CN109046366A - A kind of hetero-junctions micron box composite photo-catalyst and its preparation method and application - Google Patents
A kind of hetero-junctions micron box composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN109046366A CN109046366A CN201810766975.3A CN201810766975A CN109046366A CN 109046366 A CN109046366 A CN 109046366A CN 201810766975 A CN201810766975 A CN 201810766975A CN 109046366 A CN109046366 A CN 109046366A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 82
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 239000012085 test solution Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 230000003115 biocidal effect Effects 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910003206 NH4VO3 Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004098 Tetracycline Substances 0.000 claims description 9
- 229960002180 tetracycline Drugs 0.000 claims description 9
- 229930101283 tetracycline Natural products 0.000 claims description 9
- 235000019364 tetracycline Nutrition 0.000 claims description 9
- 150000003522 tetracyclines Chemical class 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 238000013019 agitation Methods 0.000 description 18
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229940072172 tetracycline antibiotic Drugs 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 oxygen radical Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/38—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
Abstract
The present invention provides a kind of hetero-junctions micron box composite photo-catalyst and its preparation method and application, comprising the following steps: step S1, prepares Fe2O3Micron box；Step S2, Fe is prepared2O3/BiVO4Hetero-junctions micron box composite photo-catalyst: Bi (NO is taken3)3.5H2O is dissolved in ethylene glycol, after mixing evenly by particle, the Fe prepared in the step S1 is added2O3Powder obtains mixing test solution 1, stands after stirring；Take NH4VO3It is dissolved in ethylene glycol, is slowly added in mixing test solution 1, stirring, mixing test solution 2 is obtained；It takes urea to be dissolved in ethylene glycol, is slowly added in mixing test solution 2, hot bath is stood after a certain period of time；It is centrifuged drying after removal of impurities is handled, solid is collected, obtains Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.The present invention is realized with Fe2O3/BiVO4The purpose of hetero-junctions micron box composite photocatalyst for degrading antibiotic waste water.The formation that this method will not result in waste of resources with additional pollution, and it is easy to operate, it is a kind of environmentally protective efficient process technology.
Description
Technical field
The invention belongs to environmentally conscious materials preparation research fields, and in particular to a kind of hetero-junctions micron box composite photo-catalyst
And its preparation method and application.
Background technique
Antibiotic is a kind of chemical substance that can inhibit at low concentrations or kill other microorganisms generated by microorganism.
But most antibiotic cannot be absorbed by organisms completely, there are about 90% antibiotic with original shape or metabolite form via disease
The excrement of people and livestock and poultry, urine are discharged into environment, pollute through different approaches to soil and water body.Tetracycline (TC) is used as a kind of typical case
Antibiotic, be widely used in human production activity, when it enters ecological environment, it is possible to strong to the ecosystem and human body
Health constitutes a serious threat.Now, have become extremely urgent problems from the antibiotic removed including TC in environment.
BiVO4It is a kind of stable semiconductor material, band gap is only 2.4ev, and light abstraction width is expanded to visible light
Region.It is a kind of metal oxide matter of environmentally friendly low-carbon without the heavy metal element being harmful to the human body.BiVO4With excellent
Photocatalysis performance, it is nontoxic, it can be recycled, be widely used in photocatalysis field.
Fe2O3Being made of the iron and oxygen element of soil abundance has advantage at low cost, environmentally friendly.As n-type semiconductor,
Band gap is only 2.2ev.So Fe2O3It is the photochemical catalyst of potential visible optical drive.Fe2O3In many important organic matters
Successful application catalysis reaction shows that it has good catalytic activity and reactivity.
Summary of the invention
The purpose of the present invention is provide a kind of hetero-junctions micron box composite photo-catalyst and its preparation regarding to the issue above
Methods and applications prepare Fe using hydro-thermal method as technological means2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.It realizes
With Fe2O3/BiVO4The purpose of hetero-junctions micron box composite photocatalyst for degrading antibiotic waste water.
The technical scheme is that a kind of preparation method of hetero-junctions micron box composite photo-catalyst, including it is following
Step:
Step S1, Fe is prepared2O3Micron box；
Step S2, Fe is prepared2O3/BiVO4Hetero-junctions micron box composite photo-catalyst:
Take Bi (NO3)3.5H2O is dissolved in ethylene glycol, after mixing evenly by particle, is added and is prepared in the step S1
Fe2O3Powder obtains mixing test solution 1, stands after stirring；Take NH4VO3It is dissolved in ethylene glycol, is slowly added in mixing test solution 1, stirs
It mixes, obtains mixing test solution 2；It takes urea to be dissolved in ethylene glycol, is slowly added in mixing test solution 2, hot bath is stood after a certain period of time；From
It is dry after heart removal of impurities processing, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
In above scheme, the step S1 specifically:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then 100 DEG C aging 4 days in the baking oven of preheating, collect red product and spend from
Sub- water and ethanol washing three times, are then dried overnight at 70 DEG C, obtain Fe2O3Micron box.
In above scheme, NaOH and FeCl in the step S13Molar ratio be 2.7:1.
In above scheme, Bi (NO in the step S23)3.5H2O and Fe2O3Molar ratio be 1:1~1:5.
In above scheme, the Bi (NO3)3.5H2The dosage of O is 0.6-3mmol, the Fe2O3Dosage be 3mmol.
In above scheme, Bi (NO in the step S23)3.5H2O and NH4VO3Molar ratio be 1:1.
In above scheme, the quality of urea is 3g in the step S2.
In above scheme, urea is dissolved in ethylene glycol in the step S2, after being slowly added to mixing test solution 2,80 DEG C of water-baths
24h。
A kind of hetero-junctions micron box composite photo-catalyst, utilizes the Fe2O3/BiVO4Hetero-junctions micron box complex light
The Fe that method for preparing catalyst obtains2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
Application of the hetero-junctions micron box composite photo-catalyst in Degradation of Antibiotics, the application are Fe2O3/
BiVO4Hetero-junctions micron box composite photo-catalyst is applied to the tetracycline in degradation antibiotic.
Compared with prior art, the beneficial effects of the present invention are: the present invention is realized with Fe2O3/BiVO4Hetero-junctions micron
Purpose of the box as photocatalyst for degrading antibiotic waste water.Semiconductor material is as photochemical catalyst, it is seen that light leads to as excitation
It crosses and realizes special catalysis or conversion effet with the interfacial interaction of contaminant molecule, make oxygen and the hydrone excitation of surrounding
At the oxygen radical of great oxidizing force, hydroxyl radical free radical etc. has the substance of strong oxidizing property, to reach harmful in degradation environment
The purpose of organic substance, the formation that this method will not result in waste of resources with additional pollution, and it is easy to operate.The present invention is specifically real
Apply gained Fe in example 22O3/BiVO4Hetero-junctions micron box composite photo-catalyst can be in 60min to 20mg/L tetracycline antibiosis
The Effective degradability of element reaches 77.04%, is a kind of environmentally protective efficient process technology.
Detailed description of the invention
Fig. 1 is Fe2O3/BiVO4The UV-vis of hetero-junctions micron box composite photo-catalyst schemes.
Fig. 2 is Fe2O3/BiVO4The XRD diagram of hetero-junctions micron box composite photo-catalyst.
Fig. 3 is Fe2O3/BiVO4The TEM of hetero-junctions micron box composite photo-catalyst schemes.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description, but protection scope of the present invention
It is not limited to this.
A kind of preparation method of hetero-junctions micron box composite photo-catalyst the following steps are included:
Step S1, Fe is prepared2O3Micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3Middle solution, NaOH and FeCl3Molar ratio
For 2.7:1, gained Fe (OH)3Gel continuously stirs 5 minutes at mutually synthermal 75 DEG C, then 100 DEG C in the baking oven of preheating
Aging 4 days, collect red product and with deionized water and ethanol washing three times, the dosage of deionized water is can make solid completely molten
Then solution is dried overnight at 70 DEG C, obtains Fe2O3Micron box.
Step S 2, preparation Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst:
Take Bi (NO3)3.5H2O is dissolved in ethylene glycol, and the dosage of ethylene glycol can make Bi (NO3)3.5H2O be completely dissolved for
Only, the Fe prepared in the step S1 is added after particle is uniform in magnetic agitation, ultrasonic dissolution2O3Powder obtains mixing test solution
1h is stood after 1, magnetic agitation 1h；Take NH4VO3It is dissolved in ethylene glycol, is slowly added to dropwise with dropper in mixing test solution 1, room temperature, magnetic
Power stirs 1h, obtains mixing test solution 2, NH4VO3With Bi (NO3)3.5H2The molar ratio of O is 1:1；3g urea is taken to be dissolved in second two later
Alcohol, with dropper be slowly added to mixing 2,80 DEG C of water-baths for 24 hours of test solution after, stand one evening, centrifugation, washing three times, alcohol wash three times, impurity elimination
Matter keeps sample purity higher, finally dries, and collects solid, obtains Fe2O3/BiVO4Hetero-junctions micron box.
Prepared Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst, Bi (NO3)3.5H2O and Fe2O3Mole
Than for 1:1~1:5, it is preferred that Bi (NO3)3.5H2The dosage of O is 0.6-3mmol, Fe2O3Dosage be 3mmol.
The Fe that preparation method as described above obtains2O3/BiVO4Hetero-junctions micron box composite photo-catalyst, application
In tetracycline of degrading in antibiotic waste water.
Five water bismuth nitrate (Bi (NO used in the present invention3)3.5H2O), ammonium metavanadate (NH4VO3), urea (CH4N2O),
Sodium hydroxide (NaOH), anhydrous ferric trichloride (FeCl3) it is that analysis is pure, it is purchased from traditional Chinese medicines chemical reagent Co., Ltd；Tetracycline
To mark product, Shanghai is purchased from along vigorous bioengineering Co., Ltd.
The photocatalytic activity evaluation of prepared photochemical catalyst in the present invention: in DW-01 type photochemical reactor (purchased from raising
State Science and Technology Ltd. of university city) in carry out, it is seen that light light irradiation, by 100mL tetracycline simulated wastewater be added reactor in simultaneously
Its initial value is measured, is then added photochemical catalyst obtained, magnetic agitation simultaneously opens aerator and is passed through air and keep catalyst
It is spaced 10min sampling analysis in suspension or afloat, During Illumination, takes supernatant liquor in spectrophotometric after centrifuge separation
Count λmaxAbsorbance is measured at=360nm, and passes through formula: Dr=[1-Ai/A0] × 100% calculates degradation rate, wherein A0For up to
The absorbance of tetracycline, A when to adsorption equilibriumiFor the absorbance of the tetracycline of timing sampling measurement.
Embodiment 1:
Step S1, Fe2O3The preparation of micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3Middle solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then in the baking oven of preheating 100 DEG C aging 4 days.It collects red product and spends
Ionized water and ethanol washing three times, are then dried overnight at 70 DEG C.Obtain Fe2O3Micron box.
Step S2, Fe2O3/BiVO4The preparation of hetero-junctions micron box composite photo-catalyst:
Take 0.6mmolBi (NO3)3.5H2O is dissolved in ethylene glycol, magnetic agitation, ultrasonic dissolution, after particle is uniform, is added
Enter the 3mmolFe prepared in the step S12O3Powder obtains mixing test solution 1, stands 1h after magnetic agitation 1h；Take ammonium metavanadate
It is dissolved in ethylene glycol, is slowly added to dropwise with dropper in mixing test solution 1, room temperature, magnetic agitation 1h, mixing test solution 2 is obtained；It takes later
3g urea is dissolved in ethylene glycol, is slowly added in mixing test solution 2 with dropper, 80 DEG C of water-baths are for 24 hours.Stand an evening, centrifugation, washing three
Time, alcohol is washed three times, and it is dry, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
It takes 50mg sample made from the step S2 to carry out photocatalytic degradation test in photochemical reactor, measures the light
Catalyst reaches 54.32% to the degradation rate of 20mg/L tetracycline antibiotic in 60min.
Embodiment 2:
Step S1, Fe2O3The preparation of micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then in the baking oven of preheating 100 DEG C aging 4 days.It collects red product and spends
Ionized water and ethanol washing three times, are then dried overnight at 70 DEG C.Obtain Fe2O3Micron box.
Step S2, Fe2O3/BiVO4The preparation of hetero-junctions micron box composite photo-catalyst:
Take 0.75mmolBi (NO3)3.5H2O is dissolved in ethylene glycol, magnetic agitation, ultrasonic dissolution, after particle is uniform,
The 3mmolFe prepared in the step S1 is added2O3Powder obtains mixing examination 1, stands 1h after liquid magnetic agitation 1h；Take metavanadic acid
Ammonium is dissolved in ethylene glycol, is slowly added to dropwise in mixing test solution 1 with dropper, room temperature, magnetic agitation 1h, obtains mixing test solution 2；Later
It takes 3g urea to be dissolved in ethylene glycol, is slowly added in mixing test solution 2 with dropper, 80 DEG C of water-baths are for 24 hours.Stand an evening, centrifugation, washing three
Time, alcohol is washed three times, and it is dry, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
It takes 50mg sample made from the step S2 to carry out photocatalytic degradation test in photochemical reactor, measures the light
Catalyst reaches 77.04% to the degradation rate of 20mg/L tetracycline antibiotic in 60min.
Embodiment 3:
Step S1, Fe2O3The preparation of micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then in the baking oven of preheating 100 DEG C aging 4 days.It collects red product and spends
Ionized water and ethanol washing three times, are then dried overnight at 70 DEG C.Obtain Fe2O3Micron box.
Step S2, Fe2O3/BiVO4The preparation of hetero-junctions micron box composite photo-catalyst:
Take 1mmolBi (NO3)3.5H2O is dissolved in ethylene glycol, magnetic agitation, ultrasonic dissolution, after particle is uniform, is added
The 3mmolFe prepared in step S12O3Powder obtains mixing test solution 1, stands 1h after magnetic agitation 1h；Ammonium metavanadate is taken to be dissolved in second
Glycol is slowly added to, room temperature, magnetic agitation 1h dropwise with dropper, obtains mixing test solution 2；3g urea is taken to be dissolved in ethylene glycol later,
It is slowly added in mixing test solution 2 with dropper, 80 DEG C of water-baths are for 24 hours.An evening is stood, centrifugation is washed three times, and alcohol is washed three times, and it is dry, it receives
Collect solid, obtains Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
It takes 50mg sample made from the step S2 to carry out photocatalytic degradation test in photochemical reactor, measures the light
Catalyst reaches 61.55% to the degradation rate of 20mg/L tetracycline antibiotic in 60min.
Embodiment 4:
Step S1, Fe2O3The preparation of micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then in the baking oven of preheating 100 DEG C aging 4 days.It collects red product and spends
Ionized water and ethanol washing three times, are then dried overnight at 70 DEG C.Obtain Fe2O3Micron box.
Step S2, Fe2O3/BiVO4The preparation of hetero-junctions micron box composite photo-catalyst:
Take 1.5mmolBi (NO3)3.5H2O is dissolved in ethylene glycol, magnetic agitation, ultrasonic dissolution, after particle is uniform, is added
Enter the 3mmolFe prepared in step S12O3Powder obtains mixing test solution 1, stands 1h after magnetic agitation 1h；Ammonium metavanadate is taken to be dissolved in
Ethylene glycol is slowly added to, room temperature, magnetic agitation 1h dropwise with dropper, obtains mixing test solution 2；3g urea is taken to be dissolved in second two later
Alcohol is slowly added in mixing test solution 2 with dropper, and 80 DEG C of water-baths are for 24 hours.An evening is stood, centrifugation is washed three times, and alcohol is washed three times, is done
It is dry, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
It takes 50mg sample made from the step S2 to carry out photocatalytic degradation test in photochemical reactor, measures the light
Catalyst reaches 70.62% to the degradation rate of 20mg/L tetracycline antibiotic in 60min.
Embodiment 5:
Step S1, Fe2O3The preparation of micron box:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase
Continuously stir 5 minutes at synthermal 75 DEG C, then in the baking oven of preheating 100 DEG C aging 4 days.It collects red product and spends
Ionized water and ethanol washing three times, are then dried overnight at 70 DEG C.Obtain Fe2O3Micron box.
Step S2, Fe2O3/BiVO4The preparation of hetero-junctions micron box composite photo-catalyst:
Take 3mmolBi (NO3)3.5H2O is dissolved in ethylene glycol, magnetic agitation, ultrasonic dissolution, after particle is uniform, is added
The 3mmolFe prepared in step S12O3Powder obtains mixing test solution 1, stands 1h after magnetic agitation 1h；Ammonium metavanadate is taken to be dissolved in second
Glycol is slowly added in mixing test solution 1, room temperature, magnetic agitation 1h dropwise with dropper, obtains mixing test solution 2,；3g is taken to urinate later
Element is dissolved in ethylene glycol, is slowly added in mixing test solution 2 with dropper, 80 DEG C of water-baths are for 24 hours.An evening is stood, centrifugation is washed three times, alcohol
It washes three times, it is dry, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
It takes 50mg sample made from the step S2 to carry out photocatalytic degradation test in photochemical reactor, measures the light
Catalyst reaches 68.82% to the degradation rate of 20mg/L tetracycline antibiotic in 60min.
Fig. 1 is Fe2O3/BiVO4The UV-vis of hetero-junctions micron box composite photo-catalyst schemes, and illustrates Fe in Fig. 12O3/
BiVO4The photoresponse ability of hetero-junctions micron box photochemical catalyst compares monomer BiVO4Have and is greatly enhanced.
Fig. 2 is Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst, Fe2O3Micron box, monomer BiVO4XRD
Scheme, what be will be apparent that in Fig. 2 presents Fe2O3/BiVO4Hetero-junctions micron box photochemical catalyst contains Fe2O3Micron box and list
Body BiVO4Two kinds of characteristic peaks.
Fig. 3 is Fe2O3/BiVO4The TEM of hetero-junctions micron box composite photo-catalyst schemes, as can be seen from Figure 3 monomer
BiVO4It has been distributed to Fe2O3On, form Fe2O3/BiVO4Hetero-junctions.
The series of detailed descriptions listed above are illustrated only for possible embodiments of the invention,
The protection scope that they are not intended to limit the invention, it is all without departing from equivalent embodiment made by technical spirit of the present invention or change
It should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hetero-junctions micron box composite photo-catalyst, which comprises the following steps:
Step S1, Fe is prepared2O3Micron box；
Step S2, Fe is prepared2O3/BiVO4Hetero-junctions micron box composite photo-catalyst:
Take Bi (NO3)3.5H2O is dissolved in ethylene glycol, after mixing evenly by particle, the Fe prepared in the step S1 is added2O3
Powder obtains mixing test solution 1, stands after stirring；Take NH4VO3It is dissolved in ethylene glycol, is slowly added in mixing test solution 1, stirring obtains
Mix test solution 2；It takes urea to be dissolved in ethylene glycol, is slowly added in mixing test solution 2, hot bath is stood after a certain period of time；Centrifugation removal of impurities
It is dry after processing, solid is collected, Fe is obtained2O3/BiVO4Hetero-junctions micron box composite photo-catalyst.
2. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 1, which is characterized in that described
Step S1 specifically:
NaOH solution is continuously stirred down in 5 minutes and is added to FeCl for 75 DEG C3In solution, gained Fe (OH)3Gel is in phase equality of temperature
It is continuously stirred at 75 DEG C of degree 5 minutes, then 100 DEG C aging 4 days in the baking oven of preheating, collect red product and use deionized water
Three times with ethanol washing, it is then dried overnight at 70 DEG C, obtains Fe2O3Micron box.
3. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 2, which is characterized in that described
NaOH and FeCl in step S13Molar ratio be 2.7:1.
4. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 1, which is characterized in that described
Bi (NO in step S23)3.5H2O and Fe2O3Molar ratio be 1:1~1:5.
5. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 4, which is characterized in that described
Bi(NO3)3.5H2The dosage of O is 0.6-3mmol, the Fe2O3Dosage be 3mmol.
6. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 1, which is characterized in that described
Bi (NO in step S23)3.5H2O and NH4VO3Molar ratio be 1:1.
7. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 1, which is characterized in that described
The quality of urea is 3g in step S2.
8. the preparation method of hetero-junctions micron box composite photo-catalyst according to claim 1, which is characterized in that described
Urea is dissolved in ethylene glycol in step S2, and after being slowly added to mixing test solution 2,80 DEG C of water-baths are for 24 hours.
9. a kind of hetero-junctions micron box composite photo-catalyst, which is characterized in that using described in claim 1-8 any one
Fe2O3/BiVO4The Fe that hetero-junctions micron box composite photo-catalyst preparation method obtains2O3/BiVO4Hetero-junctions micron box is multiple
Light combination catalyst.
10. application of the hetero-junctions micron box composite photo-catalyst in Degradation of Antibiotics, feature described in claim 9 exist
In the application is Fe2O3/BiVO4Hetero-junctions micron box composite photo-catalyst is applied to the tetracycline in degradation antibiotic.
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| CN111229241A (en) * | 2020-03-02 | 2020-06-05 | 齐鲁工业大学 | Bismuth vanadate, ferric oxide and zinc ferrite ternary heterostructure nanofiber photocatalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109775763A (en) * | 2019-02-01 | 2019-05-21 | 枣庄学院 | A kind of pine nut shape Fe2O3Nano particle and preparation method thereof, experimental method and application |
| CN109775763B (en) * | 2019-02-01 | 2021-04-27 | 枣庄学院 | Pinecone-shaped Fe2O3Nanoparticle and preparation method, experimental method and application thereof |
| CN111229241A (en) * | 2020-03-02 | 2020-06-05 | 齐鲁工业大学 | Bismuth vanadate, ferric oxide and zinc ferrite ternary heterostructure nanofiber photocatalyst and preparation method thereof |
| CN111229241B (en) * | 2020-03-02 | 2021-03-12 | 齐鲁工业大学 | Bismuth vanadate, ferric oxide and zinc ferrite ternary heterostructure nanofiber photocatalyst and preparation method thereof |
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