CN105457663A - Bi2WO6 / Ag3PO4 composite photocatalytic fungicide and preparation method thereof - Google Patents

Bi2WO6 / Ag3PO4 composite photocatalytic fungicide and preparation method thereof Download PDF

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CN105457663A
CN105457663A CN201510790413.9A CN201510790413A CN105457663A CN 105457663 A CN105457663 A CN 105457663A CN 201510790413 A CN201510790413 A CN 201510790413A CN 105457663 A CN105457663 A CN 105457663A
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bactericide
catalysis
composite photo
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bi2wo6
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鞠鹏
张盾
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Institute of Oceanology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling
    • 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
    • C02F2305/02—Specific form of oxidant
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

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  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention belongs to the field of photocatalysis, and in particular to a Bi2WO6 / Ag3PO4 composite photocatalytic fungicide and a preparation method thereof. The Bi2WO6 / Ag3PO4 composite photocatalytic fungicide is composed of Ag3PO4 and Bi2WO6; nano Ag3PO4 grows in situ on the surface of Bi2WO6 nanosheets; and the molar ratio of Bi2WO6 to Ag3PO4 is 1:0.1-10. The preparation method is as below: first preparing Bi2WO6 nanosheets by a hydrothermal synthesis method; then precipitating Ag3PO4 nanoparticles on the surface of Bi2WO6 nanosheets by an in situ precipitation approach to obtain the Bi2WO6 / Ag3PO4 composite photocatalytic fungicide. The preparation method of the present invention is simple, easy to control and low in cost; the constructed Bi2WO6 / Ag3PO4 heterojunction structure with visible light response accelerates the separation of photo-generated carriers, reduces the recombination rate of photo-generated electron-hole pair, has high photocatalytic activity under visible light, and highly efficient killing effect on harmful micro-organisms in water, and shows good practical value and potential applications in the field of water purification.

Description

A kind of Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide and preparation method thereof
Technical field
The invention belongs to photocatalysis field, be specifically related to a kind of Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide and preparation method thereof.
Background technology
Photocatalysis technology is a kind of mode utilizing luminous energy to carry out Substance Transformation, is also one of effective method for disinfection simultaneously.Since Japanese Scientists Matsunaga etc. [1]late Cambrian TiO 2have good bactericidal action under UV-irradiation after, the research of photo-catalyst material obtains extensive concern.TiO under light illumination 2escherichia coli in water, golden yellow glucose coccus, lactic acid bacteria and sulfate reducing bacteria etc. can not only be killed, the poisonous compound discharged by bacterium of can also simultaneously degrading, thus thorough kill bacteria.Photocatalysis technology has that catalytic performance is high, persistent, low drug resistance, pollution-free, harmless, low cost and other advantages, and specificity be there is no to microorganism and its intracellular cytoplasm reaction, there is broad spectrum antibacterial performance [2], have good application prospect.OH, O of generating in light-catalyzed reaction 2 -and h +all there is very strong oxidisability and reactivity, and to the oxidation of agent, there is non-selectivity, can microbial cell be directly acted on, direct infringement is brought to cell membrane, cell membrane, organelle, the large molecule of endocellular function, hereditary material DNA etc. [3], thus killing microorganisms at short notice.But, in photocatalysis technology, also there are some problems at present, mainly need to improve to the utilization rate of light and catalytic performance, such as conventional TiO 2only there is response to ultraviolet light [4], greatly limit its utilization to sunshine.Therefore, in order to more effectively solar energy can be utilized, exploitation is needed to have visible light-responded novel semiconductor material, modification can also be carried out to semiconductor in addition by methods such as semiconductors coupling, element doping, precious metal dopings, accelerate the separation of photo-generate electron-hole in semiconductor, improve the visible light catalytic performance of semi-conducting material.
Recent Bi 2wO 6because of its narrower energy gap (about 2.7eV), also can be had higher catalytic activity under visible light thus cause increasing concern as a kind of novel visible catalysis material by excited by visible light [5].Due at monomers B i 2wO 6in the right migration distance of the electronics that excites and hole long, the probability of body phase compound increases, and is unfavorable for the quick separating of electron-hole, causes photocatalytic activity relatively not high.Therefore, composite can be built by semiconductors coupling and can accelerate electron-hole separation, improve the photocatalysis performance of monomer material [6].Ag 3pO 4it is a kind of new and effective catalysis material, band gap is about 2.4eV, the strong oxidizing property in optical excitation hole in its distinctive indirect band gap, valence band, and its electron transfer rate is higher than hole migration speed simultaneously, thus impel electron-hole to be separated, make it have good photocatalysis performance; Simultaneously Ag vacancy defect can participate in photoelectron and catches, and provides more optical excitation hole, is also conducive to electron-hole and is separated [7].
Therefore, now need to build a kind of composite catalyst to improve Bi 2wO 6photocatalysis performance.
[1]T.Matsunaga,R.Tomada,Y.Nakajima,N.Nakamura,T.Komine.Continuous-sterilizationsystemthatusesphotosemiconductorpowers[J].AppliedandEnvironmentalMicrobiology,1988,54:1330-1333.
[2]L.S.Zhang,K.H.Wong,H.Y.Yip,C.Hu,J.C.Yu,C.Y.Chan,P.K.Wong.EffectivephotocatalyticdisinfectionofE.coliK-12usingAgBr-Ag-Bi 2WO 6nanojunctionsystemirradiatedbyvisiblelight:Theroleofdiffusinghydroxylradicals[J].EnvironmentalScience&Technology,2010,44:1392-1398.
[3]A.J.Huh,Y.J.Kwon.“Nanoantibiotics”:Anewparadigmfortreatinginfectiousdiseasesusingnanomaterialsintheantibioticsresistantera[J].JournalofControlledRelease,2011,156:128-145.
[4]K.Nakata,A.Fujishima.TiO 2photocatalysis:Designandapplications[J].JournalofPhotochemistryandPhotobiologyC:PhotochemistryReviews,2012,13:169-189.
[5]X.F.Cao,L.Zhang,X.T.Chen,Z.L.Xue.Microwave-assistedsolution-phasepreparationofflower-likeBi 2WO 6anditsvisible-light-drivenphotocatalyticproperties[J].CrystEngComm,2011,13:306-311.
[5]Y.Hu,D.Z.Li,Y.Zheng,W.Chen,Y.H.He,Y.Shao,X.Z.Fu,G.C.Xiao.BiVO 4/TiO 2nanocrystallineheterostructure:Awidespectrumresponsivephotocatalysttowardsthehighlyefficientdecompositionofgaseousbenzene[J].AppliedCatalysisB:Environmental,2011,104:30-36.
[6]Z.J.Zhang,W.Z.Wang,L.Wang,S.M.Sun.Enhancementofvisible-lightphotocatalysisbycouplingwithnarrow-band-gapsemiconductor:AcasestudyonBi 2S 3/Bi 2WO 6[J].ACSAppliedMaterials&Interfaces,2012,4:593-597.
[7]Z.G.Yi,J.H.Ye,N.Kikugawa,T.Kako,S.X.Ouyang,H.Stuart-Williams,H.Yang,J.Y.Cao,W.J.Luo,Z.S.Li,Y.Liu,R.L.Withers.Anorthophosphatesemiconductorwithphotooxidationpropertiesundervisible-lightirradiation[J].NatureMaterials,2010,9:559-564.
Summary of the invention
The object of the invention is to for problems of the prior art, a kind of Bi is provided 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide and preparation method thereof.
For achieving the above object, the present invention implements by the following technical solutions:
A kind of Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, by Bi 2wO 6and Ag 3pO 4composition, nanometer Ag 3pO 4at Bi 2wO 6nanometer sheet surface in situ grows; Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.1 ~ 10.
Described Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.1 ~ 5.
A kind of Bi 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide:
(1) Bi 2wO 6preparation: by Bi (NO 3) 35H 2o joins HNO 3in solution, magnetic agitation is to dissolving completely; Simultaneously by Na 2wO 42H 2o joins in NaOH solution, and magnetic agitation, to dissolving completely, obtains lysate respectively; Then under magnetic stirring by above-mentioned Na 2wO 4lysate dropwise joins above-mentioned Bi (NO 3) 3in lysate, obtain suspension, and regulate pH of suspension to 5 ~ 9, continue stirring 30 ~ 90min, afterwards suspension is transferred in autoclave, puts into electric heating constant-temperature blowing drying box 120 ~ 180 DEG C of heat treatment 12 ~ 36h; Then reactor is cooled to room temperature, the Bi of laminated structure can be obtained through suction filtration, washing and 40 ~ 80 DEG C of drying 2 ~ 10h 2wO 6;
(2) Bi 2wO 6/ Ag 3pO 4the preparation of composite photo-catalysis bactericide: by the Bi obtained in step (1) 2wO 6be scattered in ultra-pure water and obtain dispersion liquid, then add AgNO under magnetic stirring 3, be stirred to and dissolve to obtain mixed liquor completely, then dropwise add the precursor solution of phosphorous acid group, continue lucifuge afterwards and stir 2 ~ 8h, can Bi be obtained through suction filtration, washing and 40 ~ 80 DEG C of vacuum drying 2 ~ 10h 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide; Wherein, phosphate radical and AgNO in the precursor of phosphorous acid group 3the ratio of the amount of substance of middle silver ion is 1:3.
HNO in described step (1) 3with Bi (NO 3) 35H 2the ratio of the amount of substance of O is 3 ~ 30:1; NaOH and Na 2wO 42H 2the ratio of the amount of substance of O is 3 ~ 30:1; Bi (NO 3) 35H 2o and Na 2wO 42H 2the ratio of the amount of substance of O is 2:1.
Suspension pH value is regulated to adopt concentration to be the NH of 0.1 ~ 5.0mol/L in described step (1) 3h 2o or NaOH.
In described step (2), dispersion adopts ultrasonic disperse 10 ~ 60min, then magnetic agitation 10 ~ 60min.
Bi in described step (2) 2wO 6with the AgNO added 3the ratio of amount of substance be 1:0.3 ~ 15.
In described step (2), the precursor of phosphorous acid group is Na 2hPO 4, NaH 2pO 4, Na 3pO 4, K 2hPO 4, KH 2pO 4or K 3pO 4.
A kind of Bi 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide, described Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is as the application of photochemical catalyst or bactericide.
Described Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is as the application of the photochemical catalyst in water body purification or bactericide.
A kind of Bi 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide, described Bi 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide in water body purification.
Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is applied in water body, the visible light catalytic of harmful microorganism Escherichia coli (E.coli) and staphylococcus aureus (S.aureus) is killed, adopt 500W xenon lamp as light source, its wave-length coverage is 420 ~ 760nm; Described microorganism concn is 10 6cfu/mL; Described Bi 2wO 6/ Ag 3pO 4the consumption of composite photo-catalysis bactericide is 1.0mg/mL.
The concrete method of testing of its photocatalytic activity is: adopt 500W xenon lamp as light source, be aided with optical filter; Microbial solution is joined in reactor, then add Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, dark adsorption starts illumination after reaching balance, and in During Illumination, separated in time sampling, measures surviving bacteria concentration by colony counting method, calculates killing rate.Described light source is xenon lamp, and its wave-length coverage is 420 ~ 760nm; Described microorganism concn is 10 6cfu/mL; Described Bi 2wO 6/ Ag 3pO 4the consumption of composite photo-catalysis bactericide is 1.0mg/mL.
Beneficial effect of the present invention is:
The present invention passes through Bi 2wO 6with Ag 3pO 4compound, builds the composite with heterojunction structure, accelerates the separation of photo-generated carrier at composite material surface, and then improves the photo-catalyst performance of composite, to Bi 2wO 6and Ag 3pO 4bi-material is significant in the practical application of photocatalysis field; Concrete:
(1) preparation method's technique of adopting of the present invention simple, be easy to control, with low cost;
(2) the present invention prepare by Bi 2wO 6nanometer sheet loaded Ag 3pO 4the Bi that nano particle builds 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, has good visible absorption performance;
(3) Bi for preparing of the present invention 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide visible light catalysis activity compares Bi 2wO 6with Ag 3pO 4be significantly increased, under 500W xenon lamp irradiates, 1.0mg/mLBi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is 10 to concentration 6in the microorganism 45min of cfu/mL, killing rate can reach 99.99%;
(4) Bi for preparing of the present invention 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide has heterojunction structure, accelerate photo-generated carrier to be separated, reduce the recombination probability that photo-generate electron-hole is right, improve visible light catalysis activity and stability, there is in fields such as water body purifications good practical value and potential application prospect.
Accompanying drawing explanation
(wherein abscissa is 2 θ (angles) to X-ray diffraction (XRD) collection of illustrative plates of Fig. 1 sample prepared by the present invention, and unit is degree (degree); Ordinate is Intensity (intensity), and unit is a.u. (absolute unit));
SEM (FESEM) photo of Fig. 2 sample prepared by the present invention: (A) Ag 3pO 4, (B) Bi 2wO 6, (C, D) Bi 2wO 6/ Ag 3pO 4-0.5;
(wherein abscissa is Wavelength (wavelength) to UV-vis DRS spectrum (UV-DRS) figure of Fig. 3 sample prepared by the present invention, unit is nm (nanometer), ordinate is Absorbance (absorbance), and unit is a.u. (absolute unit));
Fig. 4 prepared by the present invention sample visible ray according to the lower sterilizing rate (wherein ordinate is Antibacterialrate (sterilizing rate), and unit is %) to Escherichia coli and staphylococcus aureus.
Detailed description of the invention
Below by way of specific embodiment, the invention will be further described, contributes to those of ordinary skill in the art and more fully understand the present invention, but do not limit the present invention in any way.
The present invention has prepared Bi by hydrothermal synthesis method and in situ Precipitation 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, this composite photo-catalysis bactericide has good visible absorption performance, the heterojunction structure built accelerates the separation of photo-generated carrier, reduce the recombination probability that photo-generate electron-hole is right, there is efficient photocatalytic activity under visible light, to harmful microorganism in water body, there is efficient killing effect, there is in fields such as water body purifications good practical value and potential application prospect.This composite photo-catalysis bactericide preparation method has the features such as simple, cheap and reproducible simultaneously.
Embodiment 1:
Bi 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide:
(1) Bi is prepared by hydrothermal synthesis method 2wO 6nanometer sheet: take 10.0mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to dissolving completely; Simultaneously by 5.0mmolNa 2wO 42H 2o joins in 30.0mL2.0mol/LNaOH solution, and magnetic agitation, to dissolving completely, obtains lysate respectively; Then under magnetic stirring by above-mentioned Na 2wO 4lysate dropwise joins above-mentioned Bi (NO 3) 3in lysate, obtain suspension, then use 2.0mol/LNH 3h 2o solution regulates the pH of suspension to be 7, continues afterwards to stir 60min; After stirring terminates, suspension is transferred to and is furnished with in teflon-lined autoclave, put into electric heating constant-temperature blowing drying box 160 DEG C of heat treatment 24h; After reaction terminates, reactor is cooled to room temperature, product is through suction filtration, and suction filtration gained precipitation, successively through ultra-pure water and absolute ethanol washing, then in 60 DEG C of dry 6h, can obtain Bi 2wO 6nanometer sheet, is designated as Bi 2wO 6(see Fig. 1-3).
(2) Bi is prepared by situ Precipitation 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide: control Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.5, take above-mentioned gained 1.0mmolBi 2wO 6join in 30mL ultra-pure water, ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Take 1.5mmolAgNO afterwards 3join above-mentioned Bi 2wO 6in dispersion liquid, be stirred to and dissolve completely, obtain mixed liquor; Simultaneously by 0.5mmolNa 2hPO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 2hPO 4lysate dropwise joins above-mentioned Bi 2wO 6with AgNO 3mixed liquor in, continue at room temperature lucifuge stir 5h; After stirring terminates, product is through suction filtration, and suction filtration gained precipitation is successively through ultra-pure water and absolute ethanol washing, and then dry 6h in 60 DEG C of vacuum drying chambers, can obtain Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, is designated as Bi 2wO 6/ Ag 3pO 4-0.5 (see Fig. 1-3).
Comparative example 1:
Monomer A g 3pO 4preparation method:
Prepared by coprecipitation.By 3.0mmolAgNO 3be dissolved in 30mL ultra-pure water, magnetic agitation makes it dissolve completely; Simultaneously by 1.0mmolNa 2hPO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate respectively; Then by above-mentioned Na 2hPO 4lysate is dropwise added drop-wise to above-mentioned AgNO under magnetic stirring 3in lysate, obtain suspension, continue at room temperature lucifuge and stir 5h; After stirring terminates, product is through suction filtration, and suction filtration postprecipitation is successively through ultra-pure water and absolute ethanol washing several, and then dry 6h in 60 DEG C of vacuum drying chambers, can obtain Ag 3pO 4monomer material, is designated as Ag 3pO 4(see Fig. 1-3).
As shown in Figure 1, a curve is Bi prepared by embodiment 1 2wO 6xRD collection of illustrative plates, position and the standard card JCPDSNo.79-2381 of all diffraction maximums fit like a glove, and all belong to rhombic Bi 2wO 6, and there is not any impurity phase, can determine that sample prepared by embodiment 1 is pure oblique side phase Bi 2wO 6.B curve is monomer A g prepared by comparative example 1 3pO 4xRD collection of illustrative plates, as seen from the figure, diffraction maximums all in figure all with the cubic system Ag of standard 3pO 4corresponding (JCPDSNo.06-0505), and do not have dephasign to occur, show that the sample prepared by comparative example 1 is pure cubic structure Ag 3pO 4.C curve in figure is Bi prepared by embodiment 1 2wO 6/ Ag 3pO 4the XRD collection of illustrative plates of-0.5 composite photo-catalysis bactericide, contains Emission in Cubic Ag in collection of illustrative plates 3pO 4with oblique side phase Bi 2wO 6all characteristic peaks, Ag is described 3pO 4and Bi 2wO 6successfully be combined with each other formation composite.In the XRD collection of illustrative plates of composite, there are not other impurity peaks, illustrate in composite just by Bi 2wO 6and Ag 3pO 4two kinds of material compositions, other impurity phases do not exist.
From Fig. 2 (A), monomer A g prepared by comparative example 1 3pO 4for being spherical particle, degree of crystallinity is higher, and size is about 200nm, and particle dispersion is good, does not have obvious agglomeration between crystal grain.From Fig. 2 (B), monomers B i prepared by embodiment 1 2wO 6for laminated structure, diameter is about 200nm, wherein part nanometer sheet flush edge, smooth, is square, separately has part nanometer sheet edge and out-of-flatness, and sheet and sheet is random is stacked.From Fig. 2 (C) and Fig. 2 (D), Bi prepared by embodiment 1 2wO 6/ Ag 3pO 4-0.5 composite photo-catalysis bactericide is by Bi 2wO 6nanometer sheet loaded Ag 3pO 4nano particle assembles, in the composite Bi 2wO 6nanometer sheet size is about 200nm, is substantially consistent with size before compound, and Ag 3pO 4nanoparticle size is about 40nm, obviously reduces than monomer material size.
Bi as can be seen from Figure 3 2wO 6, Ag 3pO 4and Bi 2wO 6/ Ag 3pO 4-0.5 composite all has good absorption in ultra-violet (UV) band and visible region, demonstrates good visible absorption performance.In addition, there is the Ag of good visible absorption performance 3pO 4with Bi 2wO 6compound substantially increases Bi 2wO 6visible absorption performance, make composite have good visible absorption performance.
Embodiment 2:
Bi 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide:
Prepared by situ Precipitation, difference from Example 1 is, control Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.25.Take above-mentioned gained 1.0mmolBi 2wO 6join in 30mL ultra-pure water, ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Take 0.75mmolAgNO afterwards 3join above-mentioned Bi 2wO 6in dispersion liquid, be stirred to and dissolve completely, obtain mixed liquor; Simultaneously by 0.25mmolNa 2hPO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 2hPO 4lysate dropwise joins above-mentioned Bi 2wO 6with AgNO 3mixed liquor in, continue at room temperature lucifuge stir 5h; After stirring terminates, product is through suction filtration, and suction filtration gained precipitation is successively through ultra-pure water and absolute ethanol washing, and then dry 6h in 60 DEG C of vacuum drying chambers, can obtain Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, is designated as Bi 2wO 6/ Ag 3pO 4-0.25.
Embodiment 3:
Bi 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide:
Prepared by situ Precipitation, difference from Example 1 is, control Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.75.Take above-mentioned gained 1.0mmolBi 2wO 6join in 30mL ultra-pure water, ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Take 2.25mmolAgNO afterwards 3join above-mentioned Bi 2wO 6in dispersion liquid, be stirred to and dissolve completely, obtain mixed liquor; Simultaneously by 0.75mmolNa 2hPO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 2hPO 4lysate dropwise joins above-mentioned Bi 2wO 6with AgNO 3mixed liquor in, continue at room temperature lucifuge stir 5h; After stirring terminates, product is through suction filtration, and suction filtration gained precipitation is successively through ultra-pure water and absolute ethanol washing, and then dry 6h in 60 DEG C of vacuum drying chambers, can obtain Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, is designated as Bi 2wO 6/ Ag 3pO 4-0.75.
Embodiment 4:
Bi 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide:
Prepared by situ Precipitation, difference from Example 1 is, control Bi 2wO 6with Ag 3pO 4mol ratio be 1:1, take above-mentioned gained 1.0mmolBi 2wO 6join in 30mL ultra-pure water, ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Take 3.0mmolAgNO afterwards 3join above-mentioned Bi 2wO 6in dispersion liquid, be stirred to and dissolve completely, obtain mixed liquor; Simultaneously by 1.0mmolNa 2hPO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 2hPO 4lysate dropwise joins above-mentioned Bi 2wO 6with AgNO 3mixed liquor in, continue at room temperature lucifuge stir 5h; After stirring terminates, product is through suction filtration, and suction filtration gained precipitation is successively through ultra-pure water and absolute ethanol washing, and then dry 6h in 60 DEG C of vacuum drying chambers, can obtain Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, is designated as Bi 2wO 6/ Ag 3pO 4-1.
Application examples 1:
Above-mentioned gained Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is applied in water body, kills the visible ray of harmful microorganism Escherichia coli and staphylococcus aureus
Using 500W xenon lamp as light source, be aided with optical filter and filter ultraviolet light, make its wave-length coverage be 420 ~ 760nm.With Escherichia coli (4.0 × 10 8and staphylococcus aureus (4.0 × 10 cfu/mL) 8cfu/mL) Bi is evaluated 2wO 6/ Ag 3pO 4the visible light catalytic bactericidal property of composite photo-catalysis bactericide:
First prepare bacterial suspension, Escherichia coli and staphylococcus aureus storage liquid are inoculated in sterilizing LB fluid nutrient medium, be then placed on 37 DEG C, in the air constant-temperature table of 150rpm, incubated overnight.Be suspended in 0.01mol/LPBS (pH=7.4) buffer solution after the bacterial suspension that cultivation obtains is centrifugal, obtaining concentration is 4.0 × 10 8the Escherichia coli of cfu/mL and staphylococcus aureus suspension.
Getting 49.5mL sterilizing 0.01mol/LPBS (pH=7.4) buffer solution in light-catalyzed reaction joins in 50mL reactor, then adds 500 μ L bacterial suspensions, makes bacterial concentration in reactant liquor be 4.0 × 10 6cfu/mL, adds photochemical catalyst prepared by 50mg the present invention.Dark adsorption carries out light-catalyzed reaction after reaching balance, and in course of reaction, separated in time sampling, determines survival rate and the sterilizing rate of bacterium by colony counting method.Concrete steps are: get 1.0mL reactant liquor, several gradient is diluted successively according to serial dilutions with 0.01mol/LPBS (pH=7.4) buffer solution, then get from the solution of different extension rate on 100 μ L to ready LB solid medium, bacterium liquid is spread upon on LB culture medium equably.Be inverted by LB culture medium, put into electro-heating standing-temperature cultivator 37 DEG C and cultivate 24h, by the bacterium colony number that counting culture medium grows, and corresponding extension rate draws bacterial concentration, to determine survival rate and the sterilizing rate of bacterium.In experiment, often group experiment all needs parallel determination 3 times, averages as end product, and blank assay and dark-state experiment test (see Fig. 4) in contrast.
As seen from Figure 4, in blank assay, the number of Escherichia coli and staphylococcus aureus has almost no change, and shows that the impact of visible ray photograph can be ignored; And under dark condition, the number of two kinds of bacteriums has certain minimizing, this is because Bi 2wO 6/ Ag 3pO 4containing Ag element in-0.5 composite photo-catalysis bactericide, have part Ag in aqueous +discharge, Ag +also there is certain bactericidal property, can have an effect with bacterium, cause bacterium apoptosis.And visible ray according under Bi 2wO 6/ Ag 3pO 4-0.5 composite photo-catalysis bactericide demonstrates good photocatalytic activity, and photo-catalyst performance is obviously better than monomers B i 2wO 6and Ag 3pO 4, after 45min reaction, all can reach 99.99% to the sterilizing rate of Escherichia coli and staphylococcus aureus.Therefore, Bi 2wO 6/ Ag 3pO 4-0.5 composite photo-catalysis bactericide has splendid photo-catalyst performance, is attributable to Ag 3pO 4with Bi 2wO 6be compounded to form heterojunction structure, accelerate the separation of photo-generate electron-hole, improve the photocatalytic activity of composite.

Claims (10)

1. a Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide, is characterized in that: Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is by Bi 2wO 6and Ag 3pO 4composition, nanometer Ag 3pO 4at Bi 2wO 6nanometer sheet surface in situ grows; Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.1 ~ 10.
2. Bi according to claim 1 2wO 6/ Ag 3pO 4heterojunction composite photocatalyst, is characterized in that: described Bi 2wO 6with Ag 3pO 4mol ratio be 1:0.1 ~ 5.
3. a Bi according to claim 1 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that:
(1) Bi 2wO 6preparation: by Bi (NO 3) 35H 2o joins HNO 3in solution, magnetic agitation is to dissolving completely; Simultaneously by Na 2wO 42H 2o joins in NaOH solution, and magnetic agitation, to dissolving completely, obtains lysate respectively; Then under magnetic stirring by above-mentioned Na 2wO 4lysate dropwise joins above-mentioned Bi (NO 3) 3in lysate, obtain suspension, and regulate pH of suspension to 5 ~ 9, continue stirring 30 ~ 90min, afterwards suspension is transferred in autoclave, puts into electric heating constant-temperature blowing drying box 120 ~ 180 DEG C of heat treatment 12 ~ 36h; Then reactor is cooled to room temperature, the Bi of laminated structure can be obtained through suction filtration, washing and 40 ~ 80 DEG C of drying 2 ~ 10h 2wO 6;
(2) Bi 2wO 6/ Ag 3pO 4the preparation of composite photo-catalysis bactericide: by the Bi obtained in step (1) 2wO 6be scattered in ultra-pure water and obtain dispersion liquid, then add AgNO under magnetic stirring 3, be stirred to and dissolve to obtain mixed liquor completely, then dropwise add the precursor solution of phosphorous acid group, continue lucifuge afterwards and stir 2 ~ 8h, can Bi be obtained through suction filtration, washing and 40 ~ 80 DEG C of vacuum drying 2 ~ 10h 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide; Wherein, phosphate radical and AgNO in the precursor of phosphorous acid group 3the ratio of the amount of substance of middle silver ion is 1:3.
4. Bi according to claim 3 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that: HNO in described step (1) 3with Bi (NO 3) 35H 2the ratio of the amount of substance of O is 3 ~ 30:1; NaOH and Na 2wO 42H 2the ratio of the amount of substance of O is 3 ~ 30:1; Bi (NO 3) 35H 2o and Na 2wO 42H 2the ratio of the amount of substance of O is 2:1.
5. Bi according to claim 3 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that: regulate suspension pH value to adopt concentration to be the NH of 0.1 ~ 5.0mol/L in described step (1) 3h 2o or NaOH.
6. Bi according to claim 3 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that: in described step (2), dispersion adopts ultrasonic disperse 10 ~ 60min, then magnetic agitation 10 ~ 60min.
7. Bi according to claim 3 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that: Bi in described step (2) 2wO 6with the AgNO added 3the ratio of amount of substance be 1:0.3 ~ 15.
8. Bi according to claim 3 2wO 6/ Ag 3pO 4the preparation method of composite photo-catalysis bactericide, is characterized in that: in described step (2), the precursor of phosphorous acid group is Na 2hPO 4, NaH 2pO 4, Na 3pO 4, K 2hPO 4, KH 2pO 4or K 3pO 4.
9. a Bi according to claim 1 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide, is characterized in that: described Bi 2wO 6/ Ag 3pO 4composite photo-catalysis bactericide is as the application of photochemical catalyst or bactericide.
10. a Bi according to claim 1 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide, is characterized in that: described Bi 2wO 6/ Ag 3pO 4the application of composite photo-catalysis bactericide in water body purification.
CN201510790413.9A 2015-11-17 2015-11-17 Bi2WO6 / Ag3PO4 composite photocatalytic fungicide and preparation method thereof Pending CN105457663A (en)

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CN112251831A (en) * 2020-11-09 2021-01-22 西安工程大学 Sterilization self-cleaning photocatalyst fiber and preparation method and application thereof

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