CN105540654A - Preparation method for multilayer TiO2 nanostructured array material - Google Patents
Preparation method for multilayer TiO2 nanostructured array material Download PDFInfo
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- CN105540654A CN105540654A CN201510917987.8A CN201510917987A CN105540654A CN 105540654 A CN105540654 A CN 105540654A CN 201510917987 A CN201510917987 A CN 201510917987A CN 105540654 A CN105540654 A CN 105540654A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention discloses a preparation method for a multilayer TiO2 nanostructured array material. The preparation method comprises the following steps: preparing a TiO2 nano-pore array film by using soft nano-imprinting technology; placing the obtained film in a hydrothermal reaction vessel for growth of the main trunk of TiO2 under certain conditions; etching the main trunk of TiO2; and growing TiO2 nanoparticles in an aqueous TiCl4 solution and then successively carrying out moistening, washing and drying. According to the invention, the soft nano-imprinting technology is employed to prepare the TiO2 nano-pore array film, so the specific surface area is increased and a seed layer for growing of the TiO2 nano-wire main trunk is provided at the same time; a wet chemical method is used for growth of the TiO2 main trunk, etching and growth of the nanoparticle successively, so low-cost, controllable and highly repeatable preparation of the multilayer TiO2 nanostructured array material is realized; and the prepared TiO2 nanostructured array material has a great specific surface area, inherits the characteristic of carrier transport of a nanostructured array and can substantially improve the performance of a device based on the TiO2 nanostructured array material.
Description
Technical field
The invention belongs to inorganic semiconductor nanometer material technical field, be specifically related to a kind of multi-level TiO
2the preparation method of nano-structure array material.
Background technology
TiO
2be the excellent wide bandgap semiconductor of a kind of environmental friendliness, stable in properties, PhotoelectrochemicalProperties Properties, be widely used in the fields such as solar cell, photochemical catalysis and gas sensor at present.Nano-structure array material refers to the material within the specific limits with the orderly stabilized nanoscale structure of certain arrangement rule.At present, TiO
2nano-structure array material is mainly divided into one dimension TiO
2nano-structure array and multi-level TiO
2nano-structure array.
Integrated TiO in the devices
2one dimension Nano structure array, as nano wire, nanotube and nanoporous etc., can provide upright electron transport passage, improves the collection effciency of current carrier; But the introducing of one dimension Nano structure array but reduces TiO
2specific surface area, affect the performance of device.
Multi-level TiO
2nano-structure array can take into account electric transmission and specific surface area two aspect performance, and they have shown good application prospect, such as: TiO
2" nanoforest ", namely at TiO
2the upper growth of nano-wire array " trunk " secondary " dendritic " nanostructure.Multi-level TiO at present
2the preparation method of nano-structure array mainly contains two classes: gas-liquid-solid (VLS) method and chemical liquid phase reaction.VLS method utilizes the metal nanoparticle being attached to elementary trunk side as the vegetative point of secondary nanostructure, can prepare racemosus nanostructure.But VLS method need at high temperature be carried out usually, expensive equipment and harsh synthesis condition limit multi-level TiO undoubtedly
2the controlled synthesis of nano-structure array.Chemical liquid phase reaction generally carries out in the aqueous solution or organic solution, has low temperature, the advantage such as cheap, a step or multistep can grow multi-level TiO
2nano-structure array.But adopt simple chemical liquid phase reaction, be difficult to accurately control reaction parameter, repeatability is poor, slightly mistake, easily obtains fine and close TiO
2film.
Summary of the invention
The object of this invention is to provide a kind of multi-level TiO
2the preparation method of nano-structure array material, solving existing preparation method needs by the equipment of costliness, synthesis condition is harsh and preparation process controllability is low problem.
The technical solution adopted in the present invention is, a kind of multi-level TiO
2the preparation method of nano-structure array material, specifically comprises the following steps:
Step 1, prepares polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) soft template;
Step 2, preparation TiO
2colloidal sol, utilizes nano impression to prepare TiO subsequently
2seed Layer;
Step 3, Hydrothermal Growth TiO
2trunk: remove ionized water and hydrochloric acid respectively, add butyl (tetra) titanate wherein after mixing, after stirring 10min, obtains mixed solution, is transferred to by mixed solution in hydrothermal reaction kettle; To step 2 gained TiO
2seed Layer carries out hydro-thermal reaction, after hydro-thermal reaction terminates, to have a shower reactor with tap water, takes out the deionized water rinse 3 ~ 5 times of hydro-thermal reaction product, finally uses nitrogen drying, for subsequent use;
Step 4, chemical etching method etching TiO
2trunk: the mixing solutions adding deionized water and hydrochloric acid in hydrothermal reaction kettle, carries out etching reaction to step 3 resulting materials; To have a shower reactor with tap water subsequently, take out the material deionized water rinse 3 ~ 5 times after etching processing, use nitrogen drying subsequently, for subsequent use;
Step 5, wet-chemical surface treatment growth TiO
2nano particle: the material product after step 4 gained etching processing is vertically placed on the TiCl that volumetric molar concentration is 40 ~ 100mM
4react 20 ~ 40min in the aqueous solution, water bath temperature is 60 ~ 80 DEG C; Wash 3 ~ 5 times with deionized water, subsequently with after nitrogen drying, obtain multi-level TiO
2nano-structure array material.
Feature of the present invention is also,
In step 1, the preparation process of PMMA/PDMS soft template is:
Step 1.1: adopt two-step electrochemical anonizing to be the H of 10% in mass concentration
3pO
4prepare anodised aluminium AAO template in solution, wherein: the first step voltage is 160V, temperature is 2 DEG C, and oxidization time is 5h; In second step, voltage is 160V, and temperature is 2 DEG C, and oxidization time is 1 ~ 5min; Subsequently gained AAO template is placed in the H that concentration is 5%
3pO
4in solution, at 45 DEG C of condition UR 30min, obtain the AAO template that aperture and pitch of holes are respectively 300nm and 450nm;
Step 1.2: be that the chlorobenzene solution of the PMMA of 10% is spin-coated in AAO template equably by mass concentration, spin coating parameters is 3000rpm × 30s; Subsequently template is placed in below 200Pa vacuum environment and is heated to 200 DEG C, be incubated 4h under 200 DEG C of conditions, be cooled to room temperature, recover normal pressure;
Step 1.3: spin coating PDMS in the template after step 1.2 processes, spin coating parameters is 500rpm × 10s, solidifies 50min under 90 DEG C of conditions; Namely PMMA/PDMS soft template is obtained after washing, drying.
In step 1.3, washing, drying process is: first utilize mass concentration to be Al under the NaOH solution removing PMMA layer of 10%
2o
3with Al layer, be dilute hydrochloric acid and the deionized water rinse 3 ~ 5 times successively of 1% subsequently by mass concentration, drying at room temperature.
In step 2, TiO
2the preparation process of colloidal sol is: be dissolved in by butyl (tetra) titanate in dehydrated alcohol, obtain solution A; Again water, dehydrated alcohol are mixed with nitric acid, obtain mixing solutions B; Stirred solution A being slowly added drop-wise in solution A by mixing solutions B subsequently, continues under room temperature to stir 24h, to obtain final product; Wherein, the mol ratio of butyl (tetra) titanate and nitric acid is 1:0.15, and the mol ratio of butyl (tetra) titanate and water is 1:1, and the mol ratio of butyl (tetra) titanate and ethanol is 1:15 ~ 30.
In step 2, TiO
2the preparation process of Seed Layer is: get appropriate TiO according to required film size
2colloidal sol is added drop-wise in substrate, subsequently the PMMA/PDMS soft template of step 1 gained is placed in TiO
2above colloidal sol, under 1 ~ 5MPa, 80 ~ 90 DEG C of conditions, impress 5 ~ 10h, after pressure release, peel off PDMS layer, then with acetonitrile, PMMA is dissolved, to obtain final product.
In step 3, in gained mixed solution, the volume ratio of deionized water and hydrochloric acid is 1:1, and the add-on of butyl (tetra) titanate is 1/60 ~ 1/30 of deionized water volume.
In step 3, hydrothermal reaction process is: first by step 2 gained TiO
2seed Layer is thermal treatment 30min at 500 DEG C, it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle subsequently, and angle of inclination is 68 ~ 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in the environment of 160 ~ 200 DEG C, reaction 50min ~ 240min.
In step 4, in mixing solutions, the amount ratio of deionized water and hydrochloric acid is volume ratio 1:0.5 ~ 2.
In step 4, etching reaction process is: be tiltedly placed in the Teflon liner of hydrothermal reaction kettle by through step 3 resulting materials, and angle of inclination is 68 ~ 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment, react 1 ~ 5h.
The invention has the beneficial effects as follows, the present invention utilizes soft nanometer embossing to prepare TiO
2nano-pore array thin film, adds specific surface area on the one hand, on the other hand again as growth TiO
2the Seed Layer of nano wire trunk; Wet chemistry method is utilized to carry out TiO successively on the seed layer subsequently
2the growth of trunk, etching and growing nano particle, achieve low cost, controlled, the multi-level TiO of high duplication
2the preparation of nano-structure array material; Obtained TiO
2nano-structure array material specific surface area is large, and takes into account the feature of nano-structure array carrier transport, can significantly improve based on TiO
2the performance of nano-structure array material devices.
Accompanying drawing explanation
Fig. 1 is a kind of multi-level TiO of the present invention
2the schema of the preparation method of nano-structure array material.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
A kind of multi-level TiO of the present invention
2the schema of the preparation method of nano-structure array material as shown in Figure 1;
Embodiment 1
Step 1, prepare polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) soft template:
Step 1.1: adopt two-step electrochemical anonizing to be the H of 10% in concentration
3pO
4prepare anodic oxidation aluminium formwork in solution, wherein: the first step voltage is 160V, temperature is 2 DEG C, and oxidization time is 5h; In second step, voltage is 160V, and temperature is 2 DEG C, and oxidization time is 1min; Subsequently gained anodic oxidation aluminium formwork is placed in the H that concentration is 5%
3pO
4in solution, at 45 DEG C of condition UR 30min, obtain aperture and pitch of holes and be respectively the certain AAO template of 300nm and 450nm, hole depth;
Step 1.2: be that the chlorobenzene solution of the PMMA (350kg/mol, AlfaAesar) of 10% is spin-coated in AAO template equably by mass concentration, spin coating parameters is 3000rpm × 30s; Subsequently template is placed in below 200Pa vacuum environment and is heated to 200 DEG C, be incubated 4h under 200 DEG C of conditions, be cooled to room temperature, recover normal pressure;
Step 1.3: spin coating PDMS (DowcorningSylgard184) in the template after step 1.2 processes, spin coating parameters is 500rpm × 10s, solidifies 50min under 90 DEG C of conditions; Be the NaOH solution cleaning of 10% by template concentration, the Al under removing PMMA layer
2o
3with Al layer, be the dilute hydrochloric acid rinse 3 times of 1% subsequently by quality solubility, with deionized water successively rinse 3 times, drying at room temperature, obtains PMMA/PDMS soft template.
Step 2, is dissolved in butyl (tetra) titanate in dehydrated alcohol, obtains solution A; Again water, dehydrated alcohol are mixed with nitric acid, obtain mixing solutions B; Stirred solution A being slowly added drop-wise in solution A by mixing solutions B subsequently, continues under room temperature to stir 24h, to obtain final product; Wherein, the mol ratio of butyl (tetra) titanate and nitric acid is 1:0.15, and the mol ratio of butyl (tetra) titanate and water is 1:1, and the mol ratio of butyl (tetra) titanate and ethanol is 1:15.
Appropriate TiO is got according to required film size
2colloidal sol is added drop-wise in substrate, subsequently the PMMA/PDMS soft template of step 1 gained is placed in TiO
2above colloidal sol, under 5MPa, 80 DEG C of conditions, impress 5h, after pressure release, peel off PDMS layer, then with acetonitrile, PMMA is dissolved, obtain TiO
2seed Layer;
Step 3, gets 15mL deionized water and 15mL hydrochloric acid (36.5 ~ 38wt%) respectively, adds 0.25ml butyl (tetra) titanate wherein after mixing, and after stirring 10min, obtains mixed solution, is transferred to by mixed solution in hydrothermal reaction kettle; By step 2 gained TiO
2seed Layer is thermal treatment 30min at 500 DEG C, as Seed Layer growth TiO
2nano wire trunk, is tiltedly placed in the Teflon liner of hydrothermal reaction kettle subsequently by it, angle of inclination is 68 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in the environment of 200 DEG C, after reaction 50min, to have a shower reactor with tap water, take out the deionized water rinse 3 times of hydro-thermal reaction product, finally use nitrogen drying, for subsequent use;
Step 4, adds deionized water in hydrothermal reaction kettle and hydrochloric acid volume ratio is the mixing solutions of 1:0.5, and tiltedly will be placed in the Teflon liner of hydrothermal reaction kettle through step 3 resulting materials, angle of inclination is 68 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment, react 1h; To have a shower reactor with tap water subsequently, take out the material deionized water rinse 3 times after etching processing, use nitrogen drying subsequently, for subsequent use;
Step 5, is vertically placed on the material product after step 4 gained etching processing the TiCl that volumetric molar concentration is 40mM
4react 40min in the aqueous solution, water bath temperature is 60 DEG C; With deionized water rinse 3 times, subsequently with after nitrogen drying, obtain multi-level TiO
2nano-structure array material.
Embodiment 2
Step 1, prepare polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) soft template:
Step 1.1: adopt two-step electrochemical anonizing to be the H of 10% in concentration
3pO
4prepare anodised aluminium (AAO) template in solution, wherein: the first step voltage is 160V, temperature is 2 DEG C, and oxidization time is 5h; In second step, voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5min; Subsequently gained AAO template is placed in the H that concentration is 5%
3pO
4in solution, at 45 DEG C of condition UR 30min, obtain aperture and pitch of holes and be respectively the certain AAO template of 300nm and 450nm, hole depth;
Step 1.2: be that the chlorobenzene solution of the PMMA (350kg/mol, AlfaAesar) of 10% is spin-coated in AAO template equably by mass concentration, spin coating parameters is 3000rpm × 30s; Subsequently template is placed in below 200Pa vacuum environment and is heated to 200 DEG C, be incubated 4h under 200 DEG C of conditions, be cooled to room temperature, recover normal pressure;
Step 1.3: spin coating PDMS (DowcorningSylgard184) in the template after step 1.2 processes, spin coating parameters is 500rpm × 10s, solidifies 50min under 90 DEG C of conditions; Be the NaOH solution cleaning of 10% by template mass concentration, the Al under removing PMMA layer
2o
3with Al layer, be dilute hydrochloric acid and the deionized water respectively rinse 5 times successively of 1% subsequently by quality solubility, drying at room temperature, obtains PMMA/PDMS soft template.
Step 2, is dissolved in butyl (tetra) titanate in dehydrated alcohol, obtains solution A; Again water, dehydrated alcohol are mixed with nitric acid, obtain mixing solutions B; Stirred solution A being slowly added drop-wise in solution A by mixing solutions B subsequently, continues under room temperature to stir 24h, to obtain final product; Wherein, the mol ratio of butyl (tetra) titanate and nitric acid is 1:0.15, and the mol ratio of butyl (tetra) titanate and water is 1:1, and the mol ratio of butyl (tetra) titanate and ethanol is 1:30.
Appropriate TiO is got according to required film size
2colloidal sol is added drop-wise in substrate, subsequently the PMMA/PDMS soft template of step 1 gained is placed in TiO
2above colloidal sol, under 1MPa, 80 DEG C of conditions, impress 10h, after pressure release, peel off PDMS layer, then with acetonitrile, PMMA is dissolved, obtain TiO
2seed Layer;
Step 3, gets 15mL deionized water and 15mL hydrochloric acid (36.5 ~ 38wt%) respectively, adds 0.5ml butyl (tetra) titanate wherein after mixing, and after stirring 10min, obtains mixed solution, is transferred to by mixed solution in hydrothermal reaction kettle; By step 2 gained TiO
2seed Layer is thermal treatment 30min at 500 DEG C, it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle subsequently, and angle of inclination is 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in the environment of 160 DEG C, after reaction 240min, to have a shower reactor with tap water, take out the deionized water rinse 5 times of hydro-thermal reaction product, finally use nitrogen drying, for subsequent use;
Step 4, adds deionized water in hydrothermal reaction kettle and hydrochloric acid volume ratio is the mixing solutions of 1:2, and tiltedly will be placed in the Teflon liner of hydrothermal reaction kettle through step 3 resulting materials, angle of inclination is 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment, react 5h; To have a shower reactor with tap water subsequently, take out the material deionized water rinse 5 times after etching processing, use nitrogen drying subsequently, for subsequent use;
Step 5, is vertically placed on the material product after step 4 gained etching processing the TiCl that volumetric molar concentration is 100mM
4react 20min in the aqueous solution, water bath temperature is 80 DEG C; Wash 5 times with deionized water subsequently, subsequently with after nitrogen drying, obtain multi-level TiO
2nano-structure array material.
Embodiment 3
Step 1, prepare polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) soft template:
Step 1.1: adopt two-step electrochemical anonizing to be the H of 10% in concentration
3pO
4prepare anodised aluminium (AAO) template in solution, wherein: the first step voltage is 160V, temperature is 2 DEG C, and oxidization time is 5h; In second step, voltage is 160V, and temperature is 2 DEG C, and oxidization time is 3min; Subsequently gained AAO template is placed in the H that concentration is 5%
3pO
4in solution, at 45 DEG C of condition UR 30min, obtain aperture and pitch of holes and be respectively the certain AAO template of 300nm and 450nm, hole depth;
Step 1.2: be that the chlorobenzene solution of the PMMA (350kg/mol, AlfaAesar) of 10% is spin-coated in AAO template equably by mass concentration, spin coating parameters is 3000rpm × 30s; Subsequently template is placed in below 200Pa vacuum environment and is heated to 200 DEG C, be incubated 4h under 200 DEG C of conditions, be cooled to room temperature, recover normal pressure;
Step 1.3: spin coating PDMS (DowcorningSylgard184) in the template after step 1.2 processes, spin coating parameters is 500rpm × 10s, solidifies 50min under 90 DEG C of conditions; Be the NaOH solution cleaning of 10% by template mass concentration, the Al under removing PMMA layer
2o
3with Al layer, be dilute hydrochloric acid and the deionized water respectively rinse 4 times successively of 1% subsequently by mass concentration, drying at room temperature, obtains PMMA/PDMS soft template.
Step 2, is dissolved in butyl (tetra) titanate in dehydrated alcohol, obtains solution A; Again water, dehydrated alcohol are mixed with nitric acid, obtain mixing solutions B; Stirred solution A being slowly added drop-wise in solution A by mixing solutions B subsequently, continues under room temperature to stir 24h, to obtain final product; Wherein, the mol ratio of butyl (tetra) titanate and nitric acid is 1:0.15, and the mol ratio of butyl (tetra) titanate and water is 1:1, and the mol ratio of butyl (tetra) titanate and ethanol is 1:20.
Appropriate TiO is got according to required film size
2colloidal sol is added drop-wise in substrate, subsequently the PMMA/PDMS soft template of step 1 gained is placed in TiO
2above colloidal sol, under 3MPa, 85 DEG C of conditions, impress 7h, after pressure release, peel off PDMS layer, then with acetonitrile, PMMA is dissolved, obtain TiO
2seed Layer;
Step 3, gets 15mL deionized water and 15mL hydrochloric acid (36.5 ~ 38wt%) respectively, adds 0.35ml butyl (tetra) titanate wherein after mixing, and after stirring 10min, obtains mixed solution, is transferred to by mixed solution in hydrothermal reaction kettle; By step 2 gained TiO
2seed Layer is thermal treatment 30min at 500 DEG C, it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle subsequently, and angle of inclination is 70 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in the environment of 180 DEG C, after reaction 120min, to have a shower reactor with tap water, take out the deionized water rinse 4 times of hydro-thermal reaction product, finally use nitrogen drying, for subsequent use;
Step 4, adds deionized water in hydrothermal reaction kettle and hydrochloric acid volume ratio is the mixing solutions of 1:1, and tiltedly will be placed in the Teflon liner of hydrothermal reaction kettle through step 3 resulting materials, angle of inclination is 70 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment, react 3h; To have a shower reactor with tap water subsequently, take out the material deionized water rinse 4 times after etching processing, use nitrogen drying subsequently, for subsequent use;
Step 5, is vertically placed on the material product after step 4 gained etching processing the TiCl that volumetric molar concentration is 70mM
4react 30min in the aqueous solution, water bath temperature is 70 DEG C; Wash 4 times with deionized water subsequently, subsequently with after nitrogen drying, obtain multi-level TiO
2nano-structure array material.
Of the present inventionly prepare multi-level TiO in conjunction with soft nano impression and wet chemistry method
2the method of nano-structure array has low cost, controlled and repeated advantages of higher, and the nanostructure of preparation has great specific surface area, and keeps the shape characteristic of vertically arrangement, is expected to significantly improve based on TiO
2the classes of semiconductors device performance of nano-structure array, as: solar cell, photocatalysis hydrogen production gas, gas sensor etc.
Utilize the multi-level TiO of the embodiment of the present invention 2 gained
2dye sensitization solar battery (A) prepared by nano-structure array material and nano-wire array dye sensitization solar battery (B) performance comparison are in table 1:
Table 1
As can be seen from Table 1, the multi-level TiO of the inventive method gained is utilized
2the short-circuit current of dye sensitization solar battery prepared by nano-structure array material and packing factor comparatively TiO
2nano-wire array dye sensitization solar battery is all improved largely, and photoelectric transformation efficiency significantly improves to 3.7% by 1.3%.
The research in past finds: the TiO prepared by soft nano impression
2the obvious comparatively plane TiO of solar cell of nanohole array assembling
2thin-film solar cells efficiency is high, and this ascribes the specific surface area of increase and the carrier transport ability of enhancing to; And wet chemistry method etching TiO
2nano-wire array also can increase the specific surface area of nano wire and improve charge collection efficiency, the final efficiency improving dye sensitization solar battery; TiCl
4surface treatment TiO
2the approach that the method that electrode obtains nano particle is also proved to be in the past as effectively increasing specific surface area.The present invention is ingenious at soft nanometer embossing and wet chemistry method, provides one and prepares multi-level TiO
2the approach of nano-structure array material, increases TiO simultaneously
2specific surface area and the feature keeping nano-structure array material carrier to transport, be expected to be applied to the fields such as solar cell, photocatalysis hydrogen production gas and gas sensor.
Claims (9)
1. a multi-level TiO
2the preparation method of nano-structure array material, is characterized in that, specifically comprises the following steps:
Step 1, prepares polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) soft template;
Step 2, preparation TiO
2colloidal sol, utilizes nano impression to prepare TiO subsequently
2seed Layer;
Step 3, Hydrothermal Growth TiO
2trunk: remove ionized water and hydrochloric acid respectively, add butyl (tetra) titanate wherein after mixing, after stirring 10min, obtains mixed solution, is transferred to by mixed solution in hydrothermal reaction kettle; To step 2 gained TiO
2seed Layer carries out hydro-thermal reaction, after hydro-thermal reaction terminates, to have a shower reactor with tap water, takes out the deionized water rinse 3 ~ 5 times of hydro-thermal reaction product, finally uses nitrogen drying, for subsequent use;
Step 4, chemical etching method etching TiO
2trunk: the mixing solutions adding deionized water and hydrochloric acid in hydrothermal reaction kettle, carries out etching reaction to step 3 resulting materials; To have a shower reactor with tap water subsequently, take out the material deionized water rinse 3 ~ 5 times after etching processing, use nitrogen drying subsequently, for subsequent use;
Step 5, wet-chemical surface treatment growth TiO
2nano particle: the material product after step 4 gained etching processing is vertically placed on the TiCl that volumetric molar concentration is 40 ~ 100mM
4react 20 ~ 40min in the aqueous solution, water bath temperature is 60 ~ 80 DEG C; Wash 3 ~ 5 times with deionized water, subsequently with after nitrogen drying, obtain multi-level TiO
2nano-structure array material.
2. the multi-level TiO of one according to claim 1
2the preparation method of nano-structure array material, is characterized in that, in step 1, the preparation process of PMMA/PDMS soft template is:
Step 1.1: adopt two-step electrochemical anonizing to be the H of 10% in mass concentration
3pO
4prepare anodised aluminium AAO template in solution, wherein: the first step voltage is 160V, temperature is 2 DEG C, and oxidization time is 5h; In second step, voltage is 160V, and temperature is 2 DEG C, and oxidization time is 1 ~ 5min; Subsequently gained AAO template is placed in the H that concentration is 5%
3pO
4in solution, at 45 DEG C of condition UR 30min, obtain the AAO template that aperture and pitch of holes are respectively 300nm and 450nm;
Step 1.2: be that the chlorobenzene solution of the PMMA of 10% is spin-coated in AAO template equably by mass concentration, spin coating parameters is 3000rpm × 30s; Subsequently template is placed in below 200Pa vacuum environment and is heated to 200 DEG C, be incubated 4h under 200 DEG C of conditions, be cooled to room temperature, recover normal pressure;
Step 1.3: spin coating PDMS in the template after step 1.2 processes, spin coating parameters is 500rpm × 10s, solidifies 50min under 90 DEG C of conditions; Namely PMMA/PDMS soft template is obtained after washing, drying.
3. the multi-level TiO of one according to claim 2
2the preparation method of nano-structure array material, is characterized in that, in step 1.3, washing, drying process is: first utilize mass concentration to be Al under the NaOH solution removing PMMA layer of 10%
2o
3with Al layer, be dilute hydrochloric acid and the deionized water rinse 3 ~ 5 times successively of 1% subsequently by mass concentration, drying at room temperature.
4. the multi-level TiO of one according to claim 1
2the preparation method of nano-structure array material, is characterized in that, in step 2, and TiO
2the preparation process of colloidal sol is: be dissolved in by butyl (tetra) titanate in dehydrated alcohol, obtain solution A; Again water, dehydrated alcohol are mixed with nitric acid, obtain mixing solutions B; Stirred solution A being slowly added drop-wise in solution A by mixing solutions B subsequently, continues under room temperature to stir 24h, to obtain final product; Wherein, the mol ratio of butyl (tetra) titanate and nitric acid is 1:0.15, and the mol ratio of butyl (tetra) titanate and water is 1:1, and the mol ratio of butyl (tetra) titanate and ethanol is 1:15 ~ 30.
5. the multi-level TiO of one according to claim 4
2the preparation method of nano-structure array material, is characterized in that, in step 2, and TiO
2the preparation process of Seed Layer is: get appropriate TiO according to required film size
2colloidal sol is added drop-wise in substrate, subsequently the PMMA/PDMS soft template of step 1 gained is placed in TiO
2above colloidal sol, under 1 ~ 5MPa, 80 ~ 90 DEG C of conditions, impress 5 ~ 10h, after pressure release, peel off PDMS layer, then with acetonitrile, PMMA is dissolved, to obtain final product.
6. the multi-level TiO of one according to claim 1
2the preparation method of nano-structure array material, is characterized in that, in step 3, in gained mixed solution, the volume ratio of deionized water and hydrochloric acid is 1:1, and the add-on of butyl (tetra) titanate is 1/60 ~ 1/30 of deionized water volume.
7. the multi-level TiO of one according to claim 6
2the preparation method of nano-structure array material, is characterized in that, in step 3, hydrothermal reaction process is: first by step 2 gained TiO
2seed Layer is thermal treatment 30min at 500 DEG C, it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle subsequently, and angle of inclination is 68 ~ 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in the environment of 160 ~ 200 DEG C, reaction 50min ~ 240min.
8. the multi-level TiO of one according to claim 1
2the preparation method of nano-structure array material, is characterized in that, in step 4, in mixing solutions, the amount ratio of deionized water and hydrochloric acid is volume ratio 1:0.5 ~ 2.
9. the multi-level TiO of one according to claim 1
2the preparation method of nano-structure array material, is characterized in that, in step 4, etching reaction process is: be tiltedly placed in the Teflon liner of hydrothermal reaction kettle by through step 3 resulting materials, and angle of inclination is 68 ~ 72 °, TiO
2face down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment, react 1 ~ 5h.
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| CN105761943A (en) * | 2016-04-14 | 2016-07-13 | 上海大学 | Nickel tin alloy nano-pore array and preparation method thereof |
| CN106179316A (en) * | 2016-07-09 | 2016-12-07 | 常州大学 | A kind of preparation method and application of titanate nanotube array |
| CN106773529A (en) * | 2016-12-02 | 2017-05-31 | 江南大学 | A kind of method that utilization room temperature transfer stamping technique prepares the titanium dioxide pattern of noresidue layer |
| CN107029691A (en) * | 2017-04-28 | 2017-08-11 | 华中科技大学 | A kind of preparation method and applications of air type light-catalyzed reaction film |
| CN108117833A (en) * | 2017-12-28 | 2018-06-05 | 浙江大学 | Titanium dioxide/polymer composite dielectric hydrophobic material and preparation method |
| CN108409155A (en) * | 2018-05-31 | 2018-08-17 | 厦门大学 | The preparation method of silica nanometer array on a kind of glass substrate |
| 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 |
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| CN105761943B (en) * | 2016-04-14 | 2018-07-10 | 上海大学 | Nickeltin nanohole array and preparation method thereof |
| CN106179316A (en) * | 2016-07-09 | 2016-12-07 | 常州大学 | A kind of preparation method and application of titanate nanotube array |
| CN106179316B (en) * | 2016-07-09 | 2018-07-17 | 常州大学 | A kind of preparation method and application of titanate nanotube array |
| CN106773529A (en) * | 2016-12-02 | 2017-05-31 | 江南大学 | A kind of method that utilization room temperature transfer stamping technique prepares the titanium dioxide pattern of noresidue layer |
| CN106773529B (en) * | 2016-12-02 | 2019-12-13 | 江南大学 | Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology |
| CN107029691A (en) * | 2017-04-28 | 2017-08-11 | 华中科技大学 | A kind of preparation method and applications of air type light-catalyzed reaction film |
| CN107029691B (en) * | 2017-04-28 | 2020-02-21 | 华中科技大学 | Preparation method and application of air type photocatalytic reaction film |
| CN108117833A (en) * | 2017-12-28 | 2018-06-05 | 浙江大学 | Titanium dioxide/polymer composite dielectric hydrophobic material and preparation method |
| CN108409155A (en) * | 2018-05-31 | 2018-08-17 | 厦门大学 | The preparation method of silica nanometer array on a kind of glass substrate |
| 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 |
| CN109817891B (en) * | 2019-03-06 | 2020-09-18 | 浙江工业大学 | Method for preparing nano structure on surface of titanium material in situ |
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