CN109778223A - A kind of ZnO modification WO3/BiVO4The preparation method of hetero-junctions and its application in photoelectrocatalysis - Google Patents
A kind of ZnO modification WO3/BiVO4The preparation method of hetero-junctions and its application in photoelectrocatalysis Download PDFInfo
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Abstract
The present invention relates to a kind of ZnO to modify WO3/BiVO4The preparation method of hetero-junctions belongs to technical field of material.It include: by WCl6WO is made with PVP3Seed layer；Sodium tungstate is dissolved in water, hydrochloric acid, ammonium oxalate is successively added, obtains clear solution；Clear solution addition there is into WO3Seed layer reaction, obtains WO3Array presoma, high annealing obtain WO3Electrode；Will be bis- (acetylacetone,2,4-pentanedione) vanadium oxide and five water bismuth nitrates be dissolved in glacial acetic acid, ethyl cellulose is added, obtains BiVO4Precursor solution；By BiVO4Precursor solution drop coating is to WO3Electrode surface, drying, anneal to obtain WO3/BiVO4Complex light anode；By WO3/BiVO4Complex light anode is placed in atomic layer deposition system, and using diethyl zinc and water, ZnO is successively grown after deposited circulation, obtains the ZnO modification WO with preferable high efficiency and stability in photoelectrocatalysis3/BiVO4Hetero-junctions.
Description
Technical field
The present invention relates to a kind of ZnO to modify WO3/BiVO4The preparation method of hetero-junctions and ZnO obtained modify WO3/BiVO4
Application of the hetero-junctions in photoelectrocatalysis belongs to technical field of material.
Background technique
The energy is the basis of human survival and development, with the rapid development of economy, fossil energy consumption amount continues to increase,
The mankind are faced with the energy shortage got worse and environmental disruption problem.Based on this, develop clean energy resource for ensureing the energy
Safety promotes environmental protection, reduces greenhouse gas emission, realizing that national economy sustainable development is of great significance.Hydrogen Energy because
It is cleaned, renewable, resource is extensive, and having very high energy density is considered as ideal energy carrier.And semiconductor
Material can decompose water energy by optical electro-chemistry (PEC) and convert solar energy into chemical energy, cause extensive concern.
WO3And BiVO4At low cost because its physics and chemical stability are good, band structure is suitable for and is acknowledged as having attraction
The photo cathode material of power and prospect.However, WO3With weaker visible light-responded (< 460nm), to the absorption system of photon
Number is low.BiVO4The service life of middle photo-generated carrier is short, is easy compound, these all limit them in the application in photoelectrocatalysis field.
Studies have shown that passing through building BiVO4/WO3II type hetero-junctions can effectively improve carrier separation efficiency.In addition, photoelectrocatalysis
The Carrier recombination of photoanode surface is the important restriction factor for restricting the catalysis reaction of its surface water oxygen.Pass through the modification of passivation layer
Surface recombination center can be greatly reduced, promote charge transport capability, so that improving photoelectrocatalysis decomposes water efficiency.Therefore, it visits
Rope one kind effectively prepares photo cathode, pushes photo-electrocatalytic technology in the application in solar energy conversion field strong.
Summary of the invention
The purpose of the present invention is being directed to the above-mentioned problems in the prior art, a kind of ZnO modification WO is provided3/BiVO4It is different
The preparation method of matter knot, ZnO obtained modify WO3/BiVO4Hetero-junctions has preferable high efficiency and stabilization in photoelectrocatalysis
Property.
Object of the invention can be realized by the following technical scheme: a kind of ZnO modification WO3/BiVO4The preparation of hetero-junctions
Method, the preparation method include the following steps:
1) WO is prepared3Seed layer: by tungsten hexachloride (WCl6) and polyvinylpyrrolidone (PVP) be dissolved in dimethylformamide
(DMF) in, the conducting surface for being coated to FTO electro-conductive glass is stirred at room temperature, dry after annealing forms WO3Seed layer；
2) WO is prepared3Array: by sodium tungstate (Na2WO4) soluble in water, hydrochloric acid (HCl) is added and adds after mixing evenly
Ammonium oxalate ((NH4)2C2O4), stirring is to obtaining clear solution；Clear solution addition there is into WO3In the reaction kettle of the FTO of seed layer
It is reacted, obtains WO3Array presoma obtains WO in sintering furnace high annealing3Electrode；
3) BiVO is prepared4Precursor solution: will be bis- (acetylacetone,2,4-pentanedione) vanadium oxide (VO (acac)2) He Wushui bismuth nitrate (Bi
(NO)3·5H2O) it is dissolved in glacial acetic acid (CH3COOH), ethyl cellulose is added, is stirred into BiVO4Precursor solution；
4) WO is prepared3/BiVO4Complex light anode: by BiVO4Precursor solution drop coating is to WO3Electrode surface, dry, annealing
Obtain WO3/BiVO4Complex light anode；
5) preparation ZnO modifies WO3/BiVO4Hetero-junctions: by WO3/BiVO4Complex light anode is placed in atomic layer deposition system
It is interior, utilize diethyl zinc (Zn (C2H5)2) it with water is raw material, ZnO is successively grown after deposited circulation, obtains ZnO modification WO3/BiVO4
Hetero-junctions.
ZnO in the present invention modifies WO3/BiVO4Hetero-junctions and WO in patent before3/BiVO4/ FeOOH ternary system is multiple
Condensation material is entirely different, WO3/BiVO4The structure of/FeOOH ternary system composite material is layered structure from bottom to top, and this
ZnO modifies WO in invention3/BiVO4Hetero-junctions is structure from inside to outside.
The raw material that the present invention uses is WCl6、PVP、DMF、Bi(NO3)3·5H2O、VO(acac)2It is fine with glacial acetic acid, ethyl
Element, diethyl zinc, water are tieed up, wherein PVP, glacial acetic acid, ethyl cellulose decompose complete volatilization during calcination processing；WCl6
The source W is provided and synthesizes WO3, Bi (NO3)3·5H2O and VO (acac)2The source Bi and the source V are provided respectively for BiVO4Synthesis, diethyl zinc mention
For the source Zn, ZnO is synthesized.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, tungsten hexachloride and polyvinyl pyrrole in step 1)
The mass ratio of alkanone is 20:1-30:1.Tungsten hexachloride provide production tungsten oxide tungsten source, and polyethylene pyrrole network alkanone be then make it is molten
The mass ratio of the slightly some viscosity of liquid, tungsten hexachloride and polyvinylpyrrolidone is controlled can be such that spin coating liquid obtains in 20:1-30:1
With more uniform spin coating.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, sodium tungstate (Na in step 2)2WO4) and oxalic acid
Ammonium ((NH4)2C2O4) mass ratio be 1:1-3:1.Sodium tungstate provides the tungsten source in hydro-thermal reaction, and ammonium oxalate is as ligand, wolframic acid
Sodium (Na2WO4) and ammonium oxalate ((NH4)2C2O4) mass ratio is excessive or the too small pattern that can all influence tungsten oxide.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, the reaction temperature in step 2) is 100-130
DEG C, reaction time 10-15h.The growth too high or too low for temperature that can all influence tungsten oxide of reaction.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, (acetylacetone,2,4-pentanedione) vanadium oxide (VO bis- in step 3)
(acac)2) He Wushui bismuth nitrate (Bi (NO)3·5H2O molal weight ratio) is 0.8:1-1.2:1.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, the temperature annealed in step 4) is 450-500
DEG C, annealing time 0.5-2h.
WO is modified in above-mentioned ZnO3/BiVO4In the preparation method of hetero-junctions, the number of deposition cycle is 30- in step 5)
100 times.Number of deposition cycles is very few, and the influence to performance is small, and effect is not significant, if but the number of deposition cycle is excessive,
Meeting reduces performance so that the compound aggravation of photo-generated carrier.
The present invention also provides above-mentioned ZnO to modify WO3/BiVO4Application of the hetero-junctions in photoelectrocatalysis, modifies WO for ZnO3/
BiVO4Hetero-junctions makees work anode, and Ag/AgCl makees reference electrode, and platinized platinum is made to electrode, under the illumination of xenon lamp, in Na2SO4's
In solution, its density of photocurrent and impedance are tested using electrochemical workstation.
It is xenon lamp simulated solar irradiation that PhotoelectrocatalytiPerformance Performance, which detects used light source, and other types of light source also can be used.
Compared with prior art, the present invention has the advantage that
1, the present invention is by technique for atomic layer deposition, by ZnO deposition in WO3/BiVO4Surface, deposition thickness controllable precise,
Convenient for the separation and passivated surface state of surface carrier in PhotoelectrocatalytiPerformance Performance test, be conducive to the raising of PhotoelectrocatalytiPerformance Performance.
2, ZnO of the present invention modifies WO3/BiVO4The preparation method simple process of hetero-junctions is controllable, has repeatability well.
3, ZnO of the present invention modifies WO3/BiVO4Hetero-junctions utilizes WO3/BiVO4Efficient hetero-junctions is constructed, ZnO is as passivation
Layer, various aspects improve PhotoelectrocatalytiPerformance Performance, are applied in photoelectrocatalysis, have high efficiency and stability.
Detailed description of the invention
Fig. 1 is the resulting WO of the embodiment of the present invention 13Seed layer scanning electron microscope (SEM) photograph (SEM)；
Fig. 2 is the resulting WO of the embodiment of the present invention 13Nanometer plate electrode scanning electron microscope (SEM) photograph (SEM)；
Fig. 3 is the resulting WO of the embodiment of the present invention 13Nano-chip arrays electrode sections scanning electron microscope (SEM) photograph (SEM)；
Fig. 4 is the resulting WO of the embodiment of the present invention 13/BiVO4The scanning electron microscope (SEM) photograph (SEM) of complex light anode；
Fig. 5 is the resulting WO of the embodiment of the present invention 13/BiVO4Electrode WO3/BiVO4The cross-sectional scans electricity of complex light anode
Mirror figure (SEM)；
Fig. 6 is that the resulting 50C ZnO of the embodiment of the present invention 1 modifies WO3/BiVO4The scanning electron microscope (SEM) photograph (SEM) of hetero-junctions；
Fig. 7 is that the resulting 50C ZnO of the embodiment of the present invention 1 modifies WO3/BiVO4The cross-sectional scans electron microscope of hetero-junctions
(SEM)；
Fig. 8 is that the resulting 50C ZnO of the embodiment of the present invention 1 modifies WO3/BiVO4The X-ray diffraction of heterojunction photovoltaic anode
Map (XRD)；
Fig. 9 is that the resulting 50C ZnO of the embodiment of the present invention 1 modifies WO3/BiVO4The transmission electron microscope picture of heterojunction photovoltaic anode
(TEM)；
Figure 10 is that the resulting 30C ZnO of the embodiment of the present invention 2 modifies WO3/BiVO4Heterojunction photovoltaic catalyticing anode material
Scanning electron microscope (SEM) photograph (SEM)；
Figure 11 is that the resulting 100C ZnO of the embodiment of the present invention 2 modifies WO3/BiVO4Heterojunction photovoltaic catalyticing anode material
Scanning electron microscope (SEM) photograph (SEM)；
Figure 12 is the resulting WO of comparative example 1 of the present invention3The X ray diffracting spectrum of nano-chip arrays photoelectrocatalysis anode material
(XRD)；
Figure 13 is the resulting BiVO of comparative example 2 of the present invention4Scanning electron microscope (SEM) photograph (SEM)；
Figure 14 is the resulting BiVO of comparative example 2 of the present invention4X-ray diffraction spectrogram (XRD)；
Figure 15 is the resulting WO of comparative example 3 of the present invention3/BiVO4X-ray diffraction spectrogram (XRD)；
Figure 16 is that 30C ZnO of the present invention modifies WO3/BiVO4Hetero-junctions, 50C ZnO modify WO3/BiVO4Hetero-junctions, 100C
ZnO modifies WO3/BiVO4Density of photocurrent comparison diagram of the heterojunction photovoltaic anode under different biass；
Figure 17 is WO of the present invention3、BiVO4、WO3/BiVO4WO is modified with 50C ZnO3/BiVO4Heterojunction photovoltaic anode is not
With the density of photocurrent comparison diagram under bias；
Figure 18 is that 50C ZnO of the present invention modifies WO3/BiVO4The stability test figure of heterojunction photovoltaic anode.
Figure 19 is WO of the present invention3、BiVO4、WO3/BiVO4WO is modified with 50C ZnO3/BiVO4The resistance of heterojunction photovoltaic anode
Anti- comparison diagram.
Specific embodiment
The following is specific embodiments of the present invention, and is described with reference to the drawings and further retouches to technical solution of the present invention work
It states, however, the present invention is not limited to these examples.
Embodiment 1
0.1g PVP and 2g WCl are weighed respectively6It is dissolved in 10mL DMF, after stirring 1h at room temperature, obtains spin coating liquid.
It takes 20 μ L to be spun on FTO glass conducting surface under 4000 revs/min of revolving speed, after 80 DEG C of dry 3h, is placed in 500 in Muffle furnace
DEG C annealing 1h, formed WO3Seed layer.Fig. 1 is the WO obtained3Scanning electron microscope (SEM) picture of seed layer, it can be seen that be by pole
Tiny WO3Particle composition, and fine and close be covered on FTO conducting surface.
By 0.25g Na2WO4It is dissolved in 30mL water, the 3M HCl of 6mL is added, after mixing evenly, add 0.2g (NH4)2C2O4, add water to 70mL and stir to formation clear solution.Above-mentioned prepared solution 28mL is taken, is added and places WO3Seed layer
FTO reaction kettle in, react 12h at 120 DEG C.Reaction terminate it is cooling after, with deionized water and ethyl alcohol cleaning electrode surface,
It is subsequently placed at 500 DEG C of Muffle furnace the 30min that anneals, obtains WO3Nano-chip arrays electrode.Fig. 2 is the WO obtained3Nano-chip arrays
Scanning electron microscope (SEM) photograph (SEM), it can be seen that be by~800nm long ,~100nm thick the nanometer sheet perpendicular to FTO electro-conductive glass forms；
Fig. 3 is WO3Nano-chip arrays electrode sections scanning electron microscope (SEM) photograph (SEM).
By (VO (acac)2) and Bi (NO)3·5H21:1 respectively takes 50 μM to be dissolved in 10mL glacial acetic acid to O in molar ratio, then
0.1g ethyl cellulose is added for increasing viscosity, is then stirred into BiVO at room temperature4Precursor solution.
It takes with the BiVO got ready410 μ L drop coating of precursor solution is to 1cm2Tungsten oxide electrode surface, at 80 DEG C after dry 3h
The 1h that anneals at 450 DEG C obtains WO3/BiVO4Complex light anode；Fig. 4 is resulting WO3/BiVO4The typical scan Electronic Speculum of electrode
Scheme (SEM), shows BiVO4Layer is to be uniformly covered on WO3Nanometer sheet surface.Fig. 5 is resulting WO3/BiVO4Electrode it is transversal
Surface scan Electronic Speculum (SEM) figure, it can be seen that its thickness does not obviously increase, and illustrates BiVO4It is relatively thin and is uniformly covered on WO3
Surface.
By WO3/BiVO4Complex light anode is placed in atomic layer deposition system, utilizes diethyl zinc (Zn (C2H5)2) with water be
Raw material, it is deposited circulation 50 times after ZnO successively grow, obtain ZnO modification WO3/BiVO4Hetero-junctions.Fig. 6 is that 50C ZnO modifies WO3/
BiVO4Scanning electron microscope (SEM) figure of hetero-junctions shows after depositing ZnO that electrode surface does not have significant change, illustrates this layer of pole ZnO
It is thin.Fig. 7 is that resulting 50C ZnO modifies WO3/BiVO4Cross-sectional scans Electronic Speculum (SEM) figure of hetero-junctions, it can be seen that with WO3/
BiVO4There is no significant difference.Fig. 8 is that obtained 50C ZnO modifies WO3/BiVO4The X ray diffracting spectrum of hetero-junctions, can be with
Find out the significantly corresponding WO of the photoelectrocatalysis anode3、BiVO4Peak position, and ZnO can't detect apparent feature because very thin
Peak.Fig. 9 is resulting WO3/BiVO4The transmission electron microscope picture of/50C photo cathode, as can be seen from the figure zinc oxide film crystallization is good
Good, thickness is about 15nm.
Embodiment 2
With embodiment 1 only distinguish ZnO layer deposition cycle be 30 times, other techniques are same as Example 1, herein no longer
It repeats.As shown in Figure 10, surface topography is not obvious for the cross-sectional scans Electronic Speculum (SEM) of prepared photoelectrocatalysis anode material
Variation, illustrates that ZnO layer is very thin.
Embodiment 3
With embodiment 1 only distinguish ZnO layer deposition cycle be 100 times, other techniques are same as Example 1, herein not
It repeats again.As shown in figure 11, surface topography is not bright for the cross-sectional scans Electronic Speculum (SEM) of prepared photoelectrocatalysis anode material
Aobvious variation.
Embodiment 4
With embodiment 1 only distinguish ZnO layer deposition cycle be 40 times, other techniques are same as Example 1, herein no longer
It repeats.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 5
With embodiment 1 only distinguish ZnO layer deposition cycle be 60 times, other techniques are same as Example 1, herein no longer
It repeats.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 6
With embodiment 1 only distinguish ZnO layer deposition cycle be 80 times, other techniques are same as Example 1, herein no longer
It repeats.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 7
With embodiment 1 only distinguish ZnO layer deposition cycle be 20 times, other techniques are same as Example 1, herein no longer
It repeats.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 8
With embodiment 1 only distinguish ZnO layer deposition cycle be 120 times, other techniques are same as Example 1, herein not
It repeats again.There is thin film even compact on surface cross-sectional scans Electronic Speculum (SEM) of prepared photoelectrocatalysis anode material
It is covered on WO3/BiVO4Surface.
Embodiment 9
It is only distinguished with embodiment 1 and 2.5g tungsten hexachloride is being added, other techniques are same as Example 1, and details are not described herein again.
Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 10
It is only distinguished with embodiment 1 and 3g tungsten hexachloride is being added, other techniques are same as Example 1, and details are not described herein again.Institute
Cross-sectional scans Electronic Speculum (SEM) surface topography of the photoelectrocatalysis anode material of preparation does not have significant change.
Embodiment 11
It is only distinguished with embodiment 1 and 2.5g tungsten hexachloride is being added, other techniques are same as Example 1, and details are not described herein again.
Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 12
It is only distinguished with embodiment 1 and 0.2g sodium tungstate is being added, other techniques are same as Example 1, and details are not described herein again.Institute
Cross-sectional scans Electronic Speculum (SEM) surface topography of the photoelectrocatalysis anode material of preparation does not have significant change.
Embodiment 13
It is only distinguished with embodiment 1 and 0.6g sodium tungstate is being added, other techniques are same as Example 1, and details are not described herein again.Institute
Cross-sectional scans Electronic Speculum (SEM) surface topography of the photoelectrocatalysis anode material of preparation does not have significant change.
Embodiment 14
It only distinguishes with embodiment 1 at 100 DEG C of reaction temperature, reaction time 15h, other techniques are same as Example 1, herein
It repeats no more.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 15
It only distinguishes with embodiment 1 at 30 DEG C of reaction temperature, reaction time 10h, other techniques are same as Example 1, herein
It repeats no more.Cross-sectional scans Electronic Speculum (SEM) surface topography of prepared photoelectrocatalysis anode material does not have significant change.
Embodiment 16
It only distinguishes with embodiment 1 in (VO (acac)2) and Bi (NO)3·5H2The molar ratio of O be 0.8:1, other techniques with
Embodiment 1 is identical, and details are not described herein again.The surface cross-sectional scans Electronic Speculum (SEM) shape of prepared photoelectrocatalysis anode material
Looks do not have significant change.
Embodiment 17
It only distinguishes with embodiment 1 in (VO (acac)2) and Bi (NO)3·5H2The molar ratio of O be 1.2:1, other techniques with
Embodiment 1 is identical, and details are not described herein again.The surface cross-sectional scans Electronic Speculum (SEM) shape of prepared photoelectrocatalysis anode material
Looks do not have significant change.
Comparative example 1
WO is only being prepared with the difference of embodiment 13Nano-chip arrays electrode, other techniques are same as Example 1, herein no longer
It repeats.The X ray diffracting spectrum (XRD) of prepared photoelectrocatalysis anode material as shown in figure 12, shows prepared material
For WO3。
Comparative example 2
The difference from embodiment 1 is that only preparing BiVO on FTO electro-conductive glass4Layer, other techniques and 1 phase of embodiment
Together, details are not described herein again.Figure 13 is BiVO4Scanning electron microscope (SEM) photograph (SEM) is one layer of un-densified film of uniform little particle.Figure 14
For the X-ray spectrogram (XRD) of the electrode material, show that prepared material is BiVO4。
Comparative example 3
The difference from embodiment 1 is that only preparing WO3/BiVO4Layer, other techniques are same as Example 1, no longer superfluous herein
It states.Figure 15 is the X-ray spectrogram (XRD) of the electrode material, shows that prepared material is WO3、BiVO4。
Application Example 1-3
WO is modified with ZnO obtained in embodiment 1-3 respectively3/BiVO4Hetero-junctions makees work anode, and Ag/AgCl makees reference
Electrode, platinized platinum are made to electrode, 0.5M L-1Na2SO4As electrolyte, selection has the electrolytic cell of silica glass window.With 300W
Xenon lamp is equipped with the optical filter of AM 1.5G as analog light source, through electrochemical workstation test sample under different biass
Density of photocurrent.
Compare Application Example 1-3
Respectively with WO obtained in comparative example 1-33、BiVO4、WO3/BiVO4For light anode, other techniques and tested
Journey is identical as Application Example 1, is not repeated herein.
Figure 16 is that 30C ZnO of the present invention modifies WO3/BiVO4Hetero-junctions, 50C ZnO modify WO3/BiVO4Hetero-junctions, 100C
ZnO modifies WO3/BiVO4Density of photocurrent comparison diagram of the heterojunction photovoltaic anode under different biass, illustrates prepared by the present invention
50C ZnO modifies WO3/BiVO4Hetero-junctions has more excellent PhotoelectrocatalytiPerformance Performance as photo cathode, that is, deposits 50 and follow
The ZnO of ring has preferable performance.
Figure 17 is WO of the present invention3、BiVO4、WO3/BiVO4WO is modified with 50C ZnO3/BiVO4Heterojunction photovoltaic anode is not
With the density of photocurrent comparison diagram under bias, illustrate 50C ZnO modification WO prepared by the present invention3/BiVO4Hetero-junctions is as photoelectricity
Anode ratio WO3、BiVO4、WO3/BiVO4Photo cathode material has more excellent PhotoelectrocatalytiPerformance Performance, and ZnO surface modification can
To improve PhotoelectrocatalytiPerformance Performance.
Figure 18 is that 50C ZnO of the present invention modifies WO3/BiVO4Hetero-junctions makees the stability test of photo cathode, You Tuke with
Find out the 50C ZnO modification WO of preparation3/BiVO46h performance still keeps stable to heterojunction photovoltaic anode material under light illumination, does not have
There is obvious decaying.
Figure 19 is WO of the present invention3、BiVO4、WO3/BiVO4Modification WO is modified with 50C ZnO3/BiVO4Heterojunction photovoltaic anode
Impedance contrast figure, illustrate 50C ZnO prepared by the present invention modification WO3/BiVO4Hetero-junctions, which makees photoelectrocatalysis anode material, to be had
More excellent charge-conduction performance has reconfirmed 50C ZnO modification WO prepared by the present invention3/BiVO4Hetero-junctions makees photoelectricity
Catalyticing anode material has more excellent PhotoelectrocatalytiPerformance Performance.
This place embodiment is not exhaustive claimed midpoint of technical range and in embodiment technology
In scheme to single or multiple technical characteristics it is same replacement be formed by new technical solution, equally all the present invention claims
In the range of protection, and between the parameter that is related to of the present invention program if not otherwise specified, then there is no can not between each other
The unique combinations of replacement.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can do various modifications or supplement or is substituted in a similar manner to described specific embodiment, but simultaneously
Spirit or beyond the scope defined by the appended claims of the invention is not deviated by.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (8)
1. a kind of ZnO modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that the preparation method includes following step
It is rapid:
1) WO is prepared3Seed layer: by tungsten hexachloride (WCl6) and polyvinylpyrrolidone (PVP) be dissolved in dimethylformamide (DMF)
In, the conducting surface for being coated to FTO electro-conductive glass is stirred at room temperature, dry after annealing forms WO3Seed layer；
2) WO is prepared3Array: by sodium tungstate (Na2WO4) soluble in water, hydrochloric acid (HCl) is added and adds oxalic acid after mixing evenly
Ammonium ((NH4)2C2O4), stirring is to obtaining clear solution；Clear solution addition there is into WO3It is carried out in the reaction kettle of the FTO of seed layer
Reaction, obtains WO3Array presoma obtains WO in sintering furnace high annealing3Electrode；
3) BiVO is prepared4Precursor solution: will be bis- (acetylacetone,2,4-pentanedione) vanadium oxide (VO (acac)2) He Wushui bismuth nitrate (Bi
(NO)3·5H2O) it is dissolved in glacial acetic acid (CH3COOH), ethyl cellulose is added, is stirred into BiVO4Precursor solution；
4) WO is prepared3/BiVO4Complex light anode: by BiVO4Precursor solution drop coating is to WO3Electrode surface, drying are annealed
WO3/BiVO4Complex light anode；
5) preparation ZnO modifies WO3/BiVO4Hetero-junctions: by WO3/BiVO4Complex light anode is placed in atomic layer deposition system, is utilized
Diethyl zinc (Zn (C2H5)2) it with water is raw material, ZnO is successively grown after deposited circulation, obtains ZnO modification WO3/BiVO4Hetero-junctions.
2. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 1)
The mass ratio of tungsten hexachloride and polyvinylpyrrolidone is 20:1-30:1.
3. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 2)
Sodium tungstate (Na2WO4) and ammonium oxalate ((NH4)2C2O4) mass ratio be 1:1-3:1.
4. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 2)
Reaction temperature be 100-130 DEG C, reaction time 10-15h.
5. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 3)
Bis- (acetylacetone,2,4-pentanedione) vanadium oxide (VO (acac)2) He Wushui bismuth nitrate (Bi (NO)3·5H2O molar ratio) is 0.8:1-1.2:1.
6. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 4)
The temperature of annealing is 450-500 DEG C, annealing time 0.5-2h.
7. ZnO according to claim 1 modifies WO3/BiVO4The preparation method of hetero-junctions, which is characterized in that in step 5)
The number of deposition cycle is 30-100 times.
8.ZnO modifies WO3/BiVO4Application of the hetero-junctions in photoelectrocatalysis, which is characterized in that ZnO is modified into WO3/BiVO4It is different
Matter knot makees work anode, and Ag/AgCl makees reference electrode, and platinized platinum is made to electrode, under the illumination of xenon lamp, in Na2SO4Solution in,
Its density of photocurrent and impedance are tested using electrochemical workstation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373680A (en) * | 2019-08-20 | 2019-10-25 | 河南师范大学 | A kind of preparation method for the ZnO/BiVO4 hetero-junctions light anode composite material decomposing water for optical electro-chemistry |
| CN114016039A (en) * | 2021-09-25 | 2022-02-08 | 西北师范大学 | Semiconductor composite light anode, preparation method and application |
| CN114180630A (en) * | 2021-12-27 | 2022-03-15 | 南京理工大学 | Multilayer nano plate-shaped WO3 and preparation method and application thereof |
| CN114236249A (en) * | 2021-12-16 | 2022-03-25 | 安徽大学 | Functional device with electric field induction and light field sensing functions and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012031357A1 (en) * | 2010-09-10 | 2012-03-15 | Ozin Geoffrey A | Photoactive material comprising nanoparticles of at least two photoactive constiuents |
| CN107190362A (en) * | 2017-07-17 | 2017-09-22 | 宁波工程学院 | A kind of high-purity ZnO/BiVO4The preparation method of heterogeneous micro belt |
| CN107316748A (en) * | 2017-07-17 | 2017-11-03 | 宁波工程学院 | High-purity ZnO/BiVO4Application of the heterogeneous nucleocapsid micro belt in photoelectrocatalysis |
-
2018
- 2018-11-26 CN CN201811419967.8A patent/CN109778223B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012031357A1 (en) * | 2010-09-10 | 2012-03-15 | Ozin Geoffrey A | Photoactive material comprising nanoparticles of at least two photoactive constiuents |
| CN107190362A (en) * | 2017-07-17 | 2017-09-22 | 宁波工程学院 | A kind of high-purity ZnO/BiVO4The preparation method of heterogeneous micro belt |
| CN107316748A (en) * | 2017-07-17 | 2017-11-03 | 宁波工程学院 | High-purity ZnO/BiVO4Application of the heterogeneous nucleocapsid micro belt in photoelectrocatalysis |
Cited By (10)
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|---|---|---|---|---|
| CN110373680A (en) * | 2019-08-20 | 2019-10-25 | 河南师范大学 | A kind of preparation method for the ZnO/BiVO4 hetero-junctions light anode composite material decomposing water for optical electro-chemistry |
| CN114016039A (en) * | 2021-09-25 | 2022-02-08 | 西北师范大学 | Semiconductor composite light anode, preparation method and application |
| CN114236249A (en) * | 2021-12-16 | 2022-03-25 | 安徽大学 | Functional device with electric field induction and light field sensing functions and application |
| CN114180630A (en) * | 2021-12-27 | 2022-03-15 | 南京理工大学 | Multilayer nano plate-shaped WO3 and preparation method and application thereof |
| CN114703500A (en) * | 2022-04-18 | 2022-07-05 | 台州学院 | Tungsten trioxide-bismuth vanadate-organic acid composite photoelectrode and preparation method and application thereof |
| CN115007137A (en) * | 2022-07-14 | 2022-09-06 | 南大恩洁优环境技术(江苏)股份公司 | Catalyst for purifying dioxin and preparation method thereof |
| CN115007137B (en) * | 2022-07-14 | 2023-07-28 | 南大恩洁优环境技术(江苏)股份公司 | Catalyst for purifying dioxin and preparation method thereof |
| CN115672307A (en) * | 2022-09-29 | 2023-02-03 | 上海第二工业大学 | Tungsten oxide-based photoelectric catalytic material growing on FTO (fluorine-doped tin oxide), preparation method and application thereof |
| CN115845832A (en) * | 2022-11-24 | 2023-03-28 | 百色学院 | ZIF-8-derivatized ZnO/BiVO 4 Preparation method and application of heterojunction compound |
| CN115845832B (en) * | 2022-11-24 | 2024-05-07 | 百色学院 | ZIF-8 derived ZnO/BiVO4Preparation method and application of heterojunction compound |
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