CN108314085A - The preparation method of tungstic trioxide nano-slice complex light anode - Google Patents
The preparation method of tungstic trioxide nano-slice complex light anode Download PDFInfo
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- CN108314085A CN108314085A CN201810115207.1A CN201810115207A CN108314085A CN 108314085 A CN108314085 A CN 108314085A CN 201810115207 A CN201810115207 A CN 201810115207A CN 108314085 A CN108314085 A CN 108314085A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
Abstract
The preparation method of tungstic trioxide nano-slice complex light anode is related to nanometer sheet complex light anode.WO is prepared on FTO matrix surfaces using hydro-thermal method3Nanometer sheet film, then pass through TiCl4Pyrohydrolysis, in WO3Film surface depositing Ti O2Nano particle finally uses chemical bath deposition, by ZnS and Bi2S3Deposit to TiO2/WO3Composite film surface obtains the ZnS Bi with excellent photoelectrochemical behaviour2S3/TiO2/WO3Composite membrane.Using composite membrane as light anode.Composite membrane under white light illumination when, can make stainless steel NaCl solution in electrode potential reduce, photoproduction cathodic protection effect is significantly higher than simple WO3Film.After light source is closed, the current potential of stainless steel is still below its corrosion potential, illustrates composite membrane in the dark state and can continue the photoproduction cathodic protection to metal, the stability for having good energy storage characteristic, and having had.
Description
Technical field
The present invention relates to nanometer sheet complex light anodes, more particularly, to excellent photoelectrochemical behaviour and stored electrons energy
The ZnS-Bi to the round-the-clock photoproduction cathodic protection of metal may be implemented in power2S3/TiO2/WO3The system of nanometer sheet complex light anode
Preparation Method
Background technology
Cathodic protection is the metal erosion protection widely used technology in field, and photoproduction cathodic protection is then to propose in recent years
A kind of novel cathode protecting process.This technology can make up that conventional cathode protection technique energy expenditure is big, maintenance cost
High deficiency has good application prospect, is a hot spot in current corrosion and protection research.The base of photoproduction cathodic protection
Present principles are, under illumination condition, the electronics of semiconductor valence band is excited to its conduction band, and the light induced electron in conduction band is then transferred to
The need metal to be protected of coupling, brings it about cathodic polarization and is protected.Based on this principle, photoproduction cathodic protection maximum skill
Art problem is that night does not have how to maintain the cathodic protection to metal under illumination condition[1]。
Currently, most study is TiO in photoproduction cathodic protection2Base light anode.Pass through the side such as doping and semiconductors coupling
Method develops compound TiO2Semi-conducting material may maintain photoproduction cathodic protection under dark-state[2-7].For example, Yang et al.[2]Pass through
The TiO of Bi doping is constructed on Ti-Bi alloys2Nanometer tube composite film finds that after cutting off illumination, the doping of Bi can be by photoproduction
Cathodic protection continues certain time.Other researchers also found SnO2The photoproduction electricity of part can be stored by chemical reaction
Son[3-4], by SnO2Nano particle and TiO2The composite film photo-anode of nanotube composition, can discharge again after illumination switchs to dark-state
Light induced electron maintains the cathodic protection to stainless steel to act on.
WO3It is to study one of widest material in optical electro-chemistry application, there is good electronic transmission performance, low toxicity
It is property, easily prepared, it is more satisfactory light anode material[8].But WO3Energy gap only compares TiO2It is smaller, the suction to visible light
Receipts are equally weaker, and the stability in alkaline environment is poor, therefore, it is necessary to WO3Certain modification or modification are carried out,
It can just be preferably applied in photoproduction cathodic protection.
Bi2S3It is a kind of typical low-gap semiconductor (~1.3eV), has good response to visible light, it can be effectively
Utilize sunlight.By Bi2S3With TiO2Equal semiconductors couplings, can not only widen the photoresponse section of composite membrane, moreover it is possible to well
Inhibit the compound of photo-generated carrier, improves photoelectric conversion efficiency.But Bi2S3Photoetch easily occurs, it is therefore necessary in Bi2S3
On the basis of modify the good ZnS of stability again to inhibit photoetch.On the other hand, Bi2S3Valence band location and WO3Conduction band position
It sets quite, the two is compound, Bi2S3Conduction band is transferred to WO3The electronics of conduction band is easy to return to Bi2S3Valence band and hole-recombination, and
It is not to be transferred to by protection metal, to reduce the efficiency of photoproduction cathodic protection.Solution is in Bi2S3And WO3Between introduce
TiO2Transition zone, Bi2S3Conduction band electron is first transferred to TiO2Conduction band is then transferred to WO3Conduction band, thus can be to avoid WO3Conduction band
Upper electronics returns to Bi2S3The process of valence band realizes efficiently separating for electron-hole pair.Pass through TiCl4Pyrohydrolysis can be in WO3
Film surface modifies one layer of TiO2Transition zone.TiO2On the one hand the presence of film layer can optimize the band structure of composite membrane, promote light
Raw electrons and holes efficiently separate；On the other hand, WO can be improved3Stability.
Bibliography
[1]H.Park,K.Y.Kim,W.Choi,Photoelectrochemical approach for metal
corrosion prevention using a semiconductor photoanode[J].The Journal of
Physical Chemistry B,2002,106:4775-4781.
[2]J.Yang,X.Wang,X.Yang,J.Li,X.Zhang,J.Zhao,Energy storage ability
and anti-corrosion properties of Bi-doped TiO2nanotube arrays[J]
.Electrochimica Acta,2015,169:227-232.
[3]H.Li,X.T.Wang,Y.Liu,B.R.Hou,Ag and SnO2co-sensitized
TiO2photoanodes for protection of 304SS under visible light[J].Corrosion
Science,2014,82:145-153.
[4]J.Hu,Q.Liu,H.Zhang,C.D.Chen,Y.Liang,R.G.Du,C.J.Lin,Facile
ultrasonic deposition of SnO2nanoparticles on TiO2nanotube films for enhanced
photoelectrochemical performances[J].Journal of Materials Chemistry A,2015,3:
22605-22613.
[5]T.Tatsuma,S.Saitoh,Y.Ohko,A.Fujishima,TiO2-WO3photoelectrochemical
anticorrosion system with an energy storage ability[J].Chemistry of
materials,2001,13:2838-2842.
[6]M.J.Zhou,Z.O.Zeng,L.Zhong,Photogenerated cathode protection
properties of nano-sized TiO2/WO3coating[J].Corrosion Science,2009,51:1386-
1391.
[7]Y.Liang,Z.C.Guan,H.P.Wang,R.G.Du,Enhanced photoelectrochemical
anticorrosion performance of WO3/TiO2nanotube composite films formed by
anodization and electrodeposition[J].Electrochemistry Communications,2017,77:
120-123.
[8]J.Yang,W.Li,J.Li,D.Sun,Q.Chen,Hydrothermal synthesis and
photoelectrochemical properties of vertically aligned tungsten trioxide
(hydrate)plate-like arrays fabricated directly on FTO substrates[J].Journal
of Materials Chemistry,2012,22:17744-17752.
Invention content
The purpose of the present invention is to provide a kind of ZnS-Bi with excellent photoproduction cathodic protection performance2S3/TiO2/WO3It receives
The preparation method of rice piece complex light anode.
The present invention includes the following steps：
1) pretreatment of FTO matrixes；
In step 1), the pretreated specific method of the FTO matrixes can be：FTO electro-conductive glass is cut rectangular
Then sample, 15~25mm of length, 10~15mm of width, 2.2~2.3mm of thickness use acetone, ethyl alcohol, deionized water super successively
Sound cleans 20~30min, is dried for standby；15 Ω of surface resistance ＜/cm of the FTO electro-conductive glass2, transmitance ＞ 90%.
2) WO is prepared3Nanometer sheet film；
In step 2), the preparation WO3The specific method of nanometer sheet film can be：(0.230~0.235) g sodium tungstates
(Na2WO4·2H2O (28~32) mL deionized waters) are dissolved in, (9~11) mL (2.8~3.2) mol/L salt is added under stiring
Acid continues stirring to formation pale yellow gum (H2WO4), add (0.200~0.220) g ammonium oxalate ((NH4)2C2O4) and (28
~32) mL deionized waters obtain preparing WO after stirring (28~32) min3The precursor solution of nanometer sheet；By the precursor solution of preparation
It is transferred in ptfe autoclave, and FTO electro-conductive glass samples is immersed in solution, FTO electro-conductive glass leans against polytetrafluoro
The inner wall of ethylene reaction kettle, and keep conductive makes it in (120~160) DEG C hydro-thermal reaction (3~6) h downwards, it is then, natural
It is cooled to room temperature, takes out FTO electro-conductive glass samples, deionized water cleaning sample is used in combination, then dried at (60~80) DEG C, i.e.,
Obtain WO3Nanometer sheet film.
3) TiO is prepared2/WO3Composite membrane；
In step 3), the preparation TiO2/WO3The specific method of composite membrane can be；(50~52) mL deionized waters are filled
Enter in container, so that water is build-up ice in refrigerator；Then, container is taken out, allows ice-out to mixture of ice and water is formed, in stirring
Under the conditions of, (1~2) mL TiCl are added into mixture of ice and water4, continue stirring until being obtained after ice thawing completely clear
TiCl4Solution；By TiCl4Solution is transferred in surface plate, and there is WO on surface3The FTO of nanometer sheet film is dipped in TiCl4In solution,
Contain WO3One face upward, surface plate is covered, then be placed in the baking oven of (68~75) DEG C and react (0.5~2) h, reaction is completed
Afterwards, FTO samples are taken out, deionized water is used in combination to clean, is then dried at (60~80) DEG C, FTO samples is finally placed in Muffle
In stove, under air conditions, with (450~460) DEG C heat treatment (1.6~2.2) h, TiO is obtained2/WO3Composite membrane.
4) ZnS-Bi is prepared2S3/TiO2/WO3Composite membrane, i.e. ZnS-Bi2S3/TiO2/WO3Nanometer sheet complex light anode.
In step 4), the preparation ZnS-Bi2S3/TiO2/WO3The specific method of composite membrane can be：Preparation contains
(0.10~0.15) mol/L Bi (NO3)3·5H2O and (0.05~0.08) mol/L Zn (NO3)2·6H2The ethylene glycol solution of O,
It is denoted as solution A, then is prepared containing (0.15~0.22) mol/L Na2S·9H2The methanol solution of O, is denoted as solution B；First,
TiO2/WO3After composite membrane vertically stands (3~5) min in solution A, spent glycol rinses sample, and is dried at (60~80) DEG C
It is dry；Then, sample is vertically stood to (3~5) min in solution B, rinses sample with methanol after taking-up, and in (60~80) DEG C
Lower drying, this process are that a chemical bath deposition recycles, and sample obtains ZnS-Bi after (5~10) a cycle2S3/TiO2/
WO3Composite membrane, i.e. ZnS-Bi2S3/TiO2/WO3Nanometer sheet complex light anode.
Photoproduction cathodic protection performance test is given below：The photoproduction cathodic protection performance test of composite membrane is in a double electrolysis
It is carried out in cell system, including optical electro-chemistry electrolytic cell and corrosion electrolytic cell.ZnS-Bi2S3/TiO2/WO3Composite membrane is as light anode
It is placed in optical electro-chemistry electrolytic cell, electrolyte therein is (0.05~0.2) mol/L Na2SO3(0.05~0.2) mol/L
Na2The mixed solution of S.In corroding electrolytic cell, by protection metal as working electrode, Pt electrodes and saturated calomel electrode
(SCE) respectively as auxiliary electrode and reference electrode, the electro-chemical test system of three electrodes is formed, electrolyte therein is (0.3
~0.8) NaCl solution of mol/L.Light anode in optical electro-chemistry electrolytic cell passes through copper with the working electrode in corrosion electrolytic cell
Line connects, and two electrolytic cells are then connected by salt bridge.When test, selection be 150W xenon lamp as white light source, directly shine
It penetrates in the composite film photo-anode in optical electro-chemistry electrolytic cell, working electrode in corrosion electrolytic cell is then tested by potentiostat
Potential change before and after illumination, with the photoproduction cathodic protection performance to metal of this evaluating combined film.
FTO of the present invention is matrix, and WO is prepared on its surface using hydro-thermal method first3Nanometer sheet film, and with this WO3Film is base
Plinth constructs composite membrane.By WO3Film immerses TiCl4In solution, TiCl is utilized4Pyrohydrolysis in WO3Film surface depositing Ti O2Particle obtains
To TiO2/WO3Composite membrane.Then by chemical bath deposition, by ZnS and Bi2S3Deposit to TiO2/WO3On composite membrane, obtain final
ZnS-Bi2S3/TiO2/WO3Composite membrane.Under white light illumination condition, which can provide for stainless steel and other metal materials
Effective photoproduction cathodic protection, antiseptic property are significantly better than pure WO3Film light anode, and the composite membrane can also be cut off in illumination
After be continuously metal material provide cathodic protection.
The main technical problem to be solved in the present invention is：In photoproduction cathodic protection, common TiO2Light anode can not be
Metal provides round-the-clock cathodic protection.With WO3Replace TiO2It is heavy by pyrohydrolysis and chemical bath as light anode basic material
Product is in WO3Film surface depositing Ti O2、Bi2S3And ZnS, construct the ZnS-Bi for providing rational band structure2S3/TiO2/WO3It is multiple
Close film.By light anode of this composite membrane effective round-the-clock cathodic protection is provided for metal.
Operation principle of the composite membrane in photoproduction cathodic protection system in the present invention：Under white light illumination, in composite membrane
Each component can absorb the energy of certain wavelength light, and to which the transition of electronics in semiconductor in interband occur, electronics is excited to
On respective conduction band.ZnS、Bi2S3、TiO2And WO3Conduction band positions reduce successively, electronics from position it is high conduction band transfer in place
Lower conduction band is set, the metal of coupling is transferred to finally by external circuit so that metal occurs cathodic polarization and is protected.Its
In some light induced electron by chemical reaction be stored in WO3In, after illumination stops, it is stored in WO3Electronics release
Come, continues as metal and cathodic protection is provided.Hole in valence band is then shifted along the direction opposite with electronics, finally in composite membrane
Surface by medium hole trapping agents consume.
The present invention uses hydro-thermal method to prepare WO in FTO matrix surfaces first3Nanometer sheet film；Secondly TiCl is utilized4Pyrohydrolysis
Reaction is in WO3Film surface depositing Ti O2Particle transition zone；Then by the method for chemical bath deposition, in TiO2/WO3Composite membrane table
The upper ZnS and Bi of face deposition2S3, finally obtain ZnS-Bi2S3/TiO2/WO3Piece composite membrane.Using the composite membrane of preparation as light anode
It is placed in optical electro-chemistry electrolytic cell and (contains Na2SO3+Na2S solution), and will be in compound film electrode and corrosion electrolytic cell by conducting wire
(containing NaCl solution) is connected by protection metal, investigates photoproduction cathodic protection performance of the composite membrane to metal.
The present invention for matrix, devises a kind of ZnS-Bi containing four components with electro-conductive glass (FTO)2S3/TiO2/WO3It is multiple
Close film light anode material.One layer of WO is prepared on the surfaces FTO using hydro-thermal method first3Nanometer sheet film, then passes through TiCl4Heat
Hydrolysis, in WO3Upper depositing Ti O2Nano particle obtains TiO2/WO3Composite membrane；Finally by chemical bath deposition, by ZnS and Bi2S3
Deposit to TiO2/WO3On composite membrane, a kind of ZnS-Bi with excellent photoelectrochemical behaviour is obtained2S3/TiO2/WO3Composite membrane.
In the composite membrane, the main function of ZnS is to inhibit Bi2S3Photoetch, improve the stability of composite membrane[9]；Bi2S3It is main
Effect is to generate light induced electron by opto-electronic conversion；TiO2It is then advantageously implemented the separation of photo-generated carrier and improves WO3Film it is steady
It is qualitative；WO3Effect be then a part of light induced electron to be transmitted to by protection metal, and store another part electronics, do not having
Release is to maintain the cathodic protection to metal in the case of illumination[5].Due to carrying out meticulously rational design to structure of composite membrane,
Excellent opto-electronic conversion performance is made it have, especially has charge storage function, good photoproduction can be provided for metal
Cathodic protection.Up to the present, there has been no about ZnS-Bi2S3/TiO2/WO3The relevant report of composite membrane.
ZnS-Bi prepared by the present invention2S3/TiO2/WO3Light anode of the composite membrane as photoproduction cathodic protection system, energy
Enough effective round-the-clock cathodic protection is provided for metal material.Composite membrane can be 403 be attached thereto in white light
Stainless steel provides effective photoproduction cathodic protection, its electrode potential in the NaCl solution of 0.5mol/L is made to reduce about 520mV.
After light source is cut off, the current potential of 403 stainless steels still is below corrosion potential 320mV or so, still has apparent cathode to protect
Shield acts on, and illustrates composite membrane in the dark state and can continue the photoproduction cathodic protection to metal, and composite membrane also have it is good steady
It is qualitative.
In conclusion the present invention uses hydro-thermal method to prepare WO on the surfaces FTO successively3Nanometer sheet film, then using at pyrohydrolysis
It manages TiO2Deposit to WO3Nanometer sheet film surface forms transition zone, and ZnS and Bi is deposited finally by chemical bath deposition method2S3, obtain
To ZnS-Bi2S3/TiO2/WO3Composite membrane.The composite membrane newly constructed has excellent as the light anode in photoproduction cathodic protection system
Good photoproduction cathodic protection performance.
Description of the drawings
Fig. 1 is the pure WO prepared using the present invention3Film and ZnS-Bi2S3/TiO2/WO3Surface topography map (the SEM of composite membrane
Figure).In Fig. 1, (a) is WO3Nanometer sheet film (b) is ZnS-Bi2S3/TiO2/WO3Composite membrane.
Fig. 2 is the ZnS-Bi prepared using the present invention2S3/TiO2/WO3X-ray energy spectrum (EDX) test result of composite membrane.
In fig. 2, the table of interpolation shows the atomic percent of each element in the composite membrane of test.
Fig. 3 is that 403 stainless steels connect in the NaCl solution of 0.5mol/L from different film light anodes in the embodiment of the present invention 1
It connects, electrode potential changes over time curve under intermittent illumination.Wherein, EcorrIndicate 403 stainless steels 0.5mol/L's
Corrosion potential in NaCl solution；(a) it is and pure WO3The current potential of stainless steel changes over time when film connects；(b) it is and ZnS-
Bi2S3/TiO2/WO3The current potential of stainless steel changes over time when composite membrane connects；Light on indicate illumination, Light off tables
Show closing illumination.
Fig. 4 is the pure WO prepared using the present invention3Film and ZnS-Bi2S3/TiO2/WO3Surface topography map (the SEM of composite membrane
Figure).In Fig. 4, (a) is pure WO3Nanometer sheet film (b) is ZnS-Bi2S3/TiO2/WO3Composite membrane.
Fig. 5 is the ZnS-Bi prepared using the present invention2S3/TiO2/WO3X-ray energy spectrum (EDX) test result of composite membrane,
The table of interpolation shows the atomic percent of each element in the composite membrane of test in figure.
Fig. 6 is that 403 stainless steels connect in the NaCl solution of 0.5mol/L from different film light anodes in the embodiment of the present invention 2
It connects, electrode potential changes over time curve under intermittent illumination.In figure 6, EcorrIndicate 403 stainless steels 0.5mol/L's
Corrosion potential in NaCl solution；(a) it is and pure WO3The current potential of stainless steel changes over time when film connects；(b) it is and ZnS-
Bi2S3/TiO2/WO3The current potential of the stainless steel of composite membrane connection changes over time；Light on indicate illumination, Light off tables
Show closing illumination.
Specific implementation mode
Embodiment 1
According to above-mentioned technical proposal, ZnS-Bi is prepared on FTO matrixes2S3/TiO2/WO3Composite membrane, and investigate its conduct
The photoproduction cathodic protection effect of 403 stainless steel of light anode pair.
The pretreatment of FTO matrixes：Commercialized FTO electro-conductive glass (15 Ω of surface resistance ＜/cm2, transmitance ＞ 90%) and it cuts
It is cut into the sample of rectangle, length 15mm, width 10mm, then thickness 2.2mm uses acetone, ethyl alcohol, deionized water ultrasound clear successively
20min is washed, is dried for standby.
WO3The preparation of nanometer sheet film：Take 0.231g sodium tungstates (Na2WO4·2H2O 30mL deionized waters) are dissolved in, are being stirred
It mixes down and 10mL 3mol/L hydrochloric acid (HCl) is added dropwise, continue stirring to formation pale yellow gum (H2WO4).0.200g grass is added
Sour ammonium ((NH4)2C2O4) and 30mL deionized waters, it obtains preparing WO after stirring 30min3The precursor solution of nanometer sheet.Then, will
The precursor solution of preparation is transferred in the ptfe autoclave of 100mL, and 2 FTO samples are immersed in solution, FTO with
Certain angle leans against the inner wall of ptfe autoclave, and keeps conduction downwards, so that it is carried out hydro-thermal at 140 DEG C anti-
Answer 4h.Then, cooled to room temperature takes out FTO samples, a large amount of deionized water cleaning sample is used in combination, then at 80 DEG C
Drying is to get to WO3Nanometer sheet film.
TiO2/WO3The preparation of composite membrane：50mL deionized waters are fitted into container, being put into refrigerator makes it build-up ice, then
Container takes out, and allows ice-out to forming mixture of ice and water.Under conditions of being vigorously stirred, it is added dropwise into mixture of ice and water
1mL TiCl4, continue stirring until ice obtains clear TiCl after melting completely4Solution.By TiCl4Solution is transferred to a table
In the ware of face, and 2 surfaces there is into WO3The FTO of nanometer sheet film is dipped in TiCl4In solution, contain WO3One face upward.By surface plate
It covers, and places it in 70 DEG C of baking oven and react 1h.After the completion of reaction, FTO samples are taken out, are used in combination deionized water lightly clear
It washes, then dries at 80 DEG C, finally sample is placed in Muffle furnace, under air conditions, 450 DEG C of heat treatment 2h obtain TiO2/
WO3Composite membrane.
ZnS-Bi2S3/TiO2/WO3The preparation of composite membrane：It first prepares and contains 0.1mol/L Bi (NO3)3·5H2O and
0.05mol/L Zn(NO3)2·6H2The ethylene glycol solution (solution A) of O, then prepare containing 0.2mol/L Na2S·9H2The methanol of O
Solution (solution B).The TiO prepared2/WO3After composite membrane vertically stands 5min in solution A, with a large amount of ethylene glycol washing samples
Product, and dried at 80 DEG C；Then, sample is put into solution B and vertically stands 5min, with a large amount of methanol lavage specimens after taking-up
Product, and dried at 80 DEG C.This process is that a chemical bath deposition recycles.Sample obtains ZnS-Bi after 5 cycles2S3/
TiO2/WO3Composite membrane.
The characterization of sample：Sample is observed using the Hitachi F-4800 type scanning electron microscope of Hitachi, Japan
(pure WO3Film and ZnS-Bi2S3/TiO2/WO3Composite membrane) apparent form, and utilize subsidiary X-ray electron spectrometer point at random
Analyse ZnS-Bi2S3/TiO2/WO3The chemical composition of composite membrane.
Photoproduction cathodic protection performance test：With pure WO3Film or ZnS-Bi2S3/TiO2/WO3Composite membrane is set as light anode
In the Na containing 0.1mol/L2SO3With 0.1mol/L Na2In the optical electro-chemistry electrolytic cell of S mixed solutions.Containing 0.5mol/L
In the corrosion electrolytic cell of NaCl solution, using 403 stainless steels as working electrode, Pt electrodes and saturated calomel electrode (SCE) are respectively
As auxiliary electrode and reference electrode.Light anode in optical electro-chemistry electrolytic cell passes through copper with the working electrode in corrosion electrolytic cell
Line connects, and two electrolytic cells are then connected by salt bridge.When test, using the xenon lamp of 150W as white light source, direct irradiation is in light sun
On extremely, current potential of 403 stainless steels before and after illumination is then recorded by potentiostat and is changed over time.
Fig. 1 is the pure WO prepared3Film and ZnS-Bi2S3/TiO2/WO3The SEM of composite film surface pattern schemes.It can be with from figure (a)
Find out WO prepared by hydro-thermal3Film is by the WO basically perpendicular to the surfaces FTO3Nanometer sheet forms, and the surface of nanometer sheet is with respect to light
It is sliding；And the nanometer sheet surface of composite membrane (b) then becomes relative coarseness, it can be seen that there are the tables of nanometer sheet for apparent particulate matter
Face.
Fig. 2 is ZnS-Bi2S3/TiO2/WO3The EDX analysis results of compound film component.The result shows that in composite membrane containing O,
S, the SnO of Ti, Zn, Sn, W and Bi element, wherein Sn essentially from the surfaces FTO2Coating, other elements are then from the compound of preparation
Film.Percentage by analyzing Bi, Zn and S can determine composite membrane by WO3、TiO2、Bi2S3It is formed with ZnS.
Fig. 3 is that 403 stainless steels electrode potential in the NaCl solution of 0.5mol/L changes with time song under different condition
Line.Wherein EcorrWhat is indicated is corrosion potential of 403 stainless steels in the solution, and value stabilization is in 20mV vs.SCE or so.
(a) it is 403 stainless steels and pure WO3Current potential versus time curve after the connection of film light anode.When 403 stainless steels and pure WO3Film connects
When connecing, under conditions of illumination, the current potential of stainless steel is negative to move on to -100mV vs.SCE or so；White light is opened in WO3Film
Afterwards, the current potential of stainless steel is negative rapidly moves on to -200mV vs.SCE or so, shows certain photoproduction cathodic protection effect.Cut-out
After light source, the current potential of stainless steel is then shuffled, until with comparable potential level before illumination.With the alternating of light source Push And Release
The current potential of Shi Jinhang, stainless steel can all occur negative shifting accordingly and shuffle.As 403 stainless steels and ZnS-Bi2S3/TiO2/WO3It is multiple
When closing the connection of film light anode, it is observed that similar potential response phenomenon.But ZnS-Bi under illumination2S3/TiO2/WO3It is multiple
Closing film can make 403 stainless steel cathodes be polarised to more negative current potential (- 500mV vs.SCE), i.e. its current potential is less than corrosion potential
About 520mV, after being especially turned off illumination, though the current potential of stainless steel is shuffled, but still is less than its corrosion potential about 320mV,
Illustrate that composite membrane remains able to provide cathodic protection for stainless steel after cutting off illumination.Potential test result favorable reproducibility, shows
Composite membrane is with good stability in intermittent irradiation process.
Embodiment 2
According to above-mentioned technical proposal, ZnS-Bi is prepared on FTO matrixes2S3/TiO2/WO3Composite membrane, and investigate its conduct
The photoproduction cathodic protection effect of 403 stainless steel of light anode pair.
The pretreatment of FTO matrixes：Commercialized FTO electro-conductive glass (15 Ω of surface resistance ＜/cm2, transmitance ＞ 90%) and it cuts
It is cut into the sample of rectangle, length 15mm, width 10mm, then thickness 2.2mm uses acetone, ethyl alcohol, deionized water ultrasound clear successively
20min is washed, is dried for standby.
WO3The preparation of nanometer sheet film：Take 0.231g sodium tungstates (Na2WO4·2H2O 30mL deionized waters) are dissolved in, are being stirred
It mixes down and 10mL 3mol/L hydrochloric acid (HCl) is added dropwise, continue stirring to formation pale yellow gum (H2WO4).0.200g grass is added
Sour ammonium ((NH4)2C2O4) and 30mL deionized waters, it obtains preparing WO after stirring 30min3The precursor solution of nanometer sheet.Then, will
The precursor solution of preparation is transferred in the ptfe autoclave of 100mL, and 3 FTO samples are immersed in solution, FTO with
Certain angle leans against the inner wall of ptfe autoclave, and keeps conduction downwards, so that it is carried out hydro-thermal at 150 DEG C anti-
Answer 3h.Then, cooled to room temperature takes out FTO samples, a large amount of deionized water cleaning sample is used in combination, then at 80 DEG C
Drying is to get to WO3Nanometer sheet film.
TiO2/WO3The preparation of composite membrane：50mL deionized waters are fitted into container, being put into refrigerator makes it build-up ice, then
Container takes out, and allows ice-out to forming mixture of ice and water.Under conditions of being vigorously stirred, it is added dropwise into mixture of ice and water
1.5mL TiCl4, continue stirring until ice obtains clear TiCl after melting completely4Solution.By TiCl4Solution is transferred to one
In surface plate, and 3 surfaces there is into WO3The FTO of nanometer sheet film is dipped in TiCl4In solution, contain WO3One face upward.By surface
In ware lid, and places it in 70 DEG C of baking oven and react 0.5h.After the completion of reaction, FTO samples are taken out, deionized water is used in combination gently
Ground cleans, and then dries at 80 DEG C, finally sample is placed in Muffle furnace, and under air conditions, 450 DEG C of heat treatment 2h are obtained
TiO2/WO3Composite membrane.
ZnS-Bi2S3/TiO2/WO3The preparation of composite membrane：It first prepares and contains 0.1mol/L Bi (NO3)3·5H2O and
0.05mol/L Zn(NO3)2·6H2The ethylene glycol solution (solution A) of O, then prepare containing 0.2mol/L Na2S·9H2The methanol of O
Solution (solution B).The TiO prepared2/WO3After composite membrane vertically stands 3min in solution A, with a large amount of ethylene glycol washing samples
Product, and dried at 80 DEG C；Then, sample is put into solution B and vertically stands 3min, with a large amount of methanol lavage specimens after taking-up
Product, and dried at 80 DEG C.This process is that a chemical bath deposition recycles.Sample obtains ZnS-Bi after 5 cycles2S3/
TiO2/WO3Composite membrane.
The characterization of sample：Sample is observed using the Hitachi F-4800 type scanning electron microscope of Hitachi, Japan
(pure WO3Film and ZnS-Bi2S3/TiO2/WO3Composite membrane) apparent form, and utilize subsidiary X-ray electron spectrometer point at random
Analyse ZnS-Bi2S3/TiO2/WO3The chemical composition of composite membrane.
Photoproduction cathodic protection performance test：With pure WO3Film or ZnS-Bi2S3/TiO2/WO3Composite membrane is set as light anode
In the Na containing 0.1mol/L2SO3With 0.1mol/L Na2In the optical electro-chemistry electrolytic cell of S mixed solutions.Containing 0.5mol/L
In the corrosion electrolytic cell of NaCl solution, using 403 stainless steels as working electrode, Pt electrodes and saturated calomel electrode (SCE) are respectively
As auxiliary electrode and reference electrode.Light anode in optical electro-chemistry electrolytic cell passes through copper with the working electrode in corrosion electrolytic cell
Line connects, and two electrolytic cells are then connected by salt bridge.When test, using the xenon lamp of 150W as white light source, direct irradiation is in light sun
On extremely, current potential of 403 stainless steels before and after illumination is then recorded by potentiostat and is changed over time.
Fig. 4 is the pure WO prepared3Film and ZnS-Bi2S3/TiO2/WO3The SEM of composite film surface pattern schemes.Comparison diagram (a) and
(b) as can be seen that sample is all made of the nanometer sheet basically perpendicular to the surfaces FTO, pure WO3The nanometer sheet surface phase of film (a)
To smooth, and the nanometer sheet surface in composite membrane (b) is then more coarse, it is observed that apparent particulate matter.
Fig. 5 is ZnS-Bi2S3/TiO2/WO3The EDX analysis results of compound film component.The result shows that in composite membrane containing O,
S, the SnO of Ti, Zn, Sn, W and Bi element, wherein Sn essentially from the surfaces FTO2Coating, other elements are then from the compound of preparation
Film.Composite membrane can be determined by WO by the atomic percent of each element3、TiO2、Bi2S3It is formed with ZnS.
Fig. 6 is that 403 stainless steels electrode potential in 0.5mol/LNaCl solution changes over time curve under different condition.Its
Middle EcorrWhat is indicated is corrosion potential of 403 stainless steels in the solution, and value stabilization is in 20mV vs.SCE or so.(a) it is
403 stainless steels and pure WO3Current potential versus time curve after the connection of film light anode.When 403 stainless steels and pure WO3When film connects,
Under conditions of not having illumination, the current potential of stainless steel is negative to move on to -100mV vs.SCE or so；White light is opened in WO3After film, no
The current potential of rust steel is negative rapidly to move on to -200mV vs.SCE or so, shows certain photoproduction cathodic protection effect.Cut off light source
Afterwards, the current potential of stainless steel is then shuffled, until with comparable potential level before illumination.With light source Push And Release alternating into
The current potential of row, stainless steel can all occur negative shifting accordingly and shuffle.403 stainless steels and ZnS-Bi2S3/TiO2/WO3Composite membrane light
When anode connects, it is observed that similar potential response phenomenon.But ZnS-Bi under illumination2S3/TiO2/WO3Composite membrane energy
403 stainless steel cathodes are enough made to be polarised to more negative current potential (- 460mV vs.SCE), i.e. its current potential about less than corrosion potential
480mV after being especially turned off illumination, though the current potential of stainless steel is shuffled, but still is less than its corrosion potential about 280mV
Vs.SCE illustrates that composite membrane remains able to provide cathodic protection for stainless steel after cutting off illumination.Potential test result reproducibility
It is good, show that composite membrane is with good stability in intermittent irradiation process.
Claims (6)
1.ZnS-Bi2S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that include the following steps：
1) pretreatment of FTO matrixes；
2) WO is prepared3Nanometer sheet film；
3) TiO is prepared2/WO3Composite membrane；
4) ZnS-Bi is prepared2S3/TiO2/WO3Composite membrane, i.e. ZnS-Bi2S3/TiO2/WO3Nanometer sheet complex light anode.
2. ZnS-Bi as described in claim 12S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that
In step 1), the pretreated specific method of the FTO matrixes is：FTO electro-conductive glass is cut into rectangular specimen, length 15~
25mm, 10~15mm of width, 2.2~2.3mm of thickness, then successively use acetone, ethyl alcohol, deionized water be cleaned by ultrasonic 20~
30min is dried for standby.
3. ZnS-Bi as claimed in claim 22S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that institute
State 15 Ω of surface resistance ＜/cm of FTO electro-conductive glass2, transmitance ＞ 90%.
4. ZnS-Bi as described in claim 12S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that
In step 2), the preparation WO3The specific method of nanometer sheet film is：0.230~0.235g sodium tungstates are dissolved in 28~32mL and go
9~11mL, 2.8~3.2mol/L hydrochloric acid is added in ionized water under stiring, continues stirring to pale yellow gum is formed, adds
0.200~0.220g ammonium oxalate and 28~32mL deionized waters obtain preparing WO after stirring 28~32min3The forerunner of nanometer sheet
Solution；The precursor solution of preparation is transferred in ptfe autoclave, and FTO electro-conductive glass samples are immersed in solution,
FTO electro-conductive glass leans against the inner wall of ptfe autoclave, and keeps conduction downwards, keeps it anti-in 120~160 DEG C of hydro-thermals
3~6h is answered, then, cooled to room temperature takes out FTO electro-conductive glass samples, deionized water cleaning sample is used in combination, then 60
It is dried to get to WO at~80 DEG C3Nanometer sheet film.
5. ZnS-Bi as described in claim 12S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that
In step 3), the preparation TiO2/WO3The specific method of composite membrane is；50~52mL deionized waters are fitted into container, in ice
Water is set to build-up ice in case；Then, container is taken out, allows ice-out to mixture of ice and water is formed, under stirring conditions, toward ice water
1~2mL TiCl are added in mixture4, continue stirring until ice obtains clear TiCl after melting completely4Solution；By TiCl4It is molten
Liquid is transferred in surface plate, and there is WO on surface3The FTO of nanometer sheet film is dipped in TiCl4In solution, contain WO3One face upward,
Surface plate is covered, then is placed in 0.5~2h of reaction in 68~75 DEG C of baking oven, after the completion of reaction, takes out FTO samples, and spend
Ionized water cleans, and then dries at 60~80 DEG C, finally FTO samples are placed in Muffle furnace, under air conditions, with 450
~460 DEG C of 1.6~2.2h of heat treatment, obtain TiO2/WO3Composite membrane.
6. ZnS-Bi as described in claim 12S3/TiO2/WO3The preparation method of nanometer sheet complex light anode, it is characterised in that
In step 4), the preparation ZnS-Bi2S3/TiO2/WO3The specific method of composite membrane is：It prepares and contains 0.10~0.15mol/
LBi(NO3)3·5H2O and 0.05~0.08mol/L Zn (NO3)2·6H2The ethylene glycol solution of O is denoted as solution A, then prepares and contain
There are 0.15~0.22mol/L Na2S·9H2The methanol solution of O, is denoted as solution B；First, TiO2/WO3Composite membrane is in solution A
After 3~5min of vertical standing, spent glycol rinses sample, and is dried at 60~80 DEG C；Then, sample is hung down in solution B
It is straight to stand 3~5min, sample is rinsed with methanol after taking-up, and dried at 60~80 DEG C, this process is that a chemical bath is heavy
Product cycle, sample obtain ZnS-Bi after 5~10 cycles2S3/TiO2/WO3Composite membrane, i.e. ZnS-Bi2S3/TiO2/WO3It receives
Rice piece complex light anode.
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| CN109468674A (en) * | 2018-12-17 | 2019-03-15 | 滨州学院 | TiO2/WO3The preparation method of nano composite membrane |
| CN110004459A (en) * | 2019-04-28 | 2019-07-12 | 安徽大学 | A kind of hetero-junctions light anode and its preparation method and application driving carbon dioxide reduction |
| CN110368962A (en) * | 2019-07-31 | 2019-10-25 | 西安建筑科技大学 | A kind of BiOI/WO3Preparation method, product and the application of hetero-junctions efficient photoelectricity treater catalysis electrode |
| CN115433943A (en) * | 2022-09-09 | 2022-12-06 | 中国科学院海洋研究所 | Energy storage type semiconductor composite photo-anode for metal corrosion protection |
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