CN105289674A - AgVO3/Ag3PO4 heterojunction composite photocatalyst and preparation method and application thereof - Google Patents

AgVO3/Ag3PO4 heterojunction composite photocatalyst and preparation method and application thereof Download PDF

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CN105289674A
CN105289674A CN201510789023.XA CN201510789023A CN105289674A CN 105289674 A CN105289674 A CN 105289674A CN 201510789023 A CN201510789023 A CN 201510789023A CN 105289674 A CN105289674 A CN 105289674A
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agvo
composite photocatalyst
heterojunction composite
preparation
heterojunction
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鞠鹏
张盾
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Institute of Oceanology of CAS
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Abstract

The invention belongs to the field of photocatalysis and specifically relates to an AgVO3/Ag3PO4 heterojunction composite photocatalyst and its preparation method and application. The AgVO3/Ag3PO4 heterojunction composite photocatalyst is composed of AgVO3 and Ag3PO4. Ag3PO4 nanoparticles grow in situ on the surface of an AgVO3 nanoribbon, wherein molar ratio of AgVO3 to Ag3PO4 is 1:0.01-1. The preparation method of the invention has a simple process, is easy to control and is low-cost. An AgVO3/Ag3PO4 heterojunction structure with visible light response is constructed, photon-generated carrier separation is accelerated, and recombination probability of photogenerated electron-hole pairs is minimized. The AgVO3/Ag3PO4 heterojunction composite photocatalyst has high-efficiency photocatalytic activity and stability in visible light, has highly-efficient killing and degradation effects on harmful microbes and dye pollutants in a water body and has good practical value and potential application prospect in fields of water body purification and the like.

Description

A kind of AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst and its preparation method and application
Technical field
The invention belongs to photocatalysis field, be specifically related to a kind of AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst and its preparation method and application.
Background technology
Photocatalysis technology is a kind of technology utilizing luminous energy to carry out Substance Transformation, from Japanese Scientists Fujishima in 1972 and Honda reported first TiO 2can after photocatalytic water produces hydrogen and oxygen under ultraviolet lighting, Photocatalitic Technique of Semiconductor because of its have 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, receive increasing concern [1], 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, greatly limit the utilization to solar energy [1].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.There is the silver vanadate (AgVO of one-dimentional structure 3, Ag 2v 4o 11, Ag 3vO 4, Ag 4v 2o 7) because of the narrower (E of band gap g<2.5eV), the characteristics such as visible absorption performance is good and environmentally friendly, receive the very big concern of researcher in photocatalysis field [2,3].Although this one-dimentional structure have specific area large, be easy to the advantages such as electron transmission, the photo-generated carrier rate of departure or relatively low in monomer silver vanadate material, have impact on photocatalytic activity [4-6].Therefore, in order to improve the photocatalysis performance of silver vanadate further, making full use of sunshine resource, heterojunction structure can be formed by semiconductors coupling method that is efficient, low cost, photo-generated carrier being effectively separated, realizing the raising of photocatalysis performance.Ag 3pO 4a kind of new and effective catalysis material, from leaf golden flower etc. [7]2010 years reported first Ag on NatureMaterials 3pO 4after efficient photocatalysis performance, Ag 3pO 4receive extensive concern, the strong oxidizing property in optical excitation hole in its distinctive indirect band gap, valence band, its electron transfer rate is higher than hole migration speed simultaneously, thus impels electron-hole to be separated, and makes 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.
Therefore, now need to build a kind of composite catalyst to improve the photocatalysis performance of silver vanadate.
[1]K.Nakata,A.Fujishima.TiO 2photocatalysis:Designandapplications[J].JournalofPhotochemistryandPhotobiologyC:PhotochemistryReviews,2012,13:169-189.
[2]J.Ren,W.Z.Wang,M.Shang,S.M.Sun,L.Zhang,J.Chang.Photocatalyticactivityofsilvervanadatewithone-dimensionalstructureunderfluorescentlight[J].JournalofHazardousMaterials,2010,183(1):950-953.
[3]L.C.Chen,G.T.Pan,T.C.K.Yang,T.W.Chung,C.M.Huang.InsituDRIFTandkineticstudiesofphotocatalyticdegradationonbenzenevaporwithvisible-light-drivensilvervanadates[J].JournalofHazardousMaterials,2010,178(1):644-651.
[4]Y.Sang,L.Kuai,C.Y.Chen,Z.Fang,B.Y.Geng.Fabricationofavisible-light-drivenplasmonicphotocatalystofAgVO 3AgBrAgnanobeltheterostructures[J].ACSAppliedMaterials&Interfaces,2014,6(7):5061-5068.
[5]J.Wang,H.Ruan,W.J.Li,D.Z.Li,Y.Hu,J.Chen,Y.Shao,Y.Zheng.HighlyefficientoxidationofgaseousbenzeneonnovelAg 3VO 4/TiO 2nanocompositephotocatalystsundervisibleandsimulatedsolarlightirradiation[J].TheJournalofPhysicalChemistryC,2012,116(26):13935-13943.
[6]Y.M.Yan,Y.Y.Liu,B.B.Huang,R.Zhang,Y.Dai,X.Y.Qin,X.Y.Zhang.EnhancedvisiblephotocatalyticactivityofaBiVO 4β-AgVO 3compositesynthesizedbyaninsitugrowthmethod[J].RSCAdvances,2014,4(39):20058-20061.
[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 AgVO is provided 3/ Ag 3pO 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 AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst, by AgVO 3and Ag 3pO 4composition; Ag 3pO 4nano particle in situ is grown on AgVO 3nanobelt surface; Wherein, AgVO 3with Ag 3pO 4mol ratio be 1:0.01 ~ 1.
A kind of AgVO 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst:
(1) AgVO 3the preparation of nanobelt: by the NH of equimolar amounts 4vO 3and AgNO 3be dissolved in respectively in ultra-pure water, obtain lysate respectively; Then by AgNO 3lysate dropwise joins NH 4vO 3obtain mixed liquor in lysate, regulate pH of mixed to 5 ~ 9, at room temperature continue lucifuge and stir formation suspension, then suspension is moved in autoclave, put into electric heating constant-temperature blowing drying box to heat-treat, be then cooled to room temperature, can AgVO be obtained after suction filtration, washing and drying 3nanobelt;
(2) AgVO 3/ Ag 3pO 4the preparation of heterojunction composite photocatalyst: by the AgVO obtained in step (1) 3nanobelt is scattered in ultra-pure water, obtains dispersion liquid; Then dropwise add the precursor solution of phosphorous acid group under magnetic stirring, obtain mixed liquor, regulate pH of mixed to 5 ~ 9, at room temperature continue lucifuge stir, and after can obtain AgVO after suction filtration, washing and drying 3/ Ag 3pO 4heterojunction composite photocatalyst.
PH of mixed is regulated to adopt concentration to be the NH of 0.1 ~ 5.0mol/L in described step (1) and step (2) 3h 2o or NaOH.
Lucifuge stirring 2 ~ 10h is at room temperature continued after described step (1) and step (2) middle adjustment mixed liquor pH value.
In described step (2), dispersion adopts ultrasonic disperse 10 ~ 60min, then magnetic agitation 10 ~ 60min.
In described step (2), the precursor of phosphorous acid group is Na 3pO 4or K 3pO 4, wherein, the presoma added and AgVO 3the ratio of amount of substance be 0.01 ~ 1:1.
In described step (1) and step (2), drying is dry under vacuum, and temperature is 50 ~ 80 DEG C, and drying time is 3 ~ 12h.
A kind of AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, described AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst is as the application of bactericide in water body.
A kind of AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, described AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst in degradation of dye.
A kind of AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, described AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst in water body purification.
AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst is applied in water body, the visible light catalytic of harmful microorganism Escherichia coli (E.coli) and staphylococcus aureus (S.aureus) 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 AgVO 3/ Ag 3pO 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 AgVO 3/ Ag 3pO 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 AgVO 3/ Ag 3pO 4the consumption of heterojunction composite photocatalyst is 1.0mg/mL.
Beneficial effect of the present invention is:
The present invention passes through AgVO 3with Ag 3pO 4compound, builds the composite with heterojunction structure, adds the separation of photo-generated carrier at composite material surface, and then improves the photocatalysis performance of composite, to AgVO 3and 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 Ag 3pO 4nano particle in situ is grown on AgVO 3the AgVO of nanobelt surface construction 3/ Ag 3pO 4heterojunction composite photocatalyst, has larger specific area and good visible absorption performance;
(3) AgVO for preparing of the present invention 3/ Ag 3pO 4heterojunction composite photocatalyst visible light catalysis activity compares AgVO 3and Ag 3pO 4be significantly increased, under 500W xenon lamp irradiates, 1.0mg/mLAgVO 3/ Ag 3pO 4heterojunction composite photocatalyst is 10 to concentration 6the microorganism 15min killing rate of cfu/mL can reach 99.99%, to concentration be 20mg/L methylene blue 25min in realize degradable;
(4) AgVO for preparing of the present invention 3/ Ag 3pO 4heterojunction composite photocatalyst has heterojunction structure, accelerate photo-generated carrier to be separated, reduce photo-generate electron-hole to recombination probability, 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) AgVO 3, (B) Ag 3pO 4, (C, D) AgVO 3/ Ag 3pO 4-0.3;
(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));
Sample photocatalytic degradation reaction Methylene Blue concentration changes with time curve (A) of Fig. 4 prepared by the present invention and (wherein in A figure, abscissa is Time (time) to the photo-catalyst rate (B) of Escherichia coli and staphylococcus aureus, unit is min (minute), and 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, ordinate is Antibacterialrate (sterilizing rate), and unit is %).
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 AgVO by hydrothermal synthesis method and in situ synthesis 3/ Ag 3pO 4heterojunction composite photocatalyst, it utilizes AgVO 3with Ag 3pO 4solubility product is different, makes Ag 3pO 4nano particle is at AgVO 3nanobelt surface in situ grows, 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 fields such as water body purifications good practical value and potential application prospect.This composite photo-catalyst preparation method has the features such as simple, cheap and reproducible simultaneously.
Embodiment 1:
AgVO 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst:
(1) AgVO is prepared by hydrothermal synthesis method 3nanobelt: by 1.0mmolNH 4vO 3be dissolved in 30mL ultra-pure water, be heated to 80 DEG C and constantly stir make it dissolve completely; Simultaneously by 1.0mmolAgNO 3be dissolved in 30mL ultra-pure water, stir and make it dissolve, obtain lysate respectively; Then under magnetic stirring by above-mentioned AgNO 3lysate dropwise joins above-mentioned NH 4vO 3in lysate, after being added dropwise to complete, use 2.0mol/LNH 3h 2o solution regulates the pH of mixed liquor to be 7, continues lucifuge afterwards and stirs 5h; Obtain suspension after stirring terminates, suspension is transferred to and is furnished with in teflon-lined autoclave, put into electric heating constant-temperature blowing drying box 180 DEG C of heat treatment 24h; After reaction terminates, reactor is cooled to room temperature, 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 AgVO 3nanobelt (see Fig. 1-3).
(2) AgVO is prepared by situ synthesis 3/ Ag 3pO 4heterojunction composite photocatalyst: take above-mentioned gained 1.0mmolAgVO 3nanobelt joins in 30mL ultra-pure water, and ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Simultaneously by 0.3mmolNa 3pO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 3pO 4lysate drips under magnetic stirring by joining above-mentioned AgVO 3in dispersion liquid, obtain mixed liquor, then use 2.0mol/LHNO 3solution regulates the pH of mixed liquor to be 7, at room temperature continues lucifuge afterwards and stirs 8h; 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 AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst, is designated as AgVO 3/ Ag 3pO 4-0.3 (see Fig. 1-3).
Comparative example 1:
Monomer A g 3pO 4preparation method:
Ag is prepared by coprecipitation 3pO 4monomer material.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, and use 2.0mol/LNH 3h 2the pH value of suspension is adjusted to 7 by O solution, continues at room temperature lucifuge and stirs 5h, stir after terminating, and 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.
As shown in Figure 1, a curve is AgVO prepared by embodiment 1 3xRD collection of illustrative plates, position and the standard card JCPDSNo.29-1154 of all diffraction maximums fit like a glove, and all belong to monoclinic system β-AgVO 3, and there is not any impurity phase, and diffraction maximum is relatively more sharp-pointed, peak is comparatively large by force, can determine that sample prepared by embodiment 1 is pure monoclinic phase β-AgVO 3, and there is good degree of crystallinity.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 diffraction maximum to occur, show that the sample prepared by comparative example 1 is pure Emission in Cubic Ag 3pO 4.C curve in figure is AgVO prepared by embodiment 1 3/ Ag 3pO 4the XRD collection of illustrative plates of-0.3 heterojunction composite photocatalyst, contains monoclinic phase AgVO in collection of illustrative plates 3with Emission in Cubic Ag 3pO 4all characteristic peaks, AgVO is described 3and Ag 3pO 4at the formation composite that is successfully combined with each other.In the XRD collection of illustrative plates of composite, there are not other impurity peaks, illustrate in composite just by AgVO 3and Ag 3pO 4two kinds of material compositions, other impurity phases do not exist.In addition, experimental result shows PO 4 3-with AgVO 3reaction do not carry out according to stoichiometric proportion, but arrive a kind of equilibrium state in the reaction, at AgVO 3nanobelt Surface Creation Ag 3pO 4after nano particle, composite structure tends towards stability, and prevents reaction to proceed.
From Fig. 2 (A), monomer A gVO 3for homogeneous banded structure, length is more than 10 μm, and width is about 200nm.Fig. 2 (B) is monomer A g 3pO 4fESEM photo, as seen from the figure, Ag 3pO 4for being spherical particle, degree of crystallinity is higher, and size is about 100nm, and particle dispersion is good, does not have obvious agglomeration between crystal grain.From Fig. 2 (C) and Fig. 2 (D), AgVO prepared by embodiment 1 3/ Ag 3pO 4-0.3 heterojunction composite photocatalyst is by AgVO 3nanobelt loaded Ag 3pO 4nano particle assembles, Ag 3pO 4nanoparticle size is 30 ~ 50nm about, and closely, be evenly distributed in AgVO 3nanobelt surface.In addition, AgVO 3/ Ag 3pO 4agVO in-0.3 composite 3the structure comparison of nanobelt is complete there is not breakage, and the nano particle of Surface Creation does not come off from nanobelt surface, shows PO 4 3-with AgVO 3reaction be more slowly and not very violent, the Ag of generation 3pO 4nano particle is arranged in AgVO closely 3nanobelt surface, defines combination more firmly composite construction.In addition, this in situ synthesis causes the Ag of generation 3pO 4nanoparticle size is less, can combine closely with nanobelt, and can not destroy nanobelt structure, effectively improves the stability of composite structure.
From Fig. 3 figure, AgVO 3, Ag 3pO 4and AgVO 3/ Ag 3pO 4-0.3 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 AgVO 3compound substantially increases the visible absorption performance of composite.
Embodiment 2:
AgVO 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst:
Difference from Example 1 is, adds 0.2mmolNa 3pO 412H 2o.Take above-mentioned gained 1.0mmolAgVO 3nanobelt joins in 30mL ultra-pure water, and ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Simultaneously by 0.2mmolNa 3pO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 3pO 4lysate drips under magnetic stirring by joining above-mentioned AgVO 3in dispersion liquid, obtain mixed liquor, then use 2.0mol/LHNO 3solution regulates the pH of mixed liquor to be 7, at room temperature continues lucifuge afterwards and stirs 8h; 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 AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst, is designated as AgVO 3/ Ag 3pO 4-0.2.
Embodiment 3:
AgVO 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst:
Difference from Example 1 is, adds 0.1mmolNa 3pO 412H 2o.Take above-mentioned gained 1.0mmolAgVO 3nanobelt joins in 30mL ultra-pure water, and ultrasonic disperse 30min, then magnetic agitation 30min, obtain dispersion liquid; Simultaneously by 0.1mmolNa 3pO 412H 2o joins in 30mL ultra-pure water, and magnetic agitation makes it dissolve completely, obtains lysate; Then by above-mentioned Na 3pO 4lysate drips under magnetic stirring by joining above-mentioned AgVO 3in dispersion liquid, obtain mixed liquor, then use 2.0mol/LHNO 3solution regulates the pH of mixed liquor to be 7, at room temperature continues lucifuge afterwards and stirs 8h; 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 AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst, is designated as AgVO 3/ Ag 3pO 4-0.1.
Application examples 1:
Above-mentioned gained AgVO 3/ Ag 3pO 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 AgVO 3/ Ag 3pO 4-0.3 heterojunction composite photocatalyst has certain absorption property because having larger specific area, but can ignore the impact of light-catalyzed reaction.Under visible ray shines, AgVO 3/ Ag 3pO 4-0.3 composite photo-catalyst demonstrates good photocatalytic activity, and photocatalysis performance is obviously better than monomer A gVO 3and Ag 3pO 4, within the 25min reaction time, can 100% be reached to the degradation rate of methylene blue.Therefore, will there is the Ag of good visible absorption performance and photocatalytic activity 3pO 4with AgVO 3being 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 AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst 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 (5.0 × 10 8and staphylococcus aureus (5.0 × 10 cfu/mL) 8cfu/mL) AgVO is evaluated 3/ Ag 3pO 4the visible light catalytic bactericidal property of heterojunction composite photocatalyst:
First prepare bacterial suspension, Escherichia coli 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 5.0 × 10 8the Escherichia coli suspension of cfu/mL.The set-up procedure of staphylococcus aureus suspension is the same, and obtaining concentration is 5.0 × 10 8the staphylococcus aureus suspension of cfu/mL.
Getting 49.5mL sterilizing 0.01mol/LPBS (pH=7.4) buffer solution in light-catalyzed reaction joins in 50mL reactor, then in 2 reactors, add 500 μ L Escherichia coli and staphylococcus aureus suspension respectively, make bacterial concentration in reactant liquor be 5.0 × 10 6cfu/mL, respectively 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, the number of two kinds of bacteriums 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 AgVO 3/ Ag 3pO 4containing Ag element in-0.3 heterojunction composite photocatalyst, 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 AgVO 3/ Ag 3pO 4-0.3 heterojunction composite photocatalyst demonstrates good photocatalytic activity, and photo-catalyst performance is obviously better than monomer A gVO 3and Ag 3pO 4, after 15min illumination, all can reach 99.99% to the photo-catalyst rate of two kinds of bacteriums.Therefore, AgVO 3/ Ag 3pO 4-0.3 heterojunction composite photocatalyst has splendid photo-catalyst performance, is attributable to Ag 3pO 4with AgVO 3be compounded to form heterojunction structure, accelerate the separation of photo-generate electron-hole, improve the photocatalytic activity of composite.Meanwhile, AgVO 3/ Ag 3pO 4-0.3 composite has larger specific area and good visible absorption performance, causes its visible light catalytic performance to improve, has good visible light catalytic bactericidal property and broad-spectrum sterilization performance, have good application prospect in photo-catalyst.

Claims (10)

1. an AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst, is characterized in that: AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst is by AgVO 3and Ag 3pO 4composition; Ag 3pO 4nano particle in situ is grown on AgVO 3nanobelt surface; Wherein, AgVO 3with Ag 3pO 4mol ratio be 1:0.01 ~ 1.
2. an AgVO according to claim 1 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that:
(1) AgVO 3the preparation of nanobelt: by the NH of equimolar amounts 4vO 3and AgNO 3be dissolved in respectively in ultra-pure water, obtain lysate respectively; Then by AgNO 3lysate dropwise joins NH 4vO 3obtain mixed liquor in lysate, regulate pH of mixed to 5 ~ 9, at room temperature continue lucifuge and stir formation suspension, then suspension is moved in autoclave, put into electric heating constant-temperature blowing drying box to heat-treat, be then cooled to room temperature, can AgVO be obtained after suction filtration, washing and drying 3nanobelt;
(2) AgVO 3/ Ag 3pO 4the preparation of heterojunction composite photocatalyst: by the AgVO obtained in step (1) 3nanobelt is scattered in ultra-pure water, obtains dispersion liquid; Then dropwise add the precursor solution of phosphorous acid group under magnetic stirring, obtain mixed liquor, regulate pH of mixed to 5 ~ 9, at room temperature continue lucifuge stir, and after can obtain AgVO after suction filtration, washing and drying 3/ Ag 3pO 4heterojunction composite photocatalyst.
3. AgVO according to claim 2 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: regulate pH of mixed to adopt concentration to be the NH of 0.1 ~ 5.0mol/L in described step (1) and step (2) 3h 2o or NaOH.
4. AgVO according to claim 2 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: at room temperature continue lucifuge stirring 2 ~ 10h after described step (1) and step (2) middle adjustment mixed liquor pH value.
5. AgVO according to claim 3 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: in described step (2), dispersion adopts ultrasonic disperse 10 ~ 60min, then magnetic agitation 10 ~ 60min.
6. AgVO according to claim 2 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: in described step (2), the precursor of phosphorous acid group is Na 3pO 4or K 3pO 4, wherein, the presoma added and AgVO 3the ratio of amount of substance be 0.01 ~ 1:1.
7. AgVO according to claim 2 3/ Ag 3pO 4the preparation method of heterojunction composite photocatalyst, is characterized in that: in described step (1) and step (2), drying is dry under vacuum, and temperature is 50 ~ 80 DEG C, and drying time is 3 ~ 12h.
8. an AgVO according to claim 1 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, is characterized in that: described AgVO 3/ Ag 3pO 4heterojunction composite photocatalyst is as the application of bactericide in water body.
9. an AgVO according to claim 1 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, is characterized in that: described AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst in degradation of dye.
10. an AgVO according to claim 1 3/ Ag 3pO 4the application of heterojunction composite photocatalyst, is characterized in that: described AgVO 3/ Ag 3pO 4the application of heterojunction composite photocatalyst in water body purification.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105772047A (en) * 2016-03-29 2016-07-20 徐州医学院 Visible-light-driven photocatalyst Ag3PO4/AVO and preparation method thereof
CN106093003A (en) * 2016-06-03 2016-11-09 通化师范学院 A kind of AgVO3the preparation method of nano belt/Ag Nanocomposites SERS substrate
CN106861728A (en) * 2016-12-28 2017-06-20 东北电力大学 A kind of preparation method of silver orthophosphate/silver bromide compound photocatalyst
CN106975504A (en) * 2017-03-30 2017-07-25 常州大学 A kind of silver metavanadate is combined the preparation method of silver carbonate photochemical catalyst
CN106984348A (en) * 2017-03-30 2017-07-28 常州大学 A kind of preparation method of the silver-colored photochemical catalyst of silver metavanadate compound phosphoric acid
CN106984311A (en) * 2017-03-30 2017-07-28 常州大学 A kind of silver metavanadate is combined the preparation method of the silver-colored photochemical catalyst of wolframic acid
CN107051558A (en) * 2017-03-30 2017-08-18 常州大学 A kind of preparation method of the silver-colored photochemical catalyst of the silver-colored compound phosphoric acid of wolframic acid
CN107737601A (en) * 2017-09-08 2018-02-27 石家庄学院 ɑ‑AgVO3/ graphene oxide/Ag3PO4Composite and its preparation method and application
CN107744823A (en) * 2017-09-26 2018-03-02 浙江工商大学 A kind of preparation method of polyoxometallic acid alkali composite visible light catalyst
CN108772080A (en) * 2018-06-29 2018-11-09 台州职业技术学院 A kind of preparation method of the one-dimensional nano line composite photo-catalyst with nano heterojunction
CN108927183A (en) * 2018-07-09 2018-12-04 福建师范大学 A kind of heterojunction photocatalyst, preparation method and its usage
CN109420497A (en) * 2017-08-21 2019-03-05 中国科学院海洋研究所 A kind of InVO4-AgVO3 hetero-junctions catalyst and its preparation method and application
CN109107575B (en) * 2018-10-31 2021-07-02 安徽师范大学 Zinc tungstate/silver vanadate composite nanomaterial, preparation method and photocatalytic application thereof
CN115490264A (en) * 2022-09-15 2022-12-20 山东黄海科技创新研究院 Preparation method and bacteriostatic application of silver vanadate mimic enzyme

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716758A (en) * 2012-06-25 2012-10-10 武汉理工大学 Composite visible-light-driven photocatalyst Ag3PO4 and Zn3(PO4)2 and preparation method thereof
CN102824921A (en) * 2012-08-28 2012-12-19 湖南科技大学 Preparation method of Ag2S/Ag3PO4 composite photocatalyst
CN104324740A (en) * 2014-10-11 2015-02-04 武汉理工大学 Flower-shaped MoS2 loaded Ag3PO4 nanosphere composite visible light catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716758A (en) * 2012-06-25 2012-10-10 武汉理工大学 Composite visible-light-driven photocatalyst Ag3PO4 and Zn3(PO4)2 and preparation method thereof
CN102824921A (en) * 2012-08-28 2012-12-19 湖南科技大学 Preparation method of Ag2S/Ag3PO4 composite photocatalyst
CN104324740A (en) * 2014-10-11 2015-02-04 武汉理工大学 Flower-shaped MoS2 loaded Ag3PO4 nanosphere composite visible light catalyst and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUIDAN LU ET AL.: ""In-situ anion-exchange synthesis AgCl/AgVO3 hybrid nanoribbons with highly photocatalytic activity"", 《MATERIALS LETTERS》 *
XUE LIN ET AL.: ""Ag3PO4 quantum dots sensitized AgVO3 nanowires:A novel Ag3PO4/AgVO3 nanojunction with enhanced visible-light photocatalytic activity"", 《CATALYSIS COMMUNICATIONS》 *

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