CN112871187B - Modified diatomite loaded BiVO 4 Composite material of BiOCl heterojunction and application - Google Patents
Modified diatomite loaded BiVO 4 Composite material of BiOCl heterojunction and application Download PDFInfo
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- CN112871187B CN112871187B CN202110064257.3A CN202110064257A CN112871187B CN 112871187 B CN112871187 B CN 112871187B CN 202110064257 A CN202110064257 A CN 202110064257A CN 112871187 B CN112871187 B CN 112871187B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002057 nanoflower Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 54
- 229910021641 deionized water Inorganic materials 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 45
- 238000001914 filtration Methods 0.000 claims description 45
- 238000009210 therapy by ultrasound Methods 0.000 claims description 45
- 238000005406 washing Methods 0.000 claims description 45
- 239000004593 Epoxy Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- -1 amino modified diatomite Chemical class 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 238000006735 epoxidation reaction Methods 0.000 claims description 11
- 238000006011 modification reaction Methods 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 238000004729 solvothermal method Methods 0.000 claims description 11
- 229960001124 trientine Drugs 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 6
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims 1
- 239000004098 Tetracycline Substances 0.000 abstract description 18
- 235000019364 tetracycline Nutrition 0.000 abstract description 18
- 150000003522 tetracyclines Chemical class 0.000 abstract description 18
- 229960002180 tetracycline Drugs 0.000 abstract description 14
- 229930101283 tetracycline Natural products 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000009471 action Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 30
- 230000004913 activation Effects 0.000 description 8
- 239000000969 carrier Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 4
- 229940040944 tetracyclines Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention relates to the technical field of diatomite composite materials, and discloses a modified diatomite-loaded BiVO 4 The composite material of the BiOCl heterojunction introduces abundant amino groups and imino groups on the surface of diatomite, and a large number of amino groups and imino groups can be used as active adsorption sites, so that the modified diatomite can effectively adsorb pollutants such as tetracycline and the like through the actions of hydrogen bond association, electrostatic action and the like, thereby realizing the functional modification of the diatomite, and the BiOCl nanoflower and Zn-doped mesoporous BiVO 4 The p-n heterojunction is formed, the separation of photo-generated electrons and holes is promoted, active substances such as hydroxyl free radicals, superoxide free radicals and the like are further generated by reaction with water, firstly, the modified diatomite carries out hydrogen bond association and electrostatic action on the tetracycline to effectively adsorb, and then the tetracycline is photo-catalytically degraded into non-toxic small molecules, so that the high-efficiency adsorption and photo-catalytic degradation processes of the tetracycline are realized.
Description
Technical Field
The invention relates to the technical field of diatomite composite materials, in particular to a modified diatomite-supported BiVO 4 -a composite material of a BiOCl heterojunction and use thereof.
Background
Tetracyclines are traditional antibiotics and are widely applied to the fields of agriculture, medicine and the like, but tetracyclines are difficult to degrade in nature, so that tetracyclines are accumulated continuously along with biological chains in biospheres, serious harm is caused to human health, animal reproduction and ecosystems, and the treatment methods of tetracyclines mainly comprise a biodegradation method, a physical adsorption method and a redox method at presentAnd the like, wherein the physical adsorption method has the characteristics of simple operation, lower cost and the like, is a common pollutant treatment method, and the photocatalyst mainly comprises TiO 2 、CdS、BiVO 4 The photo-catalytic degradation method mainly comprises the steps of irradiating light on a photo-catalyst, exciting and transiting electrons to generate photo-generated carriers, further generating hydroxyl free radicals with extremely strong activity, and degrading pollutants into nontoxic small molecules.
The diatomite is natural siliceous sedimentary rock, has the characteristics of abundant reserves, low price, easy obtainment, biological friendliness, no pollution, high specific surface area, rich micropore structure, strong adsorptivity and the like, has wide application prospect in the fields of medicine carriers, catalyst carriers, environmental protection, water pollution treatment and the like, needs to be chemically modified to further expand the practical application of the diatomite, has unique functions, meets the application of the diatomite in the aspects of adsorbing and treating pollutants such as tetracycline and the like, and can be used as BiVO 4 And (3) obtaining the double-function composite material with high adsorption performance and photocatalytic degradation by using the photocatalyst carriers such as BiOCl.
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a modified diatomite-loaded BiVO 4 The composite material of the BiOCl heterojunction and the application thereof have excellent adsorption and photocatalytic degradation performance on pollutants such as tetracycline and the like.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: modified diatomite loaded BiVO 4 -a composite of a BiOCl heterojunction, said modified diatomaceous earth supporting BiVO 4 The preparation method of the composite material of the BiOCl heterojunction comprises the following steps:
(1) Adding sodium hydroxide solution with the mass fraction of 2-4% and diatomite into a beaker, carrying out ultrasonic treatment and stirring pre-activation treatment for 2-6h, filtering the solvent, washing the product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding an epoxy silane coupling agent after ultrasonic treatment, performing epoxidation reaction, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine into a round-bottom flask, carrying out an amino modification reaction after ultrasonic treatment, filtering the solvent, washing a product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding glycol solvent, amino modified diatomite, bi (NO) into a beaker 3 ) 3 And KCl, stirring for 6-24h after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Adding nitric acid solution with pH of 5-6 and Bi (NO) into a beaker 3 ) 3 Stirring and dissolving, adding NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle for hydrothermal reaction, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain Zn doped mesoporous BiVO 4 。
(6) Adding deionized water, modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO into a beaker 4 Ultrasonic treatment for 1-3h, vacuum drying the solution to obtain modified diatomite-supported BiVO 4 -a composite of BiOCl heterojunctions.
Preferably, the epoxy silane coupling agent in the step (2) is one of 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane or 3- [ (2, 3) -glycidoxypropyl ] propyl methyl dimethoxy silane, and the mass ratio of the epoxy silane coupling agent is 100:25-60.
Preferably, the epoxidation reaction in step (2) is carried out at 30-50 ℃ for 15-30 hours.
Preferably, the mass ratio of the epoxy modified diatomite to the triethylene tetramine in the step (3) is 100:60-150.
Preferably, the amino modification reaction in the step (3) is carried out at 30-60 ℃ for 6-12h.
Preferably, in the step (4), the amino-modified diatomaceous earth, bi (NO 3 ) 3 And KCl in a mass ratio of 100:4-10:0.8-2.
Preferably, the in-situ solvothermal reaction in step (4) is carried out at 140-160 ℃ for 12-24h.
Preferably, bi (NO 3 ) 3 、NH 4 VO 3 、Zn(NO 3 ) 2 And cetyl trimethyl ammonium bromide in a mass ratio of 100:28-32:40-65.
Preferably, the hydrothermal reaction in the step (5) is carried out at 170-190 ℃ for 2-5h.
Preferably, the modified diatomite loaded BiOCl nanoflower and the Zn doped mesoporous BiVO in the step (5) 4 The mass ratio of (2) is 100:15-40.
(III) beneficial technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the modified diatomite loaded BiVO 4 The composite material of the BiOCl heterojunction comprises the steps of pre-activating diatomite by sodium hydroxide, further modifying by an epoxy silane coupling agent to obtain epoxy modified diatomite, and then carrying out ring-opening addition reaction on an introduced epoxy group and an amino group of triethylene tetramine to obtain amino modified diatomite, so that abundant amino groups and imino groups are introduced on the surface of the diatomite, a large number of amino groups and imino groups can be used as active adsorption sites, the modified diatomite can effectively adsorb pollutants such as tetracycline through the actions of hydrogen bond association, electrostatic action and the like, and the functional modification of the diatomite is realized.
The modified diatomite loaded BiVO 4 Composite material of BiOCl heterojunction, which takes amino modified diatomite with high specific surface area as a carrier, and Bi (NO 3 ) 3 And KCl on the surface of modified diatomite to generate BiOCl with unique flower-like structure and high specific surface area in situ, so that BiOCl nanoflowers uniformly grow on the surface of diatomite, and the BiOCl nanoflowers are better dispersed,the agglomeration phenomenon is improved.
The modified diatomite loaded BiVO 4 Composite material of BiOCl heterojunction, with cetyltrimethylammonium bromide as surfactant, zn (NO 3 ) 2 As a zinc source, obtaining Zn doped mesoporous BiVO through hydrothermal reaction 4 The porous material has a large number of pore structures, has higher specific surface area, is favorable for absorbing light radiation, and is doped with Zn to replace Bi crystal lattice, so that impurity energy level is generated, and mesoporous BiVO is realized 4 The light absorption edge of the light-emitting diode (R) is subjected to red shift, so that the absorption wavelength in the visible light range is widened, and the absorption and the responsiveness of the light radiation are further improved.
The modified diatomite loaded BiVO 4 The composite material of the BiOCl heterojunction is prepared by loading modified diatomite with BiOCl nanoflower and Zn doped mesoporous BiVO 4 Combining to obtain the diatomite-supported photocatalyst composite material, wherein the BiOCl nanoflower and the Zn-doped mesoporous BiVO 4 With a suitable band structure, both form a p-n heterojunction, when light is radiated on the heterojunction, zn-doped BiVO 4 The generated photo-generated electrons are transited from the valence band to the conduction band, the holes are remained in the valence band, then a built-in electric field is generated by the p-n heterojunction, and the photo-generated electrons generated by the BiOCl valence band are promoted to dope BiVO to Zn 4 The separation of photo-generated electrons and holes is realized, the recombination of photo-generated carriers is avoided, the photo-generated carriers further react with water to generate a large amount of active substances such as hydroxyl free radicals, superoxide free radicals and the like, firstly, the modified diatomite carries out hydrogen bond association and electrostatic action on the tetracycline to effectively adsorb, and then the tetracycline is photo-catalytically degraded into non-toxic small molecules, so that the high-efficiency adsorption and photo-catalytic degradation processes of the tetracycline are realized.
Detailed Description
In order to achieve the above object, the present invention provides the following specific embodiments and examples: modified diatomite loaded BiVO 4 The preparation method of the composite material of the BiOCl heterojunction comprises the following steps:
(1) Adding sodium hydroxide solution with the mass fraction of 2-4% and diatomite into a beaker, carrying out ultrasonic treatment and stirring pre-activation treatment for 2-6h, filtering the solvent, washing the product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding an epoxy silane coupling agent after ultrasonic treatment, wherein the epoxy silane coupling agent is one of 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane and 3- [ (2, 3) -glycidoxypropyl ] propyl methyl dimethoxy silane, the mass ratio of the epoxy silane coupling agent to the epoxy silane coupling agent is 100:25-60, performing epoxidation reaction for 15-30h at 30-50 ℃, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:60-150 into a round bottom flask, carrying out an amino modification reaction for 6-12h at the temperature of 30-60 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:4-10:0.8-2 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 6-24h after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 12-24h at 140-160 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Adding a nitric acid solution with pH of 5-6 and Bi (NO) with mass ratio of 100:28-32:40-65 into a beaker 3 ) 3 、NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 2-5 hours at 170-190 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn-doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:15-40 into a beaker 4 Ultrasonic treatment for 1-3h, vacuum drying the solution to obtain modified diatomite-supported BiVO 4 -a composite of BiOCl heterojunctions.
Example 1
(1) Adding a sodium hydroxide solution with the mass fraction of 2% and diatomite into a beaker, carrying out ultrasonic treatment and stirring for pre-activation treatment for 2 hours, filtering the solvent, washing the product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding 3-glycidoxypropyl triethoxysilane after ultrasonic treatment, performing epoxidation reaction for 15h at 30 ℃ with the mass ratio of the toluene solvent to the activated diatomite being 100:25, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:60 into a round-bottom flask, carrying out an amino modification reaction for 6 hours at 30 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:4:0.8 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 6h after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 12h at 140 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Adding nitric acid solution with pH of 5 and Bi (NO) with mass ratio of 100:28:40 into a beaker 3 ) 3 、 NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 2 hours at 170 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:15 into a beaker 4 Ultrasonic treatment is carried out for 1h, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
Example 2
(1) Adding a sodium hydroxide solution with the mass fraction of 4% and diatomite into a beaker, carrying out ultrasonic treatment and stirring for pre-activation treatment for 4 hours, filtering the solvent, washing the product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding 3-glycidoxypropyl trimethoxy silane after ultrasonic treatment, performing epoxidation reaction for 15h at 40 ℃, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:90 into a round-bottom flask, carrying out an amino modification reaction for 12 hours at 50 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:6:1.2 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 12 hours after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 18 hours at 150 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Add nitric acid solution with pH 6 and Bi (NO) with mass ratio of 100:29:48 to beaker 3 ) 3 、 NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 3 hours at 180 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:20 into a beaker 4 Ultrasonic treatment is carried out for 3 hours, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
Example 3
(1) Adding 3% sodium hydroxide solution and diatomite into a beaker, carrying out ultrasonic treatment and stirring for pre-activation treatment for 4 hours, filtering the solvent, washing the product to be neutral by deionized water, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round-bottom flask, adding 3- [ (2, 3) -glycidoxy ] propyl methyl dimethoxy silane into the round-bottom flask after ultrasonic treatment, performing epoxidation reaction for 24 hours at 40 ℃ according to the mass ratio of 100:45, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:120 into a round-bottom flask, carrying out an amino modification reaction for 10 hours at 40 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:8:1.6 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 12 hours after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 18 hours at 150 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Nitric acid solution with pH of 5.5 and Bi (NO) with mass ratio of 100:31:52 are added into a beaker 3 ) 3 、 NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:30 into a beaker 4 Ultrasonic treatment is carried out for 2 hours, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
Example 4
(1) Adding 3% sodium hydroxide solution and diatomite into a beaker, carrying out ultrasonic treatment and stirring for pre-activation treatment for 6 hours, filtering the solvent, washing the product to be neutral by deionized water, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding 3-glycidoxypropyl triethoxysilane after ultrasonic treatment, performing epoxidation reaction for 30h at 50 ℃ with the mass ratio of the toluene solvent to the activated diatomite being 100:60, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:150 into a round-bottom flask, carrying out an amino modification reaction at 60 ℃ for 12 hours after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:10:2 and Bi (NO 3 ) 3 And KCl, stirring for 24 hours after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 24 hours at 160 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Adding a nitric acid solution with pH of 6 and Bi (NO) with a mass ratio of 100:32:65 into a beaker 3 ) 3 、NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 5 hours at 190 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:40 into a beaker 4 Ultrasonic treatment is carried out for 3 hours, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
Comparative example 1
(1) Adding a sodium hydroxide solution with the mass fraction of 4% and diatomite into a beaker, carrying out ultrasonic treatment and stirring for pre-activation treatment for 3 hours, filtering the solvent, washing the product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding 3-glycidoxypropyl triethoxysilane into the round bottom flask after ultrasonic treatment, performing epoxidation reaction for 30 hours at 50 ℃ with the mass ratio of the toluene solvent to the activated diatomite being 100:12, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:30 into a round-bottom flask, carrying out an amino modification reaction for 8 hours at 40 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:2:0.4 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 12 hours after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 12 hours at 160 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Add nitric acid solution with pH 6 and Bi (NO) with mass ratio of 100:27:32 to beaker 3 ) 3 、 NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:7 into a beaker 4 Ultrasonic treatment is carried out for 3 hours, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
Comparative example 2
(1) Adding a sodium hydroxide solution with the mass fraction of 4% and diatomite into a beaker, carrying out ultrasonic treatment and stirring at a pre-activation position for 5 hours, filtering a solvent, washing a product with deionized water to be neutral, and drying to obtain the activated diatomite.
(2) Adding toluene solvent and activated diatomite into a round-bottom flask, adding 3- [ (2, 3) -glycidoxy ] propyl methyl dimethoxy silane into the round-bottom flask after ultrasonic treatment, performing epoxidation reaction for 15h at 40 ℃ according to the mass ratio of 100:75, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the epoxy modified diatomite.
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:180 into a round-bottom flask, carrying out an amino modification reaction for 12 hours at 30 ℃ after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the amino modified diatomite.
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:12:2.5 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 12h after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction for 24h at 150 ℃, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower.
(5) Adding a nitric acid solution with pH of 5 and Bi (NO) with mass ratio of 100:33:75 into a beaker 3 ) 3 、 NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle, carrying out hydrothermal reaction for 4 hours at 170 ℃, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain the Zn doped mesoporous BiVO 4 。
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:50 into a beaker 4 Ultrasonic treatment is carried out for 2 hours, and the solution is dried in vacuum to obtain the modified diatomite-loaded BiVO 4 -a composite of BiOCl heterojunctions.
500mL of tetracycline solution with the mass fraction of 20mg/L is added into a beaker, and 100mg of modified diatomite is added to load BiVO 4 The composite material of the BiOCl heterojunction is stirred uniformly and then is subjected to an adsorption process in the dark, and UV754N ultraviolet visible light splitting is usedThe concentration of tetracycline in the solution was measured by a densitometer at different adsorption times.
500mL of tetracycline solution with the mass fraction of 20mg/L is added into a beaker, and 100mg of modified diatomite is added to load BiVO 4 And (3) uniformly stirring the composite material of the BiOCl heterojunction, carrying out an photodegradation process under light of a 200W xenon lamp, and measuring the concentration of the tetracycline in the solution under different adsorption-photodegradation times by using a UV754N ultraviolet visible spectrophotometer.
Claims (5)
1. Modified diatomite loaded BiVO 4 -a composite of BiOCl heterojunction, characterized in that: the modified diatomite is loaded with BiVO 4 The preparation method of the composite material of the BiOCl heterojunction comprises the following steps:
(1) Adding sodium hydroxide solution with the mass fraction of 2-4% and diatomite into a beaker, carrying out ultrasonic treatment, stirring and pre-activating for 2-6 hours, filtering a solvent, washing a product with deionized water to be neutral, and drying to obtain activated diatomite;
(2) Adding toluene solvent and activated diatomite into a round bottom flask, adding an epoxy silane coupling agent after ultrasonic treatment, wherein the epoxy silane coupling agent is one of 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane or 3- [ (2, 3) -glycidoxypropyl ] propyl methyl dimethoxy silane, the mass ratio of the activated diatomite to the epoxy silane coupling agent is 100:25-60, performing epoxidation reaction, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain epoxy modified diatomite;
(3) Adding an acetone solvent, epoxy modified diatomite and triethylene tetramine with the mass ratio of 100:60-150 into a round-bottom flask, performing an amino modification reaction after ultrasonic treatment, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain amino modified diatomite;
(4) Adding an ethylene glycol solvent, amino modified diatomite with the mass ratio of 100:4-10:0.8-2 and Bi (NO) into a beaker 3 ) 3 And KCl, stirring for 6-24 hours after ultrasonic treatment, pouring the solution into a reaction kettle, performing in-situ solvothermal reaction, cooling, filtering the solvent, washing the mixed product with deionized water, and drying to obtain the modified diatomite-loaded BiOCl nanoflower;
(5) Adding nitric acid solution with pH of 5-6 and Bi (NO) into a beaker 3 ) 3 Stirring and dissolving, adding NH 4 VO 3 、Zn(NO 3 ) 2 And a surfactant cetyl trimethyl ammonium bromide, after being stirred uniformly, pouring the solution into a reaction kettle for hydrothermal reaction, cooling, filtering the solvent, washing the product with ethanol and deionized water, and drying to obtain Zn doped mesoporous BiVO 4 ；
(6) Adding deionized water and modified diatomite loaded BiOCl nanoflower and Zn doped mesoporous BiVO with the mass ratio of 100:15-40 into a beaker 4 Ultrasonic treatment for 1-3h, vacuum drying the solution to obtain modified diatomite-supported BiVO 4 -a composite of BiOCl heterojunctions.
2. The modified diatomaceous earth-supported BiVO of claim 1 4 -a composite of BiOCl heterojunction, characterized in that: the epoxidation reaction in the step (2) is carried out for 15-30 hours at the temperature of 30-50 ℃.
3. The modified diatomaceous earth-supported BiVO of claim 1 4 -a composite of BiOCl heterojunction, characterized in that: the amino modification reaction in the step (3) is carried out for 6-12h at 30-60 ℃.
4. A modified silicon according to claim 1Algae soil loaded BiVO 4 -a composite of BiOCl heterojunction, characterized in that: the in-situ solvothermal reaction in the step (4) is carried out for 12-24 hours at the temperature of 140-160 ℃.
5. The modified diatomaceous earth-supported BiVO of claim 1 4 -a composite of BiOCl heterojunction, characterized in that: the hydrothermal reaction in the step (5) is carried out for 2-5h at 170-190 ℃.
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