CN101786658A - Coaxial heterojunction TiO2 nanotube array and preparation method thereof - Google Patents
Coaxial heterojunction TiO2 nanotube array and preparation method thereof Download PDFInfo
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- CN101786658A CN101786658A CN201010111203A CN201010111203A CN101786658A CN 101786658 A CN101786658 A CN 101786658A CN 201010111203 A CN201010111203 A CN 201010111203A CN 201010111203 A CN201010111203 A CN 201010111203A CN 101786658 A CN101786658 A CN 101786658A
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Abstract
The invention provides a nanotube with a coaxial heterojunction structure of an ordered array and a preparation method for a nanotube array film with the coaxial heterojunction structure. A surface is formed by an under potential sedimentation process to chemically limit growth and the epitaxial growth is realized from the angle of a monoatomic layer. An epitaxial sensibilization heterogeneous phase is uniformly covered on the tube wall of the TiO2 nanotube to form the coaxial heterojunction structure together with the nanotube array so as to avoid the phenomenon that an epitaxial sensibilization layer blocks the nanotube. The coaxial heterojunction structure cannot reduce specific surface area and adsorbability of the TiO2 nanotube array, is beneficial to improve the contact area of a sensitizing agent and the TiO2 surface and can effectively improve the visible light response performance of the TiO2 nanotube ordered array. The photoelectric conversion efficiency of the CdS/TiO2 coaxial heterojunction nanotube array prepared by the method reaches 8.13 percent under the full spectrum simulated sun illumination. The CdS/TiO2 coaxial heterojunction nanotube array can be widely applied to the fields of photochemical catalysis, solar cell, gas sensing, biomedicine and the like.
Description
Technical field
The present invention relates to a kind of 1-dimention nano pipe array, be specifically related to a kind of nanotube of coaxial heterojunction structure of oldered array, and the preparation method with nano-pipe array thin film of this coaxial heterojunction structure.
Background technology
TiO
2Nano-tube array has good photocatalytic activity and electricity conversion.TiO
2Belong to wide band gap semiconducter, its maximum absorption wavelength is in ultraviolet region, especially, and the high-activity nano TiO of development in recent years
2Photocatalyst is owing to quantum size effect causes the further blue shift of its optical absorption band.Because UV-light accounts for the sunlight total energy less than 5%, therefore, how research makes TiO
2Photocatalytic activity expand to visible region, thereby utilize sunlight to carry out exciting of photo-generated carrier efficiently, have great importance.For this reason, many investigators pass through TiO
2The surface modification of nano-tube array is improved its absorption to visible light, has developed to have visible light-responded TiO
2Nano-tube array.
Generally speaking, the performance of photocatalyst not only depends on its crystal and electronic structure, and also with the microtexture of catalyzer, particularly surface tissue is closely related.Therefore construct from microcosmic angle and modify or composite structure, can further expand regulation and control electronic structure, the migration that promotes photogenerated charge with separate, improve photocatalysis efficiency.This principle carries out and the heterojunction structure that utilizes narrow gap semiconductor sensitization design composite semiconductor just is based on.When narrow gap semiconductor and wide band gap semiconducter formation heterojunction, can prepare the agent of band gap width continually varying novel photocatalysis, thereby obtain higher visible light-responded catalytic performance.The relative dye sensitization of heterojunction has following advantage: the motivating force that electronics injects can be optimized by confinement effect, can obtain the semiconductor material of ideal bandgap width 1.5eV, and suitably finishing can obtain the electrode materials of high stable.But two kinds of interfaces forming heterojunction must be with coupling just can help the separation of photo-generated carrier.It is more negative that its thermodynamic condition is that the phase of sensitizing agent should be able to be with, and perhaps the two fermi level there are differences, and the sensitizing agent electrons excited just can be moved to TiO under the visible light like this
2, and the hole rests on the sensitizing agent valence band, otherwise the photo-generated carrier on the narrow gap semiconductor because of can not effective mobility with recombination losses.People such as Bessekhouad adopt the precipitator method to prepare Bi
2S
3/ TiO
2And CdS/TiO
2Heterojunction, and studied degraded OrangeII under its visible light, the performance of 4-hydroxy-benzoic acid and benzamide.The result shows Bi
2S
3/ TiO
2Compare CdS/TiO
2Effectively be because Bi
2S
3Can absorb more visible light (E
g=1.28eV), and conduction band position and TiO
2More approaching, the migration of electronics is more effective.
At present, the research of composite semiconductor heterojunction is at suspended particle or TiO mostly
2Nano-particular film, the complex method of its heterojunction generally adopt pickling process, mixed sols method, hydrothermal synthesis method or electrochemistry coprecipitation method.So far to TiO
2It is less that nano-tube array carries out the relevant report of composite semiconductor heterojunction.People such as Grimes utilize the method for electrochemical co-deposition at TiO
2The nano-tube array surface deposition particle diameter be about the CdS membrana granulosa of 10～20nm, the TiO after the modification
2The nano-tube array energy gap is 2.53eV, N
2Energy gap is 2.41eV after the following 350 ℃ of thermal treatments of atmosphere, and tangible red shift has taken place spectral response range, and photoelectric property has also had comparatively significantly improvement.People such as Yan Sihua are sensitizing agent with the CdSe nanoparticle, will be through the TiO of series of preprocessing
2Nano-tube array is placed in the solution that contains the CdSe nanoparticle and floods, and makes the TiO of sensitization
2Nano-tube array, this array have stronger visible light-responded.But the photoelectric properties of these composite heterogenous junctions are still waiting further raising.Its major cause is because TiO
2The special surface structure of nano-tube array, the heterogeneous TiO that is deposited on easily mutually that adopts ordinary method to generate
2In the nanotube, even stop up nanotube, cause the reduction of specific surface area and adsorptive power.
The present invention has overcome the shortcoming of above technology, makes the heterogeneous phase of narrow gap semiconductor sensitization cover TiO equably
2On the nanotube tube wall, form coaxial heterojunction structure as shown in Figure 1, improved the optical property of nano-tube array.
Summary of the invention
The object of the present invention is to provide a kind of can satisfy heterojunction simultaneously can be with the TiO of factors such as position, surface tissue, geometry and contact form
2Nano-tube array and preparation method thereof, concrete scheme is as follows:
A kind of coaxial heterojunction TiO
2The preparation method of nano-tube array comprises the steps:
(1) preparation TiO
2Nano-tube array is as the substrate of preparation coaxial heterojunction nano-tube array;
(2) configuration reaction soln promptly disposes the solution that comprises each component of coaxial heterojunction compound respectively;
(3) with TiO
2The nano-tube array substrate carries out cyclic voltammetry scan respectively in above-mentioned each reaction soln, determine each component at TiO
2Owe electromotive force sedimentation potential interval on the nano-tube array substrate;
(4) on substrate, each component is carried out alternating deposit in the electromotive force sedimentation potential interval of determining separately of owing, finish each component atomic-layer epitaxial growth, promptly obtain the coaxial heterojunction TiO of above-claimed cpd
2Nano-tube array.
Further, the alternating deposit detailed process in the step (4) is:
At first introduce first kind of reaction soln, control sedimentation potential and depositing time make in described each component, and the component that is included in this first kind of reaction soln is owed the electromotive force deposition;
Adopt blank solution flushing electrode;
Introduce second kind of reaction soln, control sedimentation potential and depositing time make in described each component, and the component that is included in this second kind of reaction soln is owed the electromotive force deposition;
Adopt blank solution flushing electrode again;
Make all constituent elements owe electromotive force deposition separately until introducing all reaction solns respectively, and the said process repeatedly that circulates, promptly finish the alternating deposit of described each component.
Further, in step (3), the electromotive force sedimentation potential interval of owing of each component is defined as same interval.
Further, adopt the mode of in reaction soln, adding organic solvent to regulate and determine the described electromotive force sedimentation potential interval of owing.
Further, adopt the mode of the pH value of conditioned reaction solution to regulate and determine the described electromotive force sedimentation potential interval of owing.
Further, add the solution that comprises metal-doped element and/or comprise the nonmetal doping element in each reaction soln.
Further, described metal-doped element is Pt, Co, V or Ni; Described nonmetal doping element is C, N or B.
Further, in step (1), adopt electrochemistry anodic oxidation to prepare described substrate.
Further, described compound with coaxial heterojunction is CdS, Bi
2S
3, CdSe, CdTe, WO
3Or Fe
2O
3
In addition, the invention allows for a kind of coaxial heterojunction TiO that utilizes method for preparing
2Nano-tube array.
Coaxial heterojunction TiO provided by the invention
2Its characteristics of nano-tube array are: electromotive force deposition (Under Potential Deposition is owed in (1) utilization, being called for short UPD) principle makes the epitaxy that realizes monoatomic layer on heterogeneous element, therefore, heterosphere can cover on the surface of complicated shape more uniformly, the situation of stopping up nanotube can not occur depositing.(2) owing to be the epitaxy of monoatomic layer, by controlling that sedimentary cycle index can accurately be controlled the thickness of epitaxial film (being accurate to the order of magnitude of atomic radius) thus the coaxial heterojunction structure that can prepare ultra-thin geometrical dimension and can be regulated the thickness of epitaxial film easily by adjusting sedimentary cycle index and depositing time.(3) this coaxial heterojunction is except can carrying out the sensitization of narrow gap semiconductor extension, some metals or nonmetal doping also can use different solution to deposit in preparation process, can study doping content to its Effect on Performance by controlling the sedimentary number of times of these doped elements more conveniently.
The present invention has the following advantages compared to existing technology:
1, this coaxial heterojunction structure design helps improving sensitizing agent and TiO
2Surface contact area makes that the electronics of excited state is injected into TiO smoothly in the sensitizing agent
2Go in the conduction band.This surface tissue can not reduce TiO yet simultaneously
2The specific surface area of nano-tube array and adsorptive power.
2, help the geometric thickness of the heterogeneous phase of narrow gap semiconductor sensitization in the strict control coaxial heterojunction, reduce the distance that electronics and hole need be transmitted, then can effectively reduce the compound probability of current carrier.
3, the contact form of heterojunction can make heterogeneous phase of sensitization and TiO
2Nano-tube array is with ohmic contact, and structure is with the compound coaxial heterojunction of ohmic contact form, and charge migration is more smooth and easy, and it is easier to separate, so photocatalysis efficiency is also higher.
4, metal or nonmetal doping mode can improve TiO easily more easily
2The visible light-responded performance of nano-tube array.
Meaning of the present invention is to have expanded TiO
2The preparation method of nano-tube array, the advantage of the preparation method before having summed up has overcome their shortcoming.The TiO that present method is prepared
2The performance of nano-tube array has had very big improvement, can control prepared TiO accurately
2Parameters such as heterogeneous junction configuration of nano-tube array and thickness.Development for fields such as photocatalysis field, solar cell, air-sensitive sensing, biomedicines has certain prograding.
Description of drawings
(a) is narrow gap semiconductor/TiO among Fig. 1
2Coaxial heterojunction nano-tube array structure synoptic diagram; (b) be coaxial heterojunction charge transfer schematic diagram of mechanism.
Fig. 2 is preparation CdS/TiO
2The nano-tube array substrate surface FESEM photo of coaxial heterojunction; This nanotube substrate obtains in the used electrolyte solution of 3.0vol% water concentration.
Fig. 3 is the XRD figure spectrum of the preceding clean oxidation titanium nano-tube array substrate of deposition.
Fig. 4 is the XRD figure spectrum at the coaxial heterojunction nano-tube array of sedimentation potential-0.65V acquisition.
Fig. 5 is the EDX collection of illustrative plates at the coaxial heterojunction nano-tube array of sedimentation potential-0.65V acquisition.
(a) is for preparing the CdS galvanic deposit in TiO in-0.65V among Fig. 6
2Top surface FESEM photo on the nano-tube array; (b) be Photomicrograph after this top surface amplifies, the extremely thin epitaxial film of visible one deck is attached on the nanotube tube wall.
Fig. 7 is the XRD figure spectrum at the coaxial heterojunction nano-tube array of sedimentation potential-0.7V acquisition.
Fig. 8 is the EDX collection of illustrative plates at the coaxial heterojunction nano-tube array of sedimentation potential-0.7V acquisition.
(a) is for preparing the CdS galvanic deposit in TiO in-0.7V among Fig. 9
2Top surface FESEM photo on the nano-tube array; (b) be TiO
2Nano-tube array side transverse section Photomicrograph, white arrow shows the epitaxial film of nanotube tube wall surfaces externally and internally among the figure.
Figure 10 is the XRD figure spectrum at the coaxial heterojunction nano-tube array of sedimentation potential-0.75V acquisition.
Figure 11 is the EDX collection of illustrative plates at the coaxial heterojunction nano-tube array of sedimentation potential-0.75V acquisition.
(a) is for preparing the CdS galvanic deposit in TiO in-0.75V among Figure 12
2Top surface FESEM photo on the nano-tube array; (b) be TiO
2Nano-tube array side transverse section Photomicrograph shows that CdS is the particle island growth.
Figure 13 is the stack of the coaxial heterojunction nano-tube array sample XRD figure spectrum of three kinds of different sedimentation potentials acquisitions.
The CdS/TiO of Figure 14 under different sedimentation potentials, preparing
2The not sensitization TiO that coaxial heterojunction nano-tube array sample and corresponding cleaning are exposed
2Density of photocurrent of nano-tube array substrate sample (a) and corresponding photoelectric transformation efficiency (b).
Figure 15 is CdS/TiO
2Coaxial heterojunction nano-tube array transmission electron micrograph.
Figure 16 is TiO
2The cyclic voltammogram of nanotube electrode in three kinds of different solutions; (a) 10mM CdSO
4+ 50mM Na
2SO
4, (b) 10mM CdSO
4+ 0.15M EDTA, (c) 2mM Na
2S+0.15M EDTA, scanning speed is 5mV/s.
Embodiment
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
The method for preparing the coaxial heterojunction nano-tube array described in the invention is a kind of new method that electrochemical deposition technique and atomic layer epitaxy technology are combined, and has the advantage that epitaxial film is accurately controlled in electrochemistry room temperature deposition, low cost and atomic layer epitaxy concurrently.Be with other electrochemical deposition technique difference, it forms the surface chemistry limiting growth by owing the electromotive force deposition process, monoatomic layer by galvanic deposit compound component is to realize epitaxy, different atoms of elements are deposited upon in the different solution carries out, thereby can realize optimization selection respectively to the mode of deposition (deposition potential, reaction soln concentration etc.) of each element.
Fig. 1 a is narrow gap semiconductor/TiO
2Coaxial heterojunction nano-tube array structure synoptic diagram; Fig. 1 b is a coaxial heterojunction charge transfer schematic diagram of mechanism.Outer narrow band gap sensitizing agent excites generation light induced electron (e) and photohole (h) after absorbing photon (hv), because outer sensitizing agent is extremely thin, photohole only need move very short distance just can arrive the electrolytic solution dissolving; And light induced electron transfers to conducting base by conduction core in the axle.
At first adopt electrochemistry anodic oxidation to obtain TiO
2Nano-tube array is as the substrate material of preparation nanotube coaxial heterojunction.The substrate surface pattern as shown in Figure 2.Fig. 3 is the X-ray diffractogram (XRD) of substrate material, and collection of illustrative plates shows the Detitanium-ore-type structure.
Dispose reaction soln then, be the solution that comprises each component of extension sensitization narrow gap semiconductor compound, can also add the solution that comprises various metal-doped elements such as Pt, Co, V, Ni and nonmetal doping elements such as C, N, B in the above-mentioned reaction soln.
With TiO
2The nano-tube array substrate carries out cyclic voltammetry scan in containing each component solution of extension sensitizing agent, determine that each component is at TiO
2Owing between the electromotive force sedimentary province on the nano-tube array substrate.
Afterwards, on the substrate each component is being carried out alternating deposit in definite good owing separately between the electromotive force sedimentary province.Promptly at first introduce first kind of reaction soln, control sedimentation potential and depositing time make first kind of element owe the electromotive force deposition; Adopt blank solution flushing electrode then, introduce second kind of reaction soln, control sedimentation potential and depositing time make second kind of element owe the electromotive force deposition.Make all constituent elements owe the electromotive force deposition separately until introducing all reaction solns, introduce first kind of reaction soln afterwards again, so repeatedly, finish the epitaxy of component alternating atomic layers, promptly obtain the coaxial heterojunction titania nanotube array.
The part narrow gap semiconductor is as CdS, Bi
2S
3, CdSe, CdTe, WO
3, Fe
2O
3Deng compound can with TiO
2Nano-tube array forms the coaxial heterojunction nano-tube array, and present embodiment is an example with CdS, illustrates to obtain CdS/TiO
2The preparation method of coaxial heterojunction nano-tube array.The preparation method and the CdS of other narrow gap semiconductor compound are similar.
At first adopt electrochemistry anodic oxidation to obtain TiO
2Nano-tube array is as the substrate material of preparation nanotube coaxial heterojunction.
Dispose 10mM CdSO then respectively
4+ 50mM Na
2SO
4Solution and 2mMNa
2S.9H
2O solution.In order to improve TiO
2The visible light-responded performance of nano-tube array can also add the solution of doped metallic elements, as Pt, Co, V, Ni; The solution of doped with non-metals element is as C, N, B etc.
With TiO
2The nano-tube array substrate is containing the 10mM CdSO of Cd element respectively
4+ 50mM Na
2SO
4Solution and the 2mM Na that contains the S element
2S.9H
2Carry out cyclic voltammetry scan in the O solution, and by scanning gained image determine the owing the electromotive force potential region and be of two kinds of constituent element Cd and S element-0.65V～-0.75V (with respect to the Ag/AgCl reference electrode).
Respectively employing-0.65V ,-0.7V ,-0.75V is as Cd and two kinds of element common of S sedimentation potential, owes respectively to deposit under the electromotive force 5 hours (h) at each current potential, obtains CdS/TiO
2The coaxial heterojunction nano-tube array promptly obtains the coaxial heterojunction nano-tube array of CdS.
In deposition process, at first introduce the 10mM CdSO that contains the Cd element
4+ 50mM Na
2SO
4Solution, control sedimentation potential and depositing time make the Cd element owe the electromotive force deposition; Adopt blank solution flushing electrode then, introduce the 2mMNa that contains the S element
2S.9H
2O solution, control sedimentation potential and depositing time make the S element owe the electromotive force deposition, and wash electrode with blank solution once more, afterwards, introduce the 10mM CdSO that contains the Cd element again
4+ 50mM Na
2SO
4Solution is owed the electromotive force deposition to the Cd element once more, so repeatedly, finishes Cd and the epitaxy of S element alternating atomic layers, obtains CdS/TiO
2The coaxial heterojunction nano-tube array promptly obtains the coaxial heterojunction nano-tube array of CdS.
Fig. 4-6 is for owing the analysis chart of electromotive force current potential for gained sample under the-0.65V mode of deposition.
As seen from Figure 4, on anatase-type titanium oxide nano-tube array substrate, the several main diffraction peak of CdS occurred, as seen under this current potential, Cd and S element can both be at TiO
2Deposit on the nano-tube array substrate.In Fig. 5, the relative content of Cd and S element is less under-0.65V mode of deposition as can be seen, and atomic percent accounts for 1.66% and 1.92% respectively, and its stoichiometric ratio is approximately 1: 1.Surface topography from Fig. 6 is in the TiO of-sedimentary coaxial heterojunction nano-tube array of 0.65V and former exposed cleaning
2The nanotube substrate does not have obvious difference, and (Fig. 6 a).Under higher magnification, can see that the nanotube tube wall adheres to the extremely thin CdS epitaxial film of one deck (shown in Fig. 6 b).
Fig. 7-9 is for owing the analysis chart of electromotive force current potential for gained sample under the-0.70V mode of deposition.Fig. 7 and Fig. 4 compare, and the diffraction peak of CdS is being strengthened as can be seen.Fig. 8 compares with Fig. 5, and the content of Cd and S is increasing, and is respectively 3.05% and 3.91%, and stoichiometric ratio still was approximately equal to 1: 1.The relative Fig. 6 of Fig. 9, the CdS of tube wall place epitaxial film thickens to some extent.Among Fig. 9 b, the surfaces externally and internally of visible nanotube tube wall has evenly covered one deck extension sensitizing layer (as white arrow indication among the figure).As seen, under-0.70V, the deposition effect of Cd and S element is better.
Figure 10-12 is for owing the analysis chart of electromotive force current potential for gained sample under the-0.75V mode of deposition.In Figure 10, except the diffraction peak of CdS continues the diffraction peak of hydrated sodium carbonate also to have occurred strengthening, illustrate that this moment sedimentation potential is enough negative, deposit in the sedimentary absorption that has also occurred organic complex EDTA simultaneously of CdS.Continue increasing, the spectrum peak of C and Na also to have occurred except the content of Cd and S among Figure 11, confirmed XRD diffraction result shown the conclusion of the diffraction peak of hydrated sodium carbonate can appear in-0.75V deposition.Being presented under this current potential CdS among Figure 12 has been particle island deposition, has lost the feature of owing the atomic layer epitaxy of electromotive force current potential two dimension.Because the particle island growth is a body phase deposition characteristics, sedimentation rate is very fast.Find out that from Figure 12 a some particle has stopped up the nanotube mouth of pipe, cause the nano-tube array specific surface area to reduce.
TiO with the CdS extension sensitization for preparing under the above-mentioned different embodiment conditions
2The thing of coaxial heterojunction nano-tube array reaches photoelectrochemical behaviour mutually and compares research.Figure 13 is the stack of the coaxial heterojunction nano-tube array sample XRD figure spectrum of three kinds of different sedimentation potentials acquisitions, can clearly find along with sedimentation potential is negative more, the diffraction peak of CdS is strengthened gradually, and with-0.7V is the best, on the titania nanotube array substrate, obtains some amount and do not had the single-phase CdS compound of other dephasign.The CdS/TiO of Figure 14 under different sedimentation potentials, preparing
2The not sensitization TiO that coaxial heterojunction nano-tube array sample and corresponding cleaning are exposed
2Density of photocurrent and the corresponding photoelectric transformation efficiency of nano-tube array substrate sample under full spectrum analog solar irradiation.As shown in the figure, exposed TiO is not cleaned in sensitization
2The photoelectric transformation efficiency of nano-tube array substrate sample is 1.65%.In-0.65V carried out the sensitization of narrow gap semiconductor CdS electrochemical atomic layer epitaxy to it after, its photoelectric transformation efficiency brought up to 6.24%.And-after 0.7V carried out sensitization, its photoelectric transformation efficiency had been issued to 8.13% at full spectrum analog solar irradiation, illustrate that the coaxial heterojunction light anode for preparing in this current potential sensitization has more excellent visible light-responded performance.With further negative the moving to-0.75V of current potential, its photoelectric transformation efficiency is dropped rapidly to 2.76%, the coaxial heterojunction structure that preparation under this current potential is described has gone to pot, cause the sealing of nanotube opening part, reduce the specific surface area of nano-tube array, thereby have influence on the normal performance of photoelectrochemical behaviour.Figure 15 is the TEM photo of prepared coaxial heterojunction, and from the photoelectrochemical behaviour test result, this coaxial heterojunction structure can effectively improve TiO
2The visible light-responded performance of nanotube oldered array is expected to (as light hydrolytic hydrogen production and heterojunction sensitization solar battery etc.) acquisition widespread use in the photocatalytic applications field.
In addition, be TiO owing to what adopt with special surface structure
2Nano-tube array substrate, its huge specific surface area may make that blank solution is difficult to preceding a kind of reaction soln is rinsed well.If two kinds of elements forming narrow gap semiconductor are at TiO
2On the nano-tube array substrate to owe the electromotive force current potential inequality, wherein a kind of electromotive force current potential of owing of element may be corresponding to the body phase sedimentation potential of another kind of element.Therefore, if the reaction soln flushing is clean inadequately, also have residual preceding a kind of reaction soln to exist when introducing a kind of reaction soln, then adopt when owing the electromotive force current potential and deposit a kind of element, the sedimentary phenomenon of block island may appear in residual another kind of element under this current potential.Given this, the invention provides two kinds of methods and solve and adopt when owing electromotive force and depositing a kind of element, the sedimentary problem of block island appears in residual another kind of element:
A, because the pH value of deposit solution has bigger influence to owing the electromotive force sedimentation potential, therefore the pH value by regulator solution is extremely identical can transfer to unanimity with the electromotive force current potential of owing of two kinds of constituent element elements of deposited compound.
B, by in solution, introducing organic solvent, as ethylenediamine tetraacetic acid (EDTA) (EDTA2-(C
10H
14O
8N
2Na
2.2H
2O)), utilize the multiple structure of functional groups of organic solvent and sedimentary ion to carry out chelating, reduce the activity of deposition ion in solution, can significantly change and owe the electromotive force sedimentation potential.
But the method for combined with electrochemical codeposition afterwards, make it to owe electromotive force current potential zone and deposit each composed atom of extension sensitizing layer simultaneously at each element, avoided occurring the sedimentary phenomenon of residual element block island, the heterogeneous phase epitaxy layer of final acquisition covers on the nano-tube array tube wall equably, i.e. the on all four coaxial heterojunction nano-tube array structure of the surface topography of the surface tissue of epitaxial film and lower floor's nanotube.
With extension sensitization CdS narrow gap semiconductor is example, and a curve is that this nano-tube array substrate is at 10mM CdSO among Figure 16
4+ 50mM Na
2SO
4Contain cyclic voltammetry curve in the Cd unit cellulose solution, solution adopts ammoniacal liquor that the pH value is transferred to 8.5.The c curve is that this nano-tube array substrate is at 2mM Na among Figure 16
2S.9H
2O contains cyclic voltammetry curve in the S solution, also adopts ammoniacal liquor that the pH value is transferred to 8.5.A curve and c curve among contrast Figure 16, two kinds of elements of Cd and S are at TiO
2Owe electromotive force current potential and inequality on the nano-tube array substrate, then can make the electromotive force of owing of two kinds of constituent element elements be positioned at identical potential region by adding organic solvent.The b curve is and adds the TiO that obtains behind the organic solvent EDTA among Figure 16
2The nano-tube array substrate is at 10mM CdSO
4+ 0.15M
Cyclic voltammetry curve in the EDTA solution.As seen the pH value by regulator solution with introduce organic solution and can transfer to the electromotive force current potential of owing of two kinds of constituent element elements of deposited compound consistent with multiple structure of functional groups.
In sum, the present invention has raising TiO really
2The effect of the visible light-responded performance of nanotube oldered array; the foregoing description only is a preferable embodiment of the present invention; the protection domain that is not intended to limit the invention, all change and modifications of carrying out according to spirit of the present invention and design all should be included in protection scope of the present invention.
Claims (10)
1. coaxial heterojunction TiO
2The preparation method of nano-tube array comprises the steps:
(1) preparation TiO
2Nano-tube array is as the substrate of preparation coaxial heterojunction nano-tube array;
(2) configuration reaction soln promptly disposes the solution that comprises each component of coaxial heterojunction compound respectively;
(3) with TiO
2The nano-tube array substrate carries out cyclic voltammetry scan respectively in above-mentioned each reaction soln, determine each component at TiO
2Owe electromotive force sedimentation potential interval on the nano-tube array substrate;
(4) on substrate, each component is carried out alternating deposit in the electromotive force sedimentation potential interval of determining separately of owing, finish each component atomic-layer epitaxial growth, promptly obtain the coaxial heterojunction TiO of above-claimed cpd
2Nano-tube array.
2. a kind of coaxial heterojunction TiO according to claim 1
2The preparation method of nano-tube array is characterized in that, the alternating deposit detailed process in the step (4) is:
At first introduce first kind of reaction soln, control sedimentation potential and depositing time make in described each component, and the component that is included in this first kind of reaction soln is owed the electromotive force deposition;
Adopt blank solution flushing electrode;
Introduce second kind of reaction soln, control sedimentation potential and depositing time make in described each component, and the component that is included in this second kind of reaction soln is owed the electromotive force deposition;
Adopt blank solution flushing electrode again;
Make all constituent elements owe electromotive force deposition separately until introducing all reaction solns respectively, and the said process repeatedly that circulates, promptly finish the alternating deposit of described each component.
3. a kind of coaxial heterojunction TiO according to claim 1 and 2
2The preparation method of nano-tube array is characterized in that, the electromotive force sedimentation potential interval of owing with each component in step (3) is defined as same interval.
4. a kind of coaxial heterojunction TiO according to claim 3
2The preparation method of nano-tube array is characterized in that, adopts the mode of adding organic solvent in reaction soln to regulate and determines the described electromotive force sedimentation potential interval of owing.
5. a kind of coaxial heterojunction TiO according to claim 3
2The preparation method of nano-tube array is characterized in that, adopts the mode of the pH value of conditioned reaction solution to regulate and determines the described electromotive force sedimentation potential interval of owing.
6. according to the described a kind of coaxial heterojunction TiO of one of claim 1-5
2The preparation method of nano-tube array is characterized in that, adds the solution that comprises metal-doped element and/or comprise the nonmetal doping element in each reaction soln.
7. a kind of coaxial heterojunction TiO according to claim 6
2The preparation method of nano-tube array is characterized in that, described metal-doped element is Pt, Co, V or Ni; Described nonmetal doping element is C, N or B.
8. according to the described a kind of coaxial heterojunction TiO of one of claim 1-7
2The preparation method of nano-tube array is characterized in that, adopts electrochemistry anodic oxidation to prepare described substrate in step (1).
9. according to the described a kind of coaxial heterojunction TiO of one of claim 1-8
2The preparation method of nano-tube array is characterized in that, described compound with coaxial heterojunction is CdS, Bi
2S
3, CdSe, CdTe, WO
3Or Fe
2O
3
10. utilize the coaxial heterojunction TiO of the described method preparation of one of claim 1-9
2Nano-tube array.
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| CN103173764A (en) * | 2013-03-22 | 2013-06-26 | 天津大学 | TiO2 through hole nanotube and CdS compound array film and preparation method thereof |
| CN103361689A (en) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | Method for preparing titanium dioxide nanotube array photoelectrode |
| CN104931487A (en) * | 2015-06-16 | 2015-09-23 | 北京联合大学 | Supported type composite nano sensitive material for detecting isobutanol gas and preparation method thereof |
| CN109256468A (en) * | 2018-07-31 | 2019-01-22 | 中国科学院合肥物质科学研究院 | A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances |
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| CN100566820C (en) * | 2004-03-11 | 2009-12-09 | 波斯泰克基金会 | The photochemical catalyst that comprises oxide-based nanomaterial |
| CN101625930B (en) * | 2009-06-19 | 2012-04-11 | 东南大学 | Ordered nano-tube array structure electrode material, preparation method and stored energy application |
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| CN103361689A (en) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | Method for preparing titanium dioxide nanotube array photoelectrode |
| CN103361689B (en) * | 2013-05-28 | 2016-05-04 | 青岛农业大学 | The preparation method of Nano tube array of titanium dioxide optoelectronic pole |
| CN104931487A (en) * | 2015-06-16 | 2015-09-23 | 北京联合大学 | Supported type composite nano sensitive material for detecting isobutanol gas and preparation method thereof |
| CN108165938B (en) * | 2017-12-20 | 2019-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hetero-junctions photochemistry array and products thereof and application |
| CN109256468A (en) * | 2018-07-31 | 2019-01-22 | 中国科学院合肥物质科学研究院 | A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances |
| CN109821559A (en) * | 2019-03-27 | 2019-05-31 | 泉州师范学院 | A kind of preparation method and applications of core-shell structure composite photoelectric material |
| CN115074739A (en) * | 2022-07-19 | 2022-09-20 | 中国科学院海洋研究所 | CdS @ TiO for metal photo-generated cathodic protection 2 Preparation method and application of NTAs composite material |
| CN115074739B (en) * | 2022-07-19 | 2023-10-13 | 中国科学院海洋研究所 | CdS@TiO for metal photogenerated cathode protection 2 Preparation method and application of NTAs composite material |
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