CN104828863A - TiO2 nanowire diameter regulating and controlling method and TiO2 nanowire array prepared by same - Google Patents

TiO2 nanowire diameter regulating and controlling method and TiO2 nanowire array prepared by same Download PDF

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CN104828863A
CN104828863A CN201510245758.6A CN201510245758A CN104828863A CN 104828863 A CN104828863 A CN 104828863A CN 201510245758 A CN201510245758 A CN 201510245758A CN 104828863 A CN104828863 A CN 104828863A
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tio
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CN104828863B (en
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胡海龙
马国华
郭宝刚
杨杰
张行泉
蔡向阳
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Southwest University of Science and Technology
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Abstract

The invention discloses a TiO2 nanowire diameter regulating and controlling method and a TiO2 nanowire array prepared by the same. Under hydrothermal condition, a polar solution is attached to the surface of a hydrophilic solid substrate in a form of micromicelle when in a nonpolar solution; according to the method, through controlling the time and temperature of hydrothermal reaction, the interface tension of the micromicelle formed by the polar solution and the pressure difference between inner pressure and outer pressure can be controlled so as to further finely regulate and control the diameter of the TiO2 nanowire generated through the orientation reaction between Ti-based precursor and reactants such as concentrated hydrochloric acid in a certain proportion in the micromicelle. The method has the advantages that the process is simple and easy to operate; high-temperature crystallization treatment is not needed; the TiO2 nanowire prepared by the method is excellent in uniformity, is finely controllable in diameter, is good in stability and has an excellent market application prospect.

Description

TiO 2nanowire diameter regulate and control method and the TiO obtained by it 2nano-wire array
Technical field:
The invention belongs to the preparing technical field of inorganic materials, be specifically related to TiO 2nanowire diameter regulate and control method and the TiO obtained by it 2nano-wire array.
Background technology:
TiO 2nano-wire array has favorable orientation, specific surface area is large and have the series of characteristics such as unique surfactivity and photoelectricity, huge application prospect is had in environment, the energy, biology and detection, therefore the parent being subject to a lot of research worker looks at, and launches a large amount of correlative study work.Research shows that the thickness of nano wire is to photo-generated carrier surface mobility, and array surface sum surface vacancy density all has impact in various degree, thus has influence on the characteristics such as the photoelectricity of TiOx nano linear array and surfactivity.Thus the preparation of nano-wire array becomes the integral part needing to pay close attention to.
Conventional preparation TiO 2the method of nano-wire array has template, anonizing, electrochemical deposition method, high temperature chemical vapor deposition method (CVD) and hydrothermal method.Wherein, hydrothermal method process is simple, with low cost, thus becomes preparation TiO 2the best approach of nano-wire array.At present, hydrothermal method is mainly divided into Aqueous phase and oil phase method.Namely Aqueous phase utilizes titanium base presoma at high temperature, is slowly hydrolyzed by the restraining effect of concentrated hydrochloric acid, and Cl -effect under oriented growth, directly obtain monocrystalline TiO in the upper growth of fluorine-doped tin oxide conductive glass (FTO) 2nano-wire array.Research is thought due to Rutile Type TiO 2with the character mismatch between FTO impels TiO 2be epitaxially grown to nano wire.Find the concentration of presoma in addition, acid, growth time, Cl -concentration etc. all have a certain impact to the thickness of nano wire in nano-wire array.The nano-wire array of wire diameter distribution in 50 to 200 nanometers can be obtained by this method.
Oil phase hydrothermal method is reacted between non-polar solution and the interface of solid hydrophilic substrate (FTO) with titanium base presoma and concentrated hydrochloric acid, also can obtain the good monocrystalline TiO of orientation 2nano-wire array.Under hydrothermal conditions, a small amount of polar solvent can be scattered in a large amount of non-polar solutions with the form of micro-micella, and have the micro-micellar adsorption of part at hydrophilic group basal surface, under acidic conditions and chlorion effect, nano wire just starts oriented growth in this slightly micella, and forms nano-wire array.Because nano wire is formed in micro-micella, thus the size regulating micro-micella can be passed through, and correlated condition controls the thickness of nano wire further.Thus become the preparation method of nanowire diameter in a kind of desirable control nano-wire array.But oil phase hydrothermal method is to TiO 2the research of the regulatory mechanism of nano-wire array pattern but also not exclusively.Particularly for the regulation and control of micro-micellar size and the research of the regulation and control of other correlated conditions on the impact of nano wire pattern less.
In sum, although hydrothermal method prepares nano wire have the advantages such as cost is low, simple to operate, easily-controlled reaction conditions, for product structure, particularly TiO 2the precise controlling of nanowire diameter size remains a technical barrier of the art, and TiO 2the diameter of nano wire and its range of application closely related.For this reason, how by selective reaction thing and composition thereof, regulation and control and the optimization processing parameter such as temperature of reaction and reaction times finely control the diameter of reaction product thus prepare good, the high-quality TiO of homogeneity 2nano wire is the technical problem that this area needs solution badly.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art, provide one and utilize micro-micella finely regulating TiO 2the method of nanowire diameter and the TiO utilizing the method to prepare 2nano-wire array.
In order to realize foregoing invention object, the present invention takes following technical scheme: under hydrothermal conditions, polar solvent is adsorbed on solid hydrophilic substrate substrate surface with micro-micelle form in non-polar solution, and in micro-micella that titanium base presoma and concentrated hydrochloric acid are formed at polar solvent, orientation response generates TiO 2nano-wire array, wherein, TiO 2the fabricate of nanowires step comprises:
1) add two kinds of 1-2 volume titanium source presomas to 15-25 volume non-polar solution respectively, be fully uniformly mixed obtained solution A, in solution A, add the chloride polar acidic solution of 1-2 volume, and be fully uniformly mixed obtained solution B fast;
2) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate conductive glass cleaned up with conducting surface;
3) heating high-pressure reactor, controls temperature of reaction at 120 DEG C-220 DEG C, and the reaction times is 6-10h
4) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
One of ordinary skill in the art will appreciate that, the polar solvent used in above-mentioned reaction system can be selected from hydrochloric acid, acetic acid, and non-polar solution is the non-polar solution that this area is commonly used, as: toluene, normal hexane, hexanaphthene, titanium source presoma is the titanium source that this area is commonly used, as: titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, titanium ethanolate, solid hydrophilic substrate is the substrate that this areas such as FTO are commonly used.
Applicants studied each composition and proportion of composing thereof in reaction system, obtaining as drawn a conclusion: polar solvent is preferably 37% concentrated hydrochloric acid, the preferred toluene of non-polar solution, the preferred tetra-n-butyl titanate of titanium source presoma and titanium tetrachloride, the preferred FTO of solid hydrophilic substrate; In reaction system, the volume ratio of various composition is: 37% concentrated hydrochloric acid 1-2 part, preferably 1.2 parts; Non-polar solution-toluene 15-25 part, preferably 20 parts; Preferred tetra-n-butyl titanate and each 1.2 parts of titanium tetrachloride.
Wherein, because titanium tetrachloride is very easily hydrolyzed, therefore in reaction system building process, under room temperature state, in described solution A (titanium source presoma and 15-25 volume non-polar solution mixture containing titanium tetrachloride), add concentrated hydrochloric acid fast.
In order to the reproducibility and reliability of warranty test result, before use, solid hydrophilic substrate is first used acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively by applicant successively, then dry for standby.
Applicants studied the modes of emplacement of solid hydrophilic substrate FTO conducting surface in autoclave to TiO 2the impact of crystalline structure, selects to clean up and the solid hydrophilic substrate FTO conducting surface of dry for standby is upwards positioned in autoclave, can define the monocrystal nano line array with rutile structure arranged vertically in substrate.
Preparation method disclosed in this invention, its principle is not for dissolving each other due to concentrated hydrochloric acid and toluene, and during the condition of high temperature, concentrated hydrochloric acid evenly spreads in toluene with the form of micro-micella, part disperse to substrate place micro-micellar adsorption be hydrophilic FTO on the surface, TiO 2just grow and form array at micro-micella interior orientation, as shown in Fig. 1 (a).Inner at micro-micella, the Ti source be dissolved among toluene can diffuse in micro-micella, and under the restraining effect of concentrated hydrochloric acid, slowly hydrolysis forms TiO 2nucleus.Due to TiO 2in wetting ability, thus micro-micella can continue to be adsorbed on the new TiO formed 2on nucleus.In addition, due to Cl -optionally to be adsorbed on (110) crystal face and to suppress the growth of this crystal face, thus forcing TiO 2along the growth of (001) direction, finally form TiO 2nano wire, as shown in Fig. 1 (b).
TiO 2nano wire is formed at micro-micella, and thus the diameter of micro-micella is by the diameter of restriction nano wire.And according to the Young-Laplace formula under sphere condition, the radius R of micro-micella meets:
R = 2 γ Δp - - - ( 1 )
Wherein, γ is the interfacial tension between two kinds of solution, and Δ p is then pressure p in micro-micella iwith outer pressure p o
Δp＝p i-p o
Difference, i.e.: (2)
From formula (1), micro-micellar radius can reduce along with interfacial tension and reduce, or reduces along with the increase of pressure differential deltap p.
Based on said process, method of the present invention can by regulating Cl -interfacial tension and the inside and outside differential pressure size of concentration and micro-micella can reach TiO 2the object of nano wire thickness, thus achieve TiO 2the adjustment of nanometer wire diameter; And by control Cl -the interfacial tension of concentration and micro-micella and inside and outside differential pressure, can ensure TiO 2the homogeneity of nanometer wire diameter.
Under certain temperature condition, concentrated hydrochloric acid is dispersed in after among toluene with the form of micro-micella, and the inside and outside pressure suffered by micro-micella is respectively the vapour pressure of concentrated hydrochloric acid and toluene under relevant temperature.Most of composition due to concentrated hydrochloric acid is water, the vapour pressure of the vapour pressure approximate substitution concentrated hydrochloric acid of used water.The broken line graph of Fig. 3 for drawing according to the water and toluene vapour pressure at different temperatures of searching gained.As shown in Figure 3.Can find out, constantly raise with temperature, micella inside and outside differential pressure, Δ p sharply increases.In addition, interfacial tension can reduce along with the rising of temperature.Therefore, when the temperature increases, according to formula (1), the radius of micro-micella can reduce along with the rising of temperature, therefore regulates temperature of reaction can have regulating effect to nano wire thickness.
Aforementioned mixed reaction solution B is placed in autoclave by applicant, and provides differential responses temperature and reaction times, and research finds, temperature of reaction is at 120 DEG C-220 DEG C, reaction times is when being 6-10h, by control temperature and time in this condition and range, and preparation-obtained TiO 2the large I of nanowire diameter finely controls and product uniformity is good.
In order to study temperature of reaction further to TiO 2the impact of nanowire diameter size and homogeneity, applicant selects aforementioned preferred mixed reaction solution B (containing each 1.2 parts of 37% concentrated hydrochloric acid 1.2 parts, toluene 20 parts, tetra-n-butyl titanate and titanium tetrachloride) to be placed in autoclave, the solid hydrophilic substrate FTO conducting surface that will clean up also dry for standby is selected upwards to be positioned in autoclave, reaction times selects 7h, temperature of reaction is controlled at 120 DEG C-180 DEG C, the TiO that statistical study prepares 2nanowire diameter size and homogeneity thereof, result (see Fig. 4) display is along with the rising of temperature, and react its diameter of nano-wire array prepared and diminish gradually, and reunion degree increases to some extent, product uniformity is excellent and diameter is meticulous controlled.
Due in whole reaction process, the proportioning of all solution, and the incorporation of precursors is all just the same, can think that the diameter that the change of temperature of reaction result in nano wire there occurs change.Due to the rising of temperature, mainly cause reaction system Semi-polarity, the rising in various degree of non-polar solution vapour pressure, the reduction of interfacial tension and the quickening of speed of response.And under same concentrations Cl -under the restriction of ion, the diameter of nano wire can become large because of the quickening of speed of response.But experimental result shows, the rising of temperature causes the diameter of nano wire to reduce, and can think, attenuating of nano wire mainly reduces because of the rising of micro-micella Yin Wendu in reaction system.Therefore micro-micellar size can be regulated by temperature, and then the diameter of regulation and control nano wire.
Compared with existing nanowire array growth technology, the invention provides one and utilize micro-micella finely regulating TiO 2the method of nanowire diameter and the TiO prepared by the method 2nano wire.The method have technique simple to operation, without the need to high temperature Crystallizing treatment, TiO obtained by this method 2excellent and meticulous controlled, the good stability of diameter of nano wire homogeneity, has good market application foreground.
Accompanying drawing illustrates:
Fig. 1 is TiO under micro-micelle method 2preparation feedback principle schematic.
Fig. 2 is that micro-micella size is by ambient conditions principle of adjustment and control schematic diagram.
Fig. 3 is vapour pressure and the pressure reduction figure of toluene under differing temps and water.
Fig. 4 is through temperature adjusting, obtains the TiO of different diameter 2nano-wire array scanning electron microscope shape appearance figure.
Embodiment:
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
Embodiment 1:
1) solid hydrophilic substrate FTO is used successively acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively, dry for standby;
2) respectively the titanium tetrachloride of the tetra-n-butyl titanate of 1.2 volumes and 1.2 volumes is added in the toluene of 20 volumes, be fully uniformly mixed obtained solution A, in solution A, add 37% concentrated hydrochloric acid of 1.2 volumes, and be fully uniformly mixed obtained solution B fast;
3) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate FTO conductive glass cleaned up with conducting surface;
4) heating high-pressure reactor, controls temperature of reaction at 120 DEG C, and the reaction times is 7h;
5) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
Test-results as shown in fig. 4 a, TiO obtained under above-mentioned reaction conditions 2nano wire mean diameter is 84.8 ± 19.9nm.
Embodiment 2:
1) solid hydrophilic substrate FTO is used successively acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively, dry for standby;
2) respectively the titanium tetrachloride of the tetra-n-butyl titanate of 1.2 volumes and 1.2 volumes is added in the toluene of 20 volumes, be fully uniformly mixed obtained solution A, in solution A, add 37% concentrated hydrochloric acid of 1.2 volumes, and be fully uniformly mixed obtained solution B fast;
3) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate FTO conductive glass cleaned up with conducting surface;
4) heating high-pressure reactor, controls temperature of reaction at 135 DEG C, and the reaction times is 7h;
5) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
Test-results as shown in Figure 4 b, TiO obtained under above-mentioned reaction conditions 2nano wire mean diameter is 66.7 ± 12.9nm.
Embodiment 3:
1) solid hydrophilic substrate FTO is used successively acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively, dry for standby;
2) respectively the titanium tetrachloride of the tetra-n-butyl titanate of 1.2 volumes and 1.2 volumes is added in the toluene of 20 volumes, be fully uniformly mixed obtained solution A, in solution A, add 37% concentrated hydrochloric acid of 1.2 volumes, and be fully uniformly mixed obtained solution B fast;
3) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate FTO conductive glass cleaned up with conducting surface;
4) heating high-pressure reactor, controls temperature of reaction at 150 DEG C, and the reaction times is 7h;
5) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
Test-results as illustrated in fig. 4 c, TiO obtained under above-mentioned reaction conditions 2nano wire mean diameter is 27.3 ± 4.7nm.
Embodiment 4:
1) solid hydrophilic substrate FTO is used successively acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively, dry for standby;
2) respectively the titanium tetrachloride of the tetra-n-butyl titanate of 1.2 volumes and 1.2 volumes is added in the toluene of 20 volumes, be fully uniformly mixed obtained solution A, in solution A, add 37% concentrated hydrochloric acid of 1.2 volumes, and be fully uniformly mixed obtained solution B fast;
3) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate FTO conductive glass cleaned up with conducting surface;
4) heating high-pressure reactor, controls temperature of reaction at 160 DEG C, and the reaction times is 7h;
5) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
Test-results as shown in figure 4d, TiO obtained under above-mentioned reaction conditions 2nano wire mean diameter is 21.3 ± 4.8nm.

Claims (8)

1. a TiO 2nanowire diameter regulate and control method, under hydrothermal conditions, makes polar solvent be adsorbed on solid hydrophilic substrate substrate surface with micro-micelle form in non-polar solution, and titanium base presoma orientation response in the micro-micella formed by aforementioned polar solvent generates TiO 2nano-wire array, wherein, concrete steps comprise:
1) add two kinds of 1-2 volume titanium source presomas to 15-25 volume non-polar solution respectively, be fully uniformly mixed obtained solution A, in solution A, add the chloride polar acidic solution of 1-2 volume, and be fully uniformly mixed obtained solution B fast;
2) by step 1) obtained mixing solutions B transfers in band teflon-lined autoclave, is upwards positioned in tetrafluoroethylene reactor, envelope still by the solid hydrophilic substrate conductive glass cleaned up with conducting surface;
3) heating high-pressure reactor, controls temperature of reaction at 120 DEG C-220 DEG C, and the reaction times is 6-10h;
4) after reaction terminates, autoclave is naturally cooled to room temperature, take out solid hydrophilic substrate conductive glass, naturally dry in atmosphere with after deionized water repeatedly rinsing, obtain TiO 2nano-wire array.
2. the method for claim 1, is characterized in that, described polar solvent is 37% concentrated hydrochloric acid, and described non-polar solution is toluene.
3. method as claimed in claim 2, is characterized in that, at room temperature press in described solution A and add titanium source presoma, described titanium source presoma is the tetra-n-butyl titanate of 1-2 volume and the titanium tetrachloride of 1-2 volume.
4. method as claimed in claim 3, it is characterized in that, the volume of described 37% concentrated hydrochloric acid, toluene, tetra-n-butyl titanate and titanium tetrachloride is respectively: 1.2 parts, 20 parts, 1.2 parts and 1.2 parts.
5. the method for claim 1, is characterized in that, described solid hydrophilic substrate is FTO.
6. the method for claim 1, is characterized in that, before use, acetone, Virahol, dehydrated alcohol, ultrapure water ultrasonic cleaning 30min, 20min, 20min, 30min respectively first used successively by solid hydrophilic substrate, dry for standby.
7. the method for claim 1, is characterized in that, step 3) in temperature of reaction is controlled at 120 DEG C-220 DEG C, the reaction times is 7h.
8. the TiO that the method as described in any one of claim 1-7 prepares 2nano-wire array.
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