CN102543457A - Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film - Google Patents
Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film Download PDFInfo
- Publication number
- CN102543457A CN102543457A CN2012100324849A CN201210032484A CN102543457A CN 102543457 A CN102543457 A CN 102543457A CN 2012100324849 A CN2012100324849 A CN 2012100324849A CN 201210032484 A CN201210032484 A CN 201210032484A CN 102543457 A CN102543457 A CN 102543457A
- Authority
- CN
- China
- Prior art keywords
- cdte
- film
- quantum dot
- tio
- zns
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film, and relates to a TiO2 nano film. The method comprises the following steps: preparing a titanium matrix sample, preparing a TiO2 nano-tube array film at the surface of the sample, preparing a CdTe quantum dot sensitization TiO2 nano film, and finally preparing a ZnS/CdTe quantum dot sensitization TiO2 nano film. Under irradiation of white light, the film enables an electrode potential of connected metals like stainless steel to be greatly reduced in corrosive medium, and can protect good cathode of metals like stainless steel continuously for a long time in a dark state. And the nano film prepared by using the method has an efficient photoproduction cathode protection effect.
Description
Technical field
The present invention relates to a kind of TiO
2Nano thin-film especially relates to the quantum dot sensitized TiO of a kind of ZnS/CdTe
2The preparation method of nano thin-film.
Background technology
Semiconductor titanium dioxide (TiO
2) have good Optical Electro-Chemistry character, be widely used in fields such as solar cell, photocatalytic degradation pollutant and photolysis water hydrogen.Someone reports, when the TiO under the illumination
2Film is connected with metal through lead, and the light induced electron of generation is transferred to the metal surface through lead, and its electrode potential is reduced, and can play the effect of cathodic protection to metal, promptly so-called photoproduction cathodic protection.Therefore, TiO
2The preparation of film and the application in corrosion of metals control have caused corrosion research person's great attention.
Although theoretically, photoproduction cathodic protection effect utilizes TiO
2Semi-conductive photoelectric properties, consumed power not, more environmental protection has tempting application prospect; But because titanium dioxide is the semiconductor (3.2eV) of broad stopband; All can not effectively absorb for most visible light; Produced simultaneously light induced electron-hole is fast to the recombination velocity under dark attitude, and the photoproduction cathodic protection acts on and is difficult to when not having illumination keep.To above problem, at present carry out a large amount of research still needing aspect the photoproduction cathodic Protection.Aspect photocatalysis and solar cell research, some has obtained progress preferably, for example, and for improving TiO
2To the utilance of sunlight, make its absorption region expand to visible region, as to TiO
2Film mix (8, Tu Y F, Huang S Y, SangJ P.et al.Preparation of Fe-doped TiO
2Nanotube arrays and their photocatalytic activities undervisible light [J] .Materials Research Bulletin, 2010,45 (2): 224-229; 9, Nakamura R, Tanaka T, Nakato Y.Mechanism for visible light responses in anodic photocurrents at N-doped TiO
2Filmelectrodes [J] .Journal of Physical Chemistry B, 2004,108 (30): 10617-10620) or sensitization processing etc. (10, Zhu G, Xu T, Lv T A, et al.Graphene-incorporated nanocrystalline TiO
2Films for CdS quantumdot-sensitized solar cells [J] .Journal of Electroanalytical Chemistry, 2011,650 (2): 248-251; 11, XuX Q, Xu G.Electrochemical impedance spectra of CdSe quantume dots sensitized nanocrystallineTiO
2Solar cells [J] .Science China-Chemistry, 2011,54 (1): 205-210), go back the semiconductor (WO of the different energy levels of handlebar
3(12, Subasri R, Shinohara T, Mori K.TiO
2-based photoanodes for cathodic protection of copper [J] .Journal of the Electrochemical Society, 2005,152 (3): B105-B110; 13, Zhou M J, Zeng ZO, Zhong L.Energy storage ability and anti-corrosion protection properties of TiO
2-SnO
2System [J] .Mater.Corros, 2010,61 (4): 324-327), SnO
2(14, Tetsu T, Shuichi S, Yoshihisa O, et al.TiO
2-WO
3Photoelectrochemical Anticorrosion Systemwith an Energy Storage Ability [J] .Chem.Mater, 2001,13:2838-2842; 15, Zhou M J, Zeng Z O, Zhong L.Photogenerated cathode protectionproperties of nano-sized TiO
2/ WO
3Coating [J] .Corrosion Science, 2009,51 (6): 1386-1391) etc.) and coupling TiO
2, as the storage vault of electronics under the illumination, slow down the right recombination rate in light induced electron-hole, and under dark attitude with these electron transfers to metal, continued the cathodic protection effect within a certain period of time.
Quantum dot sensitized processing can be used as a kind of to TiO
2Film carries out the method for modification.Because the size dimension of quantum dot can be regulated, therefore can increase substantially TiO
2Utilance to sunlight.Simultaneously, because that optical excitation can produce is many to electron-hole pair, so can strengthen TiO well again in quantum dot
2Photoelectric respone; In addition, because quantum spot semiconductor and TiO
2The special hierarchic structure that forms (16, Chi C F; Cho H W, Teng H S, et al.Energy level alignment; Electron injection, and charge recombination characteristics in CdS/CdSe cosensitized TiO
2Photoelectrode [J] .Applied Physics Letters, 2011,98 (1)), therefore possibly make the TiO that handled through sensitization
2Under dark attitude, also has certain cathodic protection effect.
CdTe is as a kind of desirable photoelectric conversion material, and its energy gap is 1.47eV, and is good with the solar spectrum coupling, to TiO
2Sensitization is handled, and possibly have better photoelectric respone.At present, the preparation of CdTe mainly is in acid solution, adopt chemical bath deposition method (17, Gao X F, Li H B, Sun W T, et al.CdTe Quantum Dots-Sensitized TiO
2NanotubeArray Photoelectrodes [J] .Journal of Physical Chemistry C; 2009; 113 (18): 7531-7535), electrodeposition process (18, Seabold J A; Shankar K, Wilke R H T, et al.Photoelectrochemical Properties ofHeterojunction CdTe/TiO
2Electrodes Constructed Using Highly Ordered TiO
2Nanotube Arrays [J] .Chemistry of Materials, 2008,20 (16): 5266-5273) or sol-gal process (19, Li Y S, Jiang F L, Xiao Q, et al.Enhanced photocatalytic activities of TiO
2Nanocomposites doped with water-solublemercapto-capped CdTe quantum dots [J] .Applied Catalysis B-Environmental, 2010,101 (1-2): 118-129) etc., the method more complicated.Relevant in alkaline solution preparation method's report relatively lack.In addition; The poor stability of CdTe quantum dot under the illumination; Be always the restriction its application bottleneck (20, Bang J H; Kamat P V.Quantum DotSensitized Solar Cells.A Tale of Two Semiconductor Nanocrystals:CdSe and CdTe [J] .ACS Nano, 2009,3 (6): 1467-1476).
Summary of the invention
The objective of the invention is to TiO to existing preparation
2Film photoelectric efficient is lower, under dark attitude, is not having photoproduction cathodic protection effect, and quantum dot problem such as instability under illumination, and a kind of quantum dot sensitized TiO of ZnS/CdTe with efficient photoproduction cathodic protection effect is provided
2The preparation method of nano thin-film.
The present invention includes following steps:
1) preparation titanium matrix sample;
2) prepare TiO at titanium matrix specimen surface
2Film of Nano tube array, said preparation titanium surface TiO
2Nanotube can adopt anode oxidation method, and concrete grammar is following: with NH
4F is dissolved in the deionized water, adds glycerine, mixed solution, as to electrode, anodic oxidation in mixed solution is calcined sample again, cools to room temperature again with the furnace, promptly makes the TiO2 film of Nano tube array at titanium matrix specimen surface with platinum;
3) the quantum dot sensitized TiO of preparation CdTe
2Nano thin-film: the quantum dot sensitized TiO of said preparation ZnS/CdTe
2Nano thin-film adopts the constant pressure impulse electrodeposition process, and concrete grammar is following: in step 2) TiO that obtains
2Film of Nano tube array surface deposition CdTe quantum dot is with Na
2TeO
3Solution, CdSO
4With nitrilotriacetic acid trisodium (Na
3NTA) mix the back as reaction solution, use H
2SO
4The pH of conditioned reaction solution is 8～9, adopts three-electrode system, with TiO
2Film of Nano tube array is a work electrode, and Pt is to electrode, and saturated calomel electrode is a reference electrode, on chem workstation, carries out the constant pressure impulse electro-deposition, makes the quantum dot sensitized TiO of CdTe
2Nano thin-film;
4) the quantum dot sensitized TiO of preparation ZnS/CdTe
2Nano thin-film: the quantum dot sensitized TiO of CdTe that step 3) is made
2Nano thin-film is earlier at CdCl
2Soak in the solution, the oven dry after annealing is handled, and promptly makes CdTe/TiO
2Composite membrane; Adopt circulatory maceration at CdTe/TiO again
2Composite membrane surface deposition ZnS, concrete grammar is following: what will prepare contains CdTe/TiO
2The sample of composite membrane is soaked in Zn earlier
2+Ethanolic solution in (1～2) min, use alcohol flushing then; Place S again
2-Methanol solution in soak (1～2) min, use alcohol flushing again, the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film.
In step 1), the concrete grammar of said preparation titanium matrix sample can be:,, after the polishing of titanium matrix surface, clean as the titanium matrix with titanium foil, get titanium matrix sample; Said titanium matrix can be rectangle titanium matrix, and length is (1.0～1.5) cm, and wide is (1.0～1.5) cm, and thickness is (0.05～0.15) mm; The Ti content of said titanium foil is best more than 99.9%; Said polishing can be adopted 400～No. 1500 silicon carbide paper polishings, and said cleaning can be cleaned (5～10) min at acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple successively.
In step 2) in, said NH
4The proportioning of F, deionized water and glycerine can be (4.5～5) gNH
4F: (300～400) mL deionized water: (500～600) mL glycerine, wherein NH
4F calculates in mass, and deionized water and glycerine by volume are calculated; Said anodised voltage can be (20～30) V, and the anodised time can be (20～30) min; The condition of said calcining can be sample is placed in the Muffle furnace in (450～550) ℃ following calcining (1.5～2.0) h.
In step 3), said Na
2TeO
3The concentration of solution can be (2～8) mmol/L, said CdSO
4Concentration can be (0.01～0.05) mol/L; The concentration of said nitrilotriacetic acid trisodium can be (0.02～0.08) mol/L; Said H
2SO
4Concentration can be (0.05～0.20) mol/L; Said Na
2TeO
3The preparation method can be: with (0.350～0.450) g TeO
2Powder joins in (400～600) mL deionized water with (0.100～0.300) g NaOH, and 70 ℃ of refluxed (2～5) h is cooled to room temperature, gets Na
2TeO
3Said pulse parameter of on chem workstation, carrying out the constant pressure impulse electro-deposition can be: the burst length is (0.05～0.20) s, and pulse-off blanking time is (0.5～1.5) s, and the pulse electromotive force is (1.3～-1.5) V, and the circulation number of turns is (40～100).
In step 4), said CdCl
2Concentration can be (0.2～0.8) mol/L, the time of said immersion can be 0.5～5min; The condition of said oven dry can be baking (3～8) min in the baking oven of (60～80) ℃; The condition of said annealing in process can be at (350～450) ℃ following annealing in process (25～35) min; In order to improve the stability of prepared smooth anode, said employing circulatory maceration is at CdTe/TiO
2Composite membrane surface deposition ZnS (3～5) capable of circulation is inferior.
Below provide the quantum dot sensitized TiO of ZnS/CdTe
2The method of testing of the photoproduction cathodic protection effect of nano thin-film:
The double-electrolyzer system that adopts photoelectrolytic cell and corrosion electrolytic cell to form.The quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film is the light anode, places photoelectrolytic cell, and wherein electrolyte is (0.3～0.6) mol/LNa
2SO
4+ (0.3～0.6) mol/L HCOOH solution is (9～10) with (0.1～0.3) mol/LNaOH regulator solution pH.The corrosion electrolytic cell is a three-electrode system, and work electrode is protected metal, is the Pt electrode to electrode, and reference electrode is saturated calomel electrode (SCE), is medium solution with (0.1～1.0) mol/L NaCl.The light anode is connected through lead with protected metal electrode, and photoelectrolytic cell is connected through salt bridge (agar that contains 1.0mol/LKCl) with the corrosion electrolytic cell.During illumination with 150W high pressure Xe lamp as white light source, direct irradiation is TiO in photoelectrolytic cell
2The composite membrane surface.
The present invention utilizes anode oxidation method to prepare TiO earlier
2Nanotube adopts the constant pressure impulse electrodeposition process at the compound CdTe quantum dot of nanotube surface, and with the film that makes at CdCl
2Soak after a period of time annealing in process under high temperature in the solution, to strengthen the stability of quantum dot.Adopt the film surface of circulatory maceration after annealing in process to coat the ZnS shell; Under white light; This film can make the electrode potential of metals such as stainless steel in Korrosionsmedium of connection descend significantly, and when dark attitude, also can keep for a long time the good cathodic protection effect of metals such as stainless steel.
Below provide beneficial effect of the present invention:
The quantum dot sensitized TiO of ZnS/CdTe prepared in accordance with the present invention
2Nano thin-film has all even complete characteristics of coating, can be used as the light anode, and the electrode potential by the protection metal of connection is descended significantly, the more important thing is when dark attitude and still can keep good cathodic protection effect for a long time.The quantum dot sensitized film of the inventive method preparation is after annealing in process, and the defect concentration on quantum dot surface reduces, and degree of crystallinity improves, thereby stability strengthens.At 0.5mol/L Na
2SO
4In+0.5mol/LHCOOH (pH=9.6) solution; During white light; Film after annealing in process can make 403 stainless steels (stainless steel that a kind of corrosion resistance is relatively poor relatively) the electrode potential decline 450mV in the 0.5mol/LNaCl solution that is in that is attached thereto, and is lower than stainless spontaneous potential.And after stopping illumination,, but still be lower than the about 200mV of stainless spontaneous potential though the stainless steel electrode current potential has rising, promptly under dark attitude, also have good photoproduction cathodic protection effect.And without the film of annealing in process, even coated the ZnS shell, behind illumination 2h, quantum dot has decomposed basically fully.
Description of drawings
Apply the voltage system sketch map in the constant pressure impulse electro-deposition method that Fig. 1 is adopted for the embodiment of the invention 1.In Fig. 1, abscissa is time t (s), and ordinate is voltage voltage (V); Wherein, t
OnBe the burst length, t
OffBe pulse turn-off time, deposition representes deposition, and diffusion and accumulation of ions representes the diffusion and the gathering of ion.
Fig. 2 is for using the quantum dot sensitized TiO of ZnS/CdTe of the embodiment of the invention 1 preparation
2Nano thin-film surface topography (SEM figure).In Fig. 2, scale is 100nm.
Fig. 3 is for using the quantum dot sensitized TiO of ZnS/CdTe of the embodiment of the invention 1 preparation
2The photoelectricity flow graph of nano thin-film.In Fig. 3, abscissa is wavelength X/nm, and ordinate is photoelectric current Photocurrent (nA).
Fig. 4 be in the embodiment of the invention 1 403 stainless steels in 0.5mol/L NaCl solution with the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film light anode connects, and illumination front and back electrode potential in 0.5mol/L NaCl solution changes (light on representes illumination, and light off representes to close light source, promptly dark attitude) in time.In Fig. 4, abscissa is time t (h), and ordinate is current potential E (V vs.SCE).
Fig. 5 is for using the quantum dot sensitized TiO of ZnS/CdTe of the embodiment of the invention 2 preparations
2Nano thin-film surface topography (SEM figure).In Fig. 5, scale is 100nm.
Fig. 6 is for using the quantum dot sensitized TiO of ZnS/CdTe of the embodiment of the invention 2 preparations
2The photoelectricity flow graph of nano thin-film.In Fig. 6, abscissa is wavelength X/nm, and ordinate is photoelectric current Photocurrent (nA).
Fig. 7 is that 403 stainless steels are connected with quantum dot sensitized nano thin-film light anode in the embodiment of the invention 2, and illumination front and back electrode potential in 0.5mol/L NaCl solution changes (light on representes illumination, and light off representes to close light source, promptly dark attitude) in time.In Fig. 7, abscissa is time t (h), and ordinate is current potential E (V vs.SCE).
Embodiment
Following examples will combine accompanying drawing that the present invention is further described.
Embodiment 1
According to technique scheme (concrete steps), the quantum dot sensitized TiO of preparation ZnS/CdTe
2Nano thin-film, and testing film as the light anode to 403 stainless cathodic protection effects.
With the thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and wide is 10mm.Specimen surface is taken up in order of priority and is cleaned 10min at acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple after 400～No. 1500 silicon carbide paper polishings.
Take by weighing 4.5g NH
4F is dissolved in the 333mL deionized water, adds the 500mL glycerine, mixing.Under the room temperature, do electrode with platinum, in above-mentioned solution, anodic oxidation 30min under 20V voltage.Then sample is placed on and under 450 ℃, calcines 2h in the Muffle furnace and cool to room temperature with the furnace, promptly make TiO on the Ti surface
2Film of Nano tube array.
Adopt the constant pressure impulse electrodeposition process, use Autolab PGSTAT30 electrochemical workstation, at first at above-mentioned TiO
2Film of Nano tube array surface deposition CdTe quantum dot, 5mmol/L Na
2TeO
3Solution, 0.02mol/L CdSO
4And 0.05mol/LNa
3NTA (nitrilotriacetic acid trisodium) mixes as reaction solution, and using 0.1mol/L sulfuric acid regulation solution pH is 8.3.Na wherein
2TeO
3The preparation method following: with 0.399g TeO
2Powder and 0.200g NaOH join in the 500mL deionized water, and 70 ℃ of refluxed 3h are cooled to room temperature.Burst length is 0.15s, and pulse turn-off time is 1s, and the pulse electromotive force is-1.5V that the circulation number of turns is 70.Its constant pressure impulse electro-deposition sketch map is as shown in Figure 1.
In order effectively to reduce the surface defect density of quantum dot, with the film of Nano tube array for preparing at 0.5mol/L CdCl
2Soak 1min in the solution, in 70 ℃ baking oven, dry by the fire 5min, again at 400 ℃ of following annealing in process 30min.
In order to improve the stability of prepared smooth anode, adopt circulatory maceration at CdTe/TiO
2Electrode surface deposition ZnS.Sample places Zn earlier
2+Ethanolic solution in 1min, use alcohol flushing then; Place S again
2-Methanol solution in 1min, use alcohol flushing, so be a circulation.Circulate 5 times, promptly can form the ZnS of several molecule layer, can prevent the photoetch of electrode effectively on the CdTe surface.
The quantum dot sensitized TiO of test ZnS/CdTe
2Nano thin-film photoproduction cathodic protection effect.With the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film is the light anode, places photoelectrolytic cell, and wherein electrolyte is 0.5mol/LNa
2SO
4+ 0.5mol/LHCOOH solution, using 0.2mol/L NaOH regulator solution pH is 9.6.The corrosion electrolytic cell is a three-electrode system, and work electrode is protected metal, is the Pt electrode to electrode, and reference electrode is saturated calomel electrode (SCE), is medium solution with 0.5mol/LNaCl.The light anode is connected through lead with protected metal electrode, and photoelectrolytic cell is connected through salt bridge (agar that contains 1.0mol/L KCl) with the corrosion electrolytic cell.During illumination with 150W high pressure Xe lamp as white light source, direct irradiation laminated film surface in photoelectrolytic cell.
Fig. 2 is the quantum dot sensitized TiO of ZnS/CdTe that makes
2The SEM figure of nano thin-film.As can be seen from the figure, this composite membrane is more smooth, and the distribution of quantum dot is more even.Because the sensitization of quantum dot, the tube wall of nanotube is thickeied to some extent.
Fig. 3 is the optogalvanic spectra of different nano thin-films.Can find out, when film is pure TiO
2During nanometer film, shown in Fig. 3 curve (a), the absorption of light is mainly concentrated on ultraviolet region, and be that 335nm place photoelectric current reaches about maximum 5300nA at wavelength.Behind film surface deposition CdTe quantum dot, Fig. 3 curve (b) shows that its photoelectric current intensity significantly strengthens, and light abstraction width extends to about 600nm.Because CdTe (1.47eV) is the semiconductor of narrow band gap, to TiO
2Carry out sensitization and handle, can greatly enlarge light abstraction width, improve utilance effectively light.When after the surface coats the ZnS shell, (c) can find out from Fig. 3 curve, and photoelectric current intensity slightly descends, and reason is the greater band gap of ZnS (3.66eV), and is relatively poor to the response of light, hindered the absorption of light to a certain extent, but influence is little.Importantly composite membrane exists the ZnS skin can improve the stability of quantum dot.
Fig. 4 be 403 stainless steels in 0.5mol/L NaCl solution respectively be in pure TiO in the photoelectrolytic cell
2Film and through CdCl
2Solution-treated and untreated compound film electrode are coupled rear electrode current potential curve over time.Pure TiO under stainless steel and illumination
2When membrane electrode was coupled, 403 stainless current potentials were promptly reduced to pact-300mV from the about 50mV of corrosion potential, played certain photoproduction cathodic protection effect.Curve b can find out from figure; When composite membrane not being carried out annealing in process, under the illumination, the electrode potential of light anode quickly falls to-400mV about; But carrying out along with illumination; Stainless electrode potential is shuffled gradually, explains that the photo-anode film surface quantum dot of this moment is very unstable, takes place to decompose to cause current potential just becoming.After cutting off light source 2h, carry out illumination once more, at this moment stainless electrode potential and pure TiO
2Approaching when film is coupled, composite membrane is described after 2h illumination, decompose basically fully, even coated the ZnS shell, still can not reduce the decomposition of quantum dot.After composite membrane is carried out annealing in process, can find out from curve c, under the illumination; The stainless steel electrode current potential that is coupled quickly falls to-400mV about because there is certain defective in ZnS itself, just begun in a few minutes; Current potential is shuffled to some extent, but along with the carrying out of illumination, current potential is stabilized in gradually-380mV about; Annealing in process is described, can be effectively improved the stability of quantum dot.After cutting off light source 2h, carry out illumination once more, the current potential of this moment also is basicly stable about-380mV, and the TiO of ZnS/CdTe after quantum dot sensitized is described
2Nano composite membrane is stable, and can play good photoproduction cathodic protection effect to 403 stainless steels.
According to technique scheme (concrete steps), the quantum dot sensitized TiO of preparation ZnS/CdTe
2Nano thin-film, and testing film as the light anode to 403 stainless cathodic protection effects.
With the thick rectangle pure titanium foil of 0.1mm is sample, its long 10mm, and wide is 10mm.Specimen surface is taken up in order of priority and is cleaned 8min at acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple after No. 400～No. 1500 silicon carbide paper polishings.
Take by weighing the 4.5g ammonium fluoride, be dissolved in the 333mL deionized water, add the 500mL glycerine, mixing.Under the room temperature, do electrode with platinum, in above-mentioned solution, anodic oxidation 30min under the 20V voltage.Then sample is placed in the Muffle furnace and calcines 2h down and cool to room temperature with the furnace in 450 ℃.
Adopt the constant pressure impulse electrodeposition process, use Autolab PGSTAT30 electrochemical workstation, at first at above-mentioned TiO
2Film of Nano tube array surface deposition CdTe quantum dot, 5mmol/L Na
2TeO
3Solution, 0.02mol/L CdSO
4And 0.05mol/LNa
3NTA (nitrilotriacetic acid trisodium) mixes as reaction solution, and using 0.1mol/L sulfuric acid regulation solution pH is 8.3.Na wherein
2TeO
3The preparation method following: with 0.399g TeO
2Powder and 0.2g NaOH join in the 500mL deionized water, and 70 ℃ of refluxed 4h are cooled to room temperature.Burst length is 0.2s, and pulse turn-off time is 1.5s, and the pulse electromotive force is-1.3 V, and the circulation number of turns is 60.
In order to reduce the surface defect density of quantum dot effectively, with the film of Nano tube array for preparing at 0.5mol/L CdCl
2Soak 2min in the solution, in 80 ℃ baking oven, dry by the fire 3min, again at 380 ℃ of following annealing in process 25min.So just make the TiO of CdTe sensitization
2Composite membrane.
For the stability that to improve obtained above-mentioned work done in the manner of a certain author be the composite membrane of light anode, adopt circulatory maceration at CdTe/TiO
2Electrode surface deposition ZnS.Sample places 0.6mol/L Zn (NO earlier
3)
2Ethanolic solution in 1min, use alcohol flushing then; Place 0.1mol/L Na again
21min in the methanol solution of S uses alcohol flushing, so is a circulation.Circulate 5 times, promptly can form the ZnS of several molecule layer, can prevent the photoetch of composite membrane effectively on the CdTe surface.Finally made the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film.
The quantum dot sensitized TiO of test ZnS/CdTe
2Nano thin-film photoproduction cathodic protection effect.With the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film is the light anode, places photoelectrolytic cell, and wherein electrolyte is 0.5mol/L Na
2SO
4+ 0.5mol/LHCOOH solution, using 0.2mol/L NaOH regulator solution pH is 9.6.The corrosion electrolytic cell is a three-electrode system, and work electrode is protected metal, is the Pt electrode to electrode, and reference electrode is saturated calomel electrode (SCE), is medium solution with 0.5mol/L NaCl.The light anode is connected through lead with protected metal electrode, and photoelectrolytic cell is connected through salt bridge (agar that contains 1.0M KCl) with the corrosion electrolytic cell.During illumination with 150W high pressure Xe lamp as white light source, direct irradiation laminated film surface in photoelectrolytic cell.
Fig. 5 is the SEM figure of the quantum dot sensitized TiO2 nano thin-film of ZnS/CdTe that makes.As can be seen from the figure, nanotube is more even, has the quantum dot of more amount to be distributed on the tube wall and the mouth of pipe.
Fig. 6 is the optogalvanic spectra of different nano thin-films.(a) can find out from Fig. 6 curve, for pure TiO
2Nano thin-film is that 335nm place photoelectric current maximum reaches about 5000nA at wavelength, and the response of light is mainly concentrated on the ultra-violet (UV) band, and visible light is not had response basically.Behind film surface deposition CdTe quantum dot, Fig. 6 curve (b) shows that its photoelectric current intensity significantly strengthens, and light abstraction width also extends to about 600nm.Because prepared quantum dot fewer (as shown in Figure 5), the absorption of visible light amplitude there be not strong among the embodiment 1.When after the surface coats the ZnS shell, (c) can find out from Fig. 6 curve, and photoelectric current intensity descends to some extent, and reason is that also the ZnS semiconductor of broad-band gap is relatively poor to the response of light, has hindered the absorption of light to a certain extent.
Fig. 7 be 403 stainless steels in 0.5mol/L NaCl solution respectively be in pure TiO in the photoelectrolytic cell
2Film and compound film electrode are coupled rear electrode current potential curve over time, have contrasted CdCl
2Solution-treated is to the influence of composite membrane stability.Pure TiO under stainless steel and illumination
2When membrane electrode was coupled, (a) can find out from Fig. 7 curve, and its electrode potential is promptly reduced to pact-335mV from corrosion potential, played certain photoproduction cathodic protection effect.For the composite membrane without annealing in process, (b) can find out from Fig. 7 curve, under the illumination; The electrode potential of light anode quickly falls to-390mV about, but along with the carrying out of illumination, the electrode potential of light anode is shuffled gradually; The quantum dot that be described this moment is very unstable, takes place to decompose to cause current potential just becoming.After cutting off light source 2h, carry out illumination once more, this moment composite membrane electrode potential about-280mV, composite membrane be described after 2h illumination, basically fully decomposition.After composite membrane was carried out annealing in process, (c) can find out from Fig. 7 curve, under the illumination; The current potential of light anode quickly falls to-400mV about because the defective of ZnS existence itself has just begun in a few minutes; Current potential is shuffled to some extent, but along with the carrying out of illumination, current potential is stabilized in gradually-380mV about; Annealing in process is described, can be improved the stability of quantum dot effectively.After cutting off light source 2h, carry out illumination once more, the current potential of this moment is also basicly stable about-380mV, can play good photoproduction cathodic protection effect to 403 stainless steels.
Basic principle of the present invention: TiO
2Compound with the quantum spot semiconductor CdTe of narrow band gap, under rayed, the valence band Electron absorption photon excitation of CdTe transits to conduction band, and generation light induced electron-hole is right, and light induced electron transits to TiO from the conduction band of CdTe
2Conduction band; To the metal surface migration that is attached thereto, produce photogenerated current at last, cause the metal surface electron density to increase; Macro manifestations reduces for the metal surface current potential; And the spontaneous potential original far below metal, this moment metal can be in the thermodynamics stable state be cathode protecting state, promptly metal is protected and avoids corrosion.Simultaneously, the hole is from TiO
2Transfer to the hole of CdTe, realized separating of electronics and hole effectively.The TiO that has reported at present
2Film photoproduction cathodic protection effect is also relatively poor, and the technology of preparing of the metal-surface nano film that development is advanced obtains good nanometer film and can improve its photoproduction cathodic protection effect to metal.
Claims (10)
1.ZnS/CdTe quantum dot sensitized TiO
2The preparation method of nano thin-film is characterized in that may further comprise the steps:
1) preparation titanium matrix sample;
2) prepare TiO at titanium matrix specimen surface
2Film of Nano tube array, said preparation titanium surface TiO
2Nanotube can adopt anode oxidation method, and concrete grammar is following: with NH
4F is dissolved in the deionized water, adds glycerine, mixed solution, as to electrode, anodic oxidation in mixed solution is calcined sample again, cools to room temperature again with the furnace, promptly makes the TiO2 film of Nano tube array at titanium matrix specimen surface with platinum;
3) the quantum dot sensitized TiO of preparation CdTe
2Nano thin-film: the quantum dot sensitized TiO of said preparation ZnS/CdTe
2Nano thin-film adopts the constant pressure impulse electrodeposition process, and concrete grammar is following: in step 2) TiO that obtains
2Film of Nano tube array surface deposition CdTe quantum dot is with Na
2TeO
3Solution, CdSO
4With nitrilotriacetic acid trisodium (Na
3NTA) mix the back as reaction solution, use H
2SO
4The pH of conditioned reaction solution is 8～9, adopts three-electrode system, with TiO
2Film of Nano tube array is a work electrode, and Pt is to electrode, and saturated calomel electrode is a reference electrode, on chem workstation, carries out the constant pressure impulse electro-deposition, makes the quantum dot sensitized TiO of CdTe
2Nano thin-film;
4) the quantum dot sensitized TiO of preparation ZnS/CdTe
2Nano thin-film: the quantum dot sensitized TiO of CdTe that step 3) is made
2Nano thin-film is earlier at CdCl
2Soak in the solution, the oven dry after annealing is handled, and promptly makes CdTe/TiO
2Composite membrane; Adopt circulatory maceration at CdTe/TiO again
2Composite membrane surface deposition ZnS, concrete grammar is following: what will prepare contains CdTe/TiO
2The sample of composite membrane is soaked in Zn earlier
2+Ethanolic solution in (1～2) min, use alcohol flushing then; Place S again
2-Methanol solution in soak (1～2) min, use alcohol flushing again, the quantum dot sensitized TiO of ZnS/CdTe
2Nano thin-film.
2. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 1), and the concrete grammar of said preparation titanium matrix sample is:,, after the polishing of titanium matrix surface, clean as the titanium matrix with titanium foil, get titanium matrix sample.
3. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 1), and said titanium matrix is a rectangle titanium matrix, and length is (1.0～1.5) cm, and wide is (1.0～1.5) cm, and thickness is (0.05～0.15) mm; The Ti content of said titanium foil is best more than 99.9%; Said polishing can be adopted 400～No. 1500 silicon carbide paper polishings, and said cleaning can be cleaned (5～10) min at acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple successively.
4. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 2) in, said NH
4The proportioning of F, deionized water and glycerine is (4.5～5) gNH
4F: (300～400) mL deionized water: (500～600) mL glycerine, wherein NH
4F calculates in mass, and deionized water and glycerine by volume are calculated; Said anodised voltage can be (20～30) V, and the anodised time can be (20～30) min; The condition of said calcining can be sample is placed in the Muffle furnace in (450～550) ℃ following calcining (1.5～2.0) h.
5. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 3), said Na
2TeO
3The concentration of solution is (2～8) mmol/L, said CdSO
4Concentration be (0.01～0.05) mol/L; The concentration of said nitrilotriacetic acid trisodium is (0.02～0.08) mol/L; Said H
2SO
4Concentration be (0.05～0.20) mol/L.
6. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 3), said Na
2TeO
3The preparation method be: with (0.350～0.450) g TeO
2Powder joins in (400～600) mL deionized water with (0.100～0.300) g NaOH, and 70 ℃ of refluxed (2～5) h is cooled to room temperature, gets Na
2TeO
3
7. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film; It is characterized in that in step 3); Said pulse parameter of on chem workstation, carrying out the constant pressure impulse electro-deposition is: the burst length is (0.05～0.20) s; Pulse-off blanking time is (0.5～1.5) s, and the pulse electromotive force is (1.3～-1.5) V, and the circulation number of turns is (40～100).
8. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 4), said CdCl
2Concentration be (0.2～0.8) mol/L, the time of said immersion is 0.5～5min.
9. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 4), and the condition of said oven dry is baking (3～8) min in the baking oven of (60～80) ℃; The condition of said annealing in process is at (350～450) ℃ following annealing in process (25～35) min.
10. the quantum dot sensitized TiO of ZnS/CdTe as claimed in claim 1
2The preparation method of nano thin-film is characterized in that in step 4), and said employing circulatory maceration is at CdTe/TiO
2Composite membrane surface deposition ZnS circulation (3～5) is inferior.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210032484.9A CN102543457B (en) | 2012-02-14 | 2012-02-14 | Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210032484.9A CN102543457B (en) | 2012-02-14 | 2012-02-14 | Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102543457A true CN102543457A (en) | 2012-07-04 |
| CN102543457B CN102543457B (en) | 2014-06-11 |
Family
ID=46350101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210032484.9A Expired - Fee Related CN102543457B (en) | 2012-02-14 | 2012-02-14 | Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102543457B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903538A (en) * | 2012-10-17 | 2013-01-30 | 西安交通大学 | Electrochemical method for controlled preparing quantum dot sensitizing wide bandgap semiconductor electrode |
| CN102965645A (en) * | 2012-11-13 | 2013-03-13 | 同济大学 | Preparation method of CdTe/ZnS-nanocrystal-comodified TiO2 nanotube array |
| CN103952708B (en) * | 2014-04-10 | 2016-03-23 | 中国科学院海洋研究所 | For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode |
| CN107993923A (en) * | 2017-12-08 | 2018-05-04 | 青岛大学 | A kind of controllable quantum dots array preparation method based on photo-thermal effect |
| CN108314085A (en) * | 2018-02-06 | 2018-07-24 | 厦门大学 | The preparation method of tungstic trioxide nano-slice complex light anode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956222A (en) * | 2010-10-27 | 2011-01-26 | 厦门大学 | Preparation method of titanium dioxide nanotube array sensitized by cadmium sulfide nanoparticles |
-
2012
- 2012-02-14 CN CN201210032484.9A patent/CN102543457B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956222A (en) * | 2010-10-27 | 2011-01-26 | 厦门大学 | Preparation method of titanium dioxide nanotube array sensitized by cadmium sulfide nanoparticles |
Non-Patent Citations (3)
| Title |
|---|
| JASON A. SEABOLD等: "Photoelectrochemical Properties of Heterojunction CdTe/TiO2 Electrodes Constructed Using Highly Ordered TiO2 Nanotube Arrays", 《CHEM. MATER. 2008》, 29 July 2008 (2008-07-29) * |
| XIAN WANG等: "Aligned ZnO/CdTe Core Shell Nanocable Arrays on Indium Tin Oxide: Synthesis and Photoelectrochemical Properties", 《ACS NANO》, vol. 4, no. 6, 6 May 2010 (2010-05-06) * |
| ZE-QUAN LIN等: "A highly efficient ZnS/CdS@TiO2 photoelectrode for photogenerated cathodic protection of metals", 《 ELECTROCHIMICA ACTA》, 10 August 2010 (2010-08-10) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903538A (en) * | 2012-10-17 | 2013-01-30 | 西安交通大学 | Electrochemical method for controlled preparing quantum dot sensitizing wide bandgap semiconductor electrode |
| CN102903538B (en) * | 2012-10-17 | 2015-10-28 | 西安交通大学 | The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis |
| CN102965645A (en) * | 2012-11-13 | 2013-03-13 | 同济大学 | Preparation method of CdTe/ZnS-nanocrystal-comodified TiO2 nanotube array |
| CN103952708B (en) * | 2014-04-10 | 2016-03-23 | 中国科学院海洋研究所 | For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode |
| CN107993923A (en) * | 2017-12-08 | 2018-05-04 | 青岛大学 | A kind of controllable quantum dots array preparation method based on photo-thermal effect |
| CN107993923B (en) * | 2017-12-08 | 2020-02-21 | 青岛大学 | Preparation method of controllable quantum dot array based on photothermal effect |
| CN108314085A (en) * | 2018-02-06 | 2018-07-24 | 厦门大学 | The preparation method of tungstic trioxide nano-slice complex light anode |
| CN108314085B (en) * | 2018-02-06 | 2019-11-01 | 厦门大学 | The preparation method of tungstic trioxide nano-slice complex light anode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102543457B (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103205760B (en) | For the Ag of photoproduction galvanic protection 2s/TiO 2the preparation method of composite film photo-anode | |
| Zeng et al. | A low-cost photoelectrochemical tandem cell for highly-stable and efficient solar water splitting | |
| CN106555188B (en) | Ag/ graphene/titania nanotube composite film photo-anode preparation method for photoproduction cathodic protection | |
| Mor et al. | p-Type Cu− Ti− O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation | |
| CN108823573B (en) | Hydrothermal method for preparing Ni 3 S 2 /TiO 2 Method for preparing nano tube composite film photo-anode | |
| CN107723712B (en) | ZnIn for photoproduction cathodic protection2S4/TiO2Preparation method of nanotube composite film photo-anode | |
| Liu et al. | Enhanced photoelectrocatalytic degradation of 2, 4-dichlorophenoxyacetic acid by CuInS2 nanoparticles deposition onto TiO2 nanotube arrays | |
| CN106894024B (en) | Accumulation energy type tungstic acid/strontium titanates/nano titania composite film photo-anode preparation method | |
| CN103952708B (en) | For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode | |
| CN102352494A (en) | Preparation method of CdSe/CdS quantum dot sensitized TiO2 nanometer tube composite film | |
| CN106498408B (en) | A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection | |
| CN101608316B (en) | Device for producing hydrogen through decomposing water | |
| CN107557789B (en) | A kind of optical anode material and its preparation and application | |
| CN104357852B (en) | MnSe/TiO2 composite film for photogenerated cathode protection as well as preparation and application thereof | |
| CN103361689A (en) | Method for preparing titanium dioxide nanotube array photoelectrode | |
| CN102543457B (en) | Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film | |
| CN107699901A (en) | Preparation method for zinc-iron aluminum hydrotalcite/titanium dioxide composite film light anode of photoproduction cathodic protection | |
| CN103354283A (en) | Gold nanoparticle-modified dendritic titanium dioxide nanorod array electrode, as well as preparation method and application of hydrogen production by photocatalytic water splitting | |
| CN102874747B (en) | Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array | |
| Zhao et al. | A WO3/Ag–Bi oxygen-evolution catalyst for splitting water under mild conditions | |
| CN108193219A (en) | Phosphorized copper modified titanic oxide optoelectronic pole and preparation method thereof and the application in photoelectrocatalysis decomposes water | |
| CN111424301B (en) | Pulse potential mode for improving CuO photoelectrocatalysis CO2Method for conversion efficiency | |
| CN105386061A (en) | Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes | |
| CN102534725A (en) | Method for preparing Ag2S-doped TiO2 nanotube electrode | |
| CN101956194A (en) | Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140611 Termination date: 20210214 |