiOBr/Bi 4O5Br2 photocatalyst is further verified through TOC test, after 25min of dark light, the TOC removal rate of the BiOBr/Bi 4O5Br2 photocatalyst to 20mg/L ciprofloxacin can reach 44.52%, and the BiOBr/Bi 4O5Br2 photocatalyst has higher mineralization capacity under the dark light.
FIG. 26 shows that the degradation rate of 0.5g of the photocatalyst powder prepared in example 2 of the present invention to 10 mg.L -1 rhodamine B, 10 mg.L -1 methylene orange and 10 mg.L -1 methylene blue under the dark light, the degradation rate of the BiOBr/Bi 4O5Br2 photocatalyst to rhodamine B is 64.54%, the degradation rate to methylene orange is 57.75% and the degradation rate to methylene blue is 58.4%, and it can be seen that the prepared BiOBr/Bi 4O5Br2 photocatalyst also has good degradation ability to dyes under the dark light.
FIG. 27 is a graph showing the capture of active species for tetracycline degradation under dim light of the photocatalyst powder prepared in example 2 of the present invention, wherein benzoquinone is added as an-O 2 - free radical scavenger, sodium oxalate is added as an h + scavenger, tert-butanol is added as an-OH scavenger, the dark light reaction is inhibited to different degrees, and the contribution of the active species to the removal of tetracycline is h +>·O2 - in turn.
FIG. 28 is a graph of the photocatalytic mechanism of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst prepared according to the present invention under dim light. In the preparation process of the photocatalyst, an interface electric field is formed between a colloidal particle solid-liquid interface BiOBr and [ ((BiO) 2)·((BiO)3)·(BiO)4]9+), biOBr forms OVs under the action of the interface electric field due to a hydrothermal oxygen deficient environment, and e bound by BiOBr migrates to Bi 4O5Br2, so that the Bi 3+ concentration of BiOBr in BiOBr/Bi 4O5Br2 is increased, the Bi +(3-x) concentration of Bi 4O5Br2 is increased until the fermi levels of the BiOBr and the Bi are balanced, a BiOBr/Bi 4O5Br2 heterojunction is formed, the Bi +(3-x) concentration is increased in Bi 4O5Br2, a Bi +(3-x) doped Bi 4O5Br2 material is formed, a negative electric center is formed, and an acceptor level is formed at the top of a valence band, so that Bi 4O5Br2 stores h + in the BiOBr/Bi 4O5Br2 photocatalyst, and BiOBr stores e -. Under the dark light, bi 4O5Br2 stores h + can be released to oxidize and degrade pollutants, and the e - stored by the reaction with dissolved oxygen forms O 2 - free radicals.
The foregoing is merely one embodiment, not all or only one embodiment, and any equivalent modifications of the technical solution of the present invention by those skilled in the art after reading the present specification are intended to be encompassed by the claims of the present invention.
Claims (10)
1. The preparation method of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst is characterized by comprising the following steps of:
Step 1, dissolving Bi (NO 3)3·5H2 O and NaBr into water to obtain a mixed solution;
Step 2, regulating the pH value of the mixed solution to 3-9 by using alkali solution to obtain precursor solution;
and step 3, carrying out hydrothermal reaction on the precursor solution, and washing and drying the obtained precipitate to obtain the BiOBr/Bi 4O5Br2 heterojunction photocatalyst.
2. The method for preparing a BiOBr/Bi 4O5Br2 heterojunction photocatalyst as claimed in claim 1, wherein in the step 1, the molar ratio of Bi (NO 3)3·5H2 O to NaBr) is (0.5-1.5).
3. The method for preparing a BiOBr/Bi 4O5Br2 heterojunction photocatalyst as claimed in claim 1, wherein in the step 1, the concentrations of Bi (NO 3)3·5H2 O and NaBr) in the mixed solution are (0.0125-0.05) mol.L -1、(0.0125-0.05)mol·L-1 respectively.
4. The method for preparing a BiOBr/Bi 4O5Br2 heterojunction photocatalyst as claimed in claim 1, wherein in the step 2, the alkali solution is NaOH solution.
5. The method for preparing a BiOBr/Bi 4O5Br2 heterojunction photocatalyst as claimed in claim 1, wherein in the step 3, the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 8-20h.
6. The BiOBr/Bi 4O5Br2 heterojunction photocatalyst obtained by the preparation method as claimed in any one of claims 1 to 5, wherein BiOBr and Bi 4O5Br2 coexist in the BiOBr/Bi 4O5Br2 heterojunction photocatalyst, a Z-type heterojunction is formed between BiOBr and Bi 4O5Br2, and oxygen vacancies are contained in the Z-type heterojunction.
7. The use of the BiOBr/Bi 4O5Br2 heterojunction photocatalyst according to claim 6 in the catalytic degradation of organic matter under dim light or light conditions.
8. The use according to claim 7, wherein the lighting condition is visible light.
9. The use according to claim 7, wherein the organic substance is an antibiotic or an organic dye.
10. The use according to claim 9, wherein the antibiotic is tetracycline or ciprofloxacin and the organic dye is rhodamine B, methylene orange or methylene blue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457607.3A CN115920931B (en) | 2022-11-21 | 2022-11-21 | BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457607.3A CN115920931B (en) | 2022-11-21 | 2022-11-21 | BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115920931A CN115920931A (en) | 2023-04-07 |
| CN115920931B true CN115920931B (en) | 2024-04-19 |
Family
ID=86696833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211457607.3A Active CN115920931B (en) | 2022-11-21 | 2022-11-21 | BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115920931B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262050A (en) * | 2018-01-03 | 2018-07-10 | 东南大学 | A kind of two dimension composite visible light catalyst and preparation method and application |
| CN109590005A (en) * | 2018-12-14 | 2019-04-09 | 江苏大学 | A kind of high electron-transporting type nucleocapsid ZnIn2S4Nanometer sheet/Ta3N5The preparation method and application of composite photo-catalyst |
| CN110538664A (en) * | 2019-09-23 | 2019-12-06 | 重庆科技学院 | preparation method of Bi4O5Br2/BiOBr composite photocatalyst for oilfield wastewater treatment |
| CN114653381A (en) * | 2022-02-15 | 2022-06-24 | 江苏大学 | ZnIn2S4BiVO (BiVO) wrapped by nanosheets4Preparation method and application of micron rod core-shell heterojunction catalyst |
-
2022
- 2022-11-21 CN CN202211457607.3A patent/CN115920931B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262050A (en) * | 2018-01-03 | 2018-07-10 | 东南大学 | A kind of two dimension composite visible light catalyst and preparation method and application |
| CN109590005A (en) * | 2018-12-14 | 2019-04-09 | 江苏大学 | A kind of high electron-transporting type nucleocapsid ZnIn2S4Nanometer sheet/Ta3N5The preparation method and application of composite photo-catalyst |
| CN110538664A (en) * | 2019-09-23 | 2019-12-06 | 重庆科技学院 | preparation method of Bi4O5Br2/BiOBr composite photocatalyst for oilfield wastewater treatment |
| CN114653381A (en) * | 2022-02-15 | 2022-06-24 | 江苏大学 | ZnIn2S4BiVO (BiVO) wrapped by nanosheets4Preparation method and application of micron rod core-shell heterojunction catalyst |
Non-Patent Citations (4)
| Title |
|---|
| "Bi4O5Br2光催化材料研究进展";蔡宇昂等;《工业催化》;20211215;第29卷(第12期);第13-18页 * |
| "Facil construction of the phase junction of BiOBr and Bi4O5Br2 nanoplates for ciprofloxacin photodegradation";Su Xiaoxiao et al.;《Materials Science in Semiconductor》;20180615;第80卷;第123-130页 * |
| Ag/AgBr/Bi_4O_5Br_2复合催化剂的合成及性能研究;朱刚强;林杰;李宁;高健智;王成会;;广东化工;20180730(14);第22-24+61页 * |
| 张旭 ; 杨萍 ; 刘卫华 ; .自掺杂改性Bi_4O_5X_2(X=Br,I)异质结催化剂的合成及在油田废液处理上的应用.分子催化.2020,(02),第133-149页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115920931A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| El-Katori et al. | Impact of CdS/SnO2 heterostructured nanoparticle as visible light active photocatalyst for the removal methylene blue dye | |
| Qin et al. | Ultrasonic-assisted fabrication of a direct Z-scheme BiOI/Bi2O4 heterojunction with superior visible light-responsive photocatalytic performance | |
| Zhu et al. | Fabrication of 3D Bi5O7I/BiOIO3 heterojunction material with enhanced photocatalytic activity towards tetracycline antibiotics | |
| Hojamberdiev et al. | One-step hydrothermal synthesis and photocatalytic performance of ZnWO4/Bi2WO6 composite photocatalysts for efficient degradation of acetaldehyde under UV light irradiation | |
| CN112156803B (en) | Photocatalytic composite material and preparation method and application thereof | |
| Li et al. | Hydrothermal synthesized novel nanoporous g-C3N4/MnTiO3 heterojunction with direct Z-scheme mechanism | |
| Cui et al. | Photocatalytic activity of Cd1− xZnxS/K2Ti4O9 for Rhodamine B degradation under visible light irradiation | |
| Du et al. | Reduced graphene oxide modified Z-scheme AgI/Bi 2 MoO 6 heterojunctions with boosted photocatalytic activity for water treatment originated from the efficient charge pairs partition and migration | |
| CN110302826B (en) | Basic bismuth nitrate and bismuth oxyiodide composite photocatalyst and preparation method and application thereof | |
| Ma et al. | Research progress in photocatalytic activated persulfate degradation of antibiotics by bismuth-based photocatalysts | |
| Yu et al. | Low-temperature strategy for vapor phase hydrothermal synthesis of C\N\S-doped TiO2 nanorod arrays with enhanced photoelectrochemical and photocatalytic activity | |
| CN114950522A (en) | Boron nitride/indium zinc sulfide composite photocatalyst and preparation method and application thereof | |
| CN113426467A (en) | Z-type boron-doped carbon nitride and silver iodide composite visible light catalyst and preparation method thereof | |
| Li et al. | The effects of cotton cellulose on both energy band gap of gC 3 N 4–TiO 2 nanoparticles and enhanced photocatalytic properties of cotton-gC 3 N 4–TiO 2 composites | |
| CN113976147B (en) | Bi/Bi 4 O 5 Br 2 Photocatalyst, preparation method and application thereof | |
| CN117643900B (en) | Preparation method and application of S-type heterojunction copper ferrite/zinc indium sulfide visible light catalyst | |
| CN113578313B (en) | Manganese-doped sillenite photocatalyst, preparation method thereof and application thereof in synchronous degradation of hexavalent chromium and organic pollutants | |
| Ahmad et al. | Synergistic effect of doping-induced oxygen vacancies, in-built Tb4+/Tb3+ redox centers and heterojunction on the photocatalytic activity of Sm-doped ZnO/Y-doped Tb2O3 for H2 evolution | |
| CN115920931B (en) | BiOBr/Bi4O5Br2Heterojunction photocatalyst, preparation method and application thereof | |
| CN110624574B (en) | Double Bi4O5I2Preparation method of photocatalytic material and application of photocatalytic material in degrading MC-LR | |
| CN116532135A (en) | Cobalt ion doped modified up-conversion photocatalyst and preparation method and application thereof | |
| CN113582218B (en) | Oxygen defect type gray zinc oxide and preparation method and application thereof | |
| Yu et al. | Efficient removal of tetracycline hydrochloride through novel Fe/BiOBr/Bi2WO6 photocatalyst prepared by dual-strategy under visible-light irradiation | |
| Nagavenkatesh et al. | Review on the recent improvements in lanthanum ferrite perovskites for visible light driven textile dyes degradation and its various hetero-junctions catalysis mechanism | |
| CN115920939B (en) | BiOBr@Bi2O2(CO3)1-xNxPhotocatalyst with core-shell structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |