CN104032367A - Method for preparing TiO2 nano nanopillar array by combination of pre-implantation of rutile-phase TiO2 film on titanium substrate and hydrothermal synthesis - Google Patents
Method for preparing TiO2 nano nanopillar array by combination of pre-implantation of rutile-phase TiO2 film on titanium substrate and hydrothermal synthesis Download PDFInfo
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- CN104032367A CN104032367A CN201410214711.9A CN201410214711A CN104032367A CN 104032367 A CN104032367 A CN 104032367A CN 201410214711 A CN201410214711 A CN 201410214711A CN 104032367 A CN104032367 A CN 104032367A
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Abstract
The invention provides a method for pretreating a titanium substrate, pre-implanting a rutile-phase TiO2 crystal seed on the titanium substrate surface, pre-protecting the titanium metal substrate to prevent the titanium metal substrate from being etched and dissolved by an acidic or alkaline growth solution and providing a crystal seed for hydrothermal growth of TNRA. The comprises the following steps: (a) pre-implanting the rutile-phase TiO2 film on the surface of the titanium metal substrate material; and (b) carrying out hydrothermal synthesis to grow and synthesize TNRA on the surface of the crystal seed layer. The pre-implantation of the rutile-phase TiO2 film on the titanium metal surface comprises the following steps: TiCl4 solution impregnating deposition and high-temperature roasting. The pre-implantation of the rutile-phase TiO2 film on titanium substrate enhances the etching dissolution resistance of the titanium metal substrate in the hydrothermal reaction process and provides the crystal seed for the growth of the TiO2 nanopillar array; and the shape of the TiO2 nanopillar array can be controlled by the shape of the pre-implanted TiO2 film to some extent.
Description
Technical field
The present invention relates to inorganic semiconductor material technical field, relate in particular to the pre-Rutile Type TiO that implants on a kind of titanium base
2film and hydro-thermal synthesis process combine at the synthetic TiO of titanium metal substrate material surface
2nano column array (TNRA, TiO
2nanorod Arrays) method of film.
Technical background
TiO
2because its good chemical stability and physical strength and cheap price are considered to one of the most frequently used efficient semiconductor photocatalyst.From Eray S.Aydil(B.Liu in 2009, E.S.Aydil, Growth of Oriented Single-Crystalline Rutile TiO
2nanorods on Transparent Conducting Substrates for Dye-Sensitized Solar Cells, J.Am.Chem.Soc.131 (2009) 3985-3990) etc. adopt for the first time hydrothermal technique success in FTO substrate of glass, to prepare monocrystalline one-dimensional red schorl phase TiO
2nano column array, and after being applied to sun power dye-sensitized cell, one dimension TiO
2nano material receives the concern of many researchers.The TNRA of one-dimentional structure is because its higher specific surface area, the more performance such as photocatalytic activity position, good light induced electron-hole separation efficiency are widely used in photolysis water hydrogen, photocatalysis to degrade organic matter, sun power dye-sensitized cell etc.At present existing a lot of technology are for TiO
2nano-pillar synthetic, as: hydrothermal method, also have electron beam evaporation plating method, high-temperature roasting method etc., but TiO at present
2the synthetic of nano-pillar is taking glass (as: conductive glass, silica glass etc.) as substrate mostly, taking titanium as substrate, (as titanium plate, titanium net etc.) is less, this is mainly that these solution atmosphere all have very strong corrasion to cause titanium metal substrate to be dissolved in completely in solution to titanium metal because the synthetic of TNRA is to carry out under the condition of strong acid or highly basic and high temperature mostly.Wu(J.M.Wu in 2005, T.W.Zhang, Large-Scale Preparation of Ordered TitaniaNanorods with Enhanced Photocatalytic Activity, Langmuir21 (2005) 6995-7002.) etc. people with 30% H
2o
2solution generates TNRA through corrasion after 72h under 80 DEG C of conditions on titanium plate, but has the dielectric barrier that one deck is thicker between the TNRA film generating and titanium plate stratum basale, and poor with the cohesiveness of substrate.Dong(L.Q.Dong in 2011, K.Cheng, W.J.Weng, Hydrothermal growth of rutile TiO
2nanorod films on titanium substrates, Thin Solid Films519 (2011) 4634-4640) etc. people adopt first high-temperature roasting method titanium plate to be carried out pre-treatment and formed the Rutile Type TiO of one deck densification
2film, then adopts hydro-thermal technique to grow on pretreated titanium plate and forms TNRA.Yet there are no with TiCl
4solution carries out the report of synthetic TNRA on pretreated titanium plate to titanium plate, also have no at the titanium report of synthetic TNRA on the net.
Summary of the invention
The object of the invention is to overcome and existingly adopt hydrothermal method to prepare in TNRA process titanium substrate to be easily etched to dissolve and to cause the shortcoming that cannot synthesize TNRA film taking titanium metal as substrate, provide a kind of titanium substrate is carried out to pre-treatment, implant in advance Rutile Type TiO at titanium substrate surface
2crystal seed, carries out pre-protection to titanium metal substrate and prevents that it from being dissolved by acid or alkaline growth media etching, provides the method for crystal seed for the hydrothermal growth of TNRA simultaneously.
The present invention prepares TNRA technique and mainly comprises two steps on titanium metal substrate material, that is:
(a) titanium metal substrate material surface is implanted Rutile Type TiO in advance
2film;
(b) hydrothermal synthesis method is at the synthetic TNRA of crystal seed layer surface growth.
Described titanium metal substrate material is selected from the titanium metal material such as titanium plate, titanium net.Titanium metal substrate material must be for subsequent use through surface cleaning and drying treatment before beginning, and object is to remove surperficial dust and organic impurity.
The pre-implantation crystal seed treatment technology of described titanium metal substrate is characterized in that introducing one deck Rutile Type TiO on titanium metal substrate surface
2film, one side provides the protective membrane of one deck densification in follow-up hydrothermal growth TNRA process for titanium metal substrate material, on the other hand for the growth of TNRA provides crystal seed layer.Step (a) titanium metal substrate material surface is implanted Rutile Type TiO in advance
2the method of film can be selected TiCl
4pickling process or high-temperature roasting method.
Described TiCl
4pickling process is: by titanium metal substrate material at TiCl
4the aqueous solution in 70 DEG C of constant temperature dipping 50min, then in 500 DEG C of roastings.The TiCl4 strength of solution using is 0.1-0.2M, the wherein TiCl of 0.15M
4the aqueous solution is best pre-processing titanium plate concentration.
Described high-temperature roasting method is: by the roasting under 600 DEG C of conditions of titanium metal substrate material.
Described step (b) hydrothermal synthesis method is to adopt hydro-thermal synthesis process at Rutile Type TiO in the method for the synthetic TNRA of crystal seed layer surface growth
2the synthetic TiO of film surface growth
2nano column array.Its step is put into and is contained the titanium source that offers TNRA growth and the acid solution atmosphere of controlling titanium source hydrolysis rate and molecular balance for the titanium substrate that step (a) is disposed, then under hot environment, carry out hydrothermal growth, until the uniform sequential TiO of Surface Creation one deck
2nano-pillar film ensures that film and base material have good cohesiveness simultaneously.The titanium source of the described TNRA of offering growth is mainly selected from contains tetrabutyl titanate, isopropyl titanate, TiCl
3deng the Ti compound that is difficult to hydrolysis in strong acid solution, it is uniform sequential that titanium source consumption is controlled at the TNRA of generation, and can separate and be advisable preferably each other.The acid solution of the hydrolysis of described control titanium source and molecular balance mainly refers to HCl solution.The growth media using in described water-heat process can add subcontrol material according to concrete material pattern and application request in growth media, as at L.Q.Dong (L.Q.Dong, K.Cheng, W.J.Weng, Hydrothermal growth of rutile TiO
2nanorod films on titanium substrates, Thin Solid Films519 (2011) 4634-4640) prepare and in the process of TNRA, add ethanol and can increase the length of the TNRA of growth, add alkali metal chloride (as NaCl, LiCl, KCl etc.) and can control the diameter of the TNRA of generation, density and orientation uniformity coefficient; Described hydrothermal synthesis device comprises polytetrafluoroethylliner liner and stainless steel casing, and the polytetrafluoroethylliner liner that TNRA growth media is housed is inserted in stainless steel casing, and complete assembly is salable, simultaneously high temperature resistant, high pressure resistant, anticorrosive; Described hydrothermal growth TNRA process is at high temperature carried out.
The pre-Rutile Type TiO that implants in titanium metal substrate
2after dense film, having improved titanium metal substrate anti-etching dissolving power in hydrothermal reaction process on the one hand, is TiO on the other hand
2the growth of nano column array provides crystal seed, the TiO of gained
2the pattern of nano column array can be to a certain extent by the TiO implanting in advance
2the morphology control of film.This material can be applicable to the fields such as photocatalytic fuel cell light anode material, organism improvement.
Brief description of the drawings
Fig. 1 is embodiment mono-TiCl
4the impact of solution pre-treatment on titanium plate resistance to corrosion: (a) untreated titanium plate, (b) titanium plate, (c) 0.15-TiCl after 0.15MTiCl4 solution-treated
4-TNRA(hydrothermal condition: 6mL ethanol+0.23g picric acid+37.5mL HCl+37.5mL H
2o+0.6mL TTB, 180 DEG C, 6h);
Fig. 2 is the TiCl of embodiment mono-at different concns
4sEM figure (the hydrothermal condition: 6mL ethanol+0.23g picric acid+37.5mL HCl+37.5mL H of the TNRA growing on the titanium plate that solution-treated is crossed
2o+x mL TTB, 180 DEG C, 6h:(A
x) 0.10-TiCl4-TNRA, (B
x) 0.15-TiCl
4-TNRA, (C
x) 0.20-TiCl
4-TNRA (x:TTB content);
Fig. 3 is embodiment mono-0.15M TiCl
4the XRD result of the each sample of aqueous solution pre-processing titanium plate growth TNRA method: (a) untreated titanium plate, (b) 0.15M TiCl
4titanium plate, (c) 0.15-TiCl after processing
4-TNRA;
Fig. 4 is the process flow sheets of embodiment bis-high-temperature roasting method for pretreating at titanium net surface growth TNRA;
Fig. 5 is the SEM figure (hydrothermal condition: 2M HCl+0.3mL TiCl of the TNRA of the online growth of embodiment bis-different pretreatments temperature condition titaniums
3, 150 DEG C, 6h): (A
x) titanium net surface after treatment of different temperature, (B
x) relevant temperature A after treatment
xtitanium net surface growth TNRA sample, (C
x) corresponding B
xthe sectional view of sample. (x: pre-treatment maturing temperature);
Fig. 6 is embodiment bis-high-temperature roasting method for pretreating synthesize the each sample of TNRA on the net XRD figure at titanium: (a) the titanium net after differing temps roasting; (b) the TNRA film (hydrothermal condition: 2M HCl+0.3mL TiCl of growing at the titanium net surface of differing temps roasting pretreatment
3, 150 DEG C, 6h).
Embodiment
Further illustrate the present invention below by embodiment, but the present invention is not construed as limiting.
Embodiment mono-
TiCl
4solution method for pretreating, at titanium plate surface controllable growth TNRA film, comprises the following steps successively:
(1) TiCl
4the solution pre-treatment that crystal seed is implanted in substrate in advance to titanium plate
(a) under ice-water bath condition, prepare the TiCl of 0.10M, 0.15M, 0.20M
4the aqueous solution is for subsequent use;
(b) at HF:HNO
3: H
2in the polishing fluid of O=1:4:5 (volume ratio), titanium plate is carried out to polished finish, to remove its surperficial dust, organism and oxide compound etc., then use deionized water rinsing titanium plate surface, drying for standby;
(c) clean titanium plate be impregnated in to the TiCl that step (a) prepares
4in the aqueous solution, will be at 70 DEG C isothermal reaction 50min, make its surface uniform deposition one deck TiO
2;
(d) the titanium plate of handling well is carried out to calcination process, 500 DEG C, 2h.
(2) the hydrothermal method TNRA that grows on the good titanium plate of pre-treatment
(a) by 6mL ethanol, 37.5mL HCl(36%-38wt.%) and 37.5mLH
2o mixes, and takes 0.23g picric acid and is dissolved in above-mentioned solution, then gets positive four butyl esters of 0.4-1.0mL metatitanic acid (TTB) and slowly splashes in above-mentioned solution, stirs 3-5min until solution becomes transparent; Also can use other titanium sources (as: isopropyl titanate) to replace tetrabutyl titanate herein.
(b) the good titanium plate of pre-treatment in step (1) is put into the 100mL tetrafluoroethylene reactor that above-mentioned steps (a) solution is housed of being furnished with the outer courage of stainless steel, reactor is placed in to constant-temp. electronic baking oven, in 180 DEG C of hydro-thermal reaction 6h;
(c), after hydro-thermal reaction finishes, naturally cooling cooling, with deionized water lavage specimens product surface;
(d) dry at 60 DEG C to sample, in 500 DEG C of roasting 2h.Adopt the TiCl of 0.10M, 0.15M, 0.20M
4tNRA film sample prepared by pretreated titanium plate is designated as respectively 0.10-TiCl
4-TNRA, 0.15-TiCl
4-TNRA, 0.20-TiCl
4-TNRA.
Experimental result demonstration, not pretreated when titanium plate surface, directly pass through hydrothermal growth TNRA, even experiencing shorter reaction times (hydrothermal condition: 6mL ethanol+0.23g picric acid+55mL HCl+20mL H in the growth media system of weaker acid
2o+0.6mL TTB, 180 DEG C, 2h), titanium plate is also dissolved by complete etching.Correspondingly, shown by accompanying drawing 1 and 3, after the pre-treatment of TiCl4 solution, titanium surface forms the Rutile Type TiO of one deck densification
2nano particle also can well improve the resistance to corrosion of titanium plate and the uniform sequential Rutile Type TNRA of its surface growth one deck in hydro-thermal reaction.Simultaneously illustrate that by accompanying drawing 2 pattern of TNRA can control by the concentration of controlling titanium source TTB in pre-treatment TiCl4 solution and hydrothermal growth liquid.
Embodiment bis-
High Temperature Pre facture is at titanium net surface controllable growth TNRA film, and technique as shown in Figure 4, comprises the following steps successively:
(1) high temperature pre-treatment is implanted crystal seed in advance at titanium net substrate surface
(a) at HF:HNO
3: H
2in the polishing fluid of O=1:4:5 (volume ratio), titanium net is carried out to polished finish, to remove its surperficial dust, organism and oxide compound etc., then use deionized water rinsing titanium net surface, drying for standby;
(b) by the dry titanium net of polished finish in retort furnace in 450 DEG C of-700 DEG C of thermal treatment 30min, naturally cooling.
(2) hydrothermal method is at the good titanium of the pre-treatment TNRA that grows on the net
(a) the HCl solution of preparation 2M, taking water as solvent, slowly drips the TiCl of 0.3mL wherein
3solution, normal temperature magnetic agitation 3-5min;
(b) the good titanium plate of pre-treatment in step (1) is put into the 100mL tetrafluoroethylene reactor that above-mentioned steps (a) solution is housed of being furnished with the outer courage of stainless steel, reactor is placed in to constant-temp. electronic baking oven, in 150 DEG C of hydro-thermal reaction 6h;
(c), after hydro-thermal reaction finishes, naturally cooling cooling, with deionized water lavage specimens product surface;
(d) dry at 60 DEG C to sample, in 500 DEG C of roasting 2h.
Test and show, not pretreated when titanium net surface, directly pass through hydrothermal growth TNRA, titanium net is also easy to completely be dissolved, and process high-temperature roasting is implanted one deck Rutile Type TiO at titanium net surface
2after particle (accompanying drawing 6(a)), the resistance to corrosion of titanium net improves greatly, the pattern of the TNRA of the roughness of the pre-treatment maturing temperature of titanium net on titanium net surface and generation has larger impact (accompanying drawing 5), and after different maturing temperature pre-processing titanium net, hydrothermal growth all generates single Rutile Type TNRA(accompanying drawing 6(b)).
Claims (10)
1. the pre-Rutile Type TiO that implants on a titanium base
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that step is as follows: (a) titanium metal substrate material surface is implanted Rutile Type TiO in advance
2film; (b) hydrothermal synthesis method is at the synthetic TNRA of crystal seed layer surface growth.
2. the pre-Rutile Type TiO that implants on titanium base according to claim 1
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, described titanium metal substrate material is selected from titanium plate or titanium net.
3. the pre-Rutile Type TiO that implants on titanium base according to claim 1
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, step (a) titanium metal substrate material surface is implanted Rutile Type TiO in advance
2the method of film is selected from TiCl
4pickling process or high-temperature roasting method; Described TiCl
4pickling process is: by titanium metal substrate material at TiCl
470 DEG C of constant temperature dipping 50min in the aqueous solution, then in 500 DEG C of roastings; Described high-temperature roasting method is: by the roasting under 600 DEG C of conditions of titanium metal substrate material.
4. the pre-Rutile Type TiO that implants on titanium base according to claim 3
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that described TiCl
4the TiCl that pickling process is used
4concentration of aqueous solution is 0.1-0.2M.
5. according to the pre-Rutile Type TiO that implants on the titanium base described in claim 3 or 4
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that described TiCl
4the TiCl that pickling process is used
4concentration of aqueous solution is 0.15M.
6. the pre-Rutile Type TiO that implants on titanium base according to claim 1
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, described step (b) is: adopt hydro-thermal synthesis process at Rutile Type TiO
2the synthetic TiO of film surface growth
2nano column array.
7. according to the pre-Rutile Type TiO that implants on the titanium base described in claim 1 or 6
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, it is characterized in that, described step (b) is: the titanium substrate that step (a) is disposed is put into and contained the titanium source that offers TNRA growth and the acid solution atmosphere of controlling titanium source hydrolysis rate and molecular balance, then under hot environment, carries out hydrothermal growth.
8. the pre-Rutile Type TiO that implants on titanium base according to claim 7
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, described titanium source is selected from tetrabutyl titanate or isopropyl titanate, TiCl
3.
9. the pre-Rutile Type TiO that implants on titanium base according to claim 7
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, the acid solution of the hydrolysis of described control titanium source and molecular balance is HCl solution.
10. the pre-Rutile Type TiO that implants on titanium base according to claim 7
2film is combined preparation TiO with Hydrothermal Synthesis
2the method of nano column array, is characterized in that, the growth media using in described water-heat process can add subcontrol material according to concrete material pattern and application request in growth media.
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Cited By (5)
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| CN104569077A (en) * | 2015-01-26 | 2015-04-29 | 湖北大学 | Titanium dioxide film hydrogen sensor and preparation method thereof |
| CN105214634A (en) * | 2015-10-28 | 2016-01-06 | 中国科学院合肥物质科学研究院 | Rutile Type TiOx nano grass mesh screen and its production and use |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN109817891A (en) * | 2019-03-06 | 2019-05-28 | 浙江工业大学 | A kind of method of titanium material surface in situ preparation nanostructure |
| CN110639485A (en) * | 2019-10-11 | 2020-01-03 | 南京大学昆山创新研究院 | Preparation of supported TiO by distributed deposition method2Method for preparing photocatalyst |
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