CN105386061A - Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes - Google Patents

Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes Download PDF

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CN105386061A
CN105386061A CN201510769451.6A CN201510769451A CN105386061A CN 105386061 A CN105386061 A CN 105386061A CN 201510769451 A CN201510769451 A CN 201510769451A CN 105386061 A CN105386061 A CN 105386061A
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tio
anode
nanometer rod
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solution
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杜荣归
胡娟
刘青
梁燕
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Xiamen University
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto

Abstract

The invention relates to a nanorod composite-film photo-anode, in particular to a method for preparing a Bi2S3/TiO2 nanorod composite-film photo-anode. The method includes the steps of preparing a TiO2 seed film sample, preparing an FTO surface TiO2 nanorod array film, and preparing the Bi2S3/TiO2 nanorod composite-film photo-anode. A hydrothermal method and a circulation dipping method are combined; and when a prepared Bi2S3/TiO2 nanorod composite film is arranged in a mixed solution of Na2S of 0.1 mol/L and NaOH of 0.2 mol/L, and irradiation is carried out through white light, the electrode potential of 403# stainless steel, connected with the Bi2S3/TiO2 nanorod composite film, in a NaCl solution of 0.5 mol/L can be reduced by 725 mV relative to the natural corrosion potential of the stainless steel, remarkable cathode polarization occurs, and it is indicated that the composite film has the good photoproduction cathode protection effect on the stainless steel. When irradiation is carried out again after illumination is stopped for a certain period of time, the electrode potential can still be reduced to a value the same as the previous value, and good stability is achieved.

Description

Bi 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode
Technical field
The present invention relates to nanometer rod composite film photo-anode, especially relate to Bi 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode.
Background technology
The nineties in last century, Yuan etc. [1]find TiO 2nanoparticle coating can play photoproduction galvanic protection effect to Copper substrate.Its ultimate principle is: under light illumination, TiO 2the photon absorbing appropriate energy produces photo-generate electron-hole pair, and then light induced electron transfers to protected metallic surface, makes its current potential far below corrosion potential thus suppresses its corrosion reaction, and hole is caught by the hole trapping agents in medium simultaneously.In research subsequently, Fujishima etc. [2]report TiO 2coating to 304 stainless photoproduction galvanic protection effects, Tsujikawa etc. [3,4]report its photoproduction galvanic protection effect to 304 stainless steels and carbon steel.Utilize TiO 2it is a kind of needs consume electric energy and the novel cathode protected mode of environment-friendly high-efficiency that the opto-electronic conversion effect of coating carries out photoproduction galvanic protection to metal and stainless steel.Park etc. [5]in order to solve because of TiO 2the protected matrix crevice corrosion problem that coating is chapped and caused, proposes and adopts TiO 2the coupling protected metal of film light anode, to the another kind of photoproduction galvanic protection mode that metal is protected.Adopting in this way can investigation and application TiO easily 2the photoproduction galvanic protection effect of modified membrane light anode, and harmful effect is not produced to protected metallic surface.In the research of photoproduction galvanic protection, the TiO of different-shape 2nano material is as nano-particular film [6,7], nanotube films [8,9], nano wire film etc. [10]be obtained for application.At TiO 2in nano-particular film, due to the energy barrier between particle, the transmission of electronics is mainly undertaken by transition mechanism, therefore, with TiO 2nano-particular film is compared, the TiO of one-dimentional structure 2there is more efficient electric transmission efficiency [11-13].
TiO 2mainly be present in occurring in nature with Detitanium-ore-type, rutile-type and brookite type.Because brookite is rare at occurring in nature, be difficult to synthesis, therefore, the research of brookite is relatively less [14].Anatase octahedrite TiO 2can transform to Rutile Type at 400 ~ 1200 DEG C [15], the condition of transition temperature and speed of reaction and pre-reaction material has very large relation [16-18], therefore, from long-term stability, rutile TiO 2can be more stable.But, in photoproduction galvanic protection research, the TiO adopted 2substantially be all Detitanium-ore-type TiO 2.In fact, in solar cell and photocatalysis hydrogen production field, Rutile Type TiO 2be proved to be and had and anatase octahedrite TiO 2comparable effect [13,19], therefore, rutile TiO 2also can be applied in photoproduction galvanic protection.Although rutile TiO 2energy gap (3.0eV) than anatase octahedrite TiO 2(3.2eV) energy gap is little [20]but, Rutile Type TiO 2still effectively can not utilize visible ray, therefore, be necessary to widen Rutile Type TiO 2in the spectral response of visible ray.Bi 2s 3be a kind of semi-conductor of low energy gap and have large specific absorbance, in addition, its conduction band positions compares TiO 2more negative [21], this makes Bi 2s 3light induced electron in conduction band can be transferred to TiO smoothly 2conduction band, therefore, Bi 2s 3can as the effective TiO of one 2photosensitizers, Bi 2s 3with TiO 2compound may become the light anode of excellent opto-electronic conversion performance.
As the metallic substance that a class is important, stainless steel all has a wide range of applications in every field.But in many circumstances, many stainless corrosion phenomenons are still more serious, therefore, be necessary to protect it.
Summary of the invention
The object of the invention is to overcome single TiO 2nano-sized membrane effectively can not utilize the problem such as visible ray and the easy compound of photo-generated carrier, provides a kind of Bi with efficient photoproduction galvanic protection effect 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode.
The present invention includes following steps:
1) TiO is prepared 2seed film layer sample:
By FTO glass successively in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple, obtain FTO matrix sample totally, first prepare TiCl 4the aqueous solution, is then soaked in TiCl by FTO matrix sample 4in the aqueous solution, take out after thermal treatment, cleaning, calcining, is cooled to room temperature, obtains TiO 2seed film layer sample;
In step 1) in, the thickness of described FTO glass can be 2.2mm, and width can be 10 ~ 15mm, and length can be 15 ~ 20mm, surface resistance <15 Ω cm -2, the transmittance >90% of glass; The time of described ultrasonic cleaning can be 25 ~ 35min; Described preparation TiCl 4the concrete grammar of the aqueous solution can be: pipette 0.5 ~ 2mLTiCl 4solution, then add in the ice water solution of 50 ~ 60g, magneton is stirred to TiCl 4complete hydrolysis, preparation obtains TiCl 4the aqueous solution; Described heat treated temperature can be 60 ~ 80 DEG C, and the heat treated time can be 25 ~ 40min; Sample can be put into retort furnace and calcine 50 ~ 70min at 500 ~ 580 DEG C by the condition of described calcining, and temperature rise rate can be 5 DEG C/min.
2) FTO surface TiO is prepared 2nano-stick array membrane:
Tetrafluoroethylene template is put in FTO substrate, and makes its conducting surface downward, then put into tetrafluoroethylene hydrothermal reaction kettle, add TiO in a kettle. 2growth solution, after hydro-thermal reaction, takes out sample, cleaning, dries, obtain FTO surface TiO 2nano-stick array membrane;
In step 2) in, the temperature of described hydro-thermal reaction can be 130 ~ 160 DEG C, and the time of hydro-thermal reaction can be 8 ~ 11h; Described TiO 2growth solution can adopt following methods to prepare: the TiCl getting 1 ~ 2mL 4add in the hydrochloric acid soln of 20 ~ 40mL, until TiCl 4after whole hydrolysis, add the deionized water of (20 ~ 40) mL, whole process stirs with magneton all the time; Described hydrochloric acid soln can adopt mass percentage concentration be 37% concentrated hydrochloric acid solution.
3) Bi is prepared 2s 3/ TiO 2nanometer rod composite film photo-anode:
In FTO surface TiO 2nano-stick array membrane surface preparation Bi 2s 3nano particle; By Bi (NO 3) 35H 2o is dissolved in ethylene glycol solution and obtains Bi 3+precursor solution; Again by Na 2s9H 2o is dissolved in deionized water and obtains S 2-precursor solution; By step 2) the FTO surface TiO prepared 2nanometer stick array membrane sample is placed in Bi 3+precursor solution in flood, then use deionized water rinsing, after drying, then put into containing S 2-precursor solution in deposit, then use deionized water rinsing, again dry; Circulation like this 10 ~ 20 times, obtains Bi 2s 3/ TiO 2nanometer rod composite membrane, then, at N 2calcining sample under atmosphere, obtains Bi 2s 3/ TiO 2nanometer rod composite film photo-anode.
In step 3) in, described Bi (NO 3) 35H 2the proportioning of O and ethylene glycol solution can be (0.05 ~ 0.1) g: (25 ~ 30) mL, wherein, and Bi (NO 3) 35H 2o calculates in mass, and ethylene glycol solution is calculated by volume; Described Na 2s9H 2the proportioning of O and deionized water can be (0.1 ~ 0.15) g: (25 ~ 30) mL, wherein, and Na 2s9H 2o calculates in mass, and deionized water is calculated by volume; The time of described dipping can be 1 ~ 2min; The temperature of described drying can be 50 ~ 80 DEG C; The time of described deposition can be 1 ~ 2min; Described again dry temperature can be 50 ~ 80 DEG C; The temperature of described calcining can be 200 ~ 300 DEG C, and the time of calcining can be 2 ~ 5h.
Below provide Bi 2s 3/ TiO 2nanometer rod composite membrane is to the testing method of metal photoproduction galvanic protection effect:
Test macro comprises photoelectrolytic cell and corrosion electrolyzer.By Bi 2s 3/ TiO 2nanometer rod composite film photo-anode is placed in photoelectrolytic cell, and its electrolyte solution is (0.05 ~ 0.15) mol/LNa 2the mixing solutions of S+ (0.15 ~ 0.25) mol/LNaOH.Protected metal (403 stainless steel) corrodes electrolyzer for working electrode is placed in, and wherein solution is the NaCl aqueous solution of (0.3 ~ 0.8) mol/L.Pt electrode is respectively to electrode and reference electrode and saturated calomel (SCE) electrode forms three electrolysis batteries in corrosion cell.Bi 2s 3/ TiO 2be be connected by Cu wire between nanometer rod composite membrane with protected metal, photoelectrolytic cell is connected by salt bridge with corrosion electrolyzer.White light source is 150W high pressure xenon lamp.The electropotential change of protected metal electrode before and after illumination in corrosion electrolyzer is detected with potentiostat.By with there is no comparing of the electropotential of the metal of coupling photo-anode film, can the photoproduction galvanic protection effect of the right metal of evaluating combined film light anode.
Instant invention overcomes single TiO 2nano-sized membrane effectively can not utilize the problem of visible ray and the easy compound of photo-generated carrier, first grows TiO by hydrothermal method at FTO conductive glass surface 2nanometer rod film, then by circulatory maceration at TiO 2nanometer rod film surface deposition low energy gap Bi 2s 3nano particle, Bi 2s 3with TiO 2form type II type heterojunction structure complex thin film [22], be prepared into Bi 2s 3/ TiO 2nanometer rod composite membrane.This composite membrane can be used as light anode and plays excellent photoproduction galvanic protection effect to metals such as the stainless steels in corrosive medium.
Ultimate principle of the present invention: TiO 2with the semi-conductor Bi of narrow band gap 2s 3compound.Under visible light illumination, Bi 2s 3absorb photons transits to conduction band and produces photo-generate electron-hole pair.Due to Bi 2s 3can with TiO 2form type II type heterojunction structure, therefore light induced electron can be transferred to TiO 2conduction band, and then transfer to protected metallic surface, metallic surface electronics is increased and cathodic polarization occurs thus suppresses the anode dissolution reaction of metal, namely corrosion of metal receives control; Bi simultaneously 2s 3hole in valence band is caught by the hole trapping agents in solution, thus have effectively achieved the separation of electron-hole pair, improves its electricity conversion.
The present invention first adopts hydrothermal method to prepare one-dimensional single crystal rutile TiO at FTO conductive glass surface 2nanometer rod film, then, with circulatory maceration at TiO 2nanometer rod film surface deposition Bi 2s 3nano particle, preparation Bi 2s 3/ TiO 2composite membrane.Coupling with the composite membrane as light anode using the stainless steel that will be in corrosive medium, obtain stainless photoproduction galvanic protection effect.
Heterojunction structure Bi prepared in accordance with the present invention 2s 3/ TiO 2nanometer rod composite membrane, can be used as the light anode in photoproduction cathodic protection system.This composite membrane of illumination can make protected electropotential coupling with it significantly decline, when composite membrane is at 0.1mol/LNa 2in S+0.2mol/LNaOH solution, 403 stainless steels be in 0.5mol/LNaCl solution coupling with it can be made to have dropped 325mV than electropotential when not irradiating under irradiating under white light, about 375mV is have dropped than 403 Corrosion of Stainless Steel current potentials time not coupling, thus making stainless steel that significant cathodic polarization occur, corrosion reaction receives control.When transferring dark-state to after illumination, stainless electropotential rises, but still lower than its corrosion potential, shows Bi in the dark state 2s 3/ TiO 2composite membrane also has certain galvanic protection effect to stainless steel.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the embodiment of the present invention 1 2s 3/ TiO 2the exterior view of the surface topography (SEM figure) of nanometer rod composite membrane.
Fig. 2 is Bi prepared by the embodiment of the present invention 1 2s 3/ TiO 2the side elevational view of the surface topography (SEM figure) of nanometer rod composite membrane.
Fig. 3 is TiO prepared by the application embodiment of the present invention 1 2and Bi 2s 3/ TiO 2nano thin-film transient state photoelectricity flow graph under visible light illumination.(a)TiO 2，(b)Bi 2S 3/TiO 2。
Fig. 4 is that in the embodiment of the present invention 1,403 stainless steels are coupling from different film light anode in 0.5MNaCl solution, and the electropotential before and after illumination is change curve (on represents illumination, and off represents closedown light source) in time, (a) TiO 2, (b) Bi 2s 3/ TiO 2.
Fig. 5 is Bi prepared by the application embodiment of the present invention 2 2s 3/ TiO 2the exterior view of the surface topography (SEM figure) of nanometer rod composite membrane.
Fig. 6 is Bi prepared by the application embodiment of the present invention 2 2s 3/ TiO 2the side elevational view of the surface topography (SEM figure) of nanometer rod composite membrane.
Fig. 7 is TiO prepared by the application embodiment of the present invention 2 2and Bi 2s 3/ TiO 2nano thin-film transient state photoelectricity flow graph under visible light illumination.(a)TiO 2，(b)Bi 2S 3/TiO 2。
Fig. 8 is that in the embodiment of the present invention 2,403 stainless steels are coupling from different film light anode in 0.5MNaCl etchant solution, and the electropotential before and after illumination is change curve (on represents illumination, and off represents closedown light source) in time.(a)TiO 2，(b)Bi 2S 3/TiO 2。
Embodiment
Embodiment 1
According to technique scheme (concrete steps), preparation Bi 2s 3/ TiO 2nanometer rod composite membrane, and test compound film as light anode to 403 stainless galvanic protection effects.
Get the FTO conductive glass sample that 2.2mm is thick, its long 15mm, wide is 10mm.Successively ultrasonic cleaning 30min successively in acetone, dehydrated alcohol and deionized water.
TiO 2the preparation of Seed Layer: according to technique scheme, pipettes the TiCl of 1mL 4solution, careful dropping prepares TiCl in the frozen water mixing solutions of 50g 4the aqueous solution, to lie against FTO substrate in this solution and to make its conducting surface upwards, thermal treatment 30min in the baking oven of 70 DEG C, after reaction terminates, take out sample, by washed with de-ionized water, after drying, sample is put into retort furnace and calcine 60min at 550 DEG C, then naturally cool to room temperature.
FTO surface TiO 2the preparation of nano-stick array membrane: there is TiO on surface 2the FTO matrix sample of Seed Layer for the angle of about 75 ° puts into tetrafluoroethylene reactor, adds TiO with relative level face 2growth solution (1mLTiCl 4+ 30mL deionized water+30mL concentrated hydrochloric acid), take out after 150 DEG C of Water Under thermal response 10h, dry for standby again after clean with deionized water rinsing.
Bi 2s 3/ TiO 2the preparation of nanometer rod composite membrane: by the Bi (NO of 0.06g 3) 35H 2o is dissolved in the ethylene glycol solution of 25mL and obtains Bi 3+precursor solution, by the Na of 0.15g 2s9H 2o is dissolved in the deionized water solution of 25mL and obtains S 2-precursor solution.By the TiO of above-mentioned preparation 2nanometer rod membrane sample is placed in Bi 3+flood 1min in solution, then rinse with deionization, at 80 DEG C after drying, then put into containing S 2-solution in deposit 1min, then use deionized water rinsing, then at 80 DEG C after drying.Circulation like this 15 times, then sample is placed in N 2calcine under atmosphere, its temperature is 240 DEG C, and the time is 4h.Finally, naturally cool to room temperature, obtain Bi 2s 3/ TiO 2nanometer rod composite films.
Photoelectric current is tested: adopt the photoelectrochemistry test macro of laboratory assembling to measure the photoelectric current of the nanometer film of preparation.Test is carried out, respectively with TiO separately in the photoelectrolytic cell at three-electrode system 2film or Bi 2s 3/ TiO 2nanometer rod composite membrane is as light anode, and saturated calomel electrode is reference electrode, and platinum filament is supporting electrode.Measure the photoelectric current of membrane sample under white light illumination.
Bi 2s 3/ TiO 2nanometer rod composite membrane photoproduction galvanic protection is tested: the photoproduction galvanic protection performance adopting the self-assembly systems test compound film comprising photoelectrolytic cell and corrosion electrolyzer.Respectively with pure TiO 2nanometer rod film and Bi 2s 3/ TiO 2nano composite membrane is light anode, is placed in containing 0.1mol/LNa 2in the photoelectrolytic cell of S+0.2mol/LNaOH solution.Corrosion electrolyzer is three-electrode system, and protected metal (403 stainless steel), Pt electrode and saturated calomel electrode (SCE) are respectively working electrode, to electrode and reference electrode, its medium is 0.5mol/LNaCl solution.Light anode is connected by wire with 403 stainless steels, and photoelectrolytic cell is connected by salt bridge (agar containing 1.0mol/LKCl) with corrosion electrolyzer.White light source is 150W high pressure xenon lamp (direct irradiation is photoanode surface in photoelectrolytic cell).The potential variation of protected 403 stainless steel electrodes before and after illumination is detected with potentiostat.By comparing with 403 stainless electropotentials when not having a coupling smooth anode, different film light anode can be evaluated to stainless photoproduction galvanic protection effect.
Fig. 1 and Fig. 2 is respectively obtained Bi 2s 3/ TiO 2sEM figure (exterior view and side elevational view) of nano composite membrane.Can find out, composite membrane is made up of nanometer rod, and surface ratio is comparatively even, and thickness is about 10 μm.
Fig. 3 is respectively TiO 2(a) and Bi 2s 3/ TiO 2(b) nano thin-film transient state photoelectricity flow graph under visible light illumination.As can be seen from Figure 3, compared to pure TiO 2nanometer rod film, Bi 2s 3/ TiO 2nanometer rod composite membrane has high photoelectric current, and opto-electronic conversion performance is more excellent.
Fig. 4 be 403 stainless steels in 0.5mol/LNaCl solution respectively with pure TiO 2(Fig. 4 a) and Bi 2s 3/ TiO 2electropotential change curve in time before and after white light when nanometer rod (Fig. 4 b) film connects.First record the corrosion potential (open circuit potential) of 403 stainless steels before coupling and be about 50mV (vs.SCE).As 403 stainless steels and TiO 2when nanometer rod film is coupling, after white light nanometer film, 403 stainless current potentials decline, and (Fig. 4 a), has good photoproduction galvanic protection effect to about 230mV.When with Bi 2s 3/ TiO 2after nanometer rod composite membrane is coupling, under illumination, stainless electropotential can decline 325mV (Fig. 4 b), is equivalent to, lower than 403 Corrosion of Stainless Steel current potential 725mV, serve excellent photoproduction galvanic protection effect.Along with light application time extends, there is not the trend risen in this stainless steel potential value, shows that composite membrane is by good stability.When cutting off light source certain hour and again opening light source, with TiO 2and Bi 2s 3/ TiO 2the coupling 403 stainless electropotentials of nanometer rod film can reach potential value during first time white light.These results suggest that Bi 2s 3/ TiO 2composite membrane is stable, and compared to pure TiO 2nanometer rod film, can play better photoproduction galvanic protection effect to stainless steel.
Embodiment 2
According to technique scheme (concrete steps), preparation Bi 2s 3/ TiO 2nanometer rod composite membrane, and test compound film as light anode to 403 stainless galvanic protection effects.
Get the FTO conductive glass sample that 2.2mm is thick, its long 15mm, wide is 10mm.Successively ultrasonic cleaning 30min successively in acetone, dehydrated alcohol and deionized water.
TiO 2the preparation of Seed Layer: according to technique scheme, pipettes the TiCl of 1mL 4solution, careful dropping prepares TiCl in the frozen water mixing solutions of 50g 4the aqueous solution, to lie against FTO substrate in this substrate solution and to make its conducting surface upwards, thermal treatment 30min in the baking oven of 70 DEG C, after reaction terminates, take out sample, by washed with de-ionized water, after drying, sample is put into retort furnace and calcine 60min at 550 DEG C, then naturally cool to room temperature.
FTO surface TiO 2the preparation of nano-stick array membrane: there is TiO on surface 2the FTO matrix sample of Seed Layer puts into tetrafluoroethylene reactor with the angle in about 75 °, relative level face, adds TiO 2growth solution (1mLTiCl 4+ 30mL deionized water+30mL concentrated hydrochloric acid), take out after 150 DEG C of Water Under thermal response 10h, dry for standby again after clean with deionized water rinsing.
Bi 2s 3/ TiO 2the preparation of nanometer rod composite membrane: by the Bi (NO of 0.08g 3) 35H 2o is dissolved in the ethylene glycol solution of 25mL and obtains Bi 2s 3bi 3+precursor solution, by the Na of 0.1g 2s9H 2o is dissolved in Bi in the deionized water solution of 25mL 2s 3s 2-precursor solution.By the TiO of above-mentioned preparation 2nanometer rod membrane sample is placed in Bi 3+flood 1min in solution, then rinse with deionization, at 80 DEG C after drying, then put into containing S 2-solution in deposit 1min, then use deionized water rinsing, drier at 80 DEG C.Circulation like this 18 times, then sample is placed in N 2calcine under atmosphere, its temperature is 240 DEG C, and the time is 4h.Finally, naturally cool to room temperature, obtain Bi 2s 3/ TiO 2nanometer rod composite films.
Photoelectric current is tested: adopt the photoelectrochemistry test macro of laboratory assembling to measure the photoelectric current of the nanometer film of preparation.Test is carried out, respectively with TiO separately in the photoelectrolytic cell at three-electrode system 2film or Bi 2s 3/ TiO 2nanometer rod composite membrane is as light anode, and saturated calomel electrode is reference electrode, and platinum filament is supporting electrode.Measure the photoelectric current of membrane sample under white light illumination.
Bi 2s 3/ TiO 2nanometer rod composite membrane photoproduction galvanic protection is tested: the photoproduction galvanic protection performance adopting the self-assembly systems test compound film comprising photoelectrolytic cell and corrosion electrolyzer.Respectively with pure TiO 2nanometer rod film and Bi 2s 3/ TiO 2nano composite membrane is light anode, is placed in containing 0.1mol/LNa 2in the photoelectrolytic cell of S+0.2mol/LNaOH solution.Corrosion electrolyzer is three-electrode system, and protected metal (403 stainless steel), Pt electrode and saturated calomel electrode (SCE) are respectively working electrode, to electrode and reference electrode, it is situated between for the 0.5mol/LNaCl aqueous solution.Light anode is connected by wire with 403 stainless steels, and photoelectrolytic cell is connected by salt bridge (agar containing 1.0mol/LKCl) with corrosion electrolyzer.White light source is 150W high pressure xenon lamp (direct irradiation is photoanode surface in photoelectrolytic cell).The potential variation of protected 403 stainless steel electrodes before and after illumination is detected with potentiostat.By comparing with 403 stainless electropotentials when not having a coupling smooth anode, different film light anode can be evaluated to stainless photoproduction galvanic protection effect.
Fig. 5 and Fig. 6 is respectively obtained Bi 2s 3/ TiO 2sEM figure (exterior view and side elevational view) of nano composite membrane.Can find out, composite membrane is made up of nanometer rod, and surface ratio is more even.Thickness is about 10 μm.
Fig. 7 is respectively TiO 2(a) and Bi 2s 3/ TiO 2(b) nano thin-film transient state photoelectricity flow graph under visible light illumination.As can be seen from Figure 7, compared to pure TiO 2nanometer rod film, Bi 2s 3/ TiO 2nanometer rod composite membrane has high photoelectric current, and opto-electronic conversion performance is more excellent.
Fig. 8 be 403 stainless steels in 0.5mol/LNaCl solution respectively with pure TiO 2(Fig. 8 a) and Bi 2s 3/ TiO 2electropotential change curve in time before and after white light when nanometer rod (Fig. 8 b) film connects.First record the corrosion potential (open circuit potential) of 403 stainless steels before coupling and be about 50mV (vs.SCE).As 403 stainless steels and TiO 2when nanometer rod film is coupling, after white light nanometer film, 403 stainless current potentials decline, and (Fig. 8 a), has good photoproduction galvanic protection effect to about 230mV.When with Bi 2s 3/ TiO 2after nanometer rod composite membrane is coupling, under illumination, stainless electropotential can decline 310mV (Fig. 8 b), is equivalent to, lower than 403 Corrosion of Stainless Steel current potential 700mV, serve excellent photoproduction galvanic protection effect.And along with light application time prolongation, there is not the trend risen in this stainless steel electrode potential value, shows that composite membrane is by good stability.When cutting off light source certain hour and again opening light source, with TiO 2and Bi 2s 3/ TiO 2the coupling 403 stainless electropotentials of nanometer rod film can reach potential value during first time white light, these results suggest that, Bi 2s 3/ TiO 2composite membrane is stable, and compared to pure TiO 2nanometer rod film, can play better photoproduction galvanic protection effect to stainless steel.
The present invention combines with circulatory maceration with hydrothermal method, has prepared the Bi for photoproduction galvanic protection at FTO conductive glass surface 2s 3/ TiO 2nanometer rod composite film photo-anode.First, after FTO sample being cleaned up, TiCl is soaked in 4in solution, thermal treatment certain hour, calcines after taking-up again, obtains surface TiO 2seed Layer.Sample is put into containing TiCl 4with carry out hydro-thermal reaction in the solution of HCl and form monocrystalline rutile TiO on FTO surface 2nanometer rod film.Then, by the TiO of preparation 2nanometer rod film respectively alternating impregnating in containing Bi 3+ion and S 2-in the solution of ion, utilize circulatory maceration in film surface deposition Bi 2s 3nano particle, finally, makes sample at N 2calcine under atmosphere, namely obtain Bi 2s 3/ TiO 2nanometer rod composite membrane.Select suitable Bi 3+and S 2-concentration, dipping time, cycle index can control the Bi for preparing 2s 3the size and number of particle.Surface there is Bi 2s 3/ TiO 2the sample of nanometer rod composite membrane is soaked in as light anode in suitable electrolyte solution, and makes it to be connected with protected metal (stainless steel etc.) with wire, can play photoproduction galvanic protection effect to metal.Bi prepared by the present invention 2s 3/ TiO 2nanometer rod composite membrane is at 0.1mol/LNa 2in S+0.2mol/LNaOH mixing solutions; during white light; what can make to be attached thereto is in 403 stainless electropotentials its spontaneous potential decline 725mV relatively in 0.5mol/LNaCl solution; there is significant cathodic polarization, show that composite membrane has good photoproduction galvanic protection effect to stainless steel.When irradiating after stopping illumination certain hour, the numerical value that stainless steel electrode current potential is same before still can dropping to, illustrates that composite film photo-anode has satisfactory stability, sustainable use again.

Claims (10)

1.Bi 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that comprising the following steps:
1) TiO is prepared 2seed film layer sample:
By FTO glass successively in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple, obtain FTO matrix sample totally, first prepare TiCl 4the aqueous solution, is then soaked in TiCl by FTO matrix sample 4in the aqueous solution, take out after thermal treatment, cleaning, calcining, is cooled to room temperature, obtains TiO 2seed film layer sample;
2) FTO surface TiO is prepared 2nano-stick array membrane:
Tetrafluoroethylene template is put in FTO substrate, and makes its conducting surface downward, then put into tetrafluoroethylene hydrothermal reaction kettle, add TiO in a kettle. 2growth solution, after hydro-thermal reaction, takes out sample, cleaning, dries, obtain FTO surface TiO 2nano-stick array membrane;
3) Bi is prepared 2s 3/ TiO 2nanometer rod composite film photo-anode:
In FTO surface TiO 2nano-stick array membrane surface preparation Bi 2s 3nano particle; By Bi (NO 3) 35H 2o is dissolved in ethylene glycol solution and obtains Bi 3+precursor solution; Again by Na 2s9H 2o is dissolved in deionized water and obtains S 2-precursor solution; By step 2) the FTO surface TiO prepared 2nanometer stick array membrane sample is placed in Bi 3+precursor solution in flood, then use deionized water rinsing, after drying, then put into containing S 2-precursor solution in deposit, then use deionized water rinsing, again dry; Circulation like this 10 ~ 20 times, obtains Bi 2s 3/ TiO 2nanometer rod composite membrane, then, at N 2calcining sample under atmosphere, obtains Bi 2s 3/ TiO 2nanometer rod composite film photo-anode.
2. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 1) in, the thickness of described FTO glass is 2.2mm, and width is 10 ~ 15mm, and length is 15 ~ 20mm, surface resistance <15 Ω cm -2, the transmittance >90% of glass; The time of described ultrasonic cleaning can be 25 ~ 35min.
3. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 1) in, described preparation TiCl 4the concrete grammar of the aqueous solution is: pipette 0.5 ~ 2mLTiCl 4solution, then add in the ice water solution of 50 ~ 60g, magneton is stirred to TiCl 4complete hydrolysis, preparation obtains TiCl 4the aqueous solution.
4. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 1) in, described heat treated temperature is 60 ~ 80 DEG C, and the heat treated time is 25 ~ 40min; Sample can be put into retort furnace and calcine 50 ~ 70min at 500 ~ 580 DEG C by the condition of described calcining, and temperature rise rate can be 5 DEG C/min.
5. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 2) in, the temperature of described hydro-thermal reaction is 130 ~ 160 DEG C, and the time of hydro-thermal reaction is 8 ~ 11h.
6. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 2) in, described TiO 2growth solution adopts following methods preparation: the TiCl getting 1 ~ 2mL 4add in the hydrochloric acid soln of 20 ~ 40mL, until TiCl 4after whole hydrolysis, add the deionized water of (20 ~ 40) mL, whole process stirs with magneton all the time; Described hydrochloric acid soln can adopt mass percentage concentration be 37% concentrated hydrochloric acid solution.
7. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 3) in, described Bi (NO 3) 35H 2the proportioning of O and ethylene glycol solution is (0.05 ~ 0.1) g: (25 ~ 30) mL, wherein, and Bi (NO 3) 35H 2o calculates in mass, and ethylene glycol solution is calculated by volume.
8. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 3) in, described Na 2s9H 2the proportioning of O and deionized water is (0.1 ~ 0.15) g: (25 ~ 30) mL, wherein, and Na 2s9H 2o calculates in mass, and deionized water is calculated by volume.
9. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 3) in, the time of described dipping is 1 ~ 2min; The temperature of described drying can be 50 ~ 80 DEG C; The time of described deposition can be 1 ~ 2min.
10. Bi as claimed in claim 1 2s 3/ TiO 2the preparation method of nanometer rod composite film photo-anode, is characterized in that in step 3) in, described again dry temperature is 50 ~ 80 DEG C; The temperature of described calcining can be 200 ~ 300 DEG C, and the time of calcining can be 2 ~ 5h.
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