CN104264158B - Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode - Google Patents
Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode Download PDFInfo
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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 cathodic protection2The preparation method of composite film photo-anode.
Background technology
TiO2Because of chemical property and the photoelectrochemical behaviour of self excellence, in terms of the protection to metal, its preparation has caused concern greatly.Ultimate principle is: under illumination condition, TiO2Being excited and produce light induced electron, light induced electron is from TiO2Surface passes to metal so that the current potential of metal is negative to be moved, and less than its corrosion potential, thus metal is played a protective role.Compared with traditional cathode protecting process, this technology utilizes TiO2Photoelectric effect, it is not necessary to sacrificial anode, it is not required that consume electric energy, cost is lower, demonstrates tempting application prospect.But, TiO2There are some technical barriers: during (1) illumination, by TiO in actual application2The restriction of broad stopband (3.2eV), can only absorbing wavelength less than the ultraviolet 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 to compound fast, it is impossible to provide long cathodic protection to metal.
With the semiconductor coupling (such as CdSe, CdS and CdTe etc.) of low energy gap, it is to improve TiO2One of visible light-responded most effectual way.Wherein the energy gap of CdTe is 1.5eV, it is possible to absorb visible ray, with TiO2During coupling, light induced electron can be delivered to TiO by the conduction band of CdTe2Conduction band, thus improve the separation efficiency in light induced electron and hole.
Graphene, because of the electron transfer of himself excellence and hole separating power, has been subjected to special attention.Graphene has good conductive capability and there is the reason of two aspects.One is owing to Graphene is the perfact conductor in zero forbidden band so that in graphene film, carrier has the highest mobility.Two is owing to Graphene is the two-dimensional structure of monolayer, has the biggest surface area, can be as good electron acceptor.Therefore, Graphene is often used to TiO2It is modified.But merely use Graphene modification TiO2Material, i.e. Graphene-TiO2Composite, it is the highest to the utilization rate of visible ray.
Summary of the invention
It is an object of the invention to provide a kind of Graphene/CdTe-TiO for photoproduction cathodic protection2The 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 cathodic protection2The preparation method of composite film photo-anode,
1) add Fluohydric acid. in deionized water, make electrode with platinum, the Titanium base sample of pretreatment is carried out anodic oxidation, calcine after oxidation, cool to room temperature with the furnace；
2) use cyclic voltammetric deposition process to the Titanium base specimen surface deposited graphite alkene quantum dot after above-mentioned oxidation, obtain Graphene/TiO2Nanometer tube composite film；
3) use cyclic voltammetric deposition process to above-mentioned Graphene/TiO2Nanometer tube composite film surface deposition CdTe quantum, then calcines, cools to room temperature with the furnace, obtain Graphene/CdTe-TiO2Composite membrane.
The Titanium base sample of described pretreatment is using titanium foil as matrix, by Titanium base surface after polishing, ultrasonic waves for cleaning in acetone, dehydrated alcohol and deionized water successively, i.e. obtains pretreated Titanium base sample.
The thickness of described matrix is 0.1～0.5mm；Described matrix can be cuboid, and length can be 15～35mm, and width can be 10～25mm.
Further, described step 1) in deionized water add mass fraction be the hydrofluoric acid solution of 1%, then with platinum make to electrode, the Titanium base sample of pretreatment is carried out anodic oxidation, at 450～500 DEG C, calcine 1.5～2.0h after oxidation, be then cooled to room temperature；
Wherein, anodic oxidation condition be anodised running voltage be 20～30V, the anodised time is 20～30min.
Described step 2) with graphene oxide as electrolyte solution, use three-electrode system, the TiO on Titanium base sample after above-mentioned oxidation2Film of Nano tube array surface uses cyclic voltammetric deposition graphene quantum dot, obtains Graphene/TiO2Nanometer tube composite film；
Wherein, three-electrode system is TiO2/ 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 TeO2、CdSO4It is electrolyte solution with the mixed solution of hydrochloric acid, uses three-electrode system, at above-mentioned Graphene/TiO2Nanometer tube composite film surface uses cyclic voltammetric deposition CdTe quantum, then calcines 1～1.5h at 300～400 DEG C, is then cooled to room temperature and obtains Graphene/CdTe-TiO2Composite membrane；
Wherein, three-electrode system is Graphene/TiO2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
TeO in described electrolyte solution2Concentration be 0.01～0.02mol/L, CdSO4Concentration 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) the Titanium base sample of pretreatment 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 ultrasonic waves for cleaning 8～15min in acetone, dehydrated alcohol and deionized water, obtain Titanium base sample after i.e. obtaining pretreatment.
The thickness of described matrix is 0.1～0.5mm；Described matrix can be cuboid, and length can be 15～35mm, and width can be 10～25mm.
Described step 1) add Fluohydric acid. in deionized water, the mass fraction of hydrofluoric acid solution is 1%, then makees electrode with platinum, the Titanium base sample of pretreatment is carried out anodic oxidation, at 450～500 DEG C, calcine 1.5～2.0h after oxidation, be then cooled to room temperature；
Wherein, anodic oxidation condition be anodised running voltage be 20～30V, the anodised time is 20～30min.
Described step 2) with graphene oxide as electrolyte solution, use three-electrode system, the TiO on Titanium base sample after above-mentioned oxidation2Film of Nano tube array surface uses cyclic voltammetric deposition graphene quantum dot, obtains Graphene/TiO2Nanometer tube composite film；
Wherein, three-electrode system is TiO2/ 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 TeO2、CdSO4It is electrolyte solution with the mixed solution of hydrochloric acid, uses three-electrode system, at above-mentioned Graphene/TiO2Nanometer tube composite film surface uses cyclic voltammetric deposition CdTe quantum, then calcines 1～1.5h at 300～400 DEG C, is then cooled to room temperature and obtains Graphene/CdTe-TiO2Composite membrane；
Wherein, three-electrode system is Graphene/TiO2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode.
TeO in described electrolyte solution2Concentration be 0.01～0.02mol/L, CdSO4Concentration 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.
The ultimate principle of the present invention: TiO2Being combined with the quantum spot semiconductor CdTe of narrow band gap, under light illumination, the valence-band electrons of CdTe absorbs photon excitation and transits to conduction band, produces photo-generate electron-hole pair, and light induced electron transits to graphene film from the conduction of CdTe, is then transferred to TiO2Conduction band; the most backward protected metal surface being attached thereto migrates; produce photogenerated current; make metal generation cathodic polarization; cause and make electrode potential reduce; and far below the original spontaneous potential (i.e. OCP) of metal, now metal can be at Thermodynamically stable state i.e. cathode protecting state, i.e. metal and is protected and avoids corrosion.Meanwhile, hole is from TiO2Valence band transfers to Graphene, and is further diverted into the valence band of CdTe, effectively achieves the separation in electronics and hole.In this manner it is possible to overcome conventional TiO2The problem that thin film photoproduction cathodic protection effect is poor.
The present invention is by the coating for metal surfaces technology of preparing of development advanced person, it is thus achieved that have the TiO of high performance cathodes protective effect to metal2Nanometer tube composite film.The present invention first prepares the TiO of certain length on titanium foil surface by anodizing2Film of Nano tube array, then use cyclic voltammetric sedimentation to be sequentially depositing Graphene, CdTe quantum in nanotube surface.Surface there is the CdTe/TiO of Graphene sensitization2Nano composite membrane is soaked in electrolyte solution as light anode together with titanium foil matrix, is connected with metals such as protected rustless steels, metal can play photoproduction cathodic protection effect.
It is an advantage of the current invention that:
Graphene is combined to TiO by the present invention with CdTe2It is modified.Graphene/CdTe-TiO2Composite membrane, not merely with the satisfactory electrical conductivity of Graphene, is also with CdTe-TiO2Between quasiconductor effect improve TiO2Utilization ratio to visible ray.Graphene and CdTe are jointly to TiO2It is modified, than Graphene-TiO2Or CdTe-TiO2Performance is more excellent, and wherein Graphene is at TiO2And between CdTe, can preferably transmit electronics, reduce the compound of photo-generated carrier, thus improve composite membrane to 304 stainless protected effect.
Graphene/CdTe-TiO prepared by the present invention2Composite membrane; there is the complete and uniform feature of coating, can be as light anode, it is possible to use visible ray; the electrode potential by protection metal making connection during illumination significantly declines, it is often more important that closes when light source transfers dark-state to and still can maintain the good cathodic protection effect to metal for a long time.Result shows, this composite membrane is at NaOH and Na2In S solution, it is seen that when light irradiates, the 304 stainless electrode potentials being in 3.5%NaCl solution original corrosion resistance relatively poor being attached thereto can be made to decline 570mV, far below stainless spontaneous potential, show that the cathodic protection effect of composite membrane is notable.Particularly after stopping illumination, stainless electrode potential is still significantly lower than spontaneous potential about 370mV, and composite membrane also has good photoproduction cathodic protection effect to rustless steel the most in the dark state.Show the Graphene/CdTe-TiO prepared by cyclic voltammetric sedimentation2Composite membrane has more excellent photoproduction cathodic protection effect to metal.
Accompanying drawing explanation
The TiO preparing gained that Fig. 1 a provides for the embodiment of the present invention2The 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 invention2The 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 invention2Nano-tube film (a) and Graphene/CdTe-TiO2The X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Fig. 3 provides for the embodiment of the present invention2Nano-tube film and Graphene/CdTe-TiO2Composite membrane photogenerated current before and after illumination changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is density of photocurrent (μ A cm-2).On represents that illumination, off represent closedown light source i.e. dark-state.
304 rustless steels that Fig. 4 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO2Nanotube films light anode connects, and before and after illumination, electrode potential changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is electrode potential (mV vs.SCE).On represents that illumination, off represent closedown light source i.e. dark-state.
The TiO preparing gained that Fig. 5 a provides for the embodiment of the present invention2The 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 invention2The 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 invention2Nano-tube film (a) and Graphene/CdTe-TiO2The X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Fig. 7 provides for the embodiment of the present invention2Nano-tube film and Graphene/CdTe-TiO2Composite membrane photogenerated current before and after illumination changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is density of photocurrent (μ A cm-2).On represents that illumination, off represent closedown light source i.e. dark-state.
304 rustless steels that Fig. 8 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO2Nanotube films light anode connects, and before and after illumination, electrode potential changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is electrode potential (mV vs.SCE).On represents that illumination, off represent closedown light source i.e. dark-state.
The TiO preparing gained that Fig. 9 a provides for the embodiment of the present invention2The 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 invention2The 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 invention2Nano-tube film (a) and Graphene/CdTe-TiO2The X-ray diffraction spectrogram of composite membrane (b).
The TiO preparing gained that Figure 11 provides for the embodiment of the present invention2Nano-tube film and Graphene/CdTe-TiO2Composite membrane photogenerated current before and after illumination changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is density of photocurrent (μ A cm-2).On represents that illumination, off represent closedown light source i.e. dark-state.
304 rustless steels that Figure 12 provides for the embodiment of the present invention in 3.5%NaCl solution from different TiO2Nanotube films light anode connects, and before and after illumination, electrode potential changes over curve chart.Wherein, abscissa is the time (s), and vertical coordinate is electrode potential (mV vs.SCE).On represents that illumination, off represent closedown light source i.e. dark-state.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
The technical problem underlying that the present invention solves is simple TiO2When film photoelectric efficiency is low and transfers dark-state to after illumination, thin film does not has photoproduction cathodic protection effect.TiO with surface deposited graphite alkene2Nano-tube film is as substrate, and redeposited CdTe quantum, the Graphene in composite membrane can capture and be delivered to CdTe conduction band or TiO2Electronics on conduction band, thus improve the separation efficiency of photo-generate electron-hole pair, and play the effect of Electronic saving, the photoelectrochemical behaviour of thin film can be improved.Accordingly, it is desirable to provide a kind of Graphene/CdTe-TiO with efficient photoproduction cathodic protection effect2The preparation method of composite membrane.This method uses anodizing first to prepare TiO on titanium surface2Film of Nano tube array, uses cyclic voltammetric sedimentation in nanotube surface successively composite graphite alkene, CdTe quantum, forms nanometer tube composite film.This composite membrane can make the electrode potential of the metals such as the rustless steel of connection significantly decline, and still can maintain the cathodic protection effect excellent to metals such as rustless steels when transferring again dark-state after illumination to for a long time.
Embodiment 1
Taking rectangle pure titanium foil thick for 0.1mm is sample, and its long 15mm, width is 10mm.Specimen surface successively after 400～No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Measure the Fluohydric acid. of 1mL in the deionized water of 100mL, make hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after cleaning as anode, platinized platinum is negative electrode, in above-mentioned mixed liquor, aoxidizes 30min with 30V ultor.Then sample is placed in Muffle furnace at 450 DEG C calcining 2h, then cools to room temperature with the furnace, i.e. prepare TiO at titanium foil matrix surface2Film of Nano tube array.
Use cyclic voltammetric deposition process, first at TiO2Film of Nano tube array surface deposited graphite alkene quantum dot.Weigh 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3～5min, prepare graphene oxide solution.With preparation graphene oxide solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as reference electrode, Graphene is deposited on TiO2Film of Nano tube array surface, deposition voltage is-1.5～1.0V, and the number of turns of deposition is 15, i.e. prepares Graphene/TiO2Composite membrane.Then at prepared Graphene/TiO2Composite film surface deposition CdTe quantum.Weigh 0.3988g TeO2、4.16g CdSO4In the deionized water of 175mL, and add 25mL hydrochloric acid, stirring, with this mixed solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as 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 N2Calcine 1h at atmosphere 300 DEG C, then cool to room temperature with the furnace and i.e. prepare Graphene/CdTe-TiO2Composite membrane.The TiO of preparation2The surface topography of nano thin-film as shown in Figure 1a, presents film of Nano tube array pattern.Additionally, the Graphene/CdTe-TiO of preparation2The surface topography of composite membrane is as shown in Figure 1 b, it can be seen that graphene film and CdTe nano-particle are uniformly deposited on film of Nano tube array surface.
For characterizing the TiO of above-mentioned preparation2Nano-tube film and Graphene/CdTe-TiO2The structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Fig. 2 shows, pure TiO2In the X-ray diffraction spectrum of film of Nano tube array in addition to Ti (Titanium in the figure) diffraction maximum that Ti substrate produces, have also appeared Anatase TiO2(anatase TiO in figure2) diffraction maximum, TiO is described2Film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO2Except Ti and Anatase TiO in composite membrane2Diffraction maximum outside, have also appeared the diffraction maximum of Emission in Cubic CdTe (cubic CdTe in figure), it addition, composite membrane does not occurs the diffraction maximum of Graphene, it may be possible to due to Graphene diffraction maximum at 25.0 ° and TiO2Diffraction maximum 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.From figure 3, it can be seen that when thin film is pure TiO2During nanometer film, transient state photoelectric current maximum is 80 μ about A, when, after film surface deposited graphite alkene and CdTe, the transient state photoelectric current maximum of composite membrane is 560 μ A, the purest TiO27 times of film of Nano tube array, considerably beyond pure TiO2The transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe granule, photo-current intensity is obviously enhanced.Its reason is mainly due to Graphene and CdTe and TiO2After Fu He, it is possible to reduce photo-generate electron-hole is to being combined, it is possible to be effectively improved the utilization rate to light.
Electrochemical techniques are then used to test the Graphene/CdTe-TiO of above-mentioned preparation2Composite membrane as light anode to 304 stainless cathodic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO2Composite membrane is light anode, is placed in photoelectrolytic cell, and wherein electrolyte is 0.2mol/L NaOH+0.1mol/L Na2The 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, with 3.5%NaCl for 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 laminated film surface in photoelectrolytic cell.The test of PARSTAT2273 electrochemical workstation is used to be protected corrosion of metal electrochemical parameter, to investigate TiO2The photoproduction cathodic protection effect of nanometer tube composite film.Test is the most at room temperature carried out.This technology is by the rustless steel change of electrode potential, i.e. Observable effect to the photoproduction cathodic protection of composite membrane before and after light irradiates composite membrane in test corrosion electrolyzer.After turning off light source after illumination, test stainless steel electrode current potential change, can evaluate in the dark state composite film photo-anode to stainless cathodic protection effect.
Fig. 4 be 304 rustless steels in 3.5%NaCl solution from preparation with different TiO2Nanotube films light anode connects rear electrode current potential versus time curve.It can be seen that be phase step type change with the switch electrode current potential of light source.Before illumination, stainless electrode potential is spontaneous potential, and after illumination, stainless electrode potential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO2Composite membrane > CdTe-TiO2>RGO-TiO2>TiO2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO2After composite membrane coupling, under illumination, 304 stainless electrode potentials are rapidly decreased to about-750mV from-180mV, i.e. have dropped about 570mV.Stainless steel cathode is polarised to the most negative numerical value, and its surface does not produce hydrogen, illustrates that rustless steel receives good photoproduction cathodic protection, and " overprotection " does not occurs.After stopping illumination, though electrode potential has rising, but still original low about the 370mV of spontaneous potential of ratio, illustrate that under dark-state, composite membrane still has preferable cathodic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention2Composite membrane can make the significantly negative shifting of stainless steel electrode current potential under illumination condition, its reason is owing to the energy gap of CdTe is narrow, most visible ray can be absorbed, additionally, in composite membrane after graphene quantum dot sensitized treatment, the electronics orientation transmission capacity in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention2Composite membrane can play and be combined the thin film of preparation and pure TiO than bi-material2Thin film has more preferably photoproduction cathodic protection effect.
Embodiment 2
Graphene/CdTe-TiO2The preparation method of composite film photo-anode:
Taking rectangle pure titanium foil thick for 0.1mm is sample, and its long 15mm, width is 10mm.Specimen surface successively after 400～No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Measure the Fluohydric acid. of 1mL in the deionized water of 100mL, make hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after cleaning as anode, platinized platinum is negative electrode, in above-mentioned mixed liquor, aoxidizes 30min with 30V ultor.Then sample is placed in Muffle furnace at 450 DEG C calcining 2h, then cools to room temperature with the furnace, i.e. prepare TiO at titanium foil matrix surface2Film of Nano tube array.
Use cyclic voltammetric deposition process, first at TiO2Film of Nano tube array surface deposited graphite alkene quantum dot.Weigh 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3～5min, prepare graphene oxide solution.With preparation graphene oxide solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as reference electrode, Graphene is deposited on TiO2Film of Nano tube array surface, deposition voltage is-1.5～1.0V, and the number of turns of deposition is 25, i.e. prepares Graphene/TiO2Composite membrane.Then at prepared Graphene/TiO2Composite film surface deposition CdTe quantum.Weigh 0.3988g TeO2、4.16g CdSO4In the deionized water of 175mL, and add 25mL hydrochloric acid, stirring, with this mixed solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as 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 N2Calcine 1h at atmosphere 300 DEG C, then cool to room temperature with the furnace and i.e. prepare Graphene/CdTe-TiO2Composite membrane.The TiO of preparation2The surface topography of nano thin-film as shown in Figure 5 a, presents film of Nano tube array pattern.Additionally, the Graphene/CdTe-TiO of preparation2The surface topography of composite membrane is as shown in Figure 5 b, it can be seen that graphene film and CdTe nano-particle are uniformly deposited on film of Nano tube array surface.
For characterizing the TiO of above-mentioned preparation2Nano-tube film and Graphene/CdTe-TiO2The structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Fig. 6 shows, pure TiO2In the X-ray diffraction spectrum of film of Nano tube array in addition to Ti (Titanium in the figure) diffraction maximum that Ti substrate produces, have also appeared Anatase TiO2(anatase TiO in figure2) diffraction maximum, TiO is described2Film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO2Except Ti and Anatase TiO in composite membrane2Diffraction maximum outside, have also appeared the diffraction maximum of Emission in Cubic CdTe (cubic CdTe in figure), it addition, composite membrane does not occurs the diffraction maximum of Graphene, it may be possible to due to Graphene diffraction maximum at 25.0 ° and TiO2Diffraction maximum 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.From figure 7 it can be seen that when thin film is pure TiO2During nanometer film, transient state photoelectric current maximum is 80 μ about A, when, after film surface deposited graphite alkene and CdTe, the transient state photoelectric current maximum of composite membrane is 760 μ A, the purest TiO29.5 times of film of Nano tube array, considerably beyond pure TiO2The transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe granule, photo-current intensity is obviously enhanced.Its reason is mainly due to Graphene and CdTe and TiO2After Fu He, it is possible to reduce photo-generate electron-hole is to being combined, it is possible to be effectively improved the utilization rate to light.
Electrochemical techniques are then used to test the Graphene/CdTe-TiO of above-mentioned preparation2Composite membrane as light anode to 304 stainless cathodic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO2Composite membrane is light anode, is placed in photoelectrolytic cell, and wherein electrolyte is 0.2mol/L NaOH+0.1mol/L Na2The 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, with 3.5%NaCl for 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 laminated film surface in photoelectrolytic cell.The test of PARSTAT2273 electrochemical workstation is used to be protected corrosion of metal electrochemical parameter, to investigate TiO2The photoproduction cathodic protection effect of nanometer tube composite film.Test is the most at room temperature carried out.This technology is by the rustless steel change of electrode potential, i.e. Observable effect to the photoproduction cathodic protection of composite membrane before and after light irradiates composite membrane in test corrosion electrolyzer.After turning off light source after illumination, test stainless steel electrode current potential change, can evaluate in the dark state composite film photo-anode to stainless cathodic protection effect.
Fig. 8 be 304 rustless steels in 3.5%NaCl solution from preparation with different TiO2Nanotube films light anode connects rear electrode current potential versus time curve.It can be seen that be phase step type change with the switch electrode current potential of light source.Before illumination, stainless electrode potential is spontaneous potential, and after illumination, stainless electrode potential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO2Composite membrane > CdTe-TiO2>RGO-TiO2>TiO2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO2After composite membrane coupling, under illumination, 304 stainless electrode potentials are rapidly decreased to about-750mV from-180mV, i.e. have dropped about 570mV.Stainless steel cathode is polarised to the most negative numerical value, and its surface does not produce hydrogen, illustrates that rustless steel receives good photoproduction cathodic protection, and " overprotection " does not occurs.After stopping illumination, though electrode potential has rising, but still original low about the 370mV of spontaneous potential of ratio, illustrate that under dark-state, composite membrane still has preferable cathodic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention2Composite membrane can make the significantly negative shifting of stainless steel electrode current potential under illumination condition, its reason is owing to the energy gap of CdTe is narrow, most visible ray can be absorbed, additionally, in composite membrane after graphene quantum dot sensitized treatment, the electronics orientation transmission capacity in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention2Composite membrane can play and be combined the thin film of preparation and pure TiO than bi-material2Thin film has more preferably photoproduction cathodic protection effect.
Embodiment 3
Graphene/CdTe-TiO2The preparation method of composite film photo-anode:
Taking rectangle pure titanium foil thick for 0.1mm is sample, and its long 15mm, width is 10mm.Specimen surface successively after 400～No. 1500 sand paperings, successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Measure the Fluohydric acid. of 1mL in the deionized water of 100mL, make hydrofluoric acid solution.Under room temperature, with the titanium foil matrix after cleaning as anode, platinized platinum is negative electrode, in above-mentioned mixed liquor, aoxidizes 30min with 30V ultor.Then sample is placed in Muffle furnace at 450 DEG C calcining 2h, then cools to room temperature with the furnace, i.e. prepare TiO at titanium foil matrix surface2Film of Nano tube array.
Use cyclic voltammetric deposition process, first at TiO2Film of Nano tube array surface deposited graphite alkene quantum dot.Weigh 0.1g graphite oxide, be dissolved in PBS (pH, the 7.4) solution of 200mL, ultrasonic dissolution 3～5min, prepare graphene oxide solution.With preparation graphene oxide solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as reference electrode, Graphene is deposited on TiO2Film of Nano tube array surface, deposition voltage is-1.5～1.0V, and the number of turns of deposition is 50, i.e. prepares Graphene/TiO2Composite membrane.Then at prepared Graphene/TiO2Composite film surface deposition CdTe quantum.Weigh 0.3988g TeO2、4.16g CdSO4In the deionized water of 175mL, and add 25mL hydrochloric acid, stirring, with this mixed solution as electrolyte solution, with platinum for electrode, with saturated calomel electrode (SCE) as 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 N2Calcine 1h at atmosphere 300 DEG C, then cool to room temperature with the furnace and i.e. prepare Graphene/CdTe-TiO2Composite membrane.The TiO of preparation2The surface topography of nano thin-film as illustrated in fig. 9, presents film of Nano tube array pattern.Additionally, the Graphene/CdTe-TiO of preparation2The surface topography of composite membrane is as shown in figure 9b, it can be seen that graphene film and CdTe nano-particle are uniformly deposited on film of Nano tube array surface.
For characterizing the TiO of above-mentioned preparation2Nano-tube film and Graphene/CdTe-TiO2The structure of composite membrane, tests the X-ray diffraction spectrum of composite film photo-anode.The test result of Figure 10 shows, pure TiO2In the X-ray diffraction spectrum of film of Nano tube array in addition to Ti (Titanium in the figure) diffraction maximum that Ti substrate produces, have also appeared Anatase TiO2(anatase TiO in figure2) diffraction maximum, TiO is described2Film of Nano tube array is mainly based on anatase crystal.And Graphene/CdTe-TiO2Except Ti and Anatase TiO in composite membrane2Diffraction maximum outside, have also appeared the diffraction maximum of Emission in Cubic CdTe (cubic CdTe in figure), it addition, composite membrane does not occurs the diffraction maximum of Graphene, it may be possible to due to Graphene diffraction maximum at 25.0 ° and TiO2Diffraction maximum 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.It can be seen from figure 11 that when thin film is pure TiO2During nanometer film, transient state photoelectric current maximum is 80 μ about A, when, after film surface deposited graphite alkene and CdTe, the transient state photoelectric current maximum of composite membrane is 640 μ A, the purest TiO28 times of film of Nano tube array, considerably beyond pure TiO2The transient state photoelectric current of film of Nano tube array, after this result shows deposited graphite alkene and CdSe granule, photo-current intensity is obviously enhanced.Its reason is mainly due to Graphene and CdTe and TiO2After Fu He, it is possible to reduce photo-generate electron-hole is to being combined, it is possible to be effectively improved the utilization rate to light.
Electrochemical techniques are then used to test the Graphene/CdTe-TiO of above-mentioned preparation2Composite membrane as light anode to 304 stainless cathodic protection effects.Double-electrolyzer test system is formed by photoelectrolytic cell and corrosion electrolyzer.Graphene/CdTe-TiO2Composite membrane is light anode, is placed in photoelectrolytic cell, and wherein electrolyte is 0.2mol/L NaOH+0.1mol/L Na2The 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, with 3.5%NaCl for 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 laminated film surface in photoelectrolytic cell.The test of PARSTAT2273 electrochemical workstation is used to be protected corrosion of metal electrochemical parameter, to investigate TiO2The photoproduction cathodic protection effect of nanometer tube composite film.Test is the most at room temperature carried out.This technology is by the rustless steel change of electrode potential, i.e. Observable effect to the photoproduction cathodic protection of composite membrane before and after light irradiates composite membrane in test corrosion electrolyzer.After turning off light source after illumination, test stainless steel electrode current potential change, can evaluate in the dark state composite film photo-anode to stainless cathodic protection effect.
Figure 12 be 304 rustless steels in 3.5%NaCl solution from preparation with different TiO2Nanotube films light anode connects rear electrode current potential versus time curve.It can be seen that be phase step type change with the switch electrode current potential of light source.Before illumination, stainless electrode potential is spontaneous potential, and after illumination, stainless electrode potential declines rapidly first, and the amplitude wherein declined is Graphene/CdTe-TiO2Composite membrane > CdTe-TiO2>RGO-TiO2>TiO2(in figure, RGO represents Graphene).With Graphene/CdTe-TiO2After composite membrane coupling, under illumination, 304 stainless electrode potentials are rapidly decreased to about-750mV from-180mV, i.e. have dropped about 570mV.Stainless steel cathode is polarised to the most negative numerical value, and its surface does not produce hydrogen, illustrates that rustless steel receives good photoproduction cathodic protection, and " overprotection " does not occurs.After stopping illumination, though electrode potential has rising, but still original low about the 370mV of spontaneous potential of ratio, illustrate that under dark-state, composite membrane still has preferable cathodic protection effect.Graphene/CdTe-TiO prepared by the method set up by the present invention2Composite membrane can make the significantly negative shifting of stainless steel electrode current potential under illumination condition, its reason is owing to the energy gap of CdTe is narrow, most visible ray can be absorbed, additionally, in composite membrane after graphene quantum dot sensitized treatment, the electronics orientation transmission capacity in composite membrane strengthens, thus reduces the probability of electronics and hole-recombination, so, the Graphene/CdTe-TiO prepared by the present invention2Composite membrane can play and be combined the thin film of preparation and pure TiO than bi-material2Thin film has more preferably photoproduction cathodic protection effect.
Claims (8)
1. Graphene/the CdTe-TiO for photoproduction cathodic protection2The preparation side of composite film photo-anode
Method, it is characterised in that:
1) add Fluohydric acid. in deionized water, make electrode, the Titanium base sample to pretreatment with platinum
Carry out anodic oxidation, calcine after oxidation, cool to room temperature with the furnace；
2) use cyclic voltammetric deposition process to the Titanium base specimen surface deposited graphite alkene after above-mentioned oxidation
Quantum dot, obtains Graphene/TiO2Nanometer tube composite film；
3) use cyclic voltammetric deposition process to above-mentioned Graphene/TiO2Nanometer tube composite film surface deposits
CdTe quantum, then calcines, and cools to room temperature with the furnace, obtains Graphene/CdTe-TiO2Composite membrane.
2. Graphene/the CdTe-TiO as described in claim 12The preparation method of composite film photo-anode, its
It is characterised by: the Titanium base sample of described pretreatment is using titanium foil as matrix, by Titanium base surface warp
After polishing, ultrasonic waves for cleaning in acetone, dehydrated alcohol and deionized water, i.e. obtains pretreatment successively
After Titanium base sample.
3. Graphene/the CdTe-TiO as described in claim 22The preparation method of composite film photo-anode, its
It is characterised by: the thickness of described matrix is 0.1～0.5mm；Described matrix can be cuboid, and length can
Being 15～35mm, width can be 10～25mm.
4. Graphene/the CdTe-TiO as described in claim 12The preparation method of composite film photo-anode, its
It is characterised by:
Described step 1) to add mass fraction in deionized water be the hydrofluoric acid solution of 1%, then with platinum
Make electrode, the Titanium base sample of pretreatment is carried out anodic oxidation, at 450～500 DEG C after oxidation
Lower calcining 1.5～2.0h, is then cooled to room temperature；
Wherein, anodic oxidation condition be anodised running voltage be 20～30V, time anodised
Between be 20～30min.
5. Graphene/the CdTe-TiO as described in claim 12The preparation method of composite film photo-anode, its
It is characterised by:
Described step 2) with graphene oxide as electrolyte solution, use three-electrode system, at above-mentioned oxygen
The TiO on Titanium base sample after change2Film of Nano tube array surface uses cyclic voltammetric deposition
Graphene quantum dot, obtains Graphene/TiO2Nanometer tube composite film；
Wherein, three-electrode system is TiO2/ Ti is working electrode, and saturated calomel electrode (SCE) is reference
Electrode, platinum electrode is to electrode.
6. Graphene/the CdTe-TiO as described in claim 52The preparation method of composite film photo-anode, its
It is characterised by: the concentration of described graphene oxide solution is 0.5～1.0g/L；Described cyclic voltammetric deposits
Voltage be-1.5～1.0V, the number of turns of deposition is 10～50.
7. Graphene/the CdTe-TiO as described in claim 12The preparation method of composite film photo-anode, its
It is characterised by:
Described step 3) with TeO2、CdSO4It is electrolyte solution with the mixed solution of hydrochloric acid, uses three
Electrode system, at above-mentioned Graphene/TiO2Nanometer tube composite film surface uses cyclic voltammetric deposition process to sink
Long-pending CdTe quantum, then calcines 1～1.5h at 300～400 DEG C, is then cooled to room temperature and obtains
Graphene/CdTe-TiO2Composite membrane；
Wherein, three-electrode system is Graphene/TiO2/ Ti is working electrode, saturated calomel electrode (SCE)
For reference electrode, platinum electrode is to electrode.
8. Graphene/the CdTe-TiO as described in claim 72The preparation method of composite film photo-anode,
It is characterized in that: TeO in described electrolyte solution2Concentration be 0.01～0.02mol/L, CdSO4
Concentration be 0.05～0.10mol/L, the volume ratio of hydrochloric acid and water is 1:6～1:7；Described cyclic voltammetric
The voltage of deposition is-0.5～-1.1V, and the number of turns of deposition is 10～30.
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