CN115025819A - Bismuth-based MOF/bismuth tungstate composite material, preparation method thereof and application thereof in tetracycline hydrochloride degradation - Google Patents
Bismuth-based MOF/bismuth tungstate composite material, preparation method thereof and application thereof in tetracycline hydrochloride degradation Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000015556 catabolic process Effects 0.000 title claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 title claims abstract description 15
- 229960004989 tetracycline hydrochloride Drugs 0.000 title claims abstract description 15
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003403 water pollutant Substances 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 150000001621 bismuth Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 230000004298 light response Effects 0.000 abstract 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 238000000527 sonication Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000273 veterinary drug Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229960001482 bismuth subnitrate Drugs 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing 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
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
-
- 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 discloses a bismuth-based MOF/bismuth tungstate composite material, a preparation method thereof and application thereof in tetracycline hydrochloride degradation. In-situ growth of Bi with oxygen vacancy on surface of spherical Bi-MOF 2 WO 6 Preparing to obtain Bi-MOF/Bi 2 WO 6 -an OV composite material. The catalyst has excellent visible light response performance, shows extremely strong photocatalytic activity, and can be used for degrading pollutant hydrochloric acid tetra in waterA cycline.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a bismuth-based MOF/bismuth tungstate composite material, a preparation method thereof and application thereof in tetracycline hydrochloride degradation.
Background
With the increasing global population, the demand for food is also increasing, and a large amount of agricultural and veterinary drugs enter the food through various links, so that the animal and veterinary drugs become food pollutants. In order to ensure the food safety of people's life and solve the problem of food pollution, it is important to efficiently degrade chemical pollutants such as pesticide and veterinary drug residues. At present, methods for degrading chemical pollutants such as pesticide and veterinary drug residues at home and abroad mainly comprise photodegradation, ozone degradation, microbial degradation, chemical degradation and radiation degradation. Among them, photocatalytic degradation is one of the leading research hotspots as an efficient degradation technology.
The metal organic framework Materials (MOFs) have the advantages of high specific surface area, ordered tissue arrangement, strong adjustability of molecular structure-chemical property and the like, and become porous photocatalysts for efficiently degrading chemical pollutants such as pesticide and veterinary drug residues. So far, in various scientific reports about MOFs materials at home and abroad, photocatalytic MOFs materials mainly based on transition metal elements such as Ti, Zr, Fe and the like all show good photocatalytic material characteristics. However, the research on the photocatalysis of certain metal MOFs materials is very rare, for example, Bi-MOF, Bi metal has the chemical characteristics of no toxicity and sufficient energy storage, and also has flexible, diverse and special chemical coordination ratios and structures, so that MOF structures with complex and variable structures can be formed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a bismuth-based MOF/bismuth tungstate composite material, a preparation method thereof and application thereof in tetracycline hydrochloride degradation.
The first purpose of the invention is to provide a Bi-MOF/bismuth tungstate composite material (Bi-MOF/Bi) 2 WO 6 -OV composite) made of Bi with oxygen vacancies 2 WO 6 Growing in situ on the surface of the Bi-MOF.
In one embodiment of the invention, the Bi-MOF has a spherical morphology.
The second purpose of the invention is to provide a preparation method of the Bi-MOF/bismuth tungstate composite material, which comprises the following steps: and heating and reacting the mixed solution of the Bi-MOF and the tungstate to obtain the Bi-MOF/bismuth tungstate composite material.
In one embodiment of the invention, the tungstate is selected from one or more of sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate, and zinc tungstate.
In one embodiment of the invention, the mass ratio of the Bi-MOF to the tungstate is 1.0:0.3 to 1.0: 1.0.
In one embodiment of the present invention, the temperature of the heating reaction is 160-180 ℃; the heating reaction time is 20-24 h.
In one embodiment of the invention, the method further comprises the step of preparing the Bi-MOF/Bi solution for the reaction solution 2 WO 6 -separation of the OV composite material, in particular comprising: washing, centrifuging to remove impurities, and drying to obtain the Bi-MOF/Bi 2 WO 6 -an OV composite material; the drying temperature is 50-70 ℃; the drying time is 6-12 h.
In one embodiment of the invention, the Bi-MOF is prepared by the following method: dissolving bismuth salt in ethylene glycol, adding a terephthalic acid solution, mixing and stirring, and heating the mixed solution for reaction to obtain the Bi-MOF.
In one embodiment of the invention, the bismuth salt is selected from one or more of bismuth nitrate, bismuth subnitrate, bismuth oxide, bismuth acetate and bismuth citrate.
The third purpose of the invention is to provide the Bi-MOF/Bi 2 WO 6 -use of OV composite materials for the catalytic degradation of water body pollutants.
In one embodiment of the invention, the water contaminant is an antibiotic tetracycline hydrochloride.
In one embodiment of the invention, the catalytic degradation comprises the steps of: subjecting Bi-MOF/Bi 2 WO 6 Dissolving the-OV composite material in water pollutants, stirring under the condition of keeping out of the sun to realize adsorption-desorption balance, and thenAnd the reaction is carried out under the irradiation of visible light, so that the catalytic degradation of water pollutants is realized.
In one embodiment of the invention, the visible light source has a wavelength greater than 420 nm.
The technical scheme of the invention is as follows: Bi-MOF/Bi in the invention 2 WO 6 The preparation method of the-OV composite material adopts an in-situ growth method: 1. Bi-MOF is synthesized by a simple glycol-assisted solvothermal method. 2. By mixing Bi-MOF and Na 2 WO 4 ·2H 2 Heating the O mixed solution to react and synthesize Bi-MOF/Bi 2 WO 6 -an OV composite material. Further, the pollutants in the water body are degraded by common antibiotic tetracycline hydrochloride, and Bi-MOF/Bi is weighed 2 WO 6 -OV composite material, dissolved in tetracycline hydrochloride solution. Stirred in the dark to reach adsorption-desorption equilibrium. Taking samples every 3min under visible light (lambda is more than 420nm), centrifuging, taking supernatant, and measuring ultraviolet absorbance.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the Bi-MOF/Bi of the invention 2 WO 6 -OV composite material by in-situ growth of Bi with oxygen vacancies on Bi-MOF surface 2 WO 6 Greatly improves the catalytic performance of the Bi-MOF. Bi 2 WO 6 The OV is an excellent photocatalyst, and the introduction of oxygen vacancy can cause the optical band gap of a semiconductor to shrink to generate defect energy level, thereby shortening a charge transfer path and enhancing the light absorption of adsorbed molecules. Bi-MOF and Bi 2 WO 6 And the OV is in close contact to form a heterojunction, so that the recombination of photon-generated carriers is effectively inhibited.
(2) The Bi-MOF/Bi of the invention 2 WO 6 the-OV composite material can be used as an efficient catalyst for degrading water pollutants, solves the problem of pesticide and veterinary drug residue, is non-toxic and harmless, has simple preparation conditions, can be recycled and reused, and has good industrial application prospect. The composite material promotes the effective separation of photon-generated carriers by forming a favorable interface electric field and a well-matched energy band, greatly improves the catalytic performance of the material and improves the degradation efficiency.
Drawings
In order that the present disclosure may be more readily understood, a more particular description of the disclosure will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings
FIG. 1 is an SEM image of Bi-MOF prepared in example 1 of the present invention.
FIG. 2 shows Bi-MOF/Bi prepared in example 1 of the present invention 2 WO 6 SEM images of OV composites.
FIG. 3 is a graph showing the effect of Bi-MOF in the present invention in the test example 2 on the degradation of tetracycline hydrochloride.
FIG. 4 shows Bi-MOF/Bi in test example 2 of the present invention 2 WO 6 The effect graph of the OV composite material for degrading tetracycline hydrochloride is shown.
Detailed Description
The present invention is further described below in conjunction with the drawings and the embodiments so that those skilled in the art can better understand the present invention and can carry out the present invention, but the embodiments are not to be construed as limiting the present invention.
Example 1
(1) Preparation of Bi-MOF:
firstly, 2mmol of Bi (NO) 3 ) 3 ·5H 2 O was added to ethylene glycol (40mL) and dissolved by sonication. 3mmol of terephthalic acid was dissolved in N, N-dimethylformamide (30 mL). The terephthalic acid solution was then added dropwise to Bi (NO) 3 ) 3 ·5H 2 In O solution, stir at room temperature for 2 h. The mixture solution was then transferred to a 100mL teflon lined stainless steel autoclave and heated at 150 ℃ for 16 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min). The Bi-MOF obtained after drying at 60 ℃ was ground with an agate mortar to homogeneity.
(2)Bi-MOF/Bi 2 WO 6 -preparation of OV composite material:
adding 0.5mmol of Na 2 WO 4 ·2H 2 O was added to ethylene glycol (20mL) and dissolved by sonication. 0.2g of Bi-MOF was weighed out and dissolved in ethanol (40)mL). Then Na is added 2 WO 4 ·2H 2 The O solution was added dropwise to the Bi-MOF solution, and stirred vigorously at room temperature for 30 min. The mixture solution was transferred to a 100mL teflon-lined stainless steel autoclave and heated at 180 ℃ for 20 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min). Drying at 60 ℃ to obtain Bi-MOF/Bi 2 WO 6 The OV composite was ground with an agate mortar to achieve homogeneity.
Example 2
(1) Preparation of Bi-MOF:
firstly, 2.1mmol of Bi (NO) 3 ) 3 ·5H 2 O was added to ethylene glycol (40mL) and dissolved by sonication. 3mmol of terephthalic acid was dissolved in N, N-dimethylformamide (30 mL). The terephthalic acid solution was then added dropwise to Bi (NO) 3 ) 3 ·5H 2 In O solution, stir at room temperature for 1 h. The mixture solution was then transferred to a 100mL teflon lined stainless steel autoclave and heated at 150 ℃ for 16 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min). The Bi-MOF obtained after drying at 60 ℃ was ground with an agate mortar to homogeneity.
(2)Bi-MOF/Bi 2 WO 6 -preparation of OV composite material:
adding 0.3mmol of Na 2 WO 4 ·2H 2 O was added to ethylene glycol (20mL) and dissolved by sonication. 0.2g of Bi-MOF was weighed out and dissolved in ethanol (40 mL). Then adding Na 2 WO 4 ·2H 2 The O solution was added dropwise to the Bi-MOF solution and stirred vigorously at room temperature for 1 h. The mixture solution was transferred to a 100mL teflon-lined stainless steel autoclave and heated at 160 ℃ for 20 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min). Drying at 60 ℃ to obtain Bi-MOF/Bi 2 WO 6 The OV composite was ground with an agate mortar to achieve homogeneity.
Example 3
(1) Preparation of Bi-MOF:
firstly, 2.2mmol of Bi (NO) 3 ) 3 ·5H 2 O was added to ethylene glycol (40mL) and dissolved by sonication. 3mmol of terephthalic acid was dissolved in N, N-dimethylformamide (30 mL). The terephthalic acid solution was then added dropwise to Bi (NO) 3 ) 3 ·5H 2 In O solution, stir at room temperature for 2 h. The mixture solution was then transferred to a 100mL teflon lined stainless steel autoclave and heated at 150 ℃ for 16 h. After the reaction, the mixture was naturally cooled to room temperature, and washed by repeated centrifugation with ultrapure water and absolute ethanol (7500 rpm/min). The Bi-MOF obtained after drying at 60 ℃ was ground with an agate mortar to homogeneity.
(2)Bi-MOF/Bi 2 WO 6 -preparation of OV composite material:
adding 0.4mmol of Na 2 WO 4 ·2H 2 O was added to ethylene glycol (20mL) and dissolved by sonication. 0.2g of Bi-MOF was weighed out and dissolved in ethanol (40 mL). Then adding Na 2 WO 4 ·2H 2 The O solution was added dropwise to the Bi-MOF solution and stirred vigorously at room temperature for 2 h. The mixture solution was transferred to a 100mL teflon-lined stainless steel autoclave and heated at 160 ℃ for 24 h. After the reaction, the mixture was naturally cooled to room temperature, and washed by repeated centrifugation with ultrapure water and absolute ethanol (7500 rpm/min). Drying at 60 ℃ to obtain Bi-MOF/Bi 2 WO 6 The OV composite was ground with an agate mortar to achieve homogeneity.
Example 4
(1) Preparation of Bi-MOF:
firstly, 2.3mmol of Bi (NO) 3 ) 3 ·5H 2 O was added to ethylene glycol (40mL) and dissolved by sonication. 3mmol of terephthalic acid was dissolved in N, N-dimethylformamide (30 mL). The terephthalic acid solution was then added dropwise to Bi (NO) 3 ) 3 ·5H 2 In O solution, stir at room temperature for 2 h. The mixture solution was then transferred to a 100mL teflon lined stainless steel autoclave and heated at 150 ℃ for 16 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min).The Bi-MOF obtained after drying at 60 ℃ was ground with an agate mortar to homogeneity.
(2)Bi-MOF/Bi 2 WO 6 -preparation of OV composite material:
adding 0.6mmol of Na 2 WO 4 ·2H 2 O was added to ethylene glycol (20mL) and dissolved by sonication. 0.2g of Bi-MOF was weighed out and dissolved in ethanol (40 mL). Then adding Na 2 WO 4 ·2H 2 The O solution was added drop wise to the Bi-MOF solution with vigorous stirring at room temperature for 2 h. The mixture solution was transferred to a 100mL teflon-lined stainless steel autoclave and heated at 180 ℃ for 24 h. After the reaction is finished, the reaction solution is naturally cooled to room temperature, and is repeatedly centrifugally washed by ultrapure water and absolute ethyl alcohol (7500 rpm/min). Drying at 60 ℃ to obtain Bi-MOF/Bi 2 WO 6 The OV composite was ground with an agate mortar to achieve homogeneity.
Test example 1
For the Bi-MOF, Bi-MOF/Bi prepared in the invention example 1 2 WO 6 The OV composite material was subjected to SEM topography characterization, as shown in FIGS. 1-2, the Bi-MOF is a microsphere with a diameter of about 0.02mm, each microsphere is composed of a nanorod with a diameter of about 150nm and a length of about 250 nm. Bi 2 WO 6 After OV grows on the surface of the Bi-MOF in situ, the surface appearance is changed, nanorods on the surface of the Bi-MOF are hardly seen, and the microsphere structure begins to dissolve.
Test example 2
For the Bi-MOF, Bi-MOF/Bi prepared in the invention example 1 2 WO 6 The OV composite was subjected to catalytic performance studies.
Weighing 5mg of Bi-MOF or Bi-MOF/Bi 2 WO 6 -OV composite catalyst, dissolved in 30mL of 20mg/mL tetracycline hydrochloride solution. Stir in the dark for 30min to reach adsorption-desorption equilibrium. The subsequent irradiation was continued for 15min under a 300W xenon lamp equipped with UV filters as the sole light source (. lamda. > 420nm), during which a certain stirring speed had to be maintained. Centrifuging every 3min to obtain 1mL of product, measuring the supernatant with ultraviolet-visible spectrophotometer, and measuring the maximum absorption wavelength (lambda) TC 355nm, TC tetracycline hydrochloride). As shown in FIGS. 3-4, FIG. 3 shows that the Bi-MOF alone degrades tetracycline hydrochloride, and FIG. 4 shows that the Bi-MOF/Bi2WO6-OV composite material degrades tetracycline hydrochloride, such that Bi-MOF/Bi 2 WO 6 The catalytic degradation performance of the OV composite material is obviously improved compared with that of the Bi-MOF alone.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A Bi-MOF/bismuth tungstate composite material is characterized in that the Bi-MOF/bismuth tungstate composite material is prepared from Bi with oxygen vacancies 2 WO 6 Growing in situ on the surface of the Bi-MOF.
2. The Bi-MOF/bismuth tungstate composite material of claim 1, wherein the Bi-MOF has a spherical morphology.
3. A process for the preparation of a Bi-MOF/bismuth tungstate composite material as claimed in claim 1 or 2, which comprises the steps of: heating and reacting the mixed solution of Bi-MOF and tungstate to obtain the Bi-MOF/Bi 2 WO 6 -an OV composite material.
4. The method according to claim 3, wherein the mass ratio of the Bi-MOF to the tungstate is 1.0:0.3 to 1.0: 1.0.
5. The method according to claim 3, further comprising subjecting the reaction solution to Bi-MOF/Bi 2 WO 6 -separation of the OV composite material, in particular comprising: washing, centrifuging to remove impurities, and drying to obtain the Bi-MOF/Bi 2 WO 6 -an OV composite material; the drying temperature is 50-70 ℃; the drying time is 6-12 h.
6. The method of claim 3, wherein the Bi-MOF is prepared by: dissolving bismuth salt in ethylene glycol, adding a terephthalic acid solution, mixing and stirring, and heating the mixed solution for reaction to obtain the Bi-MOF.
7. Use of the Bi-MOF/bismuth tungstate composite material of claim 1 or 2 for the catalytic degradation of water body pollutants.
8. The use of claim 7, wherein the water contaminant is the antibiotic tetracycline hydrochloride.
9. Use according to claim 7, characterized in that the catalytic degradation comprises the following steps: dissolving the Bi-MOF/bismuth tungstate composite material in water pollutants, stirring under a dark condition to realize adsorption-desorption balance, and then reacting under visible light irradiation to realize catalytic degradation of the water pollutants.
10. Use according to claim 9, wherein the visible light source has a wavelength of more than 420 nm.
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