CN108149227A - A kind of TiO2-WO3/ rGO composite photoelectric energy storage materials and its preparation method and application - Google Patents
A kind of TiO2-WO3/ rGO composite photoelectric energy storage materials and its preparation method and application Download PDFInfo
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- CN108149227A CN108149227A CN201711337754.6A CN201711337754A CN108149227A CN 108149227 A CN108149227 A CN 108149227A CN 201711337754 A CN201711337754 A CN 201711337754A CN 108149227 A CN108149227 A CN 108149227A
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Abstract
The invention belongs to optical electro-chemistry cathodic protection field, in particular it relates to a kind of TiO2‑WO3/ rGO composite photoelectric energy storage materials and its preparation method and application.Composite photoelectric energy storage material is WO3/ rGO nanometer rods compound and TiO2Powder, wherein WO3/ rGO nanometer rods compound and TiO2The amount of filling (quality) of powder is 1:1.TiO prepared by the present invention2‑WO3The corrosion potential of 304 stainless steels can be reduced after/rGO composite photoelectric energy storage light anodes and the coupling of 304 stainless steels; and photic current potential and photogenerated current density show slowly return rate under the dark-state after illumination is chopped off, show there is good lasting cathode protecting function.Laboratory operating procedures of the present invention are simple, solve the problems, such as the lasting cathodic protection under cloudy day and dark condition.
Description
Technical field
The invention belongs to optical electro-chemistry cathodic protection field, in particular it relates to a kind of TiO2-WO3/ rGO is compound
Photoelectricity energy storage material and its preparation method and application.
Background technology
Metal erosion brings serious economic loss, and along with environmental pollution.Disappear in face of the growing energy
Consumption problem and serious environmental problem, friendly and using clean energy resource the anticorrosive technology there is an urgent need for development environment.In the past 20 years,
Research finds that the photovoltaic effect of semiconductor can provide light induced electron for the metallic substrates being coupled, and provides cathodic protection.Illumination can
Light induced electron is generated with excitation, if sufficient amount of light induced electron is shifted and is accumulated on the metal of coupling, so that it may merely with
Solar energy reaches effective optical electro-chemistry cathodic protection.TiO2Because it is steady with good electronic transmission performance and excellent chemistry
Qualitative and suitable position of energy band, has obtained extensive research in optical electro-chemistry field.
Since graphene in 2004 occurs, unique accurate two-dimentional (2D) structure and it is outstanding electronically and physically chemically
The potential candidate for constructing high-activity photocatalyst compound can be become.Graphene can assist in capture light induced electron, improve
Light induced electron efficiency of transmission, the light induced electron that can be also generated from semiconductor as electronic library capture/transmission.However, it is in light
In electrochemical cathodic protection field, the effect of the transmission of light induced electron, capture and assistance storage is mentioned seldom.
WO3It is a kind of electronics library material.WO3Nano particle makes it can be applied to painting because it is with energy storage capability
Light induced electron is stored in layer material, lasting cathodic protection is provided for metal.This, which will assist in, solves holding under cloudy and dark condition
Continuous cathodic protection problem.
Invention content
The problem of for above-mentioned delay cathodic protection, the object of the present invention is to provide a kind of TiO2-WO3/ rGO composite photoelectrics
Energy storage material and its preparation method and application.
To achieve the above object, the present invention takes following technical scheme：
A kind of TiO2-WO3/ rGO composite photoelectric energy storage materials, composite photoelectric energy storage material are WO3/ rGO nanometer rods compounds
And TiO2Powder, wherein WO3/ rGO nanometer rods compound and TiO2The amount of filling (quality) of powder is 1:1.
The WO3/ rGO nanometer rods compound is combined synthesis by solvent-thermal method and in situ synthesis, specifically by institute
The solution a and solution b needed presses 0.1-0.3:100 mass ratio, which is mixed in autoclave, to be synthesized, and wherein solution a is
The GO dispersion liquids of 0.5mg/mL, solution b are the WCl of a concentration of 1mM6Alcohol mixed solution.
A kind of TiO2-WO3The preparation method of/rGO composite photoelectric energy storage materials, energy storage material WO3/ rGO nanometer rods are compound
Object and TiO2Powder, wherein WO3/ rGO nanometer rods compound and TiO2The amount of filling (quality) of powder is 1:1；The WO3/rGO
Nanometer rods compound is to make WO by solvent-thermal method and growth in situ mode3In the compound that GO on pieces are formed.
Specially：
1) preparation of GO stabilising dispersions：GO is added in ethyl alcohol and forms stable dispersions；
2)WCl6The preparation of solution：Under magnetic stirring, under magnetic stirring, it is 8 by mass ratio:1-10:1 WCl6With
ZnCl2It is dissolved in the mixed solution of ethyl alcohol and polyethylene glycol；Wherein in mixed solution ethyl alcohol volume be 30-50mL, polyethylene glycol
Volume is 15-25mL.
3)WO3The preparation of/rGO nanometer rods compounds：Step 1) and step 2) acquired solution are mixed, under magnetic stirring
Uniform solution is formed, is then heated 22-26 hours at 170-190 DEG C, obtained blue precipitate is WO3/ rGO nanometer rods are answered
Close object；
4)TiO2-WO3/ rGO composite photoelectric energy storage materials：By WO made from step 3)3/ rGO nanometer rods compound and TiO2
(P25) powder equal proportion weighs, you can.
A kind of TiO2-WO3The application of/rGO composite photoelectric energy storage materials, it is characterised in that：The composite photoelectric energy storage material
As the anti-corrosion protective film for inhibiting metal erosion.
The composite photoelectric energy storage material persistently carries out in the dark state as the anti-corrosion protective film for inhibiting metal erosion
Application in protection.
A kind of TiO2-WO3/ rGO composite photoelectric energy storage electrodes, TiO2-WO3WO in/rGO composite photoelectric energy storage materials3/rGO
Nanometer rods compound and TiO2(P25) equal proportion area (10 × 10mm after powder is ground uniformly respectively2) be coated on conductive base
(FTO electro-conductive glass) surface.
Further, by the TiO2(P25) and WO3Through deionized water, mixed grinding 10 divides/rGO in mortar respectively
Clock is respectively formed slurry, by gained slurry difference equal proportion area (10 × 10mm2) be coated on conductive base (FTO is led
Electric glass) surface, then TiO is made in 80 DEG C of heat preservation 2h after natural air drying2-WO3/ rGO composite photoelectric energy storage electrodes.Wherein, FTO
Electro-conductive glass is the SnO that conductive film component is F doping2, this FTO glass is cut into 30 × 10mm2Size, first in analysis pure third
It is cleaned by ultrasonic 5 minutes in ketone, then is rinsed with deionized water.This FTO glass is dried up later.The conductive side of FTO glass length is with absolutely
Edge adhesive tape covers, and it is two pieces of 5 × 10mm to make exposed test area2。
A kind of TiO2-WO3The application of/rGO composite photoelectric energy storage electrodes, the composite photoelectric energy storage electrode is as inhibition
The anti-corrosion protective film of metal erosion.
The composite photoelectric energy storage electrode persistently carries out in the dark state as the anti-corrosion protective film for inhibiting metal erosion
Application in protection.
Further, when 304 stainless steels are coupled with light anode, 304SS-TiO2-WO3/ rGO systems are under white light illumination
With 304SS-TiO2The photic mixed potential drop of system is roughly the same, but the 304SS-TiO after white light is chopped off2-WO3/ rGO systems
In the current potentials of 304SS electrodes its initial value is returned with slower rate, show certain Electronic saving performance.
To the TiO for lasting light electrochemical cathodic protection of above-mentioned preparation2-WO3/ rGO composite photoelectric energy storage materials, will
It coats matrix surface and forms light anode, light anode is carried out to the test of optical electro-chemistry cathodic protection effect, specifically using photic
The variation of open circuit potential and photogenerated current density characterizes, by recording photoproduction current density and open circuit potential in opening/closing striation
The information that changes with time under part is measured.Specific measuring device is divided into two reaction tanks, that is, corrodes pond and photoelectrochemical
Pond is learned, as shown in Figure 2.Electrolyte in photoelectrochemistrpool pool and corrosion pond is 3.5%NaCl solution, and two ponds pass through salt bridging
It connects.Optoelectronic pole is placed in photoelectrochemistrpool pool, and 304 stainless steels are placed in corrosion pond.Using xenon lamp as light source (any optical filtering is not added
Piece) simulated solar irradiation is provided.There is the quartz window that a diameter is about 30mm in photronic positive centre, incident light passes through this
Window is irradiated to photoelectricity pole surface.
The basic principle of the present invention：Under illumination, TiO2Electronics in valence band, which is excited on conduction band, forms light induced electron.Together
When WO3Electronics in valence band, which is also excited on conduction band, forms light induced electron.Because WO3Fermi level compare TiO2Corrigendum, together
When metal 304SS fermi level also compare TiO2Corrigendum.So metal 304SS of these light induced electron fractional transmissions to coupling
Optical electro-chemistry cathodic protection is provided for it on electrode, excessive light induced electron is transferred to WO3On be stored therein in.Work as WO3And rGO
During hydridization, WO3The combination interface of/rGO hybridization compounding objects will be WO3Easier electronics is created on the interface of nanometer rods and rGO pieces
Transmission.And WO3Nanometer rods can be effectively facilitated electrolyte and be diffused into inside after rGO is introduced by shortization, the nanostructured of refinement,
Increase charge contact area and improve charging reaction.Therefore under light illumination, a large amount of light induced electron transmission is stored in WO3/ rGO hydridization
In compound.Under dark-state, WO3The light induced electron stored in/rGO is released to 304SS and provides lasting cathodic protection again.WO3It receives
The electronics for being refined as storage of rice stick provides more contacts area and more storage spaces, ensures more light induced electrons
It is stored in WO3It is final to improve under dark-state long lasting for release Electronic Performance in nanometer rods.Therefore, TiO is coated2-WO3/rGO
The photo cathode of the base material of composite photoelectric energy storage material can generate lasting optical electro-chemistry cathodic protection to metal and act on
Advantage for present invention：
The present invention is by photoelectric material and WO3Energy storage section bar material is anchored with fabulous electronic conductor graphene, passes through it
Multiphase heterojunction structure integrates the transmission performance of electronics well, further transmits light induced electron simultaneously by 2D graphene-structureds
It is stored in the WO adjoined3In structure, and then assist to solve the problems, such as the lasting cathodic protection under cloudy day and dark condition；Specifically：
1. the present invention synthesizes WO by solvent-thermal method and in situ synthesis3/ redox graphene (WO3/ rGO) nanometer rods
Compound, method is simple, only need to be by GO stabilising dispersions and WCl6Alcohol mixeding liquid be put into togerther reaction kettle alcohol heat treatment, and
It dries afterwards.Obtained WO3/ rGO compounds and pure WO3Compared to shorter tungsten oxide nanometer stick is formed, material is helped to improve
Electrochemical cycle stability.
2. the TiO of the present invention2-WO3/ rGO compounds and pure TiO2It compares, can be stored up in the dark state long lasting for release
The light induced electron deposited provides lasting cathodic protection for metal, so as to assist to solve the lasting cathode under cloudy day and dark condition
Protection problem.
3. complex light anode prepared by the present invention is mutually coupled with 304 stainless steel electrodes, under white light illumination, in corrosion
The photic current potential of 304 stainless steel electrodes in pond is reduced to 570mV, the reachable -450mV of stable potential, far below its corrosion potential,
Good cathodic polarization occurs.Show that its optical electro-chemistry cathodic protection function and effect is good.
Description of the drawings
Fig. 1 is TiO provided in an embodiment of the present invention2-WO3/ rGO (left side) and TiO2The FTO electro-conductive glass of (right side) powder coating
The optical photograph of electrode.
Fig. 2 is the optical electro-chemistry cathodic protection test device figure of photoelectric material provided in an embodiment of the present invention, wherein left figure
To measure photogenerated current density equipment connection diagram, right figure is measures photic open circuit potential equipment connection diagram.
Fig. 3 is pure WO provided in an embodiment of the present invention3(a) and WO3The SEM figures of/rGO (b, c, d) compound.
Fig. 4 is 304SS electrodes provided in an embodiment of the present invention and pure TiO2Electrode and TiO2-WO3/ rGO complex light anodes are even
After connection, photic current potential versus time curve.Wherein, abscissa is the time, and ordinate is electrode potential (vs.Ag/AgCl).
Fig. 5 for 304SS electrodes provided in an embodiment of the present invention in 3.5%NaCl solution with pure TiO2Electrode and TiO2-
WO3After the coupling of/rGO complex light anodes, the photogenerated current density versus time curve under intermittent white light.
Fig. 6 for 304SS electrodes provided in an embodiment of the present invention in 3.5%NaCl solution with pure TiO2Powder electrode and
TiO2-WO3After the coupling of/rGO complex light anodes, photic current potential versus time curve.Wherein, abscissa is the time, ordinate
For electrode potential (vs.Ag/AgCl).
Fig. 7 for 304SS electrodes provided in an embodiment of the present invention in 3.5%NaCl solution with pure TiO2Powder electrode and
TiO2-WO3After the coupling of/rGO complex light anodes, the photogenerated current density versus time curve under intermittent white light.
Fig. 8 for 304SS electrodes provided in an embodiment of the present invention in 3.5%NaCl solution with pure TiO2Powder electrode and
TiO2-WO3After the coupling of/rGO complex light anodes, photic current potential versus time curve.Wherein, abscissa is the time, ordinate
For electrode potential (vs.Ag/AgCl).
Fig. 9 for 304SS electrodes provided in an embodiment of the present invention in 3.5%NaCl solution with pure TiO2Powder electrode and
TiO2-WO3After the coupling of/rGO complex light anodes, the photogenerated current density versus time curve under intermittent white light.
Specific embodiment
Below in conjunction with the accompanying drawings, the present invention, but do not limit the invention in any way are further described by example.
The present invention is combined to synthesize WO first by solvent-thermal method and in situ synthesis3/ rGO nanometer rods compounds；So
Afterwards by WO obtained3/ rGO nanometer rods compound and TiO2Powder mull uniformly after homalographic be coated on FTO electro-conductive glass and be made
Optoelectronic pole.By the TiO of preparation2-WO3304 stainless steels can be reduced after/rGO composite photoelectric energy storage light anodes and the coupling of 304 stainless steels
Corrosion potential, and under the dark-state after illumination is chopped off photic current potential and photogenerated current density show slowly return speed
Rate shows there is good lasting cathode protecting function.Laboratory operating procedures of the present invention are simple, solve cloudy day and dark condition
Under lasting cathodic protection problem.
Embodiment 1
For the TiO of lasting light electrochemical cathodic protection2-WO3The preparation of/rGO composite photoelectric energy storage light anodes：
1) first, a certain amount of GO is added in ethyl alcohol and ultrasonic vibration disperses 2 hours, forms a concentration of 0.5mg/mL
GO stable dispersions.
2)WO3Method of the preparation of/rGO nanometer rods compounds based on simple solvent-thermal method and growth in situ：To uniform
GO stable dispersions that step 1) obtains are added in solution (by accounting for WO3The amount addition of the 0.1wt% of quality), it stirs evenly to be formed
Uniform solution is then transferred into the stainless steel cauldron of polytetrafluoroethyllining lining, and hydro-thermal is collected by centrifugation afterwards for 24 hours at 180 DEG C
Blue precipitate is washed for several times with ethyl alcohol.The product grinds to further characterize in agate mortar.
Wherein, uniform solution is：Under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492g) is dissolved in ethyl alcohol (40mL)
In the mixture of polyethylene glycol (20mL), you can.
Meanwhile pure WO3Nanometer rods are only by WCl6Alcohol mixeding liquid be put into reaction kettle alcohol heat treatment, GO is not added, to compare
Pure WO3And WO3The varying topography of/rGO compounds (referring to Fig. 3).
3)TiO2-WO3Preparing for/rGO system film light anodes is as follows：By TiO2(P25) and WO3/ rGO sample powders are starched
Uniform homalographic is coated on FTO electro-conductive glass (referring to Fig. 1 left sides) respectively；
Specifically：The SnO that FTO electro-conductive glass (using commodity purchased in market) conduction film component is adulterated for F2, it is cut into size
For 30 × 10mm2Electrode slice, be cleaned by ultrasonic 5 minutes in pure acetone is analyzed, then rinsed with deionized water.Later, by this FTO
Glass dries up.The conductive side of FTO glass length is covered with insulating tape, and it is two pieces of 10 × 10mm to make exposed test area2.It
Afterwards, the TiO of 10mg2(P25) and WO3/ rGO powders mix respectively with 0.1mL deionized waters in mortar (meanwhile with TiO2
(P25) and WO3As control, wherein, TiO2(P25) and WO3The weight ratio such as/rGO powders mix, TiO2(P25) and WO3Powder
Wait weight ratio mixing), mixture grinds 10 minutes and forms slurry.It is sudden and violent that this slurry is uniformly coated to FTO glass respectively
In the effective surface area of dew, 2h are kept the temperature to promote adhesion of thin film for 80 DEG C after natural air drying.Unlapped part insulating silicon
Glue sealing only reserves 5 × 10mm2, as shown in Fig. 1 left sides.
Pure TiO2(P25) manufacturing process and TiO of electrode2-WO3The making of/rGO system Film laminated optoelectronic poles is similar, area
TiO is not it2-WO3/ rGO complex light electrodes coated area is two pieces of 10 × 10mm2, and pure TiO2(P25) coated area is one
10 × 10mm of block2, as shown in Fig. 1 right sides.
To the above-mentioned TiO prepared2-WO3/ rGO systems film photoelectric electrode carries out the survey of optical electro-chemistry cathodic protection performance
Examination：On the device shown in experimental provision schematic diagram 2, using the CHI660D electrochemical workstations of Shanghai Chen Hua instrument company, prison
It surveys optoelectronic pole and 304SS electrodes under white light illumination and is coupled the photic of photogenerated current flow intensity (Fig. 5) between the two and coupling system
Mixed potential (Fig. 4) changes.Electrolyte in photoelectrochemistrpool pool and corrosion pond is 3.5%NaCl solution.
Pure WO obtained as seen from Figure 33(a) nanometer rods and WO3The SEM figures of/rGO (b, c and d) nanometer rods compound.It can be with
Find out, single WO3The diameter and length of nanometer rods are respectively about 33-47nm and 190nm, and WO3/ rGO nanometer rods compounds it is straight
Diameter and length are respectively about~4.8nm and 70nm.The reason is that in WO3In/rGO nanometer rods compounds, WO3Nanometer rods are in GO pieces
What upper growth was formed, GO lamellas not only provide nucleating point, can also limit WO3The growth of nanometer rods, leads to WO3/ rGO compounds
In with pure WO3Compared to forming short WO3Nanometer rods.
304SS electrodes and pure TiO as seen from Figure 42Electrode and TiO2-WO3After the coupling of/rGO complex lights electrode, photic current potential
Versus time curve..After stablizing in the dark, 304SS electrodes have been coupled pure TiO2Membrane electrode (is designated as 304SS-TiO2)
Potential is -0.09V, and 304SS electrodes have been coupled TiO2-WO3/ rGO system electrodes (are designated as 304SS-TiO2-WO3/rGO 0.1)
Potential be -0.09V.The mixed potential for being coupled electrode all bears shifting when white light starts and with the increasing of light application time at once
Add and continuously decrease.And it is shuffled at once when white light is closed and gradually returns to its initial potential value.Photic 304SS-TiO2It is mixed
The variation for closing current potential is about 530mV, and for GO in WO3The 304SS-TiO that amount in/rGO compounds is 0.1wt%2-WO3/
RGO systems are then 550mV.In third time opening and closing light cycle, with 304SS-TiO2Coupling system is compared, 304SS-TiO2-
WO3The current potential of 304SS electrodes in 0.1 systems of/rGO returns to its initial value after white light is chopped off with very slow rate.And
After 100s is chopped in illumination off, 304SS-TiO2-WO3The mixed potential of/rGO 0.1 is -0.37V, compares 304SS-TiO2(- 0.32V's)
It is more negative, show WO30.1 compound features of/rGO have gone out good Electronic saving performance.
304SS electrodes and the optoelectronic pole prepared are coupled the photic of current strength under intermittent white light as seen from Figure 5
Variation.The couple current density of 304SS electrodes and photoelectricity interpolar is suddenly increased when white light opens the light irradiation, the light under white light
Current density is sent a telegraph just, to show that electronics flows to 304SS electrodes from optoelectronic pole via electrochemical workstation, cathode being provided for 304SS
Protection.304SS-TiO2And 304SS-TiO2-WO3The photic variation of coupling current density in 0.1 systems of/rGO respectively may be about
40 and 25 μ Acm-2.After illumination is chopped off, with TiO2It compares, TiO2-WO3/ rGO 0.1 shows electronics sustained release
Energy and slowly current strength return rate.
Embodiment 2
For the TiO of lasting light electrochemical cathodic protection2-WO3The preparation of/rGO composite photoelectric energy storage light anodes：
1) first, a certain amount of GO is added in ethyl alcohol and ultrasonic vibration disperses 2 hours, forms a concentration of 0.5mg/mL
GO stable dispersions.
2)WO3Method of the preparation of/rGO nanometer rods compounds based on simple solvent-thermal method and growth in situ：To uniform
GO stable dispersions that step 1) obtains are added in solution (by accounting for WO3The amount addition of the 0.2wt% of quality), it stirs evenly to be formed
Uniform solution is then transferred into the stainless steel cauldron of polytetrafluoroethyllining lining, and hydro-thermal is collected by centrifugation afterwards for 24 hours at 180 DEG C
Blue precipitate is washed for several times with ethyl alcohol.The product grinds to further characterize in agate mortar.
Wherein, uniform solution is：Under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492g) is dissolved in ethyl alcohol (40mL)
In the mixture of polyethylene glycol (20mL), you can.
3)TiO2-WO3/ rGO system film light anodes are produced as follows：By TiO2(P25) and WO3/ rGO sample powders are starched
Uniform homalographic is coated on FTO electro-conductive glass respectively.
Specifically：The SnO that FTO electro-conductive glass (using commodity purchased in market) conduction film component is adulterated for F2, it is cut into size
For 30 × 10mm2Electrode slice, be cleaned by ultrasonic 5 minutes in pure acetone is analyzed, then rinsed with deionized water.Later, by this FTO
Glass dries up.The conductive side of FTO glass length is covered with insulating tape, and it is two pieces of 10 × 10mm to make exposed test area2.It
Afterwards, the TiO of 10mg2(P25) and WO3/ rGO powders mix respectively with 0.1mL deionized waters in mortar (meanwhile with TiO2
(P25) and WO3As control, wherein, TiO2(P25) and WO3The weight ratio such as/rGO powders mix, TiO2(P25) and WO3Powder
Wait weight ratio mixing), mixture grinds 10 minutes and forms slurry.It is sudden and violent that this slurry is uniformly coated to FTO glass respectively
In the effective surface area of dew, 2h are kept the temperature to promote adhesion of thin film for 80 DEG C after natural air drying.Unlapped part insulating silicon
Glue sealing only reserves 5 × 10mm2, as shown in Fig. 1 left sides.
Pure TiO2(P25) manufacturing process and TiO of electrode2-WO3The making of/rGO system Film laminated optoelectronic poles is similar, area
TiO is not it2-WO3/ rGO complex light electrodes coated area is two pieces of 10 × 10mm2, and pure TiO2(P25) coated area is one
10 × 10mm of block2, as shown in Fig. 1 right sides.
To the above-mentioned TiO prepared2-WO3/ rGO systems film photoelectric electrode carries out the survey of optical electro-chemistry cathodic protection performance
Examination：On the device shown in experimental provision schematic diagram 2, using the CHI660D electrochemical workstations of Shanghai Chen Hua instrument company, prison
It surveys optoelectronic pole and 304SS electrodes under white light illumination and is coupled the photic of photogenerated current flow intensity (Fig. 7) between the two and coupling system
Mixed potential (Fig. 6) changes.Electrolyte in photoelectrochemistrpool pool and corrosion pond is 3.5%NaCl solution.
304SS electrodes and pure TiO as seen from Figure 62Electrode and TiO2-WO3After the coupling of/rGO complex lights electrode, photic current potential
Versus time curve.After stablizing in the dark, 304SS electrodes have been coupled pure TiO2Membrane electrode (is designated as 304SS-TiO2)
Potential is -0.09V, and 304SS electrodes have been coupled TiO2-WO3/ rGO system electrodes (are designated as 304SS-TiO2-WO3/rGO 0.2)
Potential be 0.11V.The mixed potential for being coupled electrode all bears shifting when white light starts and with the increasing of light application time at once
Add and continuously decrease.And it is shuffled at once when white light is closed and gradually returns to its initial potential value.Photic 304SS-TiO2It is mixed
The variation for closing current potential is about 530mV, and for GO in WO3The 304SS-TiO that amount in/rGO compounds is 0.2wt%2-WO3/
RGO systems are then 570mV.In third time opening and closing light cycle, with 304SS-TiO2Coupling system is compared, 304SS-TiO2-
WO3The current potential of 304SS electrodes in/rGO0.2 systems returns to its initial value after white light is chopped off with very slow rate.And
After 100s is chopped in illumination off, 304SS-TiO2-WO3The mixed potential of/rGO 0.2 shows most negative value (- 0.42V), compares 304SS-
TiO2(- 0.32V's) is more negative, shows WO3/ rGO0.2 compound features have gone out good Electronic saving performance.
304SS electrodes and the optoelectronic pole prepared are coupled the photic of current strength under intermittent white light as seen from Figure 7
Variation.The couple current density of 304SS electrodes and photoelectricity interpolar is suddenly increased when white light opens the light irradiation, the light under white light
Current density is sent a telegraph just, to show that electronics flows to 304SS electrodes from optoelectronic pole via electrochemical workstation, cathode being provided for 304SS
Protection.304SS-TiO2And 304SS-TiO2-WO3The photic variation of coupling current density in 0.2 systems of/rGO respectively may be about
40 and 32 μ Acm-2.After illumination is chopped off, with TiO2It compares, TiO2-WO3/ rGO 0.2 shows electronics sustained release
Energy and slowly current strength return rate.
Embodiment 3
For the TiO of lasting light electrochemical cathodic protection2-WO3The preparation of/rGO composite photoelectric energy storage light anodes：
1) first, a certain amount of GO is added in ethyl alcohol and ultrasonic vibration disperses 2 hours, forms a concentration of 0.5mg/mL
GO stable dispersions.
2)WO3Method of the preparation of/rGO nanometer rods compounds based on simple solvent-thermal method and growth in situ：To uniform
GO stable dispersions that step 1) obtains are added in solution (by accounting for WO3The amount addition of the 0.3wt% of quality), it stirs evenly to be formed
Uniform solution is then transferred into the stainless steel cauldron of polytetrafluoroethyllining lining, and hydro-thermal is collected by centrifugation afterwards for 24 hours at 180 DEG C
Blue precipitate is washed for several times with ethyl alcohol.The product grinds to further characterize in agate mortar.
Wherein, uniform solution is：Under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492g) is dissolved in ethyl alcohol (40mL)
In the mixture of polyethylene glycol (20mL), you can.
3)TiO2-WO3/ rGO system film light anodes are produced as follows：By TiO2(P25) and WO3/ rGO sample powders are starched
Uniform homalographic is coated on FTO electro-conductive glass respectively.
Specifically：The SnO that FTO electro-conductive glass (using commodity purchased in market) conduction film component is adulterated for F2, it is cut into size
For 30 × 10mm2Electrode slice, be cleaned by ultrasonic 5 minutes in pure acetone is analyzed, then rinsed with deionized water.Later, by this FTO
Glass dries up.The conductive side of FTO glass length is covered with insulating tape, and it is two pieces of 10 × 10mm to make exposed test area2.It
Afterwards, the TiO of 10mg2(P25) and WO3/ rGO powders mix respectively with 0.1mL deionized waters in mortar (meanwhile with TiO2
(P25) and WO3As control, wherein, TiO2(P25) and WO3The weight ratio such as/rGO powders mix, TiO2(P25) and WO3Powder
Wait weight ratio mixing), mixture grinds 10 minutes and forms slurry.It is sudden and violent that this slurry is uniformly coated to FTO glass respectively
In the effective surface area of dew, 2h are kept the temperature to promote adhesion of thin film for 80 DEG C after natural air drying.Unlapped part insulating silicon
Glue sealing only reserves 5 × 10mm2, as shown in Fig. 1 left sides.
Pure TiO2(P25) manufacturing process and TiO of electrode2-WO3The making of/rGO system Film laminated optoelectronic poles is similar, area
TiO is not it2-WO3/ rGO complex light electrodes coated area is two pieces of 10 × 10mm2, and pure TiO2(P25) coated area is one
10 × 10mm of block2, as shown in Fig. 1 right sides.
To the above-mentioned TiO prepared2-WO3/ rGO systems film photoelectric electrode carries out the survey of optical electro-chemistry cathodic protection performance
Examination：On the device shown in experimental provision schematic diagram 2, using the CHI660D electrochemical workstations of Shanghai Chen Hua instrument company, prison
It surveys optoelectronic pole and 304SS electrodes under white light illumination and is coupled the photic of photogenerated current flow intensity (Fig. 9) between the two and coupling system
Mixed potential (Fig. 8) changes.Electrolyte in photoelectrochemistrpool pool and corrosion pond is 3.5%NaCl solution.
304SS electrodes and pure TiO as seen from Figure 82Electrode and TiO2-WO3After the coupling of/rGO complex lights electrode, photic current potential
Versus time curve.After stablizing in the dark, 304SS electrodes have been coupled pure TiO2Membrane electrode (is designated as 304SS-TiO2)
Potential is -0.09V, and 304SS electrodes have been coupled TiO2-WO3/ rGO system electrodes (are designated as 304SS-TiO2-WO3/rGO 0.3)
Potential be -0.05V.The mixed potential for being coupled electrode all bears shifting when white light starts and with the increasing of light application time at once
Add and continuously decrease.And it is shuffled at once when white light is closed and gradually returns to its initial potential value.Photic 304SS-TiO2It is mixed
The variation for closing current potential is about 530mV, and for GO in WO3The 304SS-TiO that amount in/rGO compounds is 0.3wt%2-WO3/
RGO systems are then 450mV.In third time opening and closing light cycle, with 304SS-TiO2Coupling system is compared, 304SS-TiO2-
WO3The current potential of 304SS electrodes in/rGO0.3 systems returns to its initial value after white light is chopped off with very slow rate.And
After 100s is chopped in illumination off, 304SS-TiO2-WO3The mixed potential of/rGO 0.3 shows most negative value (- 0.37V), compares 304SS-
TiO2(- 0.32V's) is more negative, shows WO3/ rGO0.3 compound features have gone out good Electronic saving performance.
304SS electrodes and the optoelectronic pole prepared are coupled the photic of current strength under intermittent white light as seen from Figure 9
Variation.The couple current density of 304SS electrodes and photoelectricity interpolar is suddenly increased when white light opens the light irradiation, the light under white light
Current density is sent a telegraph just, to show that electronics flows to 304SS electrodes from optoelectronic pole via electrochemical workstation, cathode being provided for 304SS
Protection.304SS-TiO2And 304SS-TiO2-WO3The photic variation of coupling current density in 0.3 systems of/rGO respectively may be about
40 and 35 μ Acm-2.After illumination is chopped off, with TiO2It compares, TiO2-WO3/ rGO 0.3 shows electronics sustained release
Energy and slowly current strength return rate.
Claims (9)
1. a kind of TiO2-WO3/ rGO composite photoelectric energy storage materials, it is characterised in that：Composite photoelectric energy storage material is WO3/ rGO receives
Rice stick compound and TiO2Powder, wherein WO3/ rGO nanometer rods compound and TiO2The amount of filling (quality) of powder is 1:1.
2. TiO as described in claim 12-WO3/ rGO composite photoelectric energy storage materials, it is characterised in that：The WO3/ rGO nanometers
Stick compound is combined synthesis by solvent-thermal method and in situ synthesis, and required solution a and solution b specifically are pressed 0.1-
0.3:100 mass ratio mixing, which is placed in autoclave, to be synthesized, GO dispersion liquids of the wherein solution a for 0.5mg/mL, solution b
WCl for a concentration of 1mM6Alcohol mixed solution.
3. a kind of TiO described in claim 12-WO3The preparation method of/rGO composite photoelectric energy storage materials, it is characterised in that：Storage
Energy material is WO3/ rGO nanometer rods compound and TiO2Powder, wherein WO3/ rGO nanometer rods compound and TiO2Powder is dosed
It is 1 to measure (quality):1；The WO3/ rGO nanometer rods compound is to make WO by solvent-thermal method and growth in situ mode3In GO on pieces
The compound of formation.
4. TiO as described in claim 32-WO3The preparation method of/rGO composite photoelectric energy storage materials, it is characterised in that：
1) preparation of GO stabilising dispersions：GO is added in ethyl alcohol and forms stable dispersions；
2)WCl6The preparation of solution：Under magnetic stirring, it is 8 by mass ratio:1-10:1 WCl6And ZnCl2It is dissolved in ethyl alcohol and gathers
In the mixed solution of ethylene glycol；
3)WO3The preparation of/rGO nanometer rods compounds：Step 1) and step 2) acquired solution are mixed, formed under magnetic stirring
Uniform solution then heats 22-26 hours at 170-190 DEG C, and obtained blue precipitate is WO3/ rGO nanometer rods are compound
Object；
4)TiO2-WO3/ rGO composite photoelectric energy storage materials：By WO made from step 3)3/ rGO nanometer rods compound and TiO2Powder
Equal proportion weighs, you can.
5. a kind of TiO described in claim 12-WO3The application of/rGO composite photoelectric energy storage materials, it is characterised in that：It is described multiple
Closing light electricity energy storage material is as the anti-corrosion protective film for inhibiting metal erosion.
6. TiO as described in claim 52-WO3The application of/rGO composite photoelectric energy storage materials, it is characterised in that：It is described compound
Photoelectricity energy storage material is in the anti-corrosion protective film as inhibition metal erosion, the application in persistently being protected in the dark state.
7. a kind of TiO2-WO3/ rGO composite photoelectric energy storage electrodes, it is characterised in that：TiO2-WO3/ rGO composite photoelectric energy storage materials
Middle WO3/ rGO nanometer rods compound and TiO2Equal proportion area is coated on surfaces of conductive substrates after powder is ground uniformly respectively.
8. a kind of TiO described in claim 72-WO3The application of/rGO composite photoelectric energy storage electrodes, it is characterised in that：It is described multiple
Closing light electricity energy storage electrode is as the anti-corrosion protective film for inhibiting metal erosion.
9. TiO as described in claim 82-WO3The application of/rGO composite photoelectric energy storage electrodes, it is characterised in that：It is described compound
Photoelectricity energy storage electrode is in the anti-corrosion protective film as inhibition metal erosion, the application in persistently being protected in the dark state.
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| CN109468674A (en) * | 2018-12-17 | 2019-03-15 | 滨州学院 | TiO2/WO3The preparation method of nano composite membrane |
| CN111960683A (en) * | 2020-08-11 | 2020-11-20 | 浙江工业大学 | GO-WO3/TiO2Method for preparing microsphere film electrode |
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