CN105457625A - Bi2WO6 / BiVO4 heterojunction composite photocatalyst, preparation method and application thereof - Google Patents

Bi2WO6 / BiVO4 heterojunction composite photocatalyst, preparation method and application thereof Download PDF

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CN105457625A
CN105457625A CN201510789914.5A CN201510789914A CN105457625A CN 105457625 A CN105457625 A CN 105457625A CN 201510789914 A CN201510789914 A CN 201510789914A CN 105457625 A CN105457625 A CN 105457625A
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bivo
composite photocatalyst
heterojunction composite
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The present invention belongs to the field of photocatalysis, and in particular to a Bi2WO6 / BiVO4 composite photocatalyst and a preparation method and application thereof. The Bi2WO6 / BiVO4 heterojunction composite photocatalyst is a catalyst with a three-dimensional layered nest-like structure and formed by Bi2WO6 and BiVO4, wherein the molar ratio of Bi2WO6 to BiVO4 is 1:0.05-10. A simple one-step hydrothermal method is employed for preparation of the Bi2WO6 / BiVO4 heterojunction composite photocatalyst. The preparation method of the present invention is simple, easy to control and low in cost; the constructed Bi2WO6 / BiVO4 heterojunction structure with visible light response and large specific surface area accelerates the separation of photo-generated carriers, reduces the recombination rate of photo-generated electron-hole pair, has high photocatalytic activity and stability under visible light, and highly efficient killing effect on harmful micro-organisms and dye pollutants in water, and shows good practical value and potential applications in the fields of water purification and marine antifouling.

Description

A kind of Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst and its preparation method and application
Technical field
The invention belongs to photocatalysis field, be specifically related to a kind of Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst and its preparation method and application.
Background technology
In recent years, along with develop rapidly that is scientific and technical and industrial technology, problem of environmental pollution is day by day serious, and the water resource that particularly mankind depend on for existence receives pollution in various degree, and water resource pollution has become one and directly threatened human survival, countries in the world problem demanding prompt solution.On the other hand, cause day by day serious energy crisis due to the excessive use of fossil energy, also result in serious environmental pollution simultaneously.Therefore, energy shortage and problem of environmental pollution are two huge challenges that the world today faces, and seriously govern the sustainable development of the mankind, and serious harm human health.Therefore, Control pollution, protection of the environment, realize sustainable development and receive people and more and more pay attention to, and exploitation and use efficient, environmental protection, the new technology of science and new forms of energy to become current study hotspot.
Photocatalysis technology is a kind of technology utilizing luminous energy to carry out Substance Transformation, is the chemical reaction that material carries out under light and catalyst act on simultaneously.From Japanese Scientists Fujishima in 1972 and Honda reported first TiO 2can after photocatalytic water produce hydrogen and oxygen under ultraviolet lighting, Photocatalitic Technique of Semiconductor receives increasing concern [1].In recent years, the application study development of photocatalysis technology is very rapid, this new technology has efficiently, non-selectivity, stability are high, green non-poisonous, non-secondary pollution, energy consumption are low, easy and simple to handle and the outstanding advantages such as low cost, and the solar energy of cleanliness without any pollution can be made full use of, can effective oxidative degradation organic substance and kill pathogenic microorganisms, at sewage disposal, exhaust-gas treatment, purification of air, sterilizing, catalyzing manufacturing of hydrogen, reduction CO 2etc. aspect be widely used, and respond well.At present, TiO 2because the advantages such as its stable chemical nature, nontoxic, low cost become most popular catalysis material, but due to TiO 2energy gap is 3.2eV, and the absorbing wavelength of its correspondence is 387.5nm, and light abstraction width is only confined to ultraviolet region, and this part light does not still reach and is irradiated to 5% of ground solar spectrum, greatly limit the utilization to solar energy [2].Therefore, in order to realize effective utilization of solar energy, exploitation and design have novel photocatalysis material that is visible light-responded, environmental protection and have important practical significance.
Bismuth based material is because it to have good photocatalysis performance and pattern diversity in visible ray (λ >420nm) district by extensive concern and further investigation, and the composite that bismuth and other metals are formed also has good visible light catalytic performance [3-6].As BiVO 4be a kind of novel N-shaped direct semiconductor material, its energy gap relative narrower (about 2.4eV), has good visible absorption performance, is the good novel visible catalysis material of a kind of application prospect [3]; Bi 2wO 6it is one the simplest Aurivillius type oxide, it is a kind of N-shaped direct semiconductor material, there is narrower energy gap (about 2.7eV), under visible ray shines, there is higher catalytic activity, in the depollution of environment and new energy development field, there is potential using value, become one of photochemical catalyst of extensively research at present [4].But because photoelectron in monomer photochemical catalyst-hole is separated comparatively slow, the easy compound of photo-generated carrier, causes photocatalysis performance limited, and can accelerate electron-hole separation by semiconductors coupling structure composite, improves the photocatalysis performance of material [5,6].Therefore, a kind of composite photocatalyst is now badly in need of.
[1]K.Nakata,A.Fujishima.TiO 2photocatalysis:Designandapplications[J].JournalofPhotochemistryandPhotobiologyC:PhotochemistryReviews,2012,13:169-189.
[2]X.B.Chen,S.S.Mao.Titaniumdioxidenanomaterials:Synthesis,properties,modifications,andapplications[J].ChemicalReviews,2007,107:2891-2959.
[3]M.Shang,W.Z.Wang,J.Ren,S.M.Sun,L.Zhang.AnovelBiVO 4hierarchicalnanostructure:controllablesynthesis,growthmechanism,andapplicationinphotocatalysis[J].CrystEngComm,2010,12:1754-1758.
[4]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.
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/ BiVO 4heterojunction composite photocatalyst and its preparation method and application.
For achieving the above object, the present invention implements by the following technical solutions:
A kind of Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst, by Bi 2wO 6and BiVO 4form the catalyst with three-dimensional layering nest like structure; Wherein, Bi 2wO 6with BiVO 4mol ratio be 1:0.05 ~ 10.
Described Bi 2wO 6with BiVO 4mol ratio be 1:0.1 ~ 5.
A kind of Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst: by Bi (NO 3) 35H 2o joins HNO 3in solution, magnetic agitation, to dissolving completely, obtains lysate A; Simultaneously by Na 2wO 42H 2o and NH 4vO 3join in NaOH solution, magnetic agitation, to dissolving completely, then adds polyvinylpyrrolidone (PVP), and magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned lysate B is dropwise joined in above-mentioned lysate A, 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 heat treatment; Then reactor is cooled to room temperature, the Bi with three-dimensional layering nido structure can be obtained through suction filtration, washing and drying 2wO 6/ BiVO 4heterojunction composite photocatalyst; Wherein, Na 2wO 42H 2o and NH 4vO 3the ratio of amount of substance be 1:0.1 ~ 5, Bi (NO 3) 35H 2o and Na 2wO 42H 2the ratio of the amount of substance of O is 2:1, Bi (NO 3) 35H 2o and NH 4vO 3the ratio of amount of substance be consumption and the Bi (NO of 1:1, PVP 3) 35H 2o's is 0.01 ~ 0.5gPVP/1mmolBi (NO with magnitude relation 3) 35H 2o.
Described HNO 3with Bi (NO 3) 35H 2the ratio of the amount of substance of O is 3 ~ 30:1; NaOH and Na 2wO 42H 2o and NH 4vO 3the ratio of amount of substance be 3 ~ 30:1.
Described adjustment suspension pH value adopts concentration to be the NH of 0.1 ~ 5.0mol/L 3h 2o or NaOH.
In described electric heating constant-temperature blowing drying box, heat treatment temperature is 120 ~ 180 DEG C, and the reaction time is 12 ~ 36h.
Described baking temperature is 40 ~ 80 DEG C, and drying time is 2 ~ 10h.
A kind of Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, described Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is as the application of bactericide in water body.
A kind of Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, described Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst in degradation of dye.
A kind of Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, described Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst in water body purification.
Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is applied in water body, the visible light catalytic of harmful microorganism pseudomonas aeruginosa (P.aeruginosa) and dyestuff contaminant methylene blue (MB) is killed and degraded, adopt 500W xenon lamp as light source, its wave-length coverage is 420 ~ 760nm; Described microorganism concn is 10 6cfu/mL; Described methylene blue concentration is 20mg/L; Described Bi 2wO 6/ BiVO 4the consumption of heterojunction composite photocatalyst 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; Microorganism and methylene blue solution are joined in reactor, then adds Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst, dark adsorption starts illumination after reaching balance, separated in time sampling in During Illumination, measures surviving bacteria concentration and remaining methylene blue concentration by colony counting method and ultraviolet-visible spectrophotometry, calculates killing rate and degradation rate.Described light source is xenon lamp, and its wave-length coverage is 420 ~ 760nm; Described microorganism concn is 10 6cfu/mL; Described methylene blue concentration is 20mg/L; Described Bi 2wO 6/ BiVO 4the consumption of heterojunction composite photocatalyst is 1.0mg/mL.
Beneficial effect of the present invention is:
The present invention passes through Bi 2wO 6with BiVO 4compound builds the composite with heterojunction structure, accelerates the separation of photo-generated carrier at composite material surface, and then improves photocatalysis performance, to Bi 2wO 6and BiVO 4bi-material is significant in the practical application of photocatalysis field; Concrete:
(1) the present invention adopts simple hydro-thermal method one-step synthesis Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst, preparation method's technique is simple, be easy to control, with low cost;
(2) Bi of three-dimensional layering nest like structure that what prepared by the present invention have 2wO 6/ BiVO 4heterojunction composite photocatalyst, has larger specific area and good visible absorption performance;
(3) Bi for preparing of the present invention 2wO 6/ BiVO 4heterojunction composite photocatalyst visible light catalysis activity compares Bi 2wO 6and BiVO 4be significantly increased, under 500W xenon lamp irradiates, 1.0mg/mLBi 2wO 6/ BiVO 4heterojunction composite photocatalyst is 10 to concentration 6the microorganism 30min killing rate of cfu/mL can reach 99.99%, realizes degradable to the methylene blue 30min that concentration is 20mg/L;
(4) Bi for preparing of the present invention 2wO 6/ BiVO 4heterojunction composite photocatalyst has good stability and reusing, still has efficient photocatalytic activity after recycling for 6 times;
(5) Bi for preparing of the present invention 2wO 6/ BiVO 4heterojunction composite photocatalyst has heterojunction structure, accelerate the separation of photo-generated carrier, reduce the recombination probability that photo-generate electron-hole is right, improve visible light catalysis activity and stability, there is in the field such as water body purification and marine anti-pollution 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) Bi 2wO 6, (B) BiVO 4, (C, D) Bi 2wO 6/ BiVO 4-1;
UV-vis DRS spectrum (UV-DRS) figure (A) of Fig. 3 sample prepared by the present invention and (α h ν) 2~ h ν schemes (B), and (wherein in A figure, abscissa is Wavelength (wavelength), and unit is nm (nanometer), and ordinate is Absorbance (absorbance), and unit is a.u. (absolute unit); In B figure, abscissa is h ν (energy), and unit is eV (electron-volt), and ordinate is (α h ν) 2, unit is (eV) 2));
During sample photocatalytic degradation reaction Methylene Blue concentration changes with time curve (A) of Fig. 4 prepared by the present invention and photo-catalyst react, (wherein in A figure, abscissa is Time (time), and unit is min (minute) for the survival curve (B) of pseudomonas aeruginosa; Ordinate is C t/ C 0, C 0for reaction starts front methylene blue initial concentration, C tfor the methylene blue concentration when reaction time is t; In B figure, abscissa is Time (time), and unit is min (minute), and ordinate is Celldensity (cell concentration), and unit is logCcfu/mL (clump count));
Fig. 5 is the Bi of preparation in the embodiment of the present invention 1 2wO 6/ BiVO 4(wherein in A figure, abscissa is Cyclenumber (reusing number of times) for sterilizing rate (A) after-1 heterojunction composite photocatalyst repeats 6 sterilization experiments and XRD collection of illustrative plates (B), ordinate is Antibacterialrate (sterilizing rate), and unit is %; In B figure, abscissa is 2 θ (angles), and unit is degree (degree), and ordinate is Intensity (intensity), and unit is a.u. (absolute unit)).
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 the Bi with three-dimensional layering nest like structure by simple hydrothermal synthesis method one step 2wO 6/ BiVO 4heterojunction composite photocatalyst, this composite photo-catalyst 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 and stability under visible light, have harmful microorganism in water body and dyestuff contaminant and kill efficiently and degradation effect, there is in the field such as water body purification and marine anti-pollution good practical value and potential application prospect.The preparation method of this composite photo-catalyst has the features such as simple, cheap and reproducible simultaneously.
Embodiment 1:
Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst:
Prepared by hydrothermal synthesis method.Take 3.0mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o and 1.0mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 the Bi with three-dimensional layering nest like structure 2wO 6/ BiVO 4heterojunction composite photocatalyst, is designated as Bi 2wO 6/ BiVO 4-1 (see Fig. 1-3).
Comparative example 1:
Monomers B i 2wO 6preparation method:
Prepared by hydrothermal synthesis method.Take 2.0mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o joins in 30.0mL2.0mol/LNaOH solution, is heated to 80 DEG C and magnetic agitation and makes it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, and magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 6monomer material, is designated as Bi 2wO 6(see Fig. 1-3).
Comparative example 2:
Monomers B iVO 4preparation method:
Prepared by hydrothermal synthesis method.Take 1.0mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 BiVO 4monomer material, is designated as BiVO 4(see Fig. 1-3).
As shown in Figure 1, a curve is monomers B i prepared by comparative example 1 2wO 6xRD collection of illustrative plates, position and the standard card JCPDSNo.73-1126 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 comparative example 1 is pure oblique side phase Bi 2wO 6.B curve is monomers B iVO prepared by comparative example 2 4xRD collection of illustrative plates, diffraction maximums all in figure all with the monoclinic system BiVO of standard 4corresponding (JCPDSNo.14-0688), the diffraction maximum without any impurity phase occurs, shows that sample prepared by comparative example 2 is pure monoclinic phase BiVO 4.C curve in Fig. 1 is Bi prepared by embodiment 1 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst XRD collection of illustrative plates, contains oblique side phase Bi in collection of illustrative plates 2wO 6with monoclinic phase BiVO 4all characteristic diffraction peaks, Bi is described 2wO 6and BiVO 4successfully be combined with each other and define composite.In the XRD collection of illustrative plates of composite, there are not other impurity peaks, illustrate in composite just by Bi 2wO 6and BiVO 4two kinds of material compositions, other impurity phases do not exist.
From Fig. 2 (A), monomers B i prepared by comparative example 1 2wO 6for the good monodispersed three-dimensional layering flower-like microsphere of degree of crystallinity, diameter is about 1 μm, and the flower-like microsphere structure of this layering is piled up by the two-dimensional nano thin slice of many rules to form, and each nanometer sheet size is about 100nm, and thickness is about 20nm.From Fig. 2 (B), monomers B iVO prepared by comparative example 2 4for irregular dendritic structure, primarily of multiple brilliant formations of vertical bars crystals growth, size is about 2 μm.From Fig. 2 (C) and Fig. 2 (D), Bi prepared by embodiment 1 2wO 6/ BiVO 4-1 composite material exhibits is three-dimensional layering nest like micro-sphere structure, and size is about 4 μm, piles up self assembly form by many two-dimensional nano thin slices.Bi 2wO 6/ BiVO 4the three-dimensional layering nest like micro-sphere structure of-1 heterojunction composite photocatalyst is by Bi 2wO 6and BiVO 4through anisotropic growth and Ostwald ripening process in water-heat process, the concurrent raw self-assembling reaction of arrangement oriented and ordered under the assistance of PVP is formed.This layering three-dimensional structure will have larger specific area and good visible absorption performance.
From Fig. 3 (A), Bi 2wO 6, BiVO 4and Bi 2wO 6/ BiVO 4-1 composite all has good absorption at ultraviolet region and visible region, demonstrates good visible absorption performance.Bi 2wO 6/ BiVO 4the light abstraction width of-1 can arrive about 650nm, and the BiVO with good visible absorption performance is described 4with Bi 2wO 6compound substantially increases the visible absorption performance of composite.Fig. 3 (B) is for preparing (the α h ν) of sample 2~ h ν curve map, makes a tangent line along direction of a curve, can obtain the energy gap E that sample is corresponding g, Bi 2wO 6, BiVO 4and Bi 2wO 6/ BiVO 4the energy gap E of-1 gbe respectively 2.70eV, 2.30eV and 2.07eV.Therefore, BiVO 4with Bi 2wO 6compound substantially increase Bi 2wO 6/ BiVO 4the visible absorption performance of composite, makes it have good application prospect in photocatalysis field.
Embodiment 2:
Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst:
Prepared by hydrothermal synthesis method, difference from Example 1 is, control Bi 2wO 6with BiVO 4mol ratio be 1:0.75.Take 2.75mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o and 0.75mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 6/ BiVO 4heterojunction composite photocatalyst, is designated as Bi 2wO 6/ BiVO 4-0.75.
Embodiment 3:
Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst:
Prepared by hydrothermal synthesis method, difference from Example 1 is, control Bi 2wO 6with BiVO 4mol ratio be 1:0.5.Take 2.5mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o and 0.5mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 6/ BiVO 4heterojunction composite photocatalyst, is designated as Bi 2wO 6/ BiVO 4-0.5.
Embodiment 4:
Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst:
Prepared by hydrothermal synthesis method, difference from Example 1 is, control Bi 2wO 6with BiVO 4mol ratio be 1:0.25.Take 2.25mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o and 0.25mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 6/ BiVO 4heterojunction composite photocatalyst, is designated as Bi 2wO 6/ BiVO 4-0.25.
Embodiment 5:
Bi 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst:
Prepared by hydrothermal synthesis method, difference from Example 1 is, controls electric heating constant-temperature blowing drying box heat treatment time 16h.Take 3.0mmolBi (NO 3) 35H 2o joins 30.0mL2.0mol/LHNO 3in solution, magnetic agitation is to Bi (NO 3) 35H 2o dissolves completely, obtains lysate A; Simultaneously by 1.0mmolNa 2wO 42H 2o and 1.0mmolNH 4vO 3join in 30.0mL2.0mol/LNaOH solution, be heated to 80 DEG C and magnetic agitation and make it dissolve completely, add 0.5g polyvinylpyrrolidone (PVP) afterwards, magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned B lysate is dropwise joined in above-mentioned A 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 16h; 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 6/ BiVO 4heterojunction composite photocatalyst, is designated as Bi 2wO 6/ BiVO 4-16.
Application examples 1:
Above-mentioned gained Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is applied to the visible light photocatalytic degradation of dyestuff contaminant methylene blue MB:
Using 500W xenon lamp as light source, be aided with optical filter and filter ultraviolet light, make its wave-length coverage be 420 ~ 760nm.The methylene blue solution of 50mL20mg/L is joined in 50mL reactor, add photochemical catalyst prepared by 50mg the present invention, dark adsorption carries out light-catalyzed reaction after reaching balance, separated in time sampling in course of reaction, the absorbance that supernatant liquor measures methylene blue solution under 664nm wavelength on ultraviolet-visible spectrophotometer is got after centrifugation, obtain the residual concentration of methylene blue solution, calculate degradation rate with this, blank assay and dark-state experiment test (see Fig. 4 A) in contrast.
From Fig. 4 (A), blank assay Methylene Blue is not almost degraded, and can ignore the impact of experiment.In addition, dark-state experiment shows Bi 2wO 6/ BiVO 4-1 composite photo-catalyst has certain absorption property because having larger specific area, but can ignore the impact of light-catalyzed reaction.Under visible ray shines, Bi 2wO 6/ BiVO 4-1 composite photo-catalyst demonstrates good photocatalytic activity, and photocatalysis performance is obviously better than monomers B i 2wO 6and BiVO 4, within the 30min reaction time, can 100% be reached to the degradation rate of methylene blue.Therefore, will there is the BiVO of good visible absorption performance and photocatalytic activity 4with Bi 2wO 6being compounded to form heterojunction structure can make photo-generate electron-hole effectively be separated at composite material surface, and improves visible absorption performance and the specific area of composite, enhances the visible light catalytic performance of composite.
Application examples 2:
Above-mentioned gained Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is applied in water body, kills the visible ray of harmful microorganism pseudomonas aeruginosa:
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 pseudomonas aeruginosa (P.aeruginosa, 8.5 × 10 8cfu/mL) Bi is evaluated 2wO 6/ BiVO 4the visible light catalytic bactericidal property of heterojunction composite photocatalyst:
First prepare bacterial suspension, pseudomonas aeruginosa storage liquid is 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 8.5 × 10 8the pseudomonas aeruginosa suspension of cfu/mL.
Getting 49.5mL sterilizing 0.01mol/LPBS (pH=7.4) buffer solution in photocatalysis experiment joins in 50mL reactor, then adds 500 μ L bacterial suspensions, makes bacterial concentration in reactant liquor be 8.0 × 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 B) in contrast.
From Fig. 4 (B), in blank assay, pseudomonas aeruginosa number has almost no change, and shows that the impact of visible ray photograph can be ignored; And under dark condition, number of bacteria, also without significant change, shows that the material itself that this experiment uses does not have bio-toxicity.And visible ray according under Bi 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst demonstrates good photocatalytic activity, and photo-catalyst performance is obviously better than monomers B i 2wO 6and BiVO 4, the pseudomonas aeruginosa survival of the 2.1log that only has an appointment through 30min illumination, sterilizing rate can reach 99.99%, if extend the reaction time to 60min can bacterial concentration in discovery system negligible.Therefore, Bi 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst has splendid photo-catalyst antifouling property, is attributable to BiVO 4with Bi 2wO 6be compounded to form heterojunction structure, accelerate the separation of photo-generate electron-hole, improve the photocatalytic activity of composite.Meanwhile, Bi 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst has larger specific area and good visible absorption performance, causes its visible light catalytic performance to improve, has good visible light catalytic bactericidal property.
Application examples 3:
Above-mentioned gained Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst repeated application, in water body, is killed the visible ray of harmful microorganism pseudomonas aeruginosa:
By Bi used in photo-catalyst in application examples 2 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst reclaims, and repeatedly washs respectively with ultra-pure water and absolute ethyl alcohol, carries out photo-catalyst reaction next time after drying, carry out 6 times continuously, keep other conditions constant (see Fig. 5) according to the step in application examples 2.
From Fig. 5 (A), Bi 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst does not obviously reduce for 6 times in successive reaction afterwards to the killing rate of bacterium, still remains on more than 99%, demonstrates good reusing.The Bi of 6 photo-catalyst experiments will be carried out continuously 2wO 6/ BiVO 4-1 heterojunction composite photocatalyst reclaims, and repeatedly washs respectively, carry out XRD test after drying with ultra-pure water and absolute ethyl alcohol, as shown in Fig. 5 (B), as can be seen from the figure after continuous 6 photo-catalysts reaction, and Bi 2wO 6/ BiVO 4the crystal structure of-1 heterojunction composite photocatalyst does not change, and shows good stability, has good practical value and potential application prospect in the field such as water body purification and marine anti-pollution.

Claims (10)

1. a Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst, is characterized in that: Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is by Bi 2wO 6and BiVO 4form the catalyst with three-dimensional layering nest like structure; Wherein, Bi 2wO 6with BiVO 4mol ratio be 1:0.05 ~ 10.
2. Bi according to claim 1 2wO 6/ BiVO 4heterojunction composite photocatalyst, is characterized in that: described Bi 2wO 6with BiVO 4mol ratio be 1:0.1 ~ 5.
3. a Bi according to claim 1 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: by Bi (NO 3) 35H 2o joins HNO 3in solution, magnetic agitation, to dissolving completely, obtains lysate A; Simultaneously by Na 2wO 42H 2o and NH 4vO 3join in NaOH solution, magnetic agitation, to dissolving completely, then adds polyvinylpyrrolidone (PVP), and magnetic agitation, to dissolving completely, obtains lysate B; Then under magnetic stirring above-mentioned lysate B is dropwise joined in above-mentioned lysate A, 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 heat treatment; Then reactor is cooled to room temperature, the Bi with three-dimensional layering nido structure can be obtained through suction filtration, washing and drying 2wO 6/ BiVO 4heterojunction composite photocatalyst; Wherein, Na 2wO 42H 2o and NH 4vO 3the ratio of amount of substance be 1:0.1 ~ 5, Bi (NO 3) 35H 2o and Na 2wO 42H 2the ratio of the amount of substance of O is 2:1, Bi (NO 3) 35H 2o and NH 4vO 3the ratio of amount of substance be consumption and the Bi (NO of 1:1, PVP 3) 35H 2o's is 0.01 ~ 0.5gPVP/1mmolBi (NO with magnitude relation 3) 35H 2o.
4. Bi according to claim 3 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: described HNO 3with Bi (NO 3) 35H 2the ratio of the amount of substance of O is 3 ~ 30:1; NaOH and Na 2wO 42H 2o and NH 4vO 3the ratio of amount of substance be 3 ~ 30:1.
5. Bi according to claim 3 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: described adjustment suspension pH value adopts concentration to be the NH of 0.1 ~ 5.0mol/L 3h 2o or NaOH.
6. Bi according to claim 3 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: in described electric heating constant-temperature blowing drying box, heat treatment temperature is 120 ~ 180 DEG C, and the reaction time is 12 ~ 36h.
7. Bi according to claim 3 2wO 6/ BiVO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: described baking temperature is 40 ~ 80 DEG C, and drying time is 2 ~ 10h.
8. a Bi according to claim 1 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, is characterized in that: described Bi 2wO 6/ BiVO 4heterojunction composite photocatalyst is as the bactericide in water body.
9. a Bi according to claim 1 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, is characterized in that: described Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst in degradation of dye.
10. a Bi according to claim 1 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst, is characterized in that: described Bi 2wO 6/ BiVO 4the application of heterojunction composite photocatalyst in water body purification.
CN201510789914.5A 2015-11-17 2015-11-17 Bi2WO6 / BiVO4 heterojunction composite photocatalyst, preparation method and application thereof Pending CN105457625A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106799223A (en) * 2016-12-29 2017-06-06 广州凯耀资产管理有限公司 A kind of synthetic method of Bi systems compound semiconductor photocatalytic material
CN114768792A (en) * 2022-05-21 2022-07-22 李广强 Purifying agent for sewage treatment and preparation method thereof
CN115138354A (en) * 2022-05-23 2022-10-04 陕西科技大学 Core-shell structure Cs0.32WO3/BiVO4 heterojunction and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103191725A (en) * 2013-04-26 2013-07-10 南京信息工程大学 BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof
CN104108753A (en) * 2013-04-22 2014-10-22 海南师范大学 Preparation for visible-light responsible BiVO4 catalyst
CN104971720A (en) * 2015-06-11 2015-10-14 西北师范大学 Bismuth tungstate nanocomposite, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104108753A (en) * 2013-04-22 2014-10-22 海南师范大学 Preparation for visible-light responsible BiVO4 catalyst
CN103191725A (en) * 2013-04-26 2013-07-10 南京信息工程大学 BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof
CN104971720A (en) * 2015-06-11 2015-10-14 西北师范大学 Bismuth tungstate nanocomposite, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
鞠鹏: "半导体纳米材料的合成及其毒理作用和光电催化降解污染物的研究", 《中国农业大学硕士学位论文》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106799223A (en) * 2016-12-29 2017-06-06 广州凯耀资产管理有限公司 A kind of synthetic method of Bi systems compound semiconductor photocatalytic material
CN114768792A (en) * 2022-05-21 2022-07-22 李广强 Purifying agent for sewage treatment and preparation method thereof
CN114768792B (en) * 2022-05-21 2023-10-10 济宁市盈润环保助剂有限公司 Purifying agent for sewage treatment and preparation method thereof
CN115138354A (en) * 2022-05-23 2022-10-04 陕西科技大学 Core-shell structure Cs0.32WO3/BiVO4 heterojunction and preparation method and application thereof
CN115138354B (en) * 2022-05-23 2024-03-08 深圳万知达科技有限公司 Core-shell structure Cs 0.32 WO 3 /BiVO 4 Heterojunction, preparation method and application thereof

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