CN110075878A - Graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst and preparation method thereof, application - Google Patents
Graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst and preparation method thereof, application Download PDFInfo
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- CN110075878A CN110075878A CN201910289680.6A CN201910289680A CN110075878A CN 110075878 A CN110075878 A CN 110075878A CN 201910289680 A CN201910289680 A CN 201910289680A CN 110075878 A CN110075878 A CN 110075878A
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
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- 230000000694 effects Effects 0.000 claims abstract description 14
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- 229960001699 ofloxacin Drugs 0.000 claims description 9
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- 230000003115 biocidal effect Effects 0.000 claims description 5
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 239000011630 iodine Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 239000000262 estrogen Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
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- 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
-
- B01J35/39—
-
- B01J35/51—
-
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/36—Organic compounds containing halogen
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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
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Abstract
The present invention provides a kind of graphene-supported BiOBrxI1‑xMicroballoon composite photo-catalyst, by high activity reduced graphene and BiOBrxI1‑xIt is compound to be prepared；Wherein, the dosage of high activity reduced graphene is BiOBrxI1‑xQuality 0.1%~5%, x value be 0~1.The present invention also provides graphene-supported BiOBrxI1‑xThe preparation method of microballoon composite photo-catalyst, steps are as follows: weighing high activity reduced graphene and is placed in the first organic solvent, ultrasonic disperse obtains suspension A；Weigh Bi (NO3)3·5H2O ultrasound is dissolved in the second organic solvent, obtains solution B；It takes KBr and KI to be dissolved in water and the second organic solvent, obtains solution C；Successively solution B and suspension A are added dropwise in solution C with vigorous stirring, obtain suspension D；It is transferred in autoclave after suspension D is persistently stirred a period of time, carries out hydro-thermal reaction at a set temperature, filtered after cooling and obtain crude product, successively washed with deionized water and dehydrated alcohol；It is dried after washing to get graphene-supported BiOBr is arrivedxI1‑xMicroballoon composite photo-catalyst.
Description
Technical field
The present invention relates to photocatalyst technology field more particularly to a kind of graphene-supported BiOBrxI1-xMicroballoon complex light
Catalyst and preparation method thereof, application.
Background technique
In recent years, the emerging organic pollutant of environment (antibiotic, estrogen and plasticiser etc.) has become and endangers ecological environment
With the focal issue of human survival, harm and the recovery technique of environmental pollution have become grinding for current environment science and engineering field
Study carefully hot spot.Photocatalitic Technique of Semiconductor can finally degrade environmental organic pollutant as a kind of emerging high-level oxidation technology
For the CO of environmental sound2, the small-molecule substances such as water, secondary pollution will not be generated, in sewage treatment, air cleaning and energy
Conversion aspect shows huge application prospect.
BiOX (BiOX, X=Cl, Br, I) is a kind of ternary semiconductor material with high anisotropy, valence band
For O2p and Xnp (n=3,4,5) track, conduction band is Bi6p track.Sufficiently strong photon can be the electron excitation on Xnp to Bi6p
Track generates photohole-electronics pair, and the electronics excited has to pass through k layers and can return to valence band, greatly reduces electronics
The recombination probability in hole pair；And the layer structure of BiOX has enough spaces come corresponding atom and the track of polarizing, and lures
Conductive coupling polar moment effectively can promote hole-electron pair to separate.This unique electronic structure of BiOX and layer structure make it
With excellent visible light catalytic oxidation ability, however the visible absorption wavestrip of single BiOX is relatively narrow, in light quantum
Efficiency and carrier efficiently separate and shift aspect there are still deficiency, and absorption property needs to be further increased, serious limitation
Its application in photocatalysis field.Therefore, seek a kind of feasible method to improve the photoproduction of BiOX photocatalyst and carry
The separation of stream has very important significance with transfer to its application in photocatalysis field is extended.
Graphene is that a kind of have big specific surface area (theoretical value may be up to 2630m2/ g) new carbon, graphene
It is a kind of material for two-dimensional honeycomb structure that mono-layer graphite C atom is formed using sp2 hydridization, can be used as ideal carrier material
Material goes to increase interfacial contact area and promotes the adsorption capacity of composite material, while the structure of graphene assigns its excellent electric conductivity
Energy.Graphene is compound with BiOX, by the good electronic transmission performance of graphene, light induced electron can be made along one-dimensional square
To fast transfer, inhibit the compound of photo-generated carrier.Meanwhile composite material can preferably adsorbed target pollutant, to mention
The efficiency of height degradation environment organic matter.Composite material is by integrated high-quantum efficiency, good absorption property and can reuse excellent
It puts and becomes " star " selection.
In the related technology, Ai Zhihui seminar by graphene with bismuth oxybromide is compound removes NO (J Physical
Chemistry C, 2011,115:25330), Liu Hong seminar is prepared for bismuth oxyiodide-graphene using a step hydrothermal synthesis method
Composite material and for environment methyl orange of degrading (J Colloid and Interface Science, 2013,398:
161), however the photo-quantum efficiency of these materials and stability also need to further increase.
Summary of the invention
In view of this, the present invention provides a kind of graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst, the complex light
Catalyst has visible light-responded catalytic activity preferably than single BiOX；The present invention also provides graphene-supported
BiOBrxI1-xThe preparation method of microballoon composite photo-catalyst, the present invention use solvent-thermal method " pot " response regulatory BiOX
Band gap and and graphene it is compound, to improve the photo-quantum efficiency of composite material；The composite photocatalyst that the present invention is prepared
Agent can be realized effective degradation to environment antibiotic Ofloxacin.
The present invention provides a kind of graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst, the composite photo-catalyst by
High activity reduced graphene (RGO) and BiOBrxI1-xIt is compound to be prepared；Wherein, the dosage of RGO is BiOBrxI1-xQuality
The value of 0.1%~5%, x are 0~1.
The present invention also provides above-mentioned graphene-supported BiOBrxI1-xThe preparation method of microballoon composite photo-catalyst, including
Following steps:
S1, weighs technical grade RGO and is placed in the first organic solvent, and ultrasonic disperse obtains suspension A；
S2 weighs Bi (NO3)3·5H2O ultrasound is dissolved in the second organic solvent, obtains solution B；
S3 takes KBr and KI to be dissolved in water and the second organic solvent, obtains solution C；With vigorous stirring successively by solution B
It is added dropwise in solution C with suspension A, obtains suspension D；
S4 is transferred in autoclave after suspension D is persistently stirred a period of time, and it is anti-to carry out hydro-thermal at a set temperature
It answers, is filtered after cooling and obtain crude product, successively washed with deionized water and dehydrated alcohol；It is dried after washing to get graphene is arrived
Load BiOBrxI1-xMicroballoon composite photo-catalyst.
Further, in step S1, high activity reduced graphene is prepared by following procedure: it weighs graphite oxide and is dissolved in N,
In dinethylformamide/water mixed solution, ultrasound is added hydrazine hydrate, then restores, and finally uses dehydrated alcohol and distilled water
It washs to get high activity reduced graphene is arrived.
Further, in step S1, first organic solvent selects dehydrated alcohol, normal propyl alcohol, any in n-butanol
It is a kind of.
Further, in step S2 and S3, second organic solvent selects any one in ethylene glycol or glycerine.
Further, in step S4, the reaction temperature of hydro-thermal reaction is 140 DEG C~200 DEG C, the reaction time is 6~for 24 hours；
Dry process be 50~90 DEG C be dried in vacuo 8~for 24 hours.
The present invention also provides above-mentioned graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst or according to above-mentioned preparation side
Graphene-supported BiOBr made from methodxI1-xThe application of microballoon composite photo-catalyst, the composite photo-catalyst are applied to too
Sunlight irradiation decline solution environment antibiotic Ofloxacin.
Compared with prior art, the beneficial effect of the technical solution adopted by the present invention is to be used as and carried using technical grade RGO
Body utilizes " pot " solvent-thermal method that graphene-supported BiOBr is preparedxI1-xMicroballoon composite photo-catalyst, preparation method are simple
Easy to operate, raw material is inexpensively pollution-free, and reaction condition is mild, and the introducing of graphene is conducive to suction of the photochemical catalyst to target contaminant
It is attached, while graphene has greatly facilitated the separation and transfer of composite photo-catalyst photo-generated carrier, improve light induced electron with
The utilization rate in hole, to significantly improve the efficiency of the emerging organic pollutant of composite photocatalyst for degrading environment.
Detailed description of the invention
Fig. 1 is a kind of graphene-supported BiOBr of the present inventionxI1-xThe process of the preparation method of microballoon composite photo-catalyst is shown
It is intended to.
Fig. 2 is graphene-supported BiOBr prepared by the embodiment of the present invention five0.8I0.2The SEM of microballoon composite photo-catalyst
(Scanning Electron Microscope, scanning electron microscope) is as figure.
Fig. 3 is the graphene-supported BiOBr that the present invention implements five preparations0.8I0.2The TEM of microballoon composite photo-catalyst
(Transmission Electron Microscope, transmission electron microscope) is as figure.
Fig. 4 is the graphene-supported BiOBr that the embodiment of the present invention one is prepared to embodiment sixxI1-xMicroballoon composite photocatalyst
XRD (X-ray diffraction, X-ray diffraction) figure of agent.
Fig. 5 is graphene-supported BiOBr prepared by one~embodiment of the embodiment of the present invention sixxI1-xMicroballoon composite photocatalyst
UV vis-DRS (UV-vis DRS) map of agent.
Fig. 6 is the graphene-supported BiOBr of preparation of the embodiment of the present invention0.8I0.2, graphene-supported BiOBr, graphene it is negative
Carry FTIR (the Fourier Transform infrared of BiOI microballoon composite photocatalyst for degrading Ofloxacin
Spectroscopy, fourier convert infrared spectrum analyzer) map.
Fig. 7 is graphene-supported BiOBr prepared by one~embodiment of the embodiment of the present invention sixxI1-xMicroballoon composite photocatalyst
Agent is degraded the activity rating of Ofloxacin under visible light.
Fig. 8 is the embodiment of the present invention five, the different reduced graphene load capacity preparations of eight~embodiment of embodiment 11
BiOBr0.8I0.2Microballoon composite photo-catalyst is degraded Ofloxacin activity rating under visible light.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Referring to FIG. 1, the embodiment provides a kind of graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst
Preparation method, comprising the following steps:
Step S1, the technical grade RGO for weighing certain mass are placed in appropriate first organic solvent, and ultrasonic disperse is hanged
Turbid A；Wherein, the dosage of reduced graphene is BiOBrxI1-xThe 0.1%~5% of quality；The value of x is 0~1；First is organic
Solvent selects any one in dehydrated alcohol, normal propyl alcohol or n-butanol；The preparation process of RGO are as follows: weigh 100mg graphite oxide
It is dissolved in n,N-Dimethylformamide/water mixed solution that 100mL volume ratio is 9:l, is formed after ultrasonic 30min evenly dispersed
Liquid adds 1g hydrazine hydrate, and 6h is restored at 100 DEG C, is finally restored with dehydrated alcohol and distillation water washing to get to high activity
Graphene；
Step S2 accurately weighs appropriate Bi (NO3)3·5H2O ultrasound is dissolved in the second organic solvent, obtains solution B；Its
In, the second organic solvent selects any one in ethylene glycol or glycerine；
Step S3, weighs suitable KBr and KI is dissolved in appropriate second organic solvent, obtains solution C；With vigorous stirring
Successively solution B and suspension A are added dropwise in solution C, obtain suspension D；Wherein, the amount of KBr and KI is in bromine and iodine
Total mole number when determining, the molar content of bromo element is 0~100%；
Step S4 is transferred in autoclave after suspension D is persistently stirred a period of time, at 140 DEG C~200 DEG C into
Row hydro-thermal reaction 6~for 24 hours, it is filtered after cooling and obtains crude product, successively washed with deionized water and dehydrated alcohol；Production after washing
Object is placed in a vacuum drying oven at 50~90 DEG C dry 8~for 24 hours to get to graphene-supported BiOBrxI1-xMicroballoon complex light is urged
Agent.
Below with reference to embodiment to graphene-supported BiOBr provided by the inventionxI1-xMicroballoon composite photo-catalyst and its system
Preparation Method is described in detail.
Embodiment one:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL ethylene glycol (EG), is slowly dropped under lasting stirring that fill 5mL EG (interior containing few after its dissolution
Measure the 3mmol KI of water wetting) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continues to stir
It is transferred to after 1h in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed in temperature programming drying box 160 DEG C
12h is reacted, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, washes away surface mistake
The reactant of amount, finally place the product in vacuum oven, it is compound to obtain graphene-supported BiOI microballoon by 60 DEG C of dry 12h
Photochemical catalyst is ground spare.
Graphene-supported BiOI microballoon composite photo-catalyst prepared by embodiment one can be used in Ofloxacin of degrading
(OFL)；Degradation process is as follows: light-catalyzed reaction carries out in cylindrical glass vessel, using 300W xenon lamp as light source, reaction
Magnetic agitation is used below device, top blasts air using air pump, is sufficiently mixed reaction solution with catalyst, and to reaction
System oxygen supply, the dosage of graphene-supported BiOI microballoon composite photo-catalyst are 1g/L, and the initial concentration of OFL is 20mg/L, black
30min is adsorbed under dark condition makes photochemical catalyst reach adsorption equilibrium, then turns on xenon lamp irradiation, took supernatant every 15 minutes
Sample measures the degradation rate of the concentration calculation OFL of OFL.
Embodiment two:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain 0.6mmol
KBr and 2.4mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue after stirring 1h
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed on 160 DEG C of reactions in temperature programming drying box
12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, it is excessive to wash away surface
Reactant, finally place the product in vacuum oven, 60 DEG C of dry 12h obtain graphene-supported BiOBr0.2I0.8Microballoon is multiple
Light combination catalyst is ground spare.
The graphene-supported BiOBr prepared using embodiment two0.2I0.8The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Embodiment three:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain 1.2mmol
KBr and 1.8mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue after stirring 1h
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed on 160 DEG C of reactions in temperature programming drying box
12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, it is excessive to wash away surface
Reactant, finally place the product in vacuum oven, 60 DEG C of dry 12h obtain graphene-supported BiOBr0.4I0.6Microballoon is multiple
Light combination catalyst is ground spare.
The graphene-supported BiOBr prepared using embodiment three0.4I0.6The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Example IV:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain 1.8mmol
KBr and 1.2mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue after stirring 1h
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed on 160 DEG C of reactions in temperature programming drying box
12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, it is excessive to wash away surface
Reactant, finally place the product in vacuum oven, 60 DEG C of dry 12h obtain graphene-supported BiOBr0.6I0.4Microballoon is multiple
Light combination catalyst is ground spare.
The graphene-supported BiOBr prepared using example IV0.6I0.4The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Embodiment five:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain 2.4mmol
KBr and 0.6mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue after stirring 1h
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed on 160 DEG C of reactions in temperature programming drying box
12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, it is excessive to wash away surface
Reactant, finally place the product in vacuum oven, 60 DEG C of dry 12h obtain graphene-supported BiOBr0.8I0.2Microballoon is multiple
Light combination catalyst is ground spare.
The graphene-supported BiOBr prepared using embodiment five0.8I0.2The degradation process of composite photocatalyst for degrading OFL is same
Embodiment one.
Referring to attached drawing 2 and attached drawing 3, Fig. 2 is the graphene-supported BiOBr that embodiment five is prepared0.8I0.2Complex light is urged
The scanning electron microscope (SEM) photograph of agent, Fig. 3 are the graphene-supported BiOBr that embodiment five is prepared0.8I0.2Composite photo-catalyst it is saturating
Electron microscope is penetrated, from figures 2 and 3, it will be seen that the BiOX of sheet is self-assembly of regular appearance after solvent-thermal method
The micro-sphere structure that diameter is 1-3 μm or so, and BiOX microballoon is more evenly distributed in the surface of RGO, graphene
No change has taken place after the reaction for structure, remains Large ratio surface, and load can be improved using the excellent electronic transmission performance of graphene
Sub- separative efficiency is flowed, and then promotes the photo-quantum efficiency of composite photo-catalyst.
Embodiment six:
It weighs 5mgRGO to be placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·5H2O
(3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain 3mmol
KBr) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continues to be transferred to after stirring 1h with poly- four
In the 100mL autoclave of vinyl fluoride liner, sealing is placed on 160 DEG C of reaction 12h in temperature programming drying box, to its cooling
Afterwards, it filters and obtains product, successively respectively cleaned three times with deionized water and dehydrated alcohol, wash away the excessive reactant in surface, finally
Place the product in vacuum oven, 60 DEG C of dry 12h obtain graphene-supported BiOBr microballoon composite photo-catalyst, grind standby
With.
Degradation process using the graphene-supported BiOBr microballoon composite photocatalyst for degrading OFL of the preparation of embodiment six is same
Embodiment one.
Referring to attached drawing 4, Fig. 4 is graphene-supported BiOBr made from embodiment one to embodiment sixxI1-x(x=0,0.2,
0.4, the peak type of 0.6, the 0.8,1) XRD diagram of microballoon composite photo-catalyst, BiOBr and BiOI can be marked with BiOBr and BiOI respectively
Quasi- card (JCPDS, PDF 09-0393 and 73-2026) is corresponding, and as seen from Figure 4, embodiment one to embodiment six is made
Composite photocatalyst sample be tetragonal phase, peak type is relatively strong and sharp, illustrate that the crystallinity of composite photo-catalyst is preferable, and
The presence for not observing other impurity peaks illustrates that composite photocatalyst sample purity is higher, BiOBrxI1-xIn, with the increasing of x value
Greatly, the diffraction maximum of sample is deviated to larger angle, and wherein (012) peak intensity of BiOI is gradually reduced, therewith BiOBr
(102) region feature peak intensity is gradually increased, and in Br/I=2/8,4/6,6/4,8/2, and what is obtained is not that appearance is single
BiOBr and BiOI characteristic peak illustrates the BiOBr being preparedxI1-xExist in the form of solid solution, however is being prepared
The characteristic diffraction peak of graphene is not observed in composite photocatalyst sample, this may be since the content of RGO carrier is lower
The reason of.
Referring to attached drawing 5, for the UV-vis DRS figure for the photochemical catalyst that one~embodiment of embodiment six is prepared
Spectrum, as shown in Figure 5, the absorption edge of RGO/BiOBr and RGO/BiOI after RGO is loaded are respectively 476 and 709nm, are led to
It crosses and is calculated, graphene-supported BiOBrxI1-xThe band gap of microballoon composite material is respectively 1.78ev, 1.96ev, 2.04ev,
2.47ev, 2.70ev and 2.77ev (correspond respectively to x=0,0.2,0.4,0.6,0.8,1), the ABSORPTION EDGE of composite photo-catalyst
For edge with the gradually red shift of its absorption region of the increase of I content, the composite photo-catalyst color being prepared is brick red by greyish white variation
Color adjusts the adjustable photo-quantum efficiency of band gap width, to increase the visible light-responded catalytic activity of composite photo-catalyst.
It is the photocatalyst for degrading OFL's that embodiment one, embodiment five and embodiment six are prepared referring to attached drawing 6
Infrared spectrogram, in 537.3cm-1The absorption peak at place is the stretching vibration absworption peak of Bi-O key, in 1058.9cm-1、1648.8cm-1And 3439.8cm-1The skeletal vibration of C-O, graphene and the stretching vibration of O-H that the absorption peak at place is respectively derived from RGO are inhaled
Peak is received, the oxygen-containing functional group in RGO is more advantageous to Bi because of its band part negative electrical charge3+Cation is dispersed in RGO carrier table
Face, this is conducive to BiOBrxI1-xPreparation.
Referring to attached drawing 7, the degradation for being the composite photocatalyst for degrading OFL that one~embodiment of embodiment six is prepared is living
Property, as seen from Figure 7, with the increase of Br/I stoichiometric ratio, it is seen that first increases and then decreases is presented in photocatalytic degradation efficiency
Trend, as Br/I=8:2, the degradation rate of Ofloxacin reaches as high as 99.6%, this is because with the increase of I content,
Composite photo-catalyst enhances the responding ability of visible light, and Photocatalytic activity increases, but continuing growing with I content,
The photo-generated carrier recombination rate of composite photo-catalyst increases, and OFL degradation rate declines instead.
Embodiment seven:
Accurately weigh 1.4552g Bi (NO3)3·5H2O (3mmol) is dissolved in 35mL EG, is slowly dropped into after its dissolution
Filled under to lasting stirring in 5mL EG (interior containing 2.4mmol KBr and 0.6mmol KI) solution, continue stir 1h after by its
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner, sealing is placed on 160 DEG C of reactions in temperature programming drying box
12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times with deionized water and dehydrated alcohol, it is excessive to wash away surface
Reactant, finally place the product in vacuum oven, 60 DEG C of dry 12h obtain BiOBr0.8I0.2Microballoon composite photo-catalyst,
It grinds spare.
The BiOBr prepared using embodiment seven0.8I0.2The degradation process of microsphere photocatalyst degradation OFL is the same as embodiment one.
By BET Determination of Specific Surface Area interpretation of result, BiOBr0.8I0.2Microsphere photocatalyst specific surface area is 16.60m2/ g,
The graphene-supported BiOBr of 5mg0.8I0.2The specific surface area of microballoon composite photo-catalyst is 21.07m2Photocatalysis after/g, RGO load
The specific surface area of agent has apparent increase, this is conducive to coming into full contact with for target contaminant and photochemical catalyst, to improve OFL drop
Solution rate.
Embodiment eight:
The RGO for weighing 1mg is placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·
5H2O (3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain
2.4mmol KBr and 0.6mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner after stirring 1h, sealing is placed in temperature programming drying box
160 DEG C of reaction 12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times, is washed away with deionized water and dehydrated alcohol
The excessive reactant in surface, finally place the product in vacuum oven, 60 DEG C of dry 12h are obtained graphene-supported
BiOBr0.8I0.2Microballoon composite photo-catalyst is ground spare.
The graphene-supported BiOBr of 1mg prepared by embodiment eight0.8I0.2The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Embodiment nine:
The RGO for weighing 3mg is placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·
5H2O (3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain
2.4mmol KBr and 0.6mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner after stirring 1h, sealing is placed in temperature programming drying box
160 DEG C of reaction 12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times, is washed away with deionized water and dehydrated alcohol
The excessive reactant in surface, finally place the product in vacuum oven, 60 DEG C of dry 12h are obtained graphene-supported
BiOBr0.8I0.2Microballoon composite photo-catalyst is ground spare.
The graphene-supported BiOBr of 3mg prepared by embodiment nine0.8I0.2The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Embodiment ten:
The RGO for weighing 10mg is placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·
5H2O (3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain
2.4mmol KBr and 0.6mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner after stirring 1h, sealing is placed in temperature programming drying box
160 DEG C of reaction 12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times, is washed away with deionized water and dehydrated alcohol
The excessive reactant in surface, finally place the product in vacuum oven, 60 DEG C of dry 12h are obtained graphene-supported
BiOBr0.8I0.2Microballoon composite photo-catalyst is ground spare.
The graphene-supported BiOBr of 10mg prepared by embodiment ten0.8I0.2The degradation of microballoon composite photocatalyst for degrading OFL
Journey is the same as embodiment one.
Embodiment 11:
The RGO for weighing 15mg is placed in 20mL dehydrated alcohol, ultrasonic disperse 1h；Accurately weigh 1.4552g Bi (NO3)3·
5H2O (3mmol) is dissolved in 35mL EG, is slowly dropped under lasting stirring after its dissolution and is filled 5mL EG and (inside contain
2.4mmol KBr and 0.6mmol KI) in solution, then scattered RGO is slowly dropped in above-mentioned solution, continue
It is transferred in the 100mL autoclave with polytetrafluoroethylliner liner after stirring 1h, sealing is placed in temperature programming drying box
160 DEG C of reaction 12h, after its cooling, suction filtration obtains product, is successively respectively cleaned three times, is washed away with deionized water and dehydrated alcohol
The excessive reactant in surface, finally place the product in vacuum oven, 60 DEG C of dry 12h are obtained graphene-supported
BiOBr0.8I0.2Microballoon composite photo-catalyst is ground spare.
The graphene-supported BiOBr of 15mg prepared by embodiment 110.8I0.2The degradation of microballoon composite photocatalyst for degrading OFL
Process is the same as embodiment one.
It is embodiment five, the different reduced graphene load capacity preparations of eight~embodiment of embodiment 11 referring to attached drawing 8
Composite photo-catalyst is degraded the activity of OFL under visible light exposure, as seen from Figure 8, with the increase of RGO vector contg,
The trend of first increases and then decreases is presented to the degradation of OFL for the composite photo-catalyst of preparation, and when wherein RGO load capacity is 5mg, light is urged
The degradation efficiency highest of agent, this is because BiOBr0.8I0.2It is supported on suitable RGO carrier surface, when with radiation of visible light
When, it can be by graphene surface transference, so that the separation of photo-generated carrier due to being stimulated the electronics transitted in conduction band
Efficiency improves, to cause photohole and electronics that can be more efficiently used for redox degradation OFL, to increase its degradation
Rate.However, RGO carrier excessive at this time can interfere BiOBr when further increasing graphene contentxI1-xAbsorption to light,
Therefore photo-quantum efficiency is caused to reduce and photocatalytic activity loss.
In conclusion the band gap width for the composite photo-catalyst that the embodiment of the present invention provides is with bromo element and iodine
The variation of content and change the response so as to improve catalyst to visible light, meanwhile, BiOBrxI1-xThe multilevel structure of microballoon can also
The visible light utilization efficiency of composite photo-catalyst is improved, the RGO carrier of Large ratio surface is that the excellence conductor of electronics can improve
BiOBrxI1-xThe separation and transfer efficiency of photochemical catalyst light induced electron and hole, this micro-nano composite photo-catalyst have excellent
Different Photocatalytic activity；The graphene-supported BiOBr of the embodiment of the present invention0.8I0.2Composite photo-catalyst is in visible light spoke
Reach 99.6% according to the lower degradation rate to environment antibiotic Ofloxacin, it is shown that good environmental organic pollutant purifies function
Can, it can be widely used in environmental pollution improvement and field of energy conversion.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of graphene-supported BiOBrxI1-xMicroballoon composite photo-catalyst, which is characterized in that the composite photo-catalyst is by height
Active reduction graphene and BiOBrxI1-xIt is compound to be prepared；Wherein, the dosage of high activity reduced graphene is BiOBrxI1-x's
The value of 0.1%~5%, x of quality is 0~1.
2. graphene-supported BiOBr described in claim 1xI1-xThe preparation method of microballoon composite photo-catalyst, which is characterized in that
The following steps are included:
S1, weighs high activity reduced graphene and is placed in the first organic solvent, and ultrasonic disperse obtains suspension A；
S2 weighs Bi (NO3)3·5H2O ultrasound is dissolved in the second organic solvent, obtains solution B；
S3 takes KBr and KI to be dissolved in water and the second organic solvent, obtains solution C；With vigorous stirring successively by solution B and outstanding
Turbid A is added dropwise in solution C, obtains suspension D；
S4 is transferred in autoclave after suspension D is persistently stirred a period of time, carries out hydro-thermal reaction at a set temperature,
It is filtered after cooling and obtains crude product, successively washed with deionized water and dehydrated alcohol；It is dried after washing graphene-supported to get arriving
BiOBrxI1-xMicroballoon composite photo-catalyst.
3. graphene-supported BiOBr according to claim 2xI1-xThe preparation method of microballoon composite photo-catalyst, feature
It is, in step S1, high activity reduced graphene is prepared by following procedure: being weighed graphite oxide and is dissolved in N, N- dimethyl formyl
In amine/water mixed solution, ultrasound is added hydrazine hydrate, then restores, and is finally arrived with dehydrated alcohol with distillation water washing
High activity reduced graphene.
4. graphene-supported BiOBr according to claim 2xI1-xThe preparation method of microballoon composite photo-catalyst, feature
It is, in step S1, first organic solvent selects dehydrated alcohol, normal propyl alcohol, any one in n-butanol.
5. graphene-supported BiOBr according to claim 2xI1-xThe preparation method of microballoon composite photo-catalyst, feature
It is, any one in step S2, in the second organic solvent selection ethylene glycol or glycerine.
6. graphene-supported BiOBr according to claim 2xI1-xThe preparation method of microballoon composite photo-catalyst, feature
It is, in step S4, the reaction temperature of hydro-thermal reaction is 140 DEG C~200 DEG C, the reaction time is 6~for 24 hours；Dry process is
50~90 DEG C be dried in vacuo 8~for 24 hours.
7. graphene-supported BiOBr described in claim 1xI1-xMicroballoon composite photo-catalyst is any according to claim 2-6
Graphene-supported BiOBr made from preparation method described inxI1-xThe application of microballoon composite photo-catalyst, which is characterized in that institute
Composite photo-catalyst is stated to be applied to decline solution environment antibiotic Ofloxacin in sunlight irradiation.
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