CN105688948B - A kind of photochemical catalyst and its preparation method and application - Google Patents
A kind of photochemical catalyst and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims description 21
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 40
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 12
- 244000005700 microbiome Species 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 238000000975 co-precipitation Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000975 dye Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 16
- 229960000907 methylthioninium chloride Drugs 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 12
- 230000001954 sterilising effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 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 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 Methylene Chemical group 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003911 water pollution 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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Abstract
The invention belongs to photocatalysis fields, and in particular to a kind of BiOI/BiVO4Heterojunction composite photocatalyst and its preparation method and application.BiOI/BiVO4Heterojunction composite photocatalyst is by BiOI and BiVO4Composition, wherein BiOI and BiVO4Molar ratio be 1:18~18:1.Preparation, obtains BiOI/BiVO using coprecipitation method under hydrothermal conditions4Heterojunction composite photocatalyst.It is preparation method simple process of the invention, easily controllable, low in cost, it constructs with visible light-responded BiOI/BiVO4Heterojunction structure, accelerate the separation of photo-generated carrier, reduce the recombination probability of photo-generate electron-hole pair, there is efficient photocatalytic activity and stability under visible light, to in water body harmful microorganism and dyestuff contaminant have it is efficient kill and degradation effect, there is good practical value and potential application prospect in the fields such as water body purification and marine anti-pollution.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to a kind of photochemical catalyst and its preparation method and application.
Background technique
Sustainable development is a global problem.However, environmental pollution especially water pollution the problems such as it is increasingly tight
Weight.Various noxious pollutant accumulations not only seriously destroy the ecological balance in the environment such as water body, soil and air, also endanger
The life and health of the mankind.In addition, economic development needs consume a large amount of energy, causing new energy crisis, and it is a large amount of
Exploitation and can inherently cause serious environmental problem using traditional mineral products energy.
Photocatalitic Technique of Semiconductor was a kind of technology that substance conversion is carried out using luminous energy, from Japanese Scientists in 1972
Fujishima and Honda reports TiO2Since can use ultraviolet light photocatalytic water generation hydrogen and oxygen, conductor photocatalysis skill
Art begins to have been a great concern[1].Photocatalitic Technique of Semiconductor air cleaning indoors at present, public place are kept a public place clean
The fields such as degerming and sewage treatment are all widely applied.Currently, TiO2Because have chemical property it is stable, nontoxic, low at
This advantages that, becomes most widely used catalysis material, but due to TiO2There is also such as photo-generate electron-hole recombination rate
The defects of high, low to the utilization rate of visible light and recycling is difficult, makes its application range receive very big restriction[2].Therefore, it opens
Hair can efficiently use solar energy, and environmentally protective new and effective catalysis material has important practical significance.
Bismuth based material because its visible light area (λ > 420nm) have good absorbing properties, and its pattern have it is more
Sample and get the attention and further investigate.The composites that bismuth and other metals are formed have good visible light
Catalytic performance[3-6].Such as BiOX (BiOX (X=Cl, Br, I)), generally there is cubic crystalline structure, be by [Bi2O2] piece
Layer be alternately arranged with two layers of halogens to be formed it is laminar structured, wherein BiOI because with the smallest forbidden bandwidth (about
1.80eV) and there is good absorption in visible region and have received widespread attention[3].In addition, BiVO4It is a kind of N-shaped directly half
Conductor material has relatively narrow forbidden bandwidth (about 2.4eV), the catalytic activity with higher under visible light photograph, net in environment
Change and new energy development field has potential application, becomes one of the photochemical catalyst studied extensively at present[4].But by
Photoelectron-hole separation is slower in monomer photochemical catalyst, and photo-generated carrier is easily compound, leads to the photocatalytic of semiconductor material
Can be limited, and constructing composite material by semiconductors coupling can accelerate electron-hole to separate, and improve the photocatalytic of material
Energy[5,6].Therefore, it is badly in need of developing synthesizing new composite catalyst in photocatalysis field.
[1]K.Nakata,A.Fujishima.TiO2photocatalysis:Design and applications
[J].Journal of Photochemistry and Photobiology C:Photochemistry Reviews,2012,
13:169-189.
[2]X.B.Chen,S.S.Mao.Titanium dioxide nanomaterials:Synthesis,
properties,modifications,and applications[J].Chemical Reviews,2007,107:2891-
2959.
[3]X.Xiao,W.D.Zhang,Facile synthesis of nanostructured BiOI
microspheres with high visible light-induced photocatalytic activity[J]
.Journal of Materials Chemistry,2010,20:5866-5870.
[4]R.A.He,S.W.Cao,P.Zhou,J.G.Yu,Recent advances in visible light Bi-
based photocatalysts,Chin.J.Catal.,35(2014)989-1007.
[5]Y.Y.Li,J.S.Wang,H.C.Yao,L.Y.Dang,Z.J.Li.Chemical etching
preparation of BiOI/Bi2O3heterostructures with enhanced photocatalytic
activities[J].Catalysis Communications,2011,12:660-664.
[6]Y.Park,K.J.McDonald,K.S.Choi,Progress in bismuth vanadate
photoanodes for use in solar water oxidation,Chem.Soc.Rev.,42(2013)2321-2337.
Summary of the invention
It is an object of the invention to aiming at the problems existing in the prior art, provide a kind of photochemical catalyst and preparation method thereof
And application.
To achieve the above object, the present invention is implemented using following technical scheme:
A kind of photochemical catalyst, photochemical catalyst BiOI/BiVO4Heterojunction composite, by BiOI and BiVO4Composition,
BiOI and BiVO4Molar ratio be 18:1~1:18.
The BiOI and BiVO4Molar ratio be 9:1~1:9.
A kind of preparation method of photochemical catalyst, by KI and NH4VO3It is scattered in excessive ethanol water, obtains dispersion liquid A；
Meanwhile by Bi (NO3)3·5H2O is dissolved in excessive ethanol water, obtains dispersion liquid B；In the case of stirring by solution A
It is added dropwise in solution B, is transferred in water heating kettle after above-mentioned suspension is stirred 40~80min, 160~200 DEG C of hydro-thermals 12
~36h, after hydro-thermal, by that can obtain after suction filtration, washing and 50~100 DEG C of dryings 3~for 24 hours with sheet and flower ball-shaped shape
The BiOI/BiVO of structure4。
The KI and NH4VO3Between dosage relation 1:18~18:1；Dosage relation between dispersion liquid A and dispersion liquid B
1:2~2:1；Bi (NO in dispersion liquid B3)3·5H2Final concentration of 0.25~1mol/L in O.
The acquisition dispersion liquid A and dispersion liquid B is used and is dispersed with stirring 10~60min.
The ethanol water ethyl alcohol and water volume ratio are 1:1.
A kind of application of photochemical catalyst, the BiOI/BiVO4Heterojunction composite photocatalyst is as killing in water body
Microbial inoculum.
The BiOI/BiVO4Application of the heterojunction composite photocatalyst in degradation of dye.
The BiOI/BiVO4Application of the heterojunction composite photocatalyst in water body purification.
BiOI/BiVO4Heterojunction composite photocatalyst is applied in water body, to harmful microorganism pseudomonas aeruginosa
(P.aeruginosa) and the visible light catalytic of dyestuff contaminant methylene blue (MB) is killed and degradation, using 500W xenon lamp conduct
Light source, wave-length coverage are 420~760nm；The microorganism concn is 108cfu/mL；The methylene blue concentration is 20mg/
L；The BiOI/BiVO4The dosage of heterojunction composite photocatalyst is 1.0mg/mL.
The specific test method of its photocatalytic activity are as follows: using 500W xenon lamp as light source, be aided with optical filter；By microorganism and
Methylene blue solution is added in reactor, and BiOI/BiVO is then added4Heterojunction composite photocatalyst, dark adsorption reach
Start illumination after balance, separated in time samples in During Illumination, passes through colony counting method and ultraviolet-visible spectrophotometry
Surviving bacteria concentration and remaining methylene blue concentration are measured, killing rate and degradation rate are calculated.The light source is xenon lamp, wavelength
Range is 420~760nm；The microorganism concn is 108cfu/mL；The methylene blue concentration is 20mg/L；The BiOI/
BiVO4The dosage of heterojunction composite photocatalyst is 1.0mg/mL.
The beneficial effects of the present invention are:
The present invention is by by BiOI and BiVO4Compound, building forms the composite material with heterojunction structure, accelerates photoproduction
Carrier composite material surface separation, and then improve photocatalysis performance, to BiOI and BiVO4Two kinds of materials are led in photocatalysis
The practical application in domain is of great significance.It is specific:
(1) present invention prepares BiOI/BiVO using simple co-precipitation-hydrothermal synthesis method4Heterojunction composite photocatalyst,
It is preparation method simple process, easily controllable, low in cost；
(2) BiOI/BiVO prepared by the present invention4Heterojunction composite photocatalyst has good visible absorption performance；
(3) BiOI/BiVO prepared by the present invention4Heterojunction composite photocatalyst visible light catalysis activity compared to BiOI and
BiVO4It is significantly increased, under the irradiation of 500W xenon lamp, 1.0mg/mL BiOI/BiVO4Heterojunction composite photocatalyst is to concentration
108Killing rate can reach 99.99% in the microorganism 120min of cfu/mL, to real in the methylene blue 240min of concentration 20mg/L
It is existing degradable；
(4) BiOI/BiVO prepared by the present invention4Heterojunction composite photocatalyst is with good stability and reuses
Property, still there is efficient photocatalytic activity after 5 recyclings；
(5) BiOI/BiVO prepared by the present invention4Heterojunction composite photocatalyst has heterojunction structure, accelerates photoproduction
The separation of carrier reduces the recombination probability of photo-generate electron-hole pair, improves visible light catalysis activity and stability,
The fields such as water body purification and marine anti-pollution have good practical value and potential application prospect.
Detailed description of the invention
Fig. 1 is that (wherein abscissa is 2 θ (angle), and unit is for the XRD spectrum of sample provided in an embodiment of the present invention
Degree (degree)；Ordinate is Intensity (intensity), and unit is a.u. (absolute unit))；
Fig. 2 is the FESEM photo of sample prepared by the present invention: (A) BiVO4, (B) 10%BiOI/BiVO4, (C) 30%
BiOI/BiVO4, (D) 50%BiOI/BiVO4, (E) 70%BiOI/BiVO4, (F) 90%BiOI/BiVO4, (G) BiOI；
Fig. 3 is UV-vis DRS spectrogram (UV-DRS) (wherein abscissa of sample provided in an embodiment of the present invention
For Wavelength (wavelength), unit is nm (nanometer), and ordinate is Absorbance (absorbance), and unit is a.u. (absolute
Unit))；
Fig. 4 is that sample photocatalytic degradation provided in an embodiment of the present invention reacts Methylene Blue concentration changes with time song
(abscissa is Time (time) to line in figure, and unit is min (minute), ordinate Ct/C0, C0Start preceding methylene blue for reaction
Initial concentration, CtMethylene blue concentration when for the reaction time being t).
Fig. 5 is the photocatalysis in sample photocatalytic degradation reaction provided in an embodiment of the present invention to pseudomonas aeruginosa
Sterilizing rate (ordinate is Antibacterial rate (sterilizing rate), unit % in figure).
Fig. 6 is the 30%BiOI/BiVO prepared in the embodiment of the present invention 14Heterojunction composite photocatalyst repeats 5 times
(abscissa is Cycle number (reusing number) to sterilizing rate after sterilization experiment in figure, and ordinate is
Antibacterial rate (sterilizing rate), unit %).
Specific embodiment
Below by way of specific embodiment, the invention will be further described, facilitates those skilled in the art more
It is fully understood by the present invention, but do not limit the invention in any way.
The present invention is prepared for BiOI/BiVO by co-precipitation and hydrothermal synthesis method4Heterojunction composite photocatalyst, this is compound
Photochemical catalyst has good visible absorption performance, and the heterojunction structure of building accelerates the separation of photo-generated carrier, reduces
The recombination probability of photo-generate electron-hole pair has efficient photocatalytic activity and stability under visible light, to having in water body
Evil microorganism and dyestuff contaminant have efficient killing and degradation effect, have very in the fields such as water body purification and marine anti-pollution
Good practical value and potential application prospect.The preparation method of the composite photo-catalyst is with simple and easy, price is low simultaneously
The features such as honest and clean and reproducible.
Embodiment 1:
KI the and 0.0014mol NH of 0.0006mol4VO3It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains molten
Liquid A.Meanwhile Bi (the NO of 0.002moL3)3·5H2O is dissolved in 50% ethyl alcohol ethanol water of 40mL, and stirring 30min obtains solution
B.So solution A is being added dropwise in solution B in the case of stirring.Above-mentioned suspension is transferred to after stirring 60min
In 100mL reaction kettle, 180 DEG C of hydro-thermals are for 24 hours.It after being cooled to room temperature, is filtered on the miillpore filter in 0.22 μm of aperture, product difference
It is washed for several times with ultrapure water and dehydrated alcohol, juxtaposition 60 DEG C of dry 6h in a vacuum drying oven, obtains sample labeled as 30%BiOI/
BiVO4(referring to Fig. 1-3).
Comparative example 1:
Monomer BiVO4Preparation method:
0.002mol NH4VO3It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains solution A.Meanwhile
Bi (the NO of 0.002moL3)3·5H2O is dissolved in 50% ethyl alcohol ethanol water of 40mL, and stirring 30min obtains solution B.So
Solution A is added dropwise in solution B in the case where stirring.Above-mentioned suspension is transferred to 100mL reaction kettle after stirring 60min
In, 180 DEG C of hydro-thermals are for 24 hours.After being cooled to room temperature, filtered on the miillpore filter in 0.22 μm of aperture, product use respectively ultrapure water and
Dehydrated alcohol washs for several times, juxtaposition 60 DEG C of dry 6h in a vacuum drying oven, obtains sample and is labeled as BiVO4(referring to Fig. 1-3).
BiOI as seen from Figure 1, BiVO4With the BiOI/BiVO of the amount ratio of different material4The XRD spectra of compound.These spread out
It is higher to penetrate peak intensity, peak type is preferable；Illustrate that the sample of synthesis all has preferable crystal form.In addition, it can be seen that institute from Fig. 1 a
Some diffraction maximums can be with the BiVO of tetragonal phase4(JCPDS No.14-0688) coincide well；Meanwhile all in Fig. 1 b spreading out
Penetrating peak can match with the BiOI (JCPDS No.10-0445) of orthorhombic phase.And comprising all tetragonal phases in Fig. 1 c~1g
BiVO4The characteristic peak of the BiOI (JCPDS No.10-0445) of (JCPDS No.14-0688) and orthorhombic phase, and without other
Miscellaneous peak.Illustrate the compound of synthesis by BiVO4With two kinds of object phase compositions of BiOI.
By Fig. 2A it can be seen that the BiVO of pure phase4It is made of nanometer sheet.And the BiOI/BiVO prepared by coprecipitation method4Sample
Product, can be seen that the increase with KI dosage from Fig. 2 B~2G, and pattern gradually changes and gradually to nano flower-like structure
Transformation, the BiOI of pure phase are flower-like structure (Fig. 2 G).
As a result as shown in Figure 3: BiOI/BiVO4Significant change has occurred in the light abstraction width of sample compared with BiOI.From figure
In it can be seen that BiOI and BiVO4Heterojunction structure is formd after compound, the visible absorption performance of composite material is caused to increase
By force.
Embodiment 2:
BiOI/BiVO4The preparation method of heterojunction composite photocatalyst:
By co-precipitation and hydrothermal method preparation, difference from Example 1 is, controls BiOI and BiVO4Mole
Than for 1:9.KI the and 0.0018mol NH of 0.0002mol4VO3It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains molten
Liquid A.Meanwhile Bi (the NO of 0.002moL3)3·5H2O is dissolved in 50% ethyl alcohol ethanol water of 40mL, and stirring 30min obtains solution
B.So solution A is being added dropwise in solution B in the case of stirring.Above-mentioned suspension is transferred to after stirring 60min
In 100mL reaction kettle, 180 DEG C of hydro-thermals are for 24 hours.It after being cooled to room temperature, is filtered on the miillpore filter in 0.22 μm of aperture, product difference
It is washed for several times with ultrapure water and dehydrated alcohol, juxtaposition 60 DEG C of dry 6h in a vacuum drying oven, obtains sample labeled as 10%BiOI/
BiVO4。
Embodiment 3:
BiOI/BiVO4The preparation method of heterojunction composite photocatalyst:
By co-precipitation and hydrothermal method preparation, difference from Example 1 is, controls BiOI and BiVO4Mole
Than for 5:5.KI the and 0.001mol NH of 0.001mol4VO3It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains solution
A.Meanwhile Bi (the NO of 0.002moL3)3·5H2O is dissolved in 50% ethyl alcohol ethanol water of 40mL, and stirring 30min obtains solution B.
So solution A is being added dropwise in solution B in the case of stirring.Above-mentioned suspension is transferred to 100mL after stirring 60min
In reaction kettle, 180 DEG C of hydro-thermals are for 24 hours.It after being cooled to room temperature, is filtered on the miillpore filter in 0.22 μm of aperture, product is respectively with super
For several times, juxtaposition 60 DEG C of dry 6h in a vacuum drying oven obtain sample and are labeled as 50%BiOI/ for pure water and dehydrated alcohol washing
BiVO4。
Embodiment 4:
BiOI/BiVO4The preparation method of heterojunction composite photocatalyst:
By co-precipitation and hydrothermal method preparation, difference from Example 1 is, controls BiOI and BiVO4Mole
Than for 7:3.KI the and 0.0006mol NH of 0.0014mol4VO3It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains molten
Liquid A.Meanwhile Bi (the NO of 0.002moL3)3·5H2O is dissolved in 50% ethyl alcohol ethanol water of 40mL, and stirring 30min obtains solution
B.So solution A is being added dropwise in solution B in the case of stirring.Above-mentioned suspension is transferred to after stirring 60min
In 100mL reaction kettle, 180 DEG C of hydro-thermals are for 24 hours.It after being cooled to room temperature, is filtered on the miillpore filter in 0.22 μm of aperture, product difference
It is washed for several times with ultrapure water and dehydrated alcohol, juxtaposition 60 DEG C of dry 6h in a vacuum drying oven, obtains sample labeled as 70%BiOI/
BiVO4。
Embodiment 5:
BiOI/BiVO4The preparation method of heterojunction composite photocatalyst: it is prepared by co-precipitation and hydrothermal method, with reality
Apply example 1 the difference is that, control BiOI and BiVO4Molar ratio be 9:1.KI the and 0.0002mol NH of 0.0018mol4VO3
It is dissolved in 50% ethanol water of 40mL, stirring 30min obtains solution A.Meanwhile Bi (the NO of 0.002moL3)3·5H2O is dissolved in
50% ethyl alcohol ethanol water of 40mL, stirring 30min obtain solution B.So solution A is being added dropwise in the case of stirring
In solution B.Above-mentioned suspension is transferred in 100mL reaction kettle after stirring 60min, and 180 DEG C of hydro-thermals are for 24 hours.After being cooled to room temperature,
It is filtered on the miillpore filter in 0.22 μm of aperture, product is washed for several times with ultrapure water and dehydrated alcohol respectively, and it is dry to be placed in vacuum
60 DEG C of dry 6h in dry case obtain sample labeled as 90%BiOI/BiVO4。
Application examples 1:
Above-mentioned gained BiOI/BiVO4Heterojunction composite photocatalyst can applied to dyestuff contaminant methylene blue (MB's)
Light-exposed catalytic degradation:
Using 500W xenon lamp as light source, it is aided with optical filter and filters ultraviolet light, makes 420~760nm of its wave-length coverage.It will
The methylene blue solution of 50mL 20mg/L is added in 50mL reactor, and 50mg photochemical catalyst prepared by the present invention, dark-state is added
Absorption carries out light-catalyzed reaction after reaching balance, and separated in time samples in reaction process, takes supernatant liquor after centrifuge separation
The absorbance that methylene blue solution under 664nm wavelength is measured on ultraviolet-visible spectrophotometer, obtains methylene blue solution
Residual concentration calculates degradation rate with this, and blank assay and dark-state experiment are used as control experiment (referring to fig. 4).
From fig. 4, it can be seen that blank assay and dark-state experiment Methylene Blue are hardly degraded, the influence to experiment can be neglected
Slightly.Under visible light photograph, 30%BiOI/BiVO4Heterojunction composite photocatalyst shows good photocatalytic activity, photocatalysis
Performance is substantially better than monomer BiOI and BiVO4, the degradation rate of methylene blue can reach within the 240min light-catalyzed reaction time
100%.Therefore, by BiOI and BiVO with good visible absorption performance and photocatalytic activity4It is compounded to form heterogeneous junction
Structure can be such that photo-generate electron-hole efficiently separates in composite material surface, and improve composite material visible absorption performance and
Specific surface area enhances the visible light catalytic performance of composite material.
Application examples 2:
Above-mentioned gained BiOI/BiVO4Heterojunction composite photocatalyst is applied in water body, false to harmful microorganism verdigris single
The visible light of born of the same parents bacillus is killed:
Using 500W xenon lamp as light source, it is aided with optical filter and filters ultraviolet light, makes 420~760nm of its wave-length coverage.With copper
Green Pseudomonas alba (P.aeruginosa, 3.5 × 108Cfu/mL BiOI/BiVO) is evaluated4Heterojunction composite photocatalyst can
Light-exposed catalytically bactericidal process performance:
Prepare bacterial suspension first, pseudomonas aeruginosa storing liquid is inoculated into sterilizing LB liquid medium, then
It places it in 37 DEG C, in the air constant-temperature table of 150rpm, is incubated overnight.It is suspended in after cultivating obtained bacterial suspension centrifugation
In 0.01mol/L PBS (pH=7.4) buffer, obtaining concentration is 3.5 × 108The pseudomonas aeruginosa suspension of cfu/mL.
49.5mL sterilizing 0.01mol/L PBS (pH=7.4) buffer is taken to be added to 50mL reactor in photocatalysis experiment
In, 500 μ L bacterial suspensions are then added, make bacterial concentration 8.0 × 10 in reaction solution650mg system of the present invention is added in cfu/mL
Standby photochemical catalyst.Dark adsorption carries out light-catalyzed reaction after reaching balance, and separated in time samples in reaction process, passes through
Colony counting method determines the survival rate and sterilizing rate of bacterium.Specific steps are as follows: 1.0mL reaction solution is taken, with 0.01mol/L PBS
(pH=7.4) buffer successively dilutes several gradients according to serial dilutions, then takes 100 from the solution of different extension rates
On μ L to the LB solid medium having had been prepared for, bacterium solution is equably applied on LB culture medium.LB culture medium is inverted, is put
Enter 37 DEG C of cultures in electro-heating standing-temperature cultivator and for 24 hours, passes through the bacterium colony number grown on counting culture medium and corresponding extension rate
Bacterial concentration is obtained, to determine the survival rate and sterilizing rate of bacterium.Every group of experiment is both needed to be measured in parallel 3 times in experiment, is averaged
Value is used as final result, and blank assay and dark-state experiment are used as control experiment (referring to Fig. 5).·
As seen from Figure 5, pseudomonas aeruginosa number has almost no change in blank assay, shows the shadow that visible light shines
Sound can be ignored；And under dark condition, number of bacteria shows that the material itself that this experiment uses is not given birth to also without significant change
Object toxicity.And the 30%BiOI/BiVO under visible light photograph4Heterojunction composite photocatalyst shows good photocatalytic activity,
Photo-catalyst performance is substantially better than monomer BiVO4And BiOI, there was only the P. aeruginosa of about 1.7log by the illumination of 60min
Bacillus survival, sterilizing rate can reach 99.99%.Therefore, 30%BiOI/BiVO4Heterojunction composite photocatalyst has splendid
Photo-catalyst anti-pollution, is attributable to BiOI and BiVO4Be compounded to form heterojunction structure, accelerate light induced electron-sky
The separation in cave improves the photocatalytic activity of composite material.Meanwhile BiOI/BiVO4Heterojunction composite photocatalyst has good
Visible absorption performance, cause its visible light catalytic performance improve, have good visible light catalytic bactericidal property.
Application examples 3:
Above-mentioned gained BiOI/BiVO4Heterojunction composite photocatalyst is repeatedly applied in water body, to harmful microorganism verdigris
The visible light of Pseudomonas alba is killed.
By 30%BiOI/BiVO used in photo-catalyst in application examples 24Heterojunction composite photocatalyst recycling, point
It is not washed repeatedly with ultrapure water and dehydrated alcohol, carries out photo-catalyst next time according to the step in application examples 2 after drying
Reaction, is carried out continuously 5 times, keeps other conditions constant (referring to Fig. 6).
As seen from Figure 6,30%BiOI/BiVO4Heterojunction composite photocatalyst is to the killing rate of bacterium at successive reaction 5 times
It is not substantially reduced afterwards, is still maintained at 99% or more, show good reusing.5 light will be carried out continuously to urge
Change the 30%BiOI/BiVO of sterilization experiment4Composite photo-catalyst recycling, is repeatedly washed with ultrapure water and dehydrated alcohol respectively, is passed through
XRD test is carried out after drying, as shown in fig. 6, as can be seen from the figure after the reaction of continuous 5 photo-catalysts, 30%
BiOI/BiVO4Crystal structure, peak intensity and the composition of composite photo-catalyst do not change, show good stability,
There is good practical value and potential application prospect in the fields such as water body purification and marine anti-pollution.
Claims (5)
1. a kind of preparation method of photochemical catalyst, it is characterised in that: by KI and NH4VO3It is scattered in excessive ethanol water,
Obtain dispersion liquid A；Meanwhile by Bi (NO3)3·5H2O is dissolved in excessive ethanol water, obtains dispersion liquid B；The case where stirring
It is lower that solution A is added dropwise in solution B, it is transferred in water heating kettle after suspension is stirred 40~80min, 160~200 DEG C of water
12~36h of heat, after hydro-thermal, by obtaining after suction filtration, washing and 50~100 DEG C of dryings 3~for 24 hours with sheet and flower ball-shaped
The BiOI/BiVO of structure4Heterojunction composite；
The KI and NH4VO3Between dosage relation be 1:18~18:1；Dosage relation between dispersion liquid A and dispersion liquid B is
1:2~2:1；Bi (NO in dispersion liquid B3)3·5H2Final concentration of 0.25~the 1mol/L of O.
2. the preparation method of photochemical catalyst according to claim 1, it is characterised in that: obtain dispersion liquid A and dispersion liquid B and adopt
With being dispersed with stirring 10~60min.
3. the preparation method of photochemical catalyst according to claim 1, it is characterised in that: the ethanol water ethyl alcohol and water
Volume ratio is 1:1.
4. photochemical catalyst prepared by the preparation method of any one of claim 1-3 a kind of, it is characterised in that: photochemical catalyst is
BiOI/BiVO4Heterojunction composite, by BiOI and BiVO4Composition, BiOI and BiVO4Molar ratio be 9:1~1:9；
The photochemical catalyst BiOI/BiVO4For sheet and flower ball-shaped structure.
5. a kind of application of photochemical catalyst as claimed in claim 4, it is characterised in that: the BiOI/BiVO4Heterojunction composite
As for the fungicide in water body.
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