CN115254151B - BiVO with core-shell structure 4 @BiOCl heterojunction as well as preparation method and application thereof - Google Patents
BiVO with core-shell structure 4 @BiOCl heterojunction as well as preparation method and application thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 52
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 claims abstract description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000956 coumarin Drugs 0.000 claims abstract description 10
- 235000001671 coumarin Nutrition 0.000 claims abstract description 10
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960003742 phenol Drugs 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- 241000276425 Xiphophorus maculatus Species 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 116
- 239000002243 precursor Substances 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 60
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 30
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- 238000001035 drying Methods 0.000 claims description 28
- 239000011941 photocatalyst Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
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- 239000007788 liquid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 238000001228 spectrum Methods 0.000 abstract description 6
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 152
- 238000006731 degradation reaction Methods 0.000 description 34
- 230000015556 catabolic process Effects 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000004098 Tetracycline Substances 0.000 description 25
- 229960002180 tetracycline Drugs 0.000 description 25
- 229930101283 tetracycline Natural products 0.000 description 25
- 235000019364 tetracycline Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 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 22
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- 235000019441 ethanol Nutrition 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 230000004298 light response Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
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- 238000005215 recombination Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 alkoxide compounds Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- 239000004005 microsphere Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000007281 self degradation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention provides a BiVO with a core-shell structure 4 @BiOCl heterojunction, preparation method and application thereof, and BiVO with inner core 4 ，BiVO 4 The structure is monoclinic phase, and the appearance is decahedron; biVO (BiVO) 4 Is formed with a platy tetragonal phase BiOCl, biVO on the (010) crystal face 4 The (110) crystal face of (C) is formed with a granular tetragonal phase BiOCl with oxygen vacancies, a flaky tetragonal phase BiOCl and a granular tetragonal phase BiOCl-coated BiVO 4 Forming a core-shell structure. BiVO with core-shell structure 4 The @ BiOCl heterojunction has enhanced photocatalytic performance under the full spectrum of ultraviolet-visible light-near infrared light, and improves the photocatalytic effect of the material and the broad application of the material to antibiotics, phenol, salicylic acid, bisphenol A and coumarin.
Description
Technical Field
The invention belongs to the field of functional materials, and relates to a core-shell structure BiVO4@BiOCl heterojunction with an oxygen vacancy, and a preparation method and application thereof.
Background
BiVO 4 Has the advantages of narrow energy gap, high visible light catalytic activity, strong oxidation-reduction capability, no toxicity and the like, and is widely applied to the field of photocatalysis. However BiVO 4 The semiconductor catalyst still has the defects of low photon utilization rate, high photon-generated electron-hole pair recombination rate, difficult photon-generated carrier migration, visible light absorption range and the like.
The tetragonal BiOCl has a unique layered structure, provides an excellent carrier transmission channel and has unique properties due to the characteristics of sensitivity to pH value, and the like, but has a wider band gap (3.2 eV) so as to respond to ultraviolet light only, thereby limiting the photocatalytic performance.
Document CN106391062 a-a BiVO 4 A BiOCl heterojunction photocatalyst and its preparing process are disclosed, which uses BiOCl as core and BiVO 4 Microsphere with nanosheets wrapped outside BiOCl nucleus and synthesized BiVO 4 The BiOCl photocatalyst has higher crystallinity and no other impurities; has wider visible light response range and higher photocatalytic degradability to organic dye. CN 111330602A-a carbon cloth loaded BiOCl/BiVO 4 The recyclable flexible composite photocatalytic material is prepared by adopting carbon cloth as a flexible substrate and preparing carbon cloth-loaded BiOCl/BiVO 4 The recyclable flexible composite photocatalytic material solves the current situation that the powdery catalyst is difficult to recycle and improve the characteristic of little visible light absorption of BiOCl. CN 112871187A-a modified diatomite-loaded BiVO4-BiOCl heterojunction composite material and application thereof, discloses a method for preparing modified diatomite-loaded BiOCl nanoflower and Zn-doped mesoporous BiVO 4 The diatomite loaded photocatalyst composite material is obtained by combining, and the absorption wavelength in the visible light range is widened, so that the high-efficiency adsorption and photocatalytic degradation process of the tetracycline is realized.
However, the materials prepared in the above documents are only responsive to visible light, and BiVO is prepared 4 Microsphere with nanosheets wrapped outside BiOCl core, or BiOCl/BiVO 4 At the same time, the BiVO is loaded on carbon cloth and diatomite, and the BiVO is not solved 4 The problem that BiOCl only degrades dyes rhodamine B and tetracycline is single in light response and photocatalytic activity under ultraviolet-visible light-near infrared light full spectrum.
Disclosure of Invention
The invention aims to provide a BiVO with a core-shell structure 4 @BiOCl heterojunction, preparation method and application thereof, and prepared nuclear shell structure BiVO 4 At BiVO @ BiOCl heterojunction 4 Has oxygen vacancies in the granular tetragonal phase BiOCl on the (110) crystal plane,has enhanced photocatalytic performance under the full spectrum of ultraviolet, visible light and near infrared light.
The invention is realized by the following technical scheme:
BiVO with core-shell structure 4 @ BiOCl heterojunction wherein BiVO 4 The structure is a monoclinic phase, and the appearance is a smooth decahedron shape; decahedron monoclinic phase BiVO 4 A (010) crystal face of (a) is formed with a flaky tetragonal phase BiOCl and a decahedral monoclinic phase BiVO 4 Form a granular tetragonal phase BiOCl with oxygen vacancies on the (110) crystal face to form BiOCl nano-sheets and nano-particle wrapped decahedral BiVO 4 Is a core-shell structure.
The core-shell structure BiVO 4 The preparation method of the @ BiOCl heterojunction comprises the following steps:
step 4, bi (NO 3 ) 3 ·5H 2 O is dissolved in glycol solution, and is stirred until the O is completely dissolved, so that a precursor solution C is formed;
step 5, constant volume of concentrated hydrochloric acid is prepared into dilute hydrochloric acid solution A;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding a dilute hydrochloric acid solution A in the stirring process, stirring for 4-6 hours, and then washing a sample with water, washing with alcohol and drying to obtain the BiVO with the core-shell structure and oxygen vacancies 4 @ BiOCl heterojunction photocatalyst.
Preferably, in the step 3, the stirring time is 30 to 40 minutes.
Preferably, in the step 3, the ultraviolet irradiation time is 30-40 min.
Preferably, in the step 4, bi (NO 3 ) 3 ·5H 2 The mol volume ratio of O to glycol is (0.1-0.3) mmol: (60-180) mL.
Preferably, in the step 4, the stirring time is 30 to 60 minutes. Bi (NO) in precursor solution C 3 ) 3 ·5H 2 The concentration of O was 0.002mol/L.
Preferably, in the step 5, the concentration of the diluted hydrochloric acid solution A is 10-12 mM.
Preferably, in the steps 4 and 6, the volume ratio of adding ethylene glycol to dropwise adding the diluted hydrochloric acid solution C is 3:1. in the step 6, biVO 4 、Bi(NO 3 ) 3 ·5H 2 The mol ratio of O to HCl is (0.8-1.0): (0.1-0.3): (0.2-0.72).
Preferably, in the step 6, the drying is vacuum drying at a constant temperature of 50-60 ℃ for 10-12 hours.
The core-shell structure BiVO 4 The @ BiOCl heterojunction can be used as a photocatalyst for photocatalytic degradation of organic pollutants due to the existence of a large number of oxygen vacancies.
The core-shell structure BiVO 4 The @ BiOCl heterojunction can be used as a photocatalyst for photocatalytic degradation of antibiotics, phenol, salicylic acid, bisphenol A and coumarin due to the existence of a large number of oxygen vacancies.
Compared with the prior art, the invention has the following beneficial effects:
the BiVO with the core-shell structure 4 @ BiOCl heterojunction, in decahedral BiVO 4 Nano-sheet BiOCl is generated on the (010) crystal face of BiVO 4 The (110) crystal face of the crystal (B) is provided with nano-granular BiOCl with oxygen vacancies, and the nano-granular BiOCl has oxygen vacancies and can cause unique LSPR effect to enable BiVO 4 The @ BiOCl heterojunction generates certain absorption in the near infrared region, widens the light response range, and has the light response capability under the full spectrum of ultraviolet-visible light-near infrared light. BiOCl and BiVO with two different morphologies 4 The coexistence of two phases accelerates the separation of photo-generated electrons and holes and reduces the photo-generated electron-holeThe recombination rate of the material is improved, the oxidation-reduction capability of the material under the full spectrum of ultraviolet-visible light-near infrared light is improved, and the photocatalysis effect of the material and the broad application of the material to antibiotics, phenol, salicylic acid, bisphenol A and coumarin are improved.
The BiVO with the core-shell structure 4 Preparation method of @ BiOCl heterojunction, wherein BiVO with core-shell structure is prepared by ultraviolet excitation and electrostatic action in-situ induction deposition method 4 The @ BiOCl heterojunction comprises a decahedral BiVO structure 4 After being excited by ultraviolet light, the ultraviolet light generates holes and electrons, and the holes and the electrons migrate to the (110) crystal face and the (010) crystal face respectively; bi (Bi) 3+ Positively charged alkoxide compounds with ethylene glycol [ BiOCH ] 2 CH 2 OH] 2+ Subsequently, due to electrostatic attraction, positively charged [ BiOCH ] 2 CH 2 OH] 2+ Adsorbed on BiVO 4 On the (010) crystal face with electronegativity, then Cl is added - In BiVO 4 (010) In situ induction of nano-sheet BiOCl on crystal face and Cl of another part in solution - Will be adsorbed on BiVO 4 Inducing to generate BiOCl with oxygen vacancy nano particles on (110) crystal face with electropositivity, and preparing the BiVO with core-shell structure 4 @ BiOCl heterojunction. BiOCl and BiVO with two different morphologies 4 The coexistence of two phases accelerates the separation of the photo-generated electrons and the holes, reduces the recombination rate of the photo-generated electron-hole pairs and improves the oxidation-reduction capability of the material.
Further, decahedral BiVO 4 Excited by ultraviolet light, holes and electrons migrate to the (110) crystal face and the (010) crystal face respectively; controlling the content and concentration of HCl, inducing HCl and Bi (NO 3 ) 3 ·5H 2 O is BiVO 4 (010) The reaction on the crystal face generates nano-sheet BiOCl, and the Bi source is Bi (NO 3 ) 3 ·5H 2 O; and at BiVO 4 (110) HCl on crystal plane and (110) crystal plane BiVO 4 Directly reacting to form granular BiOCl, wherein Bi source is (110) crystal face BiVO 4 ，BiVO 4 The V-O is stronger than Bi-O binding, so BiVO is used 4 Oxygen vacancies are easily formed for the Bi source.
The invention utilizes BiVO 4 (110) Induced on crystal face to generate BiOClThe LSPR effect of the oxygen vacancies of (2) to make the core-shell structure BiVO 4 The @ BiOCl heterojunction photocatalyst has higher degradation rate on antibiotics, phenol, salicylic acid, bisphenol A and coumarin under visible light and near infrared light, and has good application prospect.
Drawings
FIG. 1 shows a core-shell structure BiVO prepared according to the present invention 4 XRD pattern of @ BiOCl heterojunction;
FIG. 2 is a smooth decahedral monoclinic BiVO prepared in comparative example 1 4 Crystal SEM image
FIG. 3 shows a core-shell structure BiVO prepared according to the present invention 4 @ BiOCl heterojunction SEM;
FIG. 4 shows a core-shell structure BiVO prepared according to the present invention 4 EDS diagram of @ BiOCl heterojunction Bi, V, O and Cl;
FIG. 5 shows a core-shell structure BiVO prepared according to the present invention 4 EPR plot of @ BiOCl heterojunction;
FIG. 6 shows a core-shell structure BiVO prepared according to the present invention 4 Ultraviolet visible diffuse reflection map of @ BiOCl heterojunction;
FIG. 7 shows a core-shell structure BiVO prepared according to the present invention 4 Degradation curve of visible light degradation TC of @ BiOCl heterojunction;
FIG. 8 shows a core-shell structure BiVO prepared according to the present invention 4 A dynamics fitting curve of degradation TC under visible light of the @ BiOCl heterojunction;
FIG. 9 shows a core-shell structure BiVO prepared according to the present invention 4 Degradation curve of @ BiOCl heterojunction near-infrared light degradation TC;
FIG. 10 shows a core-shell BiVO according to the present invention 4 A dynamics fitting curve of degradation TC under the near infrared light of the @ BiOCl heterojunction;
FIG. 11 shows a core-shell BiVO according to the present invention 4 Degradation curves of TC at 740nm, 850nm, 940nm and 1100nm under the irradiation of single-color light of the @ BiOCl heterojunction;
FIG. 12 shows a core-shell BiVO according to the present invention 4 Degradation rates of TC at 740nm, 850nm, 940nm and 1100nm under irradiation of single-color light of the @ BiOCl heterojunction;
FIG. 13 is a core-shell made in accordance with the present inventionStructure BiVO 4 Degradation efficiency of phenol, CIP, BHA, BPA and coumarin by @ BiOCl heterojunction;
FIG. 14 shows a core-shell BiVO according to the present invention 4 Active species capture experiments under @ BiOCl heterojunction visible light;
FIG. 15 shows a core-shell BiVO according to the present invention 4 Active species capture experiments under @ BiOCl heterojunction near infrared 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.
Comparative example 1
Example 1
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst (BVO-BiOCl-1).
Example 2
step 4, 0.2mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 120mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor liquid B and the precursor liquid CStirring, dropwise adding 40mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5 hours, respectively washing the sample with water and alcohol for 3 times, and vacuum drying at a constant temperature of 60 ℃ for 12 hours to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst (BVO-BiOCl-2).
Example 3
step 4, 0.3mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 180mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 60mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at the constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst (BVO-BiOCl-3).
Example 4
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 5
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 6
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor liquid B and the precursor liquid C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, and stirring5h, respectively washing the sample with water and alcohol for 3 times, and vacuum drying at a constant temperature of 60 ℃ for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 7
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 8
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.84mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 9
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 30min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.85mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 10
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 45min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing the sample with water and alcohol for 3 times, drying in vacuum at the constant temperature of 60 ℃ for 12h,obtaining the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
Example 11
step 4, 0.1mmol Bi (NO 3 ) 3 ·5H 2 O was dissolved in 60mL of ethylene glycol solution, bi (NO 3 ) 3 ·5H 2 The concentration of the glycol solution of O is 0.002mol/L, and the glycol solution is stirred for 60min until the glycol solution is completely dissolved to form a precursor solution C;
step 5, preparing a 10mM dilute hydrochloric acid solution A by fixing 1000mL of volume of 0.83mL of concentrated hydrochloric acid;
step 6, mixing and stirring the precursor solution B and the precursor solution C, dropwise adding 20mL of dilute hydrochloric acid solution A in the stirring process, stirring for 5h, respectively washing a sample with water and alcohol for 3 times, and drying at a constant temperature of 60 ℃ in vacuum for 12h to obtain the BiVO with the core-shell structure 4 @ BiOCl heterojunction photocatalyst.
FIG. 1 is BiVO having core-shell structure prepared in example 1, example 2 and example 3 4 XRD patterns of the @ BiOCl heterojunction can be seen from the patterns that diffraction peaks at 18.67 degrees, 18.99 degrees, 28.82 degrees, 28.95 degrees and 30.55 degrees correspond to monoclinic phase BiVO 4 (110), (011), (-121), (040) crystal face diffraction peaks of standard card (JCPDS No. 14-0688); (101), (110) of tetragonal phase BiOCl (JCPLS No. 82-0485) occurring at 2θ=25.91 °, 32.55 °, 63.16 °, 65.81 °(005) And (213) diffraction peaks of crystal faces, and successfully preparing the BiVO with the core-shell structure 4 @ BiOCl heterojunction.
FIG. 2 is a monoclinic phase BiVO of smooth decahedral morphology prepared in comparative example 1 4 SEM image of the crystal. BiVO prepared by hydrothermal method 4 Is a decahedron having smooth, flat and relatively sharp edges, with (010) and (110) crystal planes exposed, and FIG. 3 is a BiVO having a core-shell structure prepared in example 1 4 SEM image of @ BiOCl heterojunction. From the figure, it can be seen that the nano-sheet BiOCl tightly encapsulates decahedral BiVO 4 The (010) crystal face of the nano-particle BiOCl is tightly loaded on the decahedral BiVO 4 And (110) on the (c) plane. Description of the use of Bi by in situ induced deposition 3+ Positively charged alkoxide compounds with ethylene glycol [ Bi (OCH) 2 CH 2 OH)] 2+ And is adsorbed on BiVO 4 Negatively charged (010) crystal face, then HCl, cl is added - And [ Bi (OCH) 2 CH 2 OH)] 2+ Under the action of electrostatic attraction, under BiVO 4 The (010) crystal face of the crystal is induced to generate nano-sheet BiOCl. While the Cl remains in the solution - Will be adsorbed on BiVO 4 Positively charged (110) crystal plane, biVO (110) crystal plane 4 Middle Bi 3+ As bismuth source, in BiVO 4 Is induced to generate nano-granular BiOCl with oxygen vacancies to form a core-shell structure BiVO 4 @ BiOCl heterojunction.
FIG. 4 is a BiVO having a core-shell structure prepared in example 1 4 EDS plot of @ BiOCl heterojunction Bi, V, O and Cl. In a decahedron BiVO 4 (010) Bi, V, O and Cl elements uniformly distributed on the crystal face are formed in BiVO 4 (110) Bi, V, O and Cl elements are uniformly distributed on the two surfaces of the crystal face, but O elements are absent on the two surfaces of the lower part of the (110) crystal face, and the loading on the BiVO is indirectly confirmed by using an EDS image 4 (110) The crystal face nano-granular BiOCl has oxygen vacancies.
FIG. 5 is a BiVO having a core-shell structure prepared in example 1 4 EPR plot of @ BiOCl heterojunction. BiVO characterization by EPR test 4 And BiOCl/BiVO 4 Defect structure and concentration of heterojunction. From the figure, it can be seen that the smooth decahedral monoclinic BiVO 4 The crystals had no identifiable EPR signal, indicating a smooth decahedral BiVO 4 Oxygen vacancies are absent. The presence of defects is attributed to when the g value of the EPR signal appears around 2.003. BiVO with core-shell structure 4 The @ BiOCl heterojunction showed a strong oxygen vacancy signal at g=2.003, indicating a core-shell structure BiVO 4 There are a large number of oxygen vacancies in the @ BiOCl heterojunction.
FIG. 6 is BiVO having core-shell structure prepared in example 1, example 2 and example 3 4 Ultraviolet visible diffuse reflectance pattern of @ BiOCl heterojunction. Comparative example hydrothermally prepared smooth decahedral monoclinic phase BiVO in UV-visible diffuse reflectance plot 4 Exhibits significantly enhanced light absorption in the ultraviolet-visible range of 200-800 nm, while there is substantially no light absorption in the near infrared range of 800-2200 nm. The invention prepares the BiVO with the core-shell structure by ultraviolet excitation and electrostatic action in-situ induction deposition method 4 The @ BiOCl heterojunction enhances its absorption in the near infrared range of 800-2200 nm and full spectral absorption in the ultraviolet-visible-near infrared range due to the core-shell structure BiVO 4 BiVO in @ BiOCl heterojunction 4 Is induced to generate nano-granular BiOCl with oxygen vacancy and causes unique LSPR effect to make BiVO 4 The @ BiOCl heterojunction produces some absorption in the near infrared region. Due to the synergistic effect of the LSPR effect of oxygen vacancy and heterojunction, the BiVO with the core-shell structure 4 The @ BiOCl heterojunction shows significantly enhanced visible near-infrared light absorption, improving solar energy utilization.
FIG. 7 is BiVO having core-shell structure prepared in example 1, example 2 and example 3 4 Degradation profile of @ BiOCl heterojunction degrading Tetracycline (TC) under visible light. The concentration of TC aqueous solution is 40mg/L, the reaction is performed for 30min first, and after the adsorption-desorption equilibrium is reached, the light reaction is performed, so that the self-degradation efficiency of TC is extremely low and can be ignored under the condition of no photocatalyst. Thus, the removal of TC results from photodegradation of the photocatalyst. BiVO (BiVO) 4 The degradation rate of TC reaches 90.32% at maximum after 180min of visible light irradiation of the @ BiOCl heterojunction composite photocatalyst; biVO (BiVO) 4 PhotocatalysisThe degradation rate of the agent to TC after 180min of visible light irradiation is only 50.16%; biVO (BiVO) 4 、BiVO 4 Apparent rate constants @ BiOCl are 0.00394min, respectively -1 、0.01180min -1 (see FIG. 8), biVO 4 The @ BiOCl photocatalytic activity exceeds that of BiVO 4 About 2.99 times, this is due to the synergistic effect of the LSPR effect of oxygen vacancies and the core-shell structure heterojunction, greatly improving the photocatalytic performance.
FIG. 9 is BiVO having core-shell structure prepared in example 1, example 2 and example 3 4 Degradation profile of @ BiOCl heterojunction degrading TC under near infrared light. The concentration of TC aqueous solution is 40mg/L, the reaction is performed for 30min first, and after the adsorption-desorption equilibrium is reached, the light reaction is performed, so that the self-degradation efficiency of TC is extremely low and can be ignored under the condition of no photocatalyst. Thus, the removal of TC results from photodegradation of the photocatalyst. After being irradiated by near infrared light, the sample can degrade TC to a certain extent and has a core-shell structure BiVO 4 The degradation rate of TC reaches 71.17% at maximum after 180min near infrared illumination of the @ BiOCl heterojunction; biVO (BiVO) 4 The degradation rate of the photocatalyst to TC after 180min of near infrared light irradiation is only 10.05 percent, and almost no degradation exists; biVO (BiVO) 4 、BiVO 4 Apparent rate constants @ BiOCl are 0.00062min, respectively -1 、0.00661min -1 (see FIG. 10) BiVO having a core-shell structure 4 The photo-catalytic activity of the @ BiOCl heterojunction exceeds that of BiVO 4 About 10.66 times, illustrating the core-shell structure BiVO 4 The degradation rate of the @ BiOCl heterojunction is high, and the degradation rate is due to the fact that LSPR effect generated by rich oxygen vacancies exists in the structure to cooperate with the heterojunction, so that the photocatalysis performance is greatly improved, the light response range is widened, and the utilization rate of sunlight is improved.
FIG. 11 is a BiVO having a core-shell structure prepared in example 1 4 Degradation curves of TC at 740nm, 850nm, 940nm and 1100nm under irradiation of single-color light of the @ BiOCl heterojunction. From the figure, it can be seen that the core-shell structure BiVO after 180min of illumination 4 Degradation rates of @ BiOCl heterojunction degradation TC are respectively as follows: the degradation rate of light at 740nm is 65.33%, at 850nm is 69.28%, at 940nm is 59.39% and at 1100The degradation rate at nm is 57.97%. BiVO with core-shell structure under 740, 850, 940 and 1100nm light irradiation 4 The degradation rates of the @ BiOCl heterojunction on TC are 0.00557, 0.00616, 0.00477 and 0.00476min respectively -1 (FIG. 12). The above results confirm that the prepared core-shell structure BiVO due to the effect of the LSPR effect of oxygen vacancies 4 The @ BiOCl heterojunction photocatalyst has full spectrum-driven photocatalytic activity.
FIG. 13 is a BiVO having a core-shell structure prepared in example 1 4 Degradation efficiency of the @ BiOCl heterojunction on CIP, BHA, phenol, BPA and coumarin. By degrading CIP, BHA, phenol (Phenols), BPA and Coumarin (Coumarin) respectively under visible light and near infrared light irradiation, the maximum degradation rates under visible light irradiation are respectively: 71.32%, 49.36%, 65.69%, 57.20% and 57.52%; the maximum degradation rates under near infrared light irradiation are respectively as follows: 37.88%, 48.22%, 62.86%, 53.48% and 55.45%. Shows that the prepared BiVO with the core-shell structure 4 The @ BiOCl heterojunction photocatalyst has different degrees of degradation on different types of pollutants, and has higher broad-spectrum property and application value.
FIG. 14 is a core-shell structure BiVO prepared in example 1 4 Active species capture experiments under @ BiOCl heterojunction visible light. Adding p-Benzoquinone (BQ) and sodium oxalate (Na) into the photocatalytic degradation system 2 C 2 O 4 ) And tert-butanol (TBA) as O 2 - 、h + And a capture agent for OH. As can be seen from the figure, BQ and Na are added under the condition of irradiation of visible light 2 C 2 O 4 And the photocatalytic performance of TBA was reduced by 51.64%, 16.02% and 28.82%, respectively. Illustrating that O is in the degradation reaction process under the condition of visible light 2 - Is the main active species, and then is OH and h + . Under the condition of near infrared light irradiation, BQ and Na are respectively added 2 C 2 O 4 And after TBA, the degradation capacity of the photocatalyst decreased from 71.17% to 26.58%, 66.33% and 38.35%, respectively (fig. 15). Indicating that under near infrared light O 2 - Is the main active substance in the degradation process, while the OH plays a secondary role in the degradation process, and is the more secondary active substanceThe species is h + 。
The invention relates to a BiVO with a core-shell structure 4 Preparation method and application of @ BiOCl heterojunction, and application of heterojunction in smooth decahedron BiVO by ultraviolet excitation and electrostatic action in-situ induction deposition method 4 Generating platy tetragonal phase BiOCl and BiVO on (010) crystal face 4 BiOCl with oxygen vacancy nano particles is generated on the (110) crystal face to form a core-shell structure BiVO 4 The @ BiOCl heterojunction utilizes the synergistic effect of the LSPR of the oxygen vacancy of BiOCl on the (110) crystal face and the heterojunction with the core-shell structure to ensure that the heterojunction with the core-shell structure has broad-spectrum degradation performance on antibiotics, phenol, salicylic acid, bisphenol A and coumarin under visible light and near infrared light, and has good application prospect in the aspect of purifying sewage.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (6)
1. BiVO with core-shell structure 4 The @ BiOCl heterojunction is characterized by having a core BiVO 4 ，BiVO 4 The structure is monoclinic phase, and the appearance is decahedron; biVO (BiVO) 4 Is formed with a platy tetragonal phase BiOCl, biVO on the (010) crystal face 4 The (110) crystal face of (C) is formed with a granular tetragonal phase BiOCl with oxygen vacancies, a flaky tetragonal phase BiOCl and a granular tetragonal phase BiOCl-coated BiVO 4 Forming a core-shell structure;
the core-shell structure BiVO 4 The preparation method of the @ BiOCl heterojunction comprises the following steps:
step 1, decahedral monoclinic BiVO is carried out 4 Dissolved in H 2 In the step O, ultraviolet irradiation is carried out to form a precursor liquid B; bi (NO) 3 ) 3 ∙5H 2 O is dissolved in glycol to form a precursor liquid C;
step 2, stirring and mixing the precursor liquid B and the precursor liquid C, dropwise adding a dilute hydrochloric acid solution in the stirring process for reaction, and after the reaction is completedWashing and drying the obtained sample to obtain the BiVO with the core-shell structure 4 A @ BiOCl heterojunction;
in step 1, the decahedron monoclinic phase BiVO 4 The preparation method of (2) comprises the following steps: bi (NO) 3 ) 3 ∙5H 2 O is dissolved in dilute HNO 3 In solution, then add NH 4 VO 3 Stirring to form a precursor solution A; carrying out hydrothermal reaction on the precursor solution A, washing the obtained precipitate, and drying to obtain decahedral monoclinic BiVO 4 ；
In the step 1, the ultraviolet irradiation time is 30-40 min, bi (NO 3 ) 3 ∙5H 2 The concentration of O is 0.0006-0.005 mol/L;
in the step 2, the reaction time is 4-6 hours;
BiVO 4 、Bi(NO 3 ) 3 ∙5H 2 the mol ratio of O to HCl is (0.8-1.0): (0.1 to 0.3): (0.2 to 0.72).
2. A core-shell structure BiVO as claimed in claim 1 4 The preparation method of the @ BiOCl heterojunction is characterized by comprising the following steps of:
step 1, decahedral monoclinic BiVO is carried out 4 Dissolved in H 2 In the step O, ultraviolet irradiation is carried out to form a precursor liquid B; bi (NO) 3 ) 3 ∙5H 2 O is dissolved in glycol to form a precursor liquid C;
step 2, stirring and mixing the precursor liquid B and the precursor liquid C, dropwise adding a dilute hydrochloric acid solution in the stirring process for reaction, and washing and drying an obtained sample after the reaction is finished to obtain the BiVO with the core-shell structure 4 A @ BiOCl heterojunction;
in step 1, the decahedron monoclinic phase BiVO 4 The preparation method of (2) comprises the following steps: bi (NO) 3 ) 3 ∙5H 2 O is dissolved in dilute HNO 3 In solution, then add NH 4 VO 3 Stirring to form a precursor solution A; carrying out hydrothermal reaction on the precursor solution A, washing the obtained precipitate, and drying to obtain decahedral monoclinic BiVO 4 ；
In the step 1, the ultraviolet irradiation time is 30-40 min,bi (NO) in precursor solution C 3 ) 3 ∙5H 2 The concentration of O is 0.0006-0.005 mol/L;
in the step 2, the reaction time is 4-6 hours;
BiVO 4 、Bi(NO 3 ) 3 ∙5H 2 the mol ratio of O to HCl is (0.8-1.0): (0.1 to 0.3): (0.2 to 0.72).
3. The core-shell structure BiVO of claim 2 4 The preparation method of the @ BiOCl heterojunction is characterized in that in the step 2, the concentration of the dilute hydrochloric acid solution A is 10-12 mM.
4. The core-shell structure BiVO of claim 2 4 The preparation method of the @ BiOCl heterojunction is characterized in that in the step 2, the drying is carried out at the constant temperature of 50-60 ℃ for 10-12 hours.
5. The core-shell structure BiVO of claim 1 4 Application of @ BiOCl heterojunction as a photocatalyst in photocatalytic degradation of organic pollutants.
6. The use according to claim 5, wherein the organic contaminant is phenol, salicylic acid, bisphenol a or coumarin.
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