CN102503166A - Preparation method of one-dimensional rutile TiO2 nanorod array film - Google Patents
Preparation method of one-dimensional rutile TiO2 nanorod array film Download PDFInfo
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Abstract
The invention provides a preparation method of a one-dimensional rutile TiO2 nanorod array film, and relates to a dye-sensitized solar cell photoanode material. The one-dimensional rutile TiO2 nanorod array film prepared by the method provided by the invention has high specific area and can effectively enhance the efficiency of the dye-sensitized solar cell. The preparation method comprises the following steps: preparing a rutile TiO2 nanorod array film on conductive glass, preparing the high-specific-area TiO2 nanorod array film by chemical etching, and annealing the high-specific-area TiO2 nanorod array film in a muffle furnace to obtain the high-specific-area one-dimensional rutile TiO2 nanorod array film photoanode material, wherein the thickness of the array film is 1-13 mu m. When being used in a photoanode, the one-dimensional rutile TiO2 nanorod array film can enhance the efficiency of the dye-sensitized solar cell by 5.75%. The method has the advantages of short operation time, cheap preparation process and the like, is simple to operate, can obviously enhance the performance of the dye-sensitized solar cell, and can easily implement industrialization.
Description
Technical field
The present invention relates to a kind of dye-sensitized solar cell anode material, especially relate to a kind of one-dimensional red schorl TiO
2The preparation method of nano-stick array membrane.
Background technology
Early 1990s, the federal Institute of Technology of Lausanne, SUI
Professor etc. (B.O ' Regan and M.Gratzel, Nature (London), 1991,353,737) reported based on mesoporous TiO
2Nano-particular film light anodic dye sensitization solar battery, its photoelectric transformation efficiency reaches more than 7%.Their initiative work has attracted a large amount of researchers to join in low-cost, the simple third generation solar cell of preparation technology.At present, dye sensitization solar battery most effective reached (Chiba Y., Islam A., Kakutani K., Komiya R., Koide N., Han L., Technical Digest, 15 more than 10.4%
ThInternational Photovoltaic Science and Engineering Conference, Shanghai, October, 2005,665-666).Though it is current based on mesoporous TiO
2The efficient of nano-particular film light anodic dye sensitization solar battery remains the highest, but because TiO
2The randomness of nano-particular film causes the transmission efficiency of electronics in rete low, light induced electron-hole compound serious, and this has limited the further raising of battery efficiency.In recent years, people begin to explore the light anode material of the semiconductor nano material of one dimension (1-D) high-sequential as dye sensitization solar battery.Research shows that one-dimensional array structural semiconductor light anode material has the TiO of ratio
2The electric transmission efficient that nano particle is higher (Law, M., L.E.Greene, et al. (2005)., Nature Materials 4 (6): 455-459).The rutile TiO through Hydrothermal Preparation one dimension high-sequential on conductive glass that recently bibliographical information arranged
2Nano-stick array membrane (Journal of the American Chemical Society, 2009, vol.131, No 11,3985; Nano Letter, 2008, vol.8, No.11,3781; Journal of Physical Chemistry C 114 (17): 7787), but in the light anodic is used, because TiO
2The specific surface area of nano-stick array membrane is still less, causes battery efficiency not high.People (Applied Surface Science, 2011, vol.257, No.11,5059) such as Pan Hao have reported with chemical method etching TiO
2Nanometer stick array is to improve the specific surface area of rete; But because its etching time is long; Thicknesses of layers sharply reduces after the etching, so limited to the specific surface area raising of light anode nanometer material, the efficient that is applied in the dye sensitization solar battery also only reaches 2.67%.How to improve one dimension TiO effectively
2The specific surface area of nano-stick array membrane has become a major challenge, and the solution of this problem is significant to preparing high performance dye sensitization solar battery.
Summary of the invention
The object of the invention aims to provide a kind of one-dimensional red schorl TiO that has high-specific surface area, can effectively improve efficiency of dye-sensitized solar battery
2The preparation method of nano-stick array membrane.
The present invention includes following steps:
1) cleans conductive glass;
2) Hydrothermal Preparation rutile TiO
2Nano-stick array membrane
With deionized water, hydrochloric acid and TiCl
4Be mixed with hydrothermal solution after the mixing, again conductive glass put into hydrothermal solution and utilize hydrothermal method to prepare one deck rutile TiO at conductive glass surface
2Nano-stick array membrane after hydro-thermal reaction finishes, takes out water heating kettle and in air, is cooled to room temperature, takes out the long TiO that has then
2The conductive glass substrate of nano-stick array membrane after the flushing, is dried;
3) chemical etching method prepares TiO
2Nano-stick array membrane
With the mixing solutions of deionized water and hydrochloric acid as etching solution, with step 2) in the rutile TiO that obtains
2Nano-stick array membrane is put into the water heating kettle etching that said etching solution is housed, and obtains TiO
2Nano-stick array membrane;
4) TiO
2The nano-stick array membrane anneal
The TiO that step 3) is obtained
2Nano-stick array membrane carries out anneal in retort furnace, after muffle furnace is reduced to below 80 ℃, take out sample, promptly obtains one-dimensional red schorl TiO
2Nano-stick array membrane.
In step 1), the concrete grammar of said cleaning conductive glass can adopt: conductive glass is put into acetone, absolute ethyl alcohol, deionized water successively through ultrasonic cleaning 10～15min, dry.
In step 2) in, the add-on of said hydrochloric acid can be 0.317～0.635 of said hydrothermal solution TV by volume, said TiCl
4Add-on can be 0.00826～0.0476 of said hydrothermal solution TV by volume; The concentration of said hydrochloric acid can be 36%～38%; The temperature of said hydro-thermal reaction can be 120～180 ℃, and the time of hydro-thermal can be 4～10h.
In step 3), the add-on of said hydrochloric acid can be by volume deionized water and hydrochloric acid the mixing solutions TV 0.25～0.75; The concentration of said hydrochloric acid can be 36%～38%; The temperature of said etching can be 120～180 ℃, and the time of etching can be 1～10h, resulting TiO
2Nano-stick array membrane is the TiO of high-specific surface area
2Nano-stick array membrane.
In step 4), the temperature of said anneal can be 450～600 ℃, and the time of anneal can be 0.5～2h, and the temperature rise rate of anneal can be 5 ℃/min.
Prepared one-dimensional red schorl TiO
2The nanometer stick array film thickness is 1～13 μ m.
The present invention in the conductive glass substrate surface preparation arrange fine and close rutile TiO
2Nano-stick array membrane, thicknesses of layers is at 1～13 μ m.TiO through the chemical method etching
2The nanometer stick array film thickness has only reduced about 50～500nm, and the etching of process short period of time, has greatly improved TiO
2The specific surface area of nano-stick array membrane.TiO through the chemical method etching
2Nano-stick array membrane is applied in the dye sensitization solar battery, has greatly improved the efficient of dye sensitization solar battery.That this method has is simple to operate, the running time short, the preparation process cost is cheap, the dye sensitization solar battery performance is improved obviously, is easy to realize advantage such as industriallization.
Description of drawings
Fig. 1 reacts the TiO that 6h obtains down for hydrothermal temperature among the embodiment 1 is 150 ℃
2The SEM of nano-stick array membrane (ESEM) side elevational view (magnification is 10,000 times).In Fig. 1, scale is 5 μ m.
Fig. 2 reacts the TiO that 6h obtains down for hydrothermal temperature among the embodiment 1 is 150 ℃
2The SEM vertical view of nano-stick array membrane (magnification is 50,000 times).In Fig. 2, scale is 1 μ m.
Fig. 3 is the TiO of process 3h chemical etching among the embodiment 1
2The SEM vertical view of nano-stick array membrane (magnification is 150,000 times).In Fig. 3, scale is 300nm.
Fig. 4 is the SEM vertical view (magnification is 10,000 times) of the TiO2 nano-stick array membrane of process 3h chemical etching among the embodiment 1.In Fig. 4, scale is 5 μ m.
Fig. 5 is without the TiO of etching among the embodiment 1
2TiO after nano-stick array membrane and the etching
2The XRD characterization result of nano-stick array membrane.In Fig. 5, X-coordinate is diffraction angle 2 θ (degree), and ordinate zou is the relative intensity of diffraction peak; Curve a is the TiO without etching
2Nano-stick array membrane, curve b are through the TiO after the 1h etching
2Nano-stick array membrane, curve c are through the TiO after the 3h etching
2Nano-stick array membrane, curve d are through the TiO after the 5h etching
2Nano-stick array membrane, curve e are through the TiO after the 7h etching
2Nano-stick array membrane.
Fig. 6 is the TiO of process different time etching among the embodiment 1
2The current-voltage curve of the dye sensitization solar battery that nano-stick array membrane light anode groups is dressed up (being the I-V curve).In Fig. 6, X-coordinate is voltage (V), and ordinate zou is current density (mA/cm
-2); Mark-■-be TiO of etching processing not wherein
2The I-V curve of nano-stick array membrane ,-●-,-▲-,
Be respectively etching 1h, 3h, 5h and 7h TiO afterwards
2The I-V curve of nano-stick array membrane.
The high-specific surface area TiO that Fig. 7 prepares for embodiment 2 through the 10h etching
2Nano-stick array membrane light anodic SEM side elevational view (magnification is 10,000 times).In Fig. 7, scale is 5 μ m.
The high-specific surface area TiO that Fig. 8 prepares for embodiment 2 through the 10h etching
2Nano-stick array membrane light anodic SEM vertical view (magnification is 10,000 times).In Fig. 8, scale is 5 μ m.
The high-specific surface area TiO that Fig. 9 prepares for embodiment 2 through the 10h etching
2Nano-stick array membrane light anodic SEM vertical view (magnification is 50,000 times).In Fig. 9, scale is 1 μ m.
The TiO that Figure 10 prepares for embodiment 3 through 150 ℃ of hydro-thermal 10h
2The SEM side elevational view of nano-stick array membrane (magnification is 10,000 times).In Figure 10, scale is 5 μ m.
The TiO that Figure 11 prepares for embodiment 4 through the 3h etching
2The SEM side elevational view of nano-stick array membrane (magnification is 2.5 ten thousand times).In Figure 11, scale is 2 μ m.
The TiO that Figure 12 prepares for embodiment 4 through the 3h etching
2The SEM vertical view of nano-stick array membrane (magnification is 150,000 times).In Figure 12, scale is 300nm.
The TiO that Figure 13 prepares for embodiment 5 through the 3h etching
2The SEM vertical view of nano-stick array membrane (magnification is 2.5 ten thousand times).In Figure 13, scale is 2 μ m.
Embodiment
1) the FTO conductive glass of 1cm * 1.5cm is put into acetone successively, absolute ethyl alcohol, deionized water for ultrasonic is cleaned 15min, and dry back is subsequent use in 100 ℃ of baking ovens then.
2) under the room temperature, 30ml deionized water and 30ml concentrated hydrochloric acid (36%～38%) solution are mixed back magnetic agitation 5min, drip the TiCl of 1ml then
4(this moment, the volume ratio of concentrated hydrochloric acid and overall solution volume was 0.49, TiCl
4With the volume ratio of overall solution volume be 0.016), continue to stir 20min up to the solution becomes clear, this solution is as Hydrothermal Preparation rutile TiO
2The hydrothermal solution of nanometer stick array.Three clean FTO conductive glass are inserted in the tetrafluoroethylene slot (diameter of whole slot is 3cm, and the thickness of slot is 1cm, and the slot slotted eye is of a size of long 1.2cm * wide 0.2cm * dark 0.5cm; Be about 20 ° with interfacial angle that horizontal plane becomes when slot keeps flat, the FTO conductive glass and the normal direction angle of horizontal plane that promptly are inserted on the slot are about 20 °, and the conducting surface lopsidedness is downward.)
The slot that 3) will be inserted with the FTO conductive glass is put in the water heating kettle of 100ml, pours the hydrothermal solution that join the front into.Put into baking oven after water heating kettle is sealed and carry out hydro-thermal reaction.Hydro-thermal reaction is carried out 6h under 150 ℃.Hydro-thermal is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings, obtains the long rutile TiO that has
2The FTO substrate of nano-stick array membrane.The SEM figure of the sample for preparing sees Fig. 1 and Fig. 2.From figure, can find out TiO
2Form and arrange fine and close nanometer stick array structure, its nanometer rod diameter is about 200～300nm.
4) with the slot that is inserted with the FTO conductive glass that obtains in the step 3), use a large amount of deionized water rinsings, transfer in the clean 100ml water heating kettle of another one, pour the mixing solutions of 30ml deionized water and 30ml concentrated hydrochloric acid (36.0～38.0%) into.After sealing water heating kettle, water heating kettle is put into baking oven, under 150 ℃, react 1h, 3h, 5h and 7h respectively.Hydro-thermal reaction is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings.Then the FTO conductive glass is dried, obtain the TiO of chemical method etching
2Nano-stick array membrane.
Fig. 3 and Fig. 4 are the TiO through the 3h chemical etching
2The SEM of nano-stick array membrane, visible TiO after over etching from figure
2Nanometer rod diameter in the nano-stick array membrane reduces, and is merely about 17～40nm; It is big that gap between the nanometer rod becomes, and the TiO after over etching is described
2The specific surface area of nano-stick array membrane is greatly improved.
A representative is the XRD diffraction peak of the sample for preparing in the step 3) among Fig. 5; B, c, d, e are respectively the TiO of etching 1h, 3h, 5h, 7h in the step 4)
2The XRD figure of nano-stick array membrane." * " pairing spectrum peak is the XRD spectrum peak of FTO conductive glass substrate in the XRD figure; 2 θ be the XRD peak about 36.15 ° corresponding be rutile TiO
2(101) diffraction peak; 2 θ be the XRD peak about 62.88 ° corresponding be rutile TiO
2(002) diffraction peak.By XRD spectra the TiO that directly obtains through hydrothermal method can be described
2Nano-stick array membrane is TiO
2The rutile phase.Along with the prolongation of chemical etching time, the intensity of visible (002) diffraction peak weakens gradually, and the intensity of (101) diffraction peak slightly strengthens, the TiO during this and SEM scheme before and after the etching
2The surface appearance feature of nano-stick array membrane is corresponding.
5) sample for preparing in the step 4) is put into retort furnace and anneal, annealing conditions is: 450 ℃ of annealing 2h, and temperature rise rate is 5 ℃/min; Annealing waits muffle furnace to be chilled to about 80 ℃ after finishing, and takes out sample, obtains the one-dimensional red schorl TiO of high-specific surface area
2Nano-stick array membrane light anode material.Sample is dipped into immediately in the ethanol solution of N719 dyestuff of 0.3mM, soaks 24h under the room temperature; The light anode of dyestuff was soaked in taking-up, washed away the unnecessary dyestuff of film surface with absolute ethyl alcohol, dried up, and was assembled into dye sensitization solar battery; Used electrolytic solution is I during the assembling dye sensitization solar battery
-/ I
3-Acetonitrile solution (concrete composition is: 60%～70% acetonitrile; 20%～25%DMPII; 1%～4% hydration LiI; 5%～10%4-tert .-butylpyridine and 1%～4% iodine), used heat-sealing film thickness is 25 μ m, used counter electrode prepares for the ethanol solution of the Platinic chloride of pyrolysis 2mg/ml under 400 ℃ of high temperature.Packaged battery useful area is 0.1～0.3cm
-2, test condition is AM1.5,100mW/cm
-2The current-voltage curve of the battery that records (being the I-V curve) is seen Fig. 6.Can know by Fig. 6, through the high-specific surface area rutile TiO that obtains after the 3h etching
2Nanometer stick array light anode most effective in dye-sensitized cell reached 5.75%.
1) the FTO conductive glass is put into acetone successively, absolute ethyl alcohol, deionized water for ultrasonic is cleaned 15min, and is dry in 100 ℃ of baking ovens then.
2) under the room temperature, 30ml deionized water and 30ml concentrated hydrochloric acid (36～38%) solution are mixed back magnetic agitation 5min, drip the TiCl of 1.5ml then
4(this moment, the volume ratio of concentrated hydrochloric acid and overall solution volume was 0.488, TiCl
4With the volume ratio of overall solution volume be 0.0244), continue to stir 20min up to the solution becomes clear, this solution is as Hydrothermal Preparation rutile TiO
2The hydrothermal solution of nanometer stick array.Three clean FTO conductive glass are inserted in the tetrafluoroethylene slot, and the conducting surface lopsidedness is downward.The slot size is identical with embodiment 1.
The slot that 3) will be inserted with the FTO conductive glass is put in the water heating kettle of 100ml, pours the hydrothermal solution that join the front into.Put into baking oven after water heating kettle is sealed and carry out hydro-thermal reaction.Hydro-thermal reaction is carried out 6h under 150 ℃.Hydro-thermal is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings, obtains the long rutile TiO that has
2The FTO substrate of nano-stick array membrane.The nanometer rod diameter is arranged fine and close about 200-300nm and perpendicular to the FTO substrate grown.
4) with the slot that is inserted with the FTO conductive glass that obtains in the step 3); Use a large amount of deionized water rinsings; Transfer in the clean 100ml water heating kettle of another one; Pour the mixing solutions (concentrated hydrochloric acid account for the volume(tric)fraction of overall solution volume be 0.75) at this moment, of 30ml deionized water and 30ml concentrated hydrochloric acid (36.0～38.0%) into.After sealing water heating kettle, water heating kettle is put into baking oven, at 150 ℃ of following etching 10h.Hydro-thermal reaction is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings.Then the FTO conductive glass is dried, obtain the TiO of chemical method etching
2Nano-stick array membrane.See Fig. 7～9, TiO after the etching
2The nano-stick array membrane specific surface area increases, the nanorod surfaces roughen, and single nanometer rod diameter is about 17～40nm; Because etching time is long, have by the visible nanometer rod top of Fig. 8 to be poured on the tendency of fasciculation structure together.
5) sample for preparing in the step 4) is put into retort furnace and anneal, annealing conditions is: 600 ℃ of annealing 2h, and temperature rise rate is 5 ℃/min; Annealing waits muffle furnace to be chilled to about 80 ℃ after finishing, and takes out sample, obtains the TiO of high-specific surface area
2Nanometer stick array light anode material.
Embodiment 3
1) the FTO conductive glass is put into acetone successively, absolute ethyl alcohol, deionized water for ultrasonic is cleaned 15min, and is dry in 100 ℃ of baking ovens then.
2) under the room temperature, 30ml deionized water and 30ml concentrated hydrochloric acid (36～38%) solution are mixed back magnetic agitation 5min, drip the TiCl of 1ml then
4(this moment, the volume ratio of concentrated hydrochloric acid and overall solution volume was 0.492, TiCl
4With the volume ratio of overall solution volume be 0.0164), continue to stir 20min up to the solution becomes clear, this solution is as Hydrothermal Preparation rutile TiO
2The hydrothermal solution of nanometer stick array.Three clean FTO conductive glass are inserted in the tetrafluoroethylene slot, and the conducting surface lopsidedness is downward.The slot size is identical with embodiment 1.
The slot that 3) will be inserted with the FTO conductive glass is put in the water heating kettle of 100ml, pours the hydrothermal solution that join the front into.Put into baking oven after water heating kettle is sealed and carry out hydro-thermal reaction.Hydro-thermal reaction is carried out 10h under 150 ℃.Hydro-thermal is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings, obtains the long rutile TiO that has
2The FTO substrate of nano-stick array membrane.The nanometer rod diameter is arranged densification about 200～300nm and perpendicular to the FTO substrate grown, can know that by the SEM side elevational view among Figure 10 thicknesses of layers is (to scrape off rete from the FTO substrate during SEM test, be bonded on the conductive resin and observe) about 8.3 μ m.
4) with the slot that is inserted with the FTO conductive glass that obtains in the step 3); Use a large amount of deionized water rinsings; Transfer in the clean 100ml water heating kettle of another one; Pour the mixing solutions (concentrated hydrochloric acid account for the volume(tric)fraction of overall solution volume be 0.75) at this moment, of 30ml deionized water and 30ml concentrated hydrochloric acid (36～38%) into.After sealing water heating kettle, water heating kettle is put into baking oven, at 150 ℃ of following etching 1h.Hydro-thermal reaction is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings.Then the FTO conductive glass is dried, obtain the TiO of chemical method etching
2Nano-stick array membrane.TiO through the 1h chemical etching
2The nano-stick array membrane and the TiO of etching not
2It is not obvious that nano-stick array membrane is compared variation, but nanometer rod still has tangible etching vestige; TiO through the 1h chemical etching
2The specific surface area of nano-stick array membrane increases to some extent, but compares the TiO through 3～5h etching
2Nano-stick array membrane, the specific surface area of its increase is still too little.
5) sample for preparing in the step 4) is put into retort furnace and anneal, annealing conditions is: 450 ℃ of annealing 2h, and temperature rise rate is 5 ℃/min; Annealing waits muffle furnace to be chilled to about 80 ℃ after finishing, and takes out sample, obtains the TiO of high-specific surface area
2Nanometer stick array light anode material.
1) the FTO conductive glass is put into acetone successively, absolute ethyl alcohol, deionized water for ultrasonic is cleaned 15min, and is dry in 100 ℃ of baking ovens then.
2) under the room temperature, 40ml deionized water and 20ml concentrated hydrochloric acid (36～38%) solution are mixed back magnetic agitation 5min, drip the TiCl of 0.5ml then
4(this moment, the volume ratio of concentrated hydrochloric acid and overall solution volume was 0.317, TiCl
4With the volume ratio of overall solution volume be 0.00826), continue to stir 20min up to the solution becomes clear, this solution is as Hydrothermal Preparation rutile TiO
2The hydrothermal solution of nanometer stick array.Three clean FTO conductive glass are inserted in the tetrafluoroethylene slot, and the conducting surface lopsidedness is downward.The slot size is identical with embodiment 1.
The slot that 3) will be inserted with the FTO conductive glass is put in the water heating kettle of 100ml, pours the hydrothermal solution that join the front into.Put into baking oven after water heating kettle is sealed and carry out hydro-thermal reaction.Hydro-thermal reaction is carried out 4h under 120 ℃.Hydro-thermal is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings, obtains the long rutile TiO that has
2The FTO substrate of nano-stick array membrane.The nano-stick array membrane that obtains is arranged fine and close, but about thicknesses of layers 12 μ m, the nanometer rod diameter is about 100～150nm.
4) with the slot that is inserted with the FTO conductive glass that obtains in the step 3); Use a large amount of deionized water rinsings; Transfer in the clean 100ml water heating kettle of another one; Pour the mixing solutions (concentrated hydrochloric acid account for the volume(tric)fraction of overall solution volume be 0.25) at this moment, of 45ml deionized water and 15ml concentrated hydrochloric acid (36～38%) into.After sealing water heating kettle, water heating kettle is put into baking oven, at 120 ℃ of following etching 3h.Hydro-thermal reaction is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings.Then the FTO conductive glass is dried, obtain the high-specific surface area TiO of chemical method etching
2Nano-stick array membrane.Can know by Figure 11 and Figure 12, through the TiO of 3h etching
2The nano-stick array membrane diameter is that nanorod surfaces is coarse about 20nm; Thicknesses of layers is about 950nm.
5) sample for preparing in the step 4) is put into retort furnace and anneal, annealing conditions is: 450 ℃ of annealing 0.5h, and temperature rise rate is 5 ℃/min; Annealing waits muffle furnace to be chilled to about 80 ℃ after finishing, and takes out sample, obtains the TiO of high-specific surface area
2Nanometer stick array light anode material.
Embodiment 5
1) the FTO conductive glass is put into acetone successively, absolute ethyl alcohol, deionized water for ultrasonic is cleaned 15min, and is dry in 100 ℃ of baking ovens then.
2) under the room temperature, 20ml deionized water and 40ml concentrated hydrochloric acid (36～38%) solution are mixed back magnetic agitation 5min, drip the TiCl of 3ml then
4(this moment, the volume ratio of concentrated hydrochloric acid and overall solution volume was 0.635, TiCl
4With the volume ratio of overall solution volume be 0.0476), continue to stir 20min up to the solution becomes clear, this solution is as Hydrothermal Preparation rutile TiO
2The hydrothermal solution of nanometer stick array.Three clean FTO conductive glass are inserted in the tetrafluoroethylene slot, and the conducting surface lopsidedness is downward.The slot size is identical with embodiment 1.
The slot that 3) will be inserted with the FTO conductive glass is put in the water heating kettle of 100ml, pours the hydrothermal solution that join the front into.Put into baking oven after water heating kettle is sealed and carry out hydro-thermal reaction.Hydro-thermal reaction is carried out 4h under 180 ℃.Hydro-thermal is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings, obtains the long rutile TiO that has
2The FTO substrate of nano-stick array membrane.The nanometer rod diameter is arranged densification about 50～150nm and perpendicular to the FTO substrate grown, thicknesses of layers is about 13 μ m.
4) with the slot that is inserted with the FTO conductive glass that obtains in the step 3); Use a large amount of deionized water rinsings; Transfer in the clean 100ml water heating kettle of another one; Pour the mixing solutions (concentrated hydrochloric acid account for the volume(tric)fraction of overall solution volume be 0.75) at this moment, of 15ml deionized water and 45ml concentrated hydrochloric acid (36～38%) into.After sealing water heating kettle, water heating kettle is put into baking oven, at 180 ℃ of following etching 3h.Hydro-thermal reaction is taken out water heating kettle after finishing from baking oven, in air, be cooled to room temperature.Taking-up is inserted with the slot of FTO conductive glass, uses a large amount of deionized water rinsings.Then the FTO conductive glass is dried, obtain the TiO of chemical method etching
2Nano-stick array membrane.Can know etching TiO afterwards by Figure 13
2The nano-stick array membrane specific surface area increases, the nanorod surfaces roughen, and single nanometer rod diameter is about 17～40nm.
5) sample for preparing in the step 4) is put into retort furnace and anneal, annealing conditions is: 600 ℃ of annealing 2h, and temperature rise rate is 5 ℃/min; Annealing waits muffle furnace to be chilled to about 80 ℃ after finishing, and takes out sample, obtains the TiO of high-specific surface area
2Nanometer stick array light anode material.
Claims (9)
1. one-dimensional red schorl TiO
2The preparation method of nano-stick array membrane is characterized in that may further comprise the steps:
1) cleans conductive glass;
2) Hydrothermal Preparation rutile TiO
2Nano-stick array membrane
With deionized water, hydrochloric acid and TiCl
4Be mixed with hydrothermal solution after the mixing, again conductive glass put into hydrothermal solution and utilize hydrothermal method to prepare one deck rutile TiO at conductive glass surface
2Nano-stick array membrane after hydro-thermal reaction finishes, takes out water heating kettle and in air, is cooled to room temperature, takes out the long TiO that has then
2The conductive glass substrate of nano-stick array membrane after the flushing, is dried;
3) chemical etching method prepares TiO
2Nano-stick array membrane
With the mixing solutions of deionized water and hydrochloric acid as etching solution, with step 2) in the rutile TiO that obtains
2Nano-stick array membrane is put into the water heating kettle etching that said etching solution is housed, and obtains TiO
2Nano-stick array membrane;
4) TiO
2The nano-stick array membrane anneal
The TiO that step 3) is obtained
2Nano-stick array membrane carries out anneal in retort furnace, after muffle furnace is reduced to below 80 ℃, take out sample, promptly obtains one-dimensional red schorl TiO
2Nano-stick array membrane.
2. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 1), and the concrete grammar of said cleaning conductive glass is: conductive glass is put into acetone, absolute ethyl alcohol, deionized water successively through ultrasonic cleaning 10～15min, dry.
3. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 2) in, the add-on of said hydrochloric acid is 0.317～0.635 of said hydrothermal solution TV by volume, said TiCl
4Add-on can be 0.00826～0.0476 of said hydrothermal solution TV by volume.
4. like claim 1 or 3 described a kind of one-dimensional red schorl TiO
2The preparation method of nano-stick array membrane is characterized in that in step 2) in, the concentration of said hydrochloric acid is 36%～38%.
5. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 2) in, the temperature of said hydro-thermal reaction is 120～180 ℃, the time of hydro-thermal is 4～10h.
6. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 3), the add-on of said hydrochloric acid be by volume deionized water and hydrochloric acid the mixing solutions TV 0.25～0.75.
7. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 3), and the concentration of said hydrochloric acid is 36%～38%.
8. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 3), and the temperature of said etching is 120～180 ℃, and the time of etching is 1～10h.
9. a kind of one-dimensional red schorl TiO as claimed in claim 1
2The preparation method of nano-stick array membrane is characterized in that in step 4), and the temperature of said anneal is 450～600 ℃, and the time of anneal is 0.5～2h, and the temperature rise rate of anneal is 5 ℃/min.
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| WO2019214079A1 (en) * | 2018-05-07 | 2019-11-14 | 苏州大学 | Tio2 nanocolumn-au nanoparticle composite array, preparation method and application thereof |
| WO2024051019A1 (en) * | 2022-09-05 | 2024-03-14 | 深圳先进技术研究院 | Preparation method for quantum dot sensitized composite photo-anode, and quantum dot sensitized composite photo-anode and use therof |
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