CN104264158A - Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode - Google Patents
Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode Download PDFInfo
- Publication number
- CN104264158A CN104264158A CN201410491607.4A CN201410491607A CN104264158A CN 104264158 A CN104264158 A CN 104264158A CN 201410491607 A CN201410491607 A CN 201410491607A CN 104264158 A CN104264158 A CN 104264158A
- Authority
- CN
- China
- Prior art keywords
- graphene
- tio
- cdte
- electrode
- composite membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a graphene/CdTe-TiO2 composite membrane photo-anode for photo-induced cathodic protection and relates to a composite membrane photo-anode. The invention provides an efficient preparation method of the graphene/CdTe-TiO2 composite membrane photo-anode for photo-induced cathodic protection. The method comprises the following steps: sequentially carrying out anodic oxidation and calcining by taking a titanium foil as a matrix, taking a hydrofluoric solution as an electrolyte solution and taking platinum as a counter electrode, so that a TiO2 nanotube array membrane can be prepared on the titanium surface; firstly, by using a cyclic voltammetric deposition method, depositing graphene quantum dots on the surface of the TiO2 nanotube array membrane, and by taking a prepared graphene oxide solution as an electrolyte solution, taking platinum as a counter electrode and taking saturated calomel electrode (SCE) as a reference electrode, depositing graphene on the surface of the TiO2 nanotube array membrane, so that a graphene/TiO2 composite membrane is obtained; and then depositing CdTe quantum dots on the surface of the obtained graphene/TiO2 composite membrane, and by taking a mixed solution of TeO2, CdSO4 and a hydrochloric acid as an electrolyte solution, taking platinum as a counter electrode and taking a saturated calomel electrode (SCE) as a reference electrode, depositing CdTe on the surface of the graphene/TiO2 composite membrane, so that a graphene/CdTe-TiO2 composite membrane is prepared finally.
Description
Technical field
The present invention relates to a kind of composite film photo-anode, especially relate to a kind of Graphene/CdTe-TiO for photoproduction galvanic protection
2the preparation method of composite film photo-anode.
Background technology
TiO
2because of chemical property and the photoelectrochemical behaviour of self excellence, great concern is being caused to its preparation in the protection of metal.Ultimate principle is: under illumination condition, TiO
2excited and produce light induced electron, light induced electron is from TiO
2surface passes to metal, such that the current potential of metal is negative to be moved, and lower than its corrosion potential, thus metal is played a protective role.Compared with traditional cathode protecting process, this technology utilizes TiO
2photovoltaic effect, do not need sacrificial anode, do not need yet consume electric energy, cost is lower, demonstrates tempting application prospect.But, TiO
2there are some technical barriers: during (1) illumination, by TiO in actual application
2the restriction of broad stopband (3.2eV), absorbing wavelength can only be less than the UV-light of 380nm, most visible ray all can not be effectively utilised, and photoelectric efficiency is low.(2) when transferring dark-state to after illumination, the photo-generate electron-hole of generation is fast to compound, can not to metal carrying for long galvanic protection.
With the semiconductor coupling (as CdSe, CdS and CdTe etc.) of low energy gap, be improve TiO
2one of visible light-responded most effectual way.Wherein the energy gap of CdTe is 1.5eV, can absorb visible ray, with TiO
2during coupling, light induced electron can be delivered to TiO by the conduction band of CdTe
2conduction band, thus improve the separation efficiency in light induced electron and hole.
Graphene, because of the transfer transport of himself excellence and hole separating power, has been subjected to special concern.Graphene has the reason that good conductive capability exists two aspects.One is because Graphene is the perfact conductor in zero forbidden band, makes current carrier in graphene film have very high mobility.Two is because Graphene is the two-dirnentional structure of individual layer, has very large surface-area, can as good electron acceptor(EA).Therefore, Graphene is often used to TiO
2carry out modification.But merely adopt Graphene modification TiO
2material, i.e. Graphene-TiO
2matrix material, it is not high to the utilization ratio of visible ray.
Summary of the invention
The object of the present invention is to provide a kind of Graphene/CdTe-TiO for photoproduction galvanic protection
2the preparation method of composite film photo-anode.
For achieving the above object, the technical solution used in the present invention is:
A kind of Graphene/CdTe-TiO for photoproduction galvanic protection
2the preparation method of composite film photo-anode,
1) add hydrofluoric acid in deionized water, do electrode, carry out anodic oxidation to pretreated Titanium base sample with platinum, after oxidation, calcining, cools to room temperature with the furnace;
2) adopt cyclic voltammetric deposition method to the Titanium base specimen surface deposited graphite alkene quantum dot after above-mentioned oxidation, obtain Graphene/TiO
2nanometer tube composite film;
3) adopt cyclic voltammetric deposition method to above-mentioned Graphene/TiO
2nanometer tube composite film surface deposition CdTe quantum, then calcines, cools to room temperature with the furnace, obtains Graphene/CdTe-TiO
2composite membrane.
Described pretreated Titanium base sample is using titanium foil as matrix, by Titanium base surface after polishing, successively in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple, namely obtains pretreated Titanium base sample.
The thickness of described matrix is 0.1 ~ 0.5mm; Described matrix can be rectangular parallelepiped, and length can be 15 ~ 35mm, and width can be 10 ~ 25mm.
Further, described step 1) add the hydrofluoric acid solution that massfraction is 1% in deionized water, then do electrode with platinum, anodic oxidation is carried out to pretreated Titanium base sample, at 450 ~ 500 DEG C, calcine 1.5 ~ 2.0h after oxidation, be cooled to room temperature subsequently;
Wherein, anodic oxidation condition is anodised operating voltage is 20 ~ 30V, and the anodised time is 20 ~ 30min.
Described step 2) be electrolyte solution with graphene oxide, adopt three-electrode system, the TiO on the Titanium base sample after above-mentioned oxidation
2film of Nano tube array surface adopts cyclic voltammetric deposition graphene quantum dot, obtains Graphene/TiO
2nanometer tube composite film;
Wherein, three-electrode system is TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
The concentration of described graphene oxide solution is 0.5 ~ 1.0g/L; The voltage of described cyclic voltammetric deposition is-1.5 ~ 1.0V, and the number of turns of deposition is 10 ~ 50.
Described step 3) with TeO
2, CdSO
4be electrolyte solution with the mixing solutions of hydrochloric acid, adopt three-electrode system, at above-mentioned Graphene/TiO
2nanometer tube composite film surface adopts cyclic voltammetric deposition CdTe quantum, then at 300 ~ 400 DEG C, calcines 1 ~ 1.5h, is cooled to room temperature subsequently and obtains Graphene/CdTe-TiO
2composite membrane;
Wherein, three-electrode system is Graphene/TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
TeO in described electrolyte solution
2concentration be 0.01 ~ 0.02mol/L, CdSO
4concentration be 0.05 ~ 0.10mol/L, the volume ratio of hydrochloric acid and water is 1:6 ~ 1:7; The voltage of described cyclic voltammetric deposition is-0.5 ~-1.1V, and the number of turns of deposition is 10 ~ 30.
Further,
Described step 1) pretreated Titanium base sample is using titanium foil as matrix, the Ti content of titanium foil can be 99.9%, by Titanium base surface after 400 ~ No. 1500 sand paper are polished step by step, successively at acetone, dehydrated alcohol and deionized water for ultrasonic ripple cleaning 8 ~ 15min, after namely obtaining pre-treatment, obtain Titanium base sample.
The thickness of described matrix is 0.1 ~ 0.5mm; Described matrix can be rectangular parallelepiped, and length can be 15 ~ 35mm, and width can be 10 ~ 25mm.
Described step 1) add hydrofluoric acid in deionized water, the massfraction of hydrofluoric acid solution is 1%, then does electrode with platinum, carries out anodic oxidation to pretreated Titanium base sample, at 450 ~ 500 DEG C, calcine 1.5 ~ 2.0h after oxidation, be cooled to room temperature subsequently;
Wherein, anodic oxidation condition is anodised operating voltage is 20 ~ 30V, and the anodised time is 20 ~ 30min.
Described step 2) be electrolyte solution with graphene oxide, adopt three-electrode system, the TiO on the Titanium base sample after above-mentioned oxidation
2film of Nano tube array surface adopts cyclic voltammetric deposition graphene quantum dot, obtains Graphene/TiO
2nanometer tube composite film;
Wherein, three-electrode system is TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
The concentration of described graphene oxide solution is 0.5 ~ 1.0g/L; The voltage of described cyclic voltammetric deposition is-1.5 ~ 1.0V, and the number of turns of deposition is 10 ~ 50.
Described step 3) with TeO
2, CdSO
4be electrolyte solution with the mixing solutions of hydrochloric acid, adopt three-electrode system, at above-mentioned Graphene/TiO
2nanometer tube composite film surface adopts cyclic voltammetric deposition CdTe quantum, then at 300 ~ 400 DEG C, calcines 1 ~ 1.5h, is cooled to room temperature subsequently and obtains Graphene/CdTe-TiO
2composite membrane;
Wherein, three-electrode system is Graphene/TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
TeO in described electrolyte solution
2concentration be 0.01 ~ 0.02mol/L, CdSO
4concentration be 0.05 ~ 0.10mol/L, the volume ratio of hydrochloric acid and water is 1:6 ~ 1:7; The voltage of described cyclic voltammetric deposition is-0.5 ~-1.1V, and the number of turns of deposition is 10 ~ 30.
Ultimate principle of the present invention: TiO
2with the quantum spot semiconductor CdTe compound of narrow band gap, under light illumination, the valence-band electrons absorb photons excite transitions of CdTe is to conduction band, and produce photo-generate electron-hole pair, light induced electron transits to graphene film from the conduction of CdTe, then transfers to TiO
2conduction band; the most backward protected metallic surface migration be attached thereto; produce photogenerated current; make metal generation cathodic polarization; cause and electropotential is reduced; and the spontaneous potential (i.e. open circuit potential) original far below metal, now metal can be in Thermodynamically stable state and cathode protecting state, and namely metal is protected and avoids corrosion.Meanwhile, hole is from TiO
2valence band transfers to Graphene, and transfers to the valence band of CdTe further, effectively achieves being separated of electronics and hole.Like this, just TiO in the past can be overcome
2the problem that film photoproduction galvanic protection effect is poor.
The present invention, by the coating for metal surfaces technology of preparing of development advanced person, obtains TiO metal to high performance cathodes protective effect
2nanometer tube composite film.The present invention first prepares the TiO of certain length on the surface by anonizing at titanium foil
2film of Nano tube array, then adopt cyclic voltammetric sedimentation in nanotube surface successively deposited graphite alkene, CdTe quantum.Surface there is the CdTe/TiO of Graphene sensitization
2nano composite membrane is soaked in electrolyte solution together with titanium foil matrix as light anode, is connected, can plays photoproduction galvanic protection effect to metal with metals such as protected stainless steels.
The invention has the advantages that:
Graphene combines to TiO with CdTe by the present invention
2carry out modification.Graphene/CdTe-TiO
2composite membrane, not only utilizes the satisfactory electrical conductivity of Graphene, also can utilize CdTe-TiO
2between semi-conductor effect improve TiO
2to the utilising efficiency of visible ray.Graphene and CdTe are jointly to TiO
2carry out modification, than Graphene-TiO
2or CdTe-TiO
2performance is more excellent, and wherein Graphene is at TiO
2and electronics can be transmitted better between CdTe, reduce the compound of photo-generated carrier, thus improve composite membrane to 304 stainless protected effect.
Graphene/CdTe-TiO prepared by the present invention
2composite membrane; there is the complete and uniform feature of coating, can be used as light anode, can visible ray be utilized; make the electropotential of the protected metal of connection significantly decline during illumination, the more important thing is that closedown light source still can maintain the good galvanic protection effect to metal for a long time when transferring dark-state to.Result shows, this composite membrane is at NaOH and Na
2in S solution; during radiation of visible light; what can make to be attached thereto is in 304 relatively poor stainless electropotential decline 570mV of original solidity to corrosion in 3.5%NaCl solution, far below stainless spontaneous potential, shows that the galvanic protection effect of composite membrane is remarkable.Particularly after stopping illumination, stainless electropotential is still starkly lower than spontaneous potential and is about 370mV, and namely composite membrane also has good photoproduction galvanic protection effect to stainless steel in the dark state.Show the Graphene/CdTe-TiO prepared by cyclic voltammetric sedimentation
2composite membrane has more excellent photoproduction galvanic protection effect to metal.
Accompanying drawing explanation
The TiO preparing gained that Fig. 1 a provides for the embodiment of the present invention
2the surface topography (SEM figure) of nano-tube film.Wherein, scale is 100nm.
Graphene/the CdTe-TiO preparing gained that Fig. 1 b provides for the embodiment of the present invention
2the surface topography (SEM figure) of composite membrane.Wherein, scale is 100nm.
The TiO preparing gained that Fig. 2 provides for the embodiment of the present invention
2nano-tube film (a) and Graphene/CdTe-TiO
2the X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Fig. 3 provides for the embodiment of the present invention
2nano-tube film and Graphene/CdTe-TiO
2composite membrane is photogenerated current change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is density of photocurrent (μ A cm
-2).On represents illumination, and off represents closedown light source and dark-state.
304 stainless steels that Fig. 4 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO
2nanotube films light anode connects, electropotential change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is electropotential (mV vs.SCE).On represents illumination, and off represents closedown light source and dark-state.
The TiO preparing gained that Fig. 5 a provides for the embodiment of the present invention
2the surface topography (SEM figure) of nano-tube film.Wherein, scale is 100nm.
Graphene/the CdTe-TiO preparing gained that Fig. 5 b provides for the embodiment of the present invention
2the surface topography (SEM figure) of composite membrane.Wherein, scale is 100nm.
The TiO preparing gained that Fig. 6 provides for the embodiment of the present invention
2nano-tube film (a) and Graphene/CdTe-TiO
2the X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Fig. 7 provides for the embodiment of the present invention
2nano-tube film and Graphene/CdTe-TiO
2composite membrane is photogenerated current change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is density of photocurrent (μ A cm
-2).On represents illumination, and off represents closedown light source and dark-state.
304 stainless steels that Fig. 8 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO
2nanotube films light anode connects, electropotential change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is electropotential (mV vs.SCE).On represents illumination, and off represents closedown light source and dark-state.
The TiO preparing gained that Fig. 9 a provides for the embodiment of the present invention
2the surface topography (SEM figure) of nano-tube film.Wherein, scale is 100nm.
Graphene/the CdTe-TiO preparing gained that Fig. 9 b provides for the embodiment of the present invention
2the surface topography (SEM figure) of composite membrane.Wherein, scale is 100nm.
The TiO preparing gained that Figure 10 provides for the embodiment of the present invention
2nano-tube film (a) and Graphene/CdTe-TiO
2the X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Figure 11 provides for the embodiment of the present invention
2nano-tube film and Graphene/CdTe-TiO
2composite membrane is photogenerated current change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is density of photocurrent (μ A cm
-2).On represents illumination, and off represents closedown light source and dark-state.
304 stainless steels that Figure 12 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO
2nanotube films light anode connects, electropotential change curve in time before and after illumination.Wherein, X-coordinate is the time (s), and ordinate zou is electropotential (mV vs.SCE).On represents illumination, and off represents closedown light source and dark-state.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
The technical problem underlying that the present invention solves is simple TiO
2when transferring dark-state after the low and illumination of film photoelectric efficiency to, film does not have photoproduction galvanic protection effect.With the TiO of surface deposition Graphene
2nano-tube film as substrate, then deposits CdTe quantum, and the Graphene in composite membrane can be caught and is delivered to CdTe conduction band or TiO
2electronics on conduction band, thus improve the right separation efficiency of photo-generate electron-hole, and play the effect of Electronic saving, the photoelectrochemical behaviour of film can be improved.Therefore, need to provide a kind of Graphene/CdTe-TiO with efficient photoproduction galvanic protection effect
2the preparation method of composite membrane.This method adopts anonizing first at titanium surface preparation TiO
2film of Nano tube array, adopts cyclic voltammetric sedimentation in nanotube surface successively composite graphite alkene, CdTe quantum, forms nanometer tube composite film.This composite membrane can make the electropotential of the metals such as the stainless steel of connection significantly decline, and still can maintain the galvanic protection effect excellent to metals such as stainless steels for a long time when transferring again dark-state to after illumination.
Embodiment 1
Getting the thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and width is 10mm.Specimen surface successively after 400 ~ No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
The hydrofluoric acid measuring 1mL, in the deionized water of 100mL, makes hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after clean for anode, platinized platinum is negative electrode, in above-mentioned mixed solution, with 30V ultor oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, namely obtain TiO at titanium foil matrix surface
2film of Nano tube array.
Adopt cyclic voltammetric deposition method, first at TiO
2film of Nano tube array surface deposition graphene quantum dot.Take 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3 ~ 5min, obtained graphene oxide solution.With the graphene oxide solution of preparation for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, Graphene be deposited on TiO
2film of Nano tube array surface, deposition voltage is-1.5 ~ 1.0V, and the number of turns of deposition is 15, i.e. obtained Graphene/TiO
2composite membrane.Then at obtained Graphene/TiO
2composite film surface deposition CdTe quantum.Take 0.3988g TeO
2, 4.16g CdSO
4to in the deionized water of 175mL, and add 25mL hydrochloric acid, stir, with this mixing solutions for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, deposition voltage is-0.5 ~-1.1V, the number of turns of deposition is 25, is then placed in tube furnace sample in N
2calcine 1h at atmosphere 300 DEG C, then cool to room temperature i.e. obtained Graphene/CdTe-TiO with the furnace
2composite membrane.The TiO of preparation
2the surface topography of nano thin-film as shown in Figure 1a, presents film of Nano tube array pattern.In addition, the Graphene/CdTe-TiO of preparation
2the surface topography of composite membrane as shown in Figure 1 b, can see that graphene film and CdTe nano particle are deposited on film of Nano tube array surface equably.
For characterizing the TiO of above-mentioned preparation
2nano-tube film and Graphene/CdTe-TiO
2the structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Fig. 2 shows, pure TiO
2in the X-ray diffraction spectrum of film of Nano tube array except Ti (in the figure Titanium) diffraction peak that Ti substrate produces, have also appeared Anatase TiO
2(anatase TiO in figure
2) diffraction peak, TiO is described
2film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO
2except Ti and Anatase TiO in composite membrane
2diffraction peak outside, have also appeared the diffraction peak of Emission in Cubic CdTe (in figure cubic CdTe), in addition, in composite membrane, do not occur the diffraction peak of Graphene, may be due to Graphene 25.0 ° place diffraction peak and TiO
2diffraction peak overlap each other.
For characterizing photo-generated carrier separating power and the recombination rate of different nano thin-film, test the transient state optogalvanic spectra of different nano thin-film.As can be seen from Figure 3, when film is pure TiO
2during nanometer film, transient state photoelectric current maximum value is 80 μ about A, and when after film surface deposition Graphene and CdTe, the transient state photoelectric current maximum value of composite membrane is 560 μ A, is about pure TiO
27 times of film of Nano tube array, considerably beyond pure TiO
2the transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe particle, photo-current intensity significantly strengthens.Its reason is mainly due to Graphene and CdTe and TiO
2after compound, the compound that photo-generate electron-hole is right can be reduced, effectively can improve the utilization ratio to light.
Electrochemical techniques are then adopted to test the Graphene/CdTe-TiO of above-mentioned preparation
2composite membrane as light anode to 304 stainless galvanic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO
2composite membrane is light anode, is placed in photoelectrolytic cell, and wherein ionogen is 0.2mol/L NaOH+0.1mol/L Na
2the aqueous solution of S.Corrosion electrolyzer is three-electrode system, and working electrode is protected metal, and reference electrode is saturated calomel electrode (SCE), is platinum electrode to electrode, take 3.5%NaCl as corrosive medium solution.Light anode is connected by wire with protected metal electrode, and photoelectrolytic cell is connected by the agar bridge containing 1.0mol/L KCl with corrosion electrolyzer.Using 300W high pressure Xe lamp as visible light source, test time direct irradiation is laminated film surface in photoelectrolytic cell.PARSTAT2273 electrochemical workstation is adopted to test protected corrosion of metal electrochemical parameter, to investigate TiO
2the photoproduction galvanic protection effect of nanometer tube composite film.Test is all at room temperature carried out.This technology is by the change of stainless steel electropotential before and after rayed composite membrane in test corrosion electrolyzer, and namely Observable is to the effect of the photoproduction galvanic protection of composite membrane.After closing light source again after illumination, the change of test stainless steel electrode current potential, can evaluate in the dark state composite film photo-anode to stainless galvanic protection effect.
Fig. 4 be 304 stainless steels in 3.5%NaCl solution from preparation with different TiO
2nanotube films light anode connects rear electrode current potential curve over time.Can find out, the switch electrode current potential with light source is phase step type change.Before illumination, stainless electropotential is spontaneous potential, and after illumination, stainless electropotential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO
2composite membrane >CdTe-TiO
2>RGO-TiO
2>TiO
2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO
2after composite membrane is coupling, under illumination, 304 stainless electropotentials are down to rapidly about-750mV from-180mV, namely have dropped about 570mV.Stainless steel cathode is polarised to so negative numerical value, and its surface does not produce hydrogen, illustrates that stainless steel receives good photoproduction galvanic protection, and does not occur " overprotection ".After stopping illumination, though electropotential has rising, but still about 370mV lower than original spontaneous potential, under dark-state is described, composite membrane still has good galvanic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention
2composite membrane can make under illumination condition that stainless steel electrode current potential is significantly negative to be moved, its reason is because the energy gap of CdTe is narrow, most visible ray can be absorbed, in addition, in composite membrane after graphene quantum dot sensitized treatment, the directed transmission capacity of the electronics in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention
2composite membrane can play the film and pure TiO prepared than bi-material compound
2film has better photoproduction galvanic protection effect.
Embodiment 2
Graphene/CdTe-TiO
2the preparation method of composite film photo-anode:
Getting the thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and width is 10mm.Specimen surface successively after 400 ~ No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
The hydrofluoric acid measuring 1mL, in the deionized water of 100mL, makes hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after clean for anode, platinized platinum is negative electrode, in above-mentioned mixed solution, with 30V ultor oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, namely obtain TiO at titanium foil matrix surface
2film of Nano tube array.
Adopt cyclic voltammetric deposition method, first at TiO
2film of Nano tube array surface deposition graphene quantum dot.Take 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3 ~ 5min, obtained graphene oxide solution.With the graphene oxide solution of preparation for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, Graphene be deposited on TiO
2film of Nano tube array surface, deposition voltage is-1.5 ~ 1.0V, and the number of turns of deposition is 25, i.e. obtained Graphene/TiO
2composite membrane.Then at obtained Graphene/TiO
2composite film surface deposition CdTe quantum.Take 0.3988g TeO
2, 4.16g CdSO
4to in the deionized water of 175mL, and add 25mL hydrochloric acid, stir, with this mixing solutions for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, deposition voltage is-0.5 ~-1.1V, the number of turns of deposition is 25, is then placed in tube furnace sample in N
2calcine 1h at atmosphere 300 DEG C, then cool to room temperature i.e. obtained Graphene/CdTe-TiO with the furnace
2composite membrane.The TiO of preparation
2the surface topography of nano thin-film as shown in Figure 5 a, presents film of Nano tube array pattern.In addition, the Graphene/CdTe-TiO of preparation
2the surface topography of composite membrane as shown in Figure 5 b, can see that graphene film and CdTe nano particle are deposited on film of Nano tube array surface equably.
For characterizing the TiO of above-mentioned preparation
2nano-tube film and Graphene/CdTe-TiO
2the structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Fig. 6 shows, pure TiO
2in the X-ray diffraction spectrum of film of Nano tube array except Ti (in the figure Titanium) diffraction peak that Ti substrate produces, have also appeared Anatase TiO
2(anatase TiO in figure
2) diffraction peak, TiO is described
2film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO
2except Ti and Anatase TiO in composite membrane
2diffraction peak outside, have also appeared the diffraction peak of Emission in Cubic CdTe (in figure cubic CdTe), in addition, in composite membrane, do not occur the diffraction peak of Graphene, may be due to Graphene 25.0 ° place diffraction peak and TiO
2diffraction peak overlap each other.
For characterizing photo-generated carrier separating power and the recombination rate of different nano thin-film, test the transient state optogalvanic spectra of different nano thin-film.As can be seen from Figure 7, when film is pure TiO
2during nanometer film, transient state photoelectric current maximum value is 80 μ about A, and when after film surface deposition Graphene and CdTe, the transient state photoelectric current maximum value of composite membrane is 760 μ A, is about pure TiO
29.5 times of film of Nano tube array, considerably beyond pure TiO
2the transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe particle, photo-current intensity significantly strengthens.Its reason is mainly due to Graphene and CdTe and TiO
2after compound, the compound that photo-generate electron-hole is right can be reduced, effectively can improve the utilization ratio to light.
Electrochemical techniques are then adopted to test the Graphene/CdTe-TiO of above-mentioned preparation
2composite membrane as light anode to 304 stainless galvanic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO
2composite membrane is light anode, is placed in photoelectrolytic cell, and wherein ionogen is 0.2mol/L NaOH+0.1mol/L Na
2the aqueous solution of S.Corrosion electrolyzer is three-electrode system, and working electrode is protected metal, and reference electrode is saturated calomel electrode (SCE), is platinum electrode to electrode, take 3.5%NaCl as corrosive medium solution.Light anode is connected by wire with protected metal electrode, and photoelectrolytic cell is connected by the agar bridge containing 1.0mol/L KCl with corrosion electrolyzer.Using 300W high pressure Xe lamp as visible light source, test time direct irradiation is laminated film surface in photoelectrolytic cell.PARSTAT2273 electrochemical workstation is adopted to test protected corrosion of metal electrochemical parameter, to investigate TiO
2the photoproduction galvanic protection effect of nanometer tube composite film.Test is all at room temperature carried out.This technology is by the change of stainless steel electropotential before and after rayed composite membrane in test corrosion electrolyzer, and namely Observable is to the effect of the photoproduction galvanic protection of composite membrane.After closing light source again after illumination, the change of test stainless steel electrode current potential, can evaluate in the dark state composite film photo-anode to stainless galvanic protection effect.
Fig. 8 be 304 stainless steels in 3.5%NaCl solution from preparation with different TiO
2nanotube films light anode connects rear electrode current potential curve over time.Can find out, the switch electrode current potential with light source is phase step type change.Before illumination, stainless electropotential is spontaneous potential, and after illumination, stainless electropotential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO
2composite membrane >CdTe-TiO
2>RGO-TiO
2>TiO
2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO
2after composite membrane is coupling, under illumination, 304 stainless electropotentials are down to rapidly about-750mV from-180mV, namely have dropped about 570mV.Stainless steel cathode is polarised to so negative numerical value, and its surface does not produce hydrogen, illustrates that stainless steel receives good photoproduction galvanic protection, and does not occur " overprotection ".After stopping illumination, though electropotential has rising, but still about 370mV lower than original spontaneous potential, under dark-state is described, composite membrane still has good galvanic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention
2composite membrane can make under illumination condition that stainless steel electrode current potential is significantly negative to be moved, its reason is because the energy gap of CdTe is narrow, most visible ray can be absorbed, in addition, in composite membrane after graphene quantum dot sensitized treatment, the directed transmission capacity of the electronics in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention
2composite membrane can play the film and pure TiO prepared than bi-material compound
2film has better photoproduction galvanic protection effect.
Embodiment 3
Graphene/CdTe-TiO
2the preparation method of composite film photo-anode:
Getting the thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and width is 10mm.Specimen surface successively after 400 ~ No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
The hydrofluoric acid measuring 1mL, in the deionized water of 100mL, makes hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after clean for anode, platinized platinum is negative electrode, in above-mentioned mixed solution, with 30V ultor oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, namely obtain TiO at titanium foil matrix surface
2film of Nano tube array.
Adopt cyclic voltammetric deposition method, first at TiO
2film of Nano tube array surface deposition graphene quantum dot.Take 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3 ~ 5min, obtained graphene oxide solution.With the graphene oxide solution of preparation for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, Graphene be deposited on TiO
2film of Nano tube array surface, deposition voltage is-1.5 ~ 1.0V, and the number of turns of deposition is 50, i.e. obtained Graphene/TiO
2composite membrane.Then at obtained Graphene/TiO
2composite film surface deposition CdTe quantum.Take 0.3988g TeO
2, 4.16g CdSO
4to in the deionized water of 175mL, and add 25mL hydrochloric acid, stir, with this mixing solutions for electrolyte solution, be to electrode with platinum, with saturated calomel electrode (SCE) for reference electrode, deposition voltage is-0.5 ~-1.1V, the number of turns of deposition is 25, is then placed in tube furnace sample in N
2calcine 1h at atmosphere 300 DEG C, then cool to room temperature i.e. obtained Graphene/CdTe-TiO with the furnace
2composite membrane.The TiO of preparation
2the surface topography of nano thin-film as illustrated in fig. 9, presents film of Nano tube array pattern.In addition, the Graphene/CdTe-TiO of preparation
2the surface topography of composite membrane as shown in figure 9b, can see that graphene film and CdTe nano particle are deposited on film of Nano tube array surface equably.
For characterizing the TiO of above-mentioned preparation
2nano-tube film and Graphene/CdTe-TiO
2the structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Figure 10 shows, pure TiO
2in the X-ray diffraction spectrum of film of Nano tube array except Ti (in the figure Titanium) diffraction peak that Ti substrate produces, have also appeared Anatase TiO
2(anatase TiO in figure
2) diffraction peak, TiO is described
2film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO
2except Ti and Anatase TiO in composite membrane
2diffraction peak outside, have also appeared the diffraction peak of Emission in Cubic CdTe (in figure cubic CdTe), in addition, in composite membrane, do not occur the diffraction peak of Graphene, may be due to Graphene 25.0 ° place diffraction peak and TiO
2diffraction peak overlap each other.
For characterizing photo-generated carrier separating power and the recombination rate of different nano thin-film, test the transient state optogalvanic spectra of different nano thin-film.As can be seen from Figure 11, when film is pure TiO
2during nanometer film, transient state photoelectric current maximum value is 80 μ about A, and when after film surface deposition Graphene and CdTe, the transient state photoelectric current maximum value of composite membrane is 640 μ A, is about pure TiO
28 times of film of Nano tube array, considerably beyond pure TiO
2the transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe particle, photo-current intensity significantly strengthens.Its reason is mainly due to Graphene and CdTe and TiO
2after compound, the compound that photo-generate electron-hole is right can be reduced, effectively can improve the utilization ratio to light.
Electrochemical techniques are then adopted to test the Graphene/CdTe-TiO of above-mentioned preparation
2composite membrane as light anode to 304 stainless galvanic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO
2composite membrane is light anode, is placed in photoelectrolytic cell, and wherein ionogen is 0.2mol/L NaOH+0.1mol/L Na
2the aqueous solution of S.Corrosion electrolyzer is three-electrode system, and working electrode is protected metal, and reference electrode is saturated calomel electrode (SCE), is platinum electrode to electrode, take 3.5%NaCl as corrosive medium solution.Light anode is connected by wire with protected metal electrode, and photoelectrolytic cell is connected by the agar bridge containing 1.0mol/L KCl with corrosion electrolyzer.Using 300W high pressure Xe lamp as visible light source, test time direct irradiation is laminated film surface in photoelectrolytic cell.PARSTAT2273 electrochemical workstation is adopted to test protected corrosion of metal electrochemical parameter, to investigate TiO
2the photoproduction galvanic protection effect of nanometer tube composite film.Test is all at room temperature carried out.This technology is by the change of stainless steel electropotential before and after rayed composite membrane in test corrosion electrolyzer, and namely Observable is to the effect of the photoproduction galvanic protection of composite membrane.After closing light source again after illumination, the change of test stainless steel electrode current potential, can evaluate in the dark state composite film photo-anode to stainless galvanic protection effect.
Figure 12 be 304 stainless steels in 3.5%NaCl solution from preparation with different TiO
2nanotube films light anode connects rear electrode current potential curve over time.Can find out, the switch electrode current potential with light source is phase step type change.Before illumination, stainless electropotential is spontaneous potential, and after illumination, stainless electropotential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO
2composite membrane >CdTe-TiO
2>RGO-TiO
2>TiO
2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO
2after composite membrane is coupling, under illumination, 304 stainless electropotentials are down to rapidly about-750mV from-180mV, namely have dropped about 570mV.Stainless steel cathode is polarised to so negative numerical value, and its surface does not produce hydrogen, illustrates that stainless steel receives good photoproduction galvanic protection, and does not occur " overprotection ".After stopping illumination, though electropotential has rising, but still about 370mV lower than original spontaneous potential, under dark-state is described, composite membrane still has good galvanic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention
2composite membrane can make under illumination condition that stainless steel electrode current potential is significantly negative to be moved, its reason is because the energy gap of CdTe is narrow, most visible ray can be absorbed, in addition, in composite membrane after graphene quantum dot sensitized treatment, the directed transmission capacity of the electronics in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention
2composite membrane can play the film and pure TiO prepared than bi-material compound
2film has better photoproduction galvanic protection effect.
Claims (8)
1. Graphene/the CdTe-TiO for photoproduction galvanic protection
2the preparation side of composite film photo-anode
Method, is characterized in that:
1) add hydrofluoric acid in deionized water, do electrode, carry out anodic oxidation to pretreated Titanium base sample with platinum, after oxidation, calcining, cools to room temperature with the furnace;
2) adopt cyclic voltammetric deposition method to the Titanium base specimen surface deposited graphite alkene quantum dot after above-mentioned oxidation, obtain Graphene/TiO
2nanometer tube composite film;
3) adopt cyclic voltammetric deposition method to above-mentioned Graphene/TiO
2nanometer tube composite film surface deposition CdTe quantum, then calcines, cools to room temperature with the furnace, obtains Graphene/CdTe-TiO
2composite membrane.
2. by Graphene/CdTe-TiO according to claim 1
2the preparation method of composite film photo-anode, it is characterized in that: described pretreated Titanium base sample is using titanium foil as matrix, by Titanium base surface after polishing, successively in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple, namely obtain pretreated Titanium base sample.
3. by Graphene/CdTe-TiO according to claim 2
2the preparation method of composite film photo-anode, is characterized in that: the thickness of described matrix is 0.1 ~ 0.5mm; Described matrix can be rectangular parallelepiped, and length can be 15 ~ 35mm, and width can be 10 ~ 25mm.
4. by Graphene/CdTe-TiO according to claim 1
2the preparation method of composite film photo-anode, is characterized in that:
Described step 1) add the hydrofluoric acid solution that massfraction is 1% in deionized water, then do electrode with platinum, anodic oxidation is carried out to pretreated Titanium base sample, at 450 ~ 500 DEG C, calcines 1.5 ~ 2.0h after oxidation, be cooled to room temperature subsequently;
Wherein, anodic oxidation condition is anodised operating voltage is 20 ~ 30V, and the anodised time is 20 ~ 30min.
5. by Graphene/CdTe-TiO according to claim 1
2the preparation method of composite film photo-anode, is characterized in that:
Described step 2) be electrolyte solution with graphene oxide, adopt three-electrode system, the TiO on the Titanium base sample after above-mentioned oxidation
2film of Nano tube array surface adopts cyclic voltammetric deposition graphene quantum dot, obtains Graphene/TiO
2nanometer tube composite film;
Wherein, three-electrode system is TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
6. by Graphene/CdTe-TiO according to claim 5
2the preparation method of composite film photo-anode, is characterized in that: the concentration of described graphene oxide solution is 0.5 ~ 1.0g/L; The voltage of described cyclic voltammetric deposition is-1.5 ~ 1.0V, and the number of turns of deposition is 10 ~ 50.
7. by Graphene/CdTe-TiO according to claim 1
2the preparation method of composite film photo-anode, is characterized in that:
Described step 3) with TeO
2, CdSO
4be electrolyte solution with the mixing solutions of hydrochloric acid, adopt three-electrode system, at above-mentioned Graphene/TiO
2nanometer tube composite film surface adopts cyclic voltammetric deposition CdTe quantum, then at 300 ~ 400 DEG C, calcines 1 ~ 1.5h, is cooled to room temperature subsequently and obtains Graphene/CdTe-TiO
2composite membrane;
Wherein, three-electrode system is Graphene/TiO
2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
8. by Graphene/CdTe-TiO according to claim 7
2the preparation method of composite film photo-anode, is characterized in that: TeO in described electrolyte solution
2concentration be 0.01 ~ 0.02mol/L, CdSO
4concentration be 0.05 ~ 0.10mol/L, the volume ratio of hydrochloric acid and water is 1:6 ~ 1:7; The voltage of described cyclic voltammetric deposition is-0.5 ~-1.1V, and the number of turns of deposition is 10 ~ 30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410491607.4A CN104264158B (en) | 2014-09-23 | 2014-09-23 | Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410491607.4A CN104264158B (en) | 2014-09-23 | 2014-09-23 | Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104264158A true CN104264158A (en) | 2015-01-07 |
| CN104264158B CN104264158B (en) | 2017-01-11 |
Family
ID=52155726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410491607.4A Active CN104264158B (en) | 2014-09-23 | 2014-09-23 | Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104264158B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851615A (en) * | 2015-03-27 | 2015-08-19 | 上海大学 | Electrophoresis method for controllably preparing graphene quantum dot high-capacitance three-dimensional electrode |
| CN105749914A (en) * | 2016-02-01 | 2016-07-13 | 郑州大学 | Symmetric difunctional photocatalyst, double-chamber photoreactor and method for photocatalytic reduction of carbon dioxide |
| CN106498408A (en) * | 2016-12-13 | 2017-03-15 | 中国科学院海洋研究所 | A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection |
| CN106555188A (en) * | 2016-11-24 | 2017-04-05 | 中国科学院海洋研究所 | For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection |
| CN111962083A (en) * | 2020-08-15 | 2020-11-20 | 青岛农业大学 | Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection |
| CN112442667A (en) * | 2020-11-05 | 2021-03-05 | 航天精工股份有限公司 | Photo-generated cathode protection nano coating |
| CN114369832A (en) * | 2021-12-03 | 2022-04-19 | 南方海洋科学与工程广东省实验室(湛江) | Auxiliary anode and preparation method and application thereof |
| CN115343341A (en) * | 2021-05-14 | 2022-11-15 | 天津理工大学 | Gold/graphene/titanium dioxide nanotube array/Ti sensing electrode and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361689A (en) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | Method for preparing titanium dioxide nanotube array photoelectrode |
-
2014
- 2014-09-23 CN CN201410491607.4A patent/CN104264158B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361689A (en) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | Method for preparing titanium dioxide nanotube array photoelectrode |
Non-Patent Citations (4)
| Title |
|---|
| JUAN ZHANG等: ""Highly efficient CdSe/CdS co-sensitized TiO2 nanotube films for photocathodic protection of stainless steel"", 《ELECTROCHIMICA ACTA》, vol. 83, no. 12, 14 August 2012 (2012-08-14), pages 59 - 64, XP 028945028, DOI: doi:10.1016/j.electacta.2012.07.120 * |
| XIANGQIN GUO等: ""Graphene incorporated nanocrystalline TiO2films for thephotocathodic protection of 304 stainless steel"", 《APPLIED SURFACE SCIENCE》, vol. 283, no. 11, 5 July 2013 (2013-07-05), pages 498 - 504, XP 028698345, DOI: doi:10.1016/j.apsusc.2013.06.135 * |
| 刘选能: ""硫族半导体/石墨烯复合物修饰TiO2纳米管阵列及光催化应用"", 《中国优秀硕士学位论文全文数据库》, 15 May 2014 (2014-05-15), pages 26 - 36 * |
| 王尧: ""碳基纳米复合材料修饰电极及其性能研究"", 《万方学位论文》, 29 November 2013 (2013-11-29), pages 16 - 28 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851615A (en) * | 2015-03-27 | 2015-08-19 | 上海大学 | Electrophoresis method for controllably preparing graphene quantum dot high-capacitance three-dimensional electrode |
| CN105749914A (en) * | 2016-02-01 | 2016-07-13 | 郑州大学 | Symmetric difunctional photocatalyst, double-chamber photoreactor and method for photocatalytic reduction of carbon dioxide |
| CN105749914B (en) * | 2016-02-01 | 2018-01-19 | 郑州大学 | A kind of method of symmetrical difunctional photochemical catalyst, dual chamber Photoreactor and photocatalytic reduction of carbon oxide |
| CN106555188A (en) * | 2016-11-24 | 2017-04-05 | 中国科学院海洋研究所 | For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection |
| CN106555188B (en) * | 2016-11-24 | 2019-03-19 | 中国科学院海洋研究所 | Ag/ graphene/titania nanotube composite film photo-anode preparation method for photoproduction cathodic protection |
| CN106498408A (en) * | 2016-12-13 | 2017-03-15 | 中国科学院海洋研究所 | A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection |
| CN106498408B (en) * | 2016-12-13 | 2019-07-02 | 中国科学院海洋研究所 | A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection |
| CN111962083A (en) * | 2020-08-15 | 2020-11-20 | 青岛农业大学 | Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection |
| CN112442667A (en) * | 2020-11-05 | 2021-03-05 | 航天精工股份有限公司 | Photo-generated cathode protection nano coating |
| CN115343341A (en) * | 2021-05-14 | 2022-11-15 | 天津理工大学 | Gold/graphene/titanium dioxide nanotube array/Ti sensing electrode and preparation method and application thereof |
| CN114369832A (en) * | 2021-12-03 | 2022-04-19 | 南方海洋科学与工程广东省实验室(湛江) | Auxiliary anode and preparation method and application thereof |
| CN114369832B (en) * | 2021-12-03 | 2024-01-26 | 南方海洋科学与工程广东省实验室(湛江) | Auxiliary anode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104264158B (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104264158B (en) | Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode | |
| Ahmet et al. | Demonstration of a 50 cm 2 BiVO 4 tandem photoelectrochemical-photovoltaic water splitting device | |
| Cao et al. | p-Type CuBi 2 O 4: an easily accessible photocathodic material for high-efficiency water splitting | |
| CN104164693A (en) | A preparing method of a graphene sensitized CdSe/TiO2 nanotube composite membrane | |
| CN103205760B (en) | For the Ag of photoproduction galvanic protection 2s/TiO 2the preparation method of composite film photo-anode | |
| KR100766701B1 (en) | System for the production of hydrogen from water electrolysis using photoelectric cells | |
| CN107723712B (en) | ZnIn for photoproduction cathodic protection2S4/TiO2Preparation method of nanotube composite film photo-anode | |
| CN102352494A (en) | Preparation method of CdSe/CdS quantum dot sensitized TiO2 nanometer tube composite film | |
| CN103952708B (en) | For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode | |
| JP2018043193A (en) | Light-transmitting oxygen evolution catalyst and production method of the same, and chemical reactor using the same | |
| CN108546970B (en) | Bi2Se3/TiO2Nano composite film and preparation and application thereof | |
| CN106894024B (en) | Accumulation energy type tungstic acid/strontium titanates/nano titania composite film photo-anode preparation method | |
| Chen et al. | High catalytic activity of a PbS counter electrode prepared via chemical bath deposition for quantum dots-sensitized solar cells | |
| CN105386061A (en) | Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes | |
| CN104047043A (en) | Preparation method of TiO2/SnO2 semiconductor two-layer composite film photo anode | |
| JP2017054917A (en) | Photoelectric conversion layer and manufacturing method of the same | |
| CN114086185B (en) | Photoanode film and preparation method and application thereof | |
| Juodkazytė et al. | Study on charge transfer processes in thin-film heterojunction between cuprous oxide and hematite | |
| Liu et al. | Photo-assisted seawater-electrolyte Mg/H2O batteries for simultaneous generation of electricity and hydrogen | |
| CN108034950A (en) | A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof | |
| CN102543457B (en) | Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film | |
| Zhang et al. | Indium oxide thin film as potential photoanodes for corrosion protection of stainless steel under visible light | |
| CN109972149B (en) | Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film | |
| CN110344096B (en) | AgSbS2Sensitized TiO2Composite membrane material and preparation and application thereof | |
| Cheng et al. | The photocathodic properties of a Pb (Zr 0.2 Ti 0.8) O 3 wrapped CaFe 2 O 4 layer on ITO coated quartz for water splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |