CN105883715B - With high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes and its construction method - Google Patents
With high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes and its construction method Download PDFInfo
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Abstract
The present invention relates to one kind to have high degree of periodicity Ti Au alloy nanotube photonic crystal electrodes and its construction method, and photonic crystal electrode is by TiO2With Uniform Doped in TiO2Au compositions in lattice are divided into two layers up and down, wherein, upper strata is nano-pore, and lower floor is nano-tube array；Construction method is specific as follows：(1) it is anode by pretreated Ti Au alloy sheets, platinum plate electrode is used as to electrode, and using the ethylene glycol solution of fluoride and water as anodization electrolyte solution, water bath with thermostatic control, anodic oxidation obtains being attached with the Ti Au alloy sheets of nanotube；(2) after the Ti Au alloy sheets for being attached with nanotube are ultrasonically treated, continue water bath with thermostatic control, anodic oxidation obtains electrode sample；(3) electrode sample is cleaned, infiltrated in ethanol, it is dry, it is heat-treated to get to purpose product Ti Au alloy nanotube photonic crystal electrodes.Compared with prior art, the PhotoelectrocatalytiPerformance Performance of photonic crystal electrode of the invention is good, and preparation process is simple, at low cost, application value height etc..
Description
Technical field
The present invention relates to a kind of construction methods of electrode, more particularly, to one kind there is high degree of periodicity Ti-Au alloys to receive
Mitron photonic crystal electrode and its construction method.
Background technology
The coupling of radiation field and material is the most basic form of nature dynamic process, and photonic crystal is exactly a kind of
It can control its internal radiation pattern and external radiation field that there is the artificial crystal material of response.This crystalline material most root
This feature is exactly with forbidden photon band --- and photon band gap also enables photonic crystal just because of the presence of photon band gap
The photon of specific frequency is blocked, so as to be captured.At present, photonic crystal has extensively in opto-electronic device and the communications field
General and important application, this kind of typical application include high efficient LED, photonic crystal optical waveguides, photonic crystal light
Fibre, photon crystal laser, high-performance speculum and high emissivity small microwave antenna etc..The ordered porous property of photonic crystal and
The controllability of photon band gap can be used for making photonic crystal resonant cavity, photon crystal polarization piece and various types of biographies
Sensor.Particularly, since its unique visible light absorption makes it also be applied in photoelectrocatalysis field.
TiO2Due to having many advantages, such as that good light stability, nontoxic, be easy to get has obtained extensive research in photocatalysis field, especially
It is one-dimensional orderly TiO2Nano-tube array (TiO2NT), there are larger specific surface area and the photoelectric properties stablized and receive
Concern.But TiO2Due to the energy gap with 3.2eV, it is only capable of absorbing the ultraviolet light for accounting for about sunlight 4%, to solar energy
Utilization rate it is very low；Meanwhile light induced electron and hole are easily compound, reduce the utilization rate to light induced electron.In order to improve
TiO2Photocatalytic activity and the utilization rate to sunlight, researchers pass through to TiO2NT carries out the transformation of space structure
To obtaining with visible light-responded electrode, such as by TiO2NT and orderly TiO2Nano net combines and constructs out photonic crystal
Structure realizes the absorption of visible light region.Although the response of visible ray is obtained to a certain extent, with regard to opto-electronic conversion
For whether this evaluation electrode material of efficiency has the index of efficient photoelectricity treater catalytic performance, efficiency is still than relatively low.Therefore,
Further promote TiO2The visible light-responded and photoelectric conversion efficiency of electrode is very necessary.
Noble metal Au is due to local surface plasma resonance effect and with certain visible light-responded, and its size
Again inseparable with the size of Au, on nanoscale, Au nano particles are smaller, more easily given play to surface that itself has etc.
Ion resonance effect obtains higher photocatalytic activity.The surface plasma resonance that noble metal Au has is imitated in researcher's design
It should be with TiO2Anti-light corrosivity is combined the light for the high stability for constructing the high visible for providing high degree of periodicity structure response
Electro catalytic electrode material.The mostly of previous literature report are to be repaiied gold nano grain using electrochemical deposition or the method for photo-reduction
Adorn TiO2On nanotube, but obtained Au nano particles are often unevenly distributed and size differs, it is easy to make
The phenomenon that being blocked into nanometer nozzle artificially reduces the absorbing properties of electrode, influences its photocatalysis effect.
Invention content
The purpose of the invention is to overcome TiO2Visible ray is not responding to NT and conventional Ti O2Existing for NT carrying methods
Defect provides a kind of bimetallic and synchronizes the Ti-Au that anodization acquisition has the high degree of periodicity layering of excellent PhotoelectrocatalytiPerformance Performance
Alloy nanotube photonic crystal electrode and its construction method.
The purpose of the present invention can be achieved through the following technical solutions：
One kind has high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes, by TiO2With Uniform Doped in TiO2It is brilliant
Au compositions in lattice, which is characterized in that the crystalline electrode is formed by upper and lower two layers, wherein, upper strata is nano-pore composition
Stratum reticulare, lower floor are nano-tube array.The direction in the hole being oriented parallel in nano-tube array in the hole in stratum reticulare.
The nano-pore is the hexagon nano-pore structure in periodic distribution.
The average diameter of the nano-pore is 100-200nm, pore wall thickness 20-40nm.
Construction method with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes, includes the following steps：
(1) it is anode by pretreated Ti-Au alloy sheets, platinum plate electrode is used as to electrode, using fluoride and water
Ethylene glycol solution as anodization electrolyte solution, under water bath with thermostatic control effect, anodic oxidation obtains being attached with nanotube
Ti-Au alloy sheets；
(2) step (1) the Ti-Au alloy sheets obtained for being attached with nanotube are ultrasonically treated to the nanotube on removal surface,
By treated, Ti-Au alloy sheets continue under water bath with thermostatic control effect again, and anodic oxidation obtains electrode sample；
(3) electrode sample that step (2) obtains is cleaned, infiltrated in ethanol, it is dry, it is heat-treated and is produced to get to purpose
Object Ti-Au alloy nanotube photonic crystal electrodes.
Step (1) Anodic is 0.5-1.5cm with the spacing to electrode.
Fluorochemical is HF, a concentration of 0.1-0.3molL in ethylene glycol solution in step (1)-1；
A concentration of 0.8~1.2molL of the water in ethylene glycol solution-1。
Pretreated Ti-Au alloy sheets refer in step (1)：Ti-Au alloy sheets containing 0.02-0.4at%Au are polished
To the uniform and smooth such as minute surface in surface, then it is cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively, is finally placed in nitrogen
It is dry under gas atmosphere.
In step (1)：
The temperature of water bath with thermostatic control is 5-15 DEG C；
The process conditions of anodic oxidation are：2~4h of anodic oxidation under the conditions of 90~130V constant voltages.
In step (2)：
The temperature of water bath with thermostatic control is 5-15 DEG C；
The process conditions of anodic oxidation are：5~30min of anodic oxidation under the conditions of 90~130V constant voltages.
In step (3)：
Process of thermal treatment condition is：In air atmosphere, it is permanent after being warming up to 400-500 DEG C with the rate of 3-5 DEG C/min
Temperature calcining 0.5-2h, then room temperature is cooled to the rate of 3-5 DEG C/min.
For a conventional step anodizing process can only obtain simple one-dimensional nano structure, two steps of the invention
Ultrasonic behavior in anodizing process can effectively remove the nanotube obtained by first step anodizing process and in alloy sheets
There are the hexagon gravure of high-sequential, these gravures can be as the template of second step anodization, so as to effectively keep away on surface
Exempt from the random growth of anodization nanotube.Thus obtained advanced nano TiO2-Au NTPC periodically divide due to having
Layer nanostructured, can capture visible ray as layer of photonic crystals, be established to show higher PhotoelectrocatalytiPerformance Performance
Basis.
The present invention is by the TiO with high degree of periodicity2Photonic crystal and the Au nanometers with surface plasma resonance effect
Particle is combined, and the nano-particle modified TiO of the Au adulterated in situ are prepared for the first time2Nanotube photonic crystal (TiO2-Au
NTPC) electrode material.
Compared with prior art, the present invention has the following advantages：
(1) substrate that the present invention uses realizes the Uniform Doped of Ti and Au on atom level for Ti-Au alloys, and
And after alloy carries out anodization and the calcining of air high temperature, Au simple substance is formd in TiO2High uniformity adulterates in lattice
Structure.Au and TiO2The interface of contact will appear electronics aggregation, form Schottky barrier.Under DC Electric Field, photoproduction electricity
The transmission of son can be quicker, and can efficiently reduce the recombination rate of photo-generate electron-hole so that Ti-Au alloy nanos
The photo-quantum efficiency of pipe photonic crystal electrode significantly improves, and photoelectric catalytically active is remarkably reinforced.
(2) the alloy nanotube photonic crystal electrode that the present invention is prepared is made of nano-pore and nano-tube array,
The nano-pore structure on upper strata can capture visible ray as layer of photonic crystals, improve the absorbing properties and then rush of electrode
Into the PhotoelectrocatalytiPerformance Performance for promoting electrode.
(3) with conventional Ti O2The TiO being prepared in NT and Ti metallic substrates2NTPC is compared, and the present invention is prepared
High degree of periodicity layering Ti-Au alloy nanotube photonic crystals electrode have stronger visible absorption, anti-light corrosivity,
Faster electron transmission performance and excellent photoelectric catalytically active, this alloy nanotube photon crystal material is in visible photoelectricity
There is certain novelty and usability in catalytic field.
(4) the preparation method step of the Ti-Au alloy nanotube photonic crystals of high degree of periodicity of the present invention is simple, and operation is easy
Row, the requirement to reaction temperature and raw material is easy to implement, and prepares and divide in photocatalysis, photoelectrocatalysis, novel energy
There is potential application value in the fields such as analysis detection.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the electrode material that the embodiment of the present invention 1 is constructed；
Fig. 2 is the photocurrent response figure of the embodiment of the present invention 1, embodiment 2 and embodiment 3；
Fig. 3 is the photocurrent response figure of the embodiment of the present invention 1, embodiment 4, embodiment 5 and embodiment 6.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Before anodization, by Ti0.2Au (0.2at%Au) alloy sheets successively with 180 mesh, 320 mesh, 600 mesh and metallographic sand
Paper is polished, and makes its surface uniform and smooth and bright like a mirror face, and then each ultrasound is clear in acetone, ethyl alcohol, isopropanol and distilled water successively
15min is washed, is finally dried in a nitrogen atmosphere.It is anode by pretreated Ti-Au alloy sheets under 10 DEG C of waters bath with thermostatic control,
Platinum plate electrode is used as to electrode, electrode spacing 1cm, using containing 0.2molL-1HF and 1molL-1H2The ethylene glycol of O
Solution is as anodization electrolyte solution, under 10 DEG C of waters bath with thermostatic control effects, the anodic oxidation 3h under the conditions of 120V constant voltages, then
The nanotube being prepared is ultrasonically treated in deionized water, nanotube is removed from Ti-Au alloys plate surface, then will
Ti-Au alloy sheets that treated are then in the case where 10 DEG C of waters bath with thermostatic control act on, the anodic oxidation 10min under the conditions of 120V constant voltages.
After treating two step anodizing process, after obtained electrode is cleaned with distilled water, 1h is infiltrated in ethanol, is then followed by nitrogen
It is dry under gas atmosphere, it is finally placed in tube furnace and is heat-treated in air atmosphere, is warming up to the heating rate of 5 DEG C/min
After 450 DEG C, the calcining at constant temperature 1h at 450 DEG C is finally cooled to room temperature with the rate of temperature fall of 5 DEG C/min, finally obtains TiO2-Au
NTPC electrode materials.
Fig. 1 is the scanning electron microscope (SEM) photograph for the electrode material that the embodiment of the present invention 1 is constructed, it can be seen that electrode is receiving by upper strata
The layering nanostructured of the nanotube composition of metre hole/lower floor, hexagon nano-pore structure of the upper strata for high degree of periodicity, diameter
Mean size is about 150nm, and pore wall thickness is about 30nm.
Embodiment 2：
The pretreatment of Ti-Au alloy sheets and anodization electrolyte solution are the same as embodiment 1.In the case where 10 DEG C of waters bath with thermostatic control act on,
The nanotube being prepared, is then ultrasonically treated by the anodic oxidation 3h under the conditions of 120V constant voltages in deionized water,
Nanotube is removed from Ti-Au alloys plate surface, then Ti-Au alloy sheets are then acted in 10 DEG C of waters bath with thermostatic control by treated
Under, the anodic oxidation 20min under the conditions of 120V constant voltages.After treating two step anodizing process, obtained electrode is distilled
Water cleaning after, infiltrate 1h in ethanol, be then followed by drying in a nitrogen atmosphere, be finally placed in tube furnace in air atmosphere into
Row heat treatment, after being warming up to 450 DEG C with the heating rate of 5 DEG C/min, the calcining at constant temperature 1h at 450 DEG C, finally with 5 DEG C/min's
Rate of temperature fall is cooled to room temperature, finally obtains TiO2- Au NTPC electrode materials.
Embodiment 3：
The pretreatment of Ti-Au alloy sheets and anodization electrolyte solution are the same as embodiment 1.In the case where 10 DEG C of waters bath with thermostatic control act on,
The nanotube being prepared, is then ultrasonically treated by the anodic oxidation 3h under the conditions of 120V constant voltages in deionized water,
Nanotube is removed from Ti-Au alloys plate surface, then Ti-Au alloy sheets are then acted in 10 DEG C of waters bath with thermostatic control by treated
Under, the anodic oxidation 30min under the conditions of 120V constant voltages.After treating two step anodizing process, obtained electrode is distilled
Water cleaning after, infiltrate 1h in ethanol, be then followed by drying in a nitrogen atmosphere, be finally placed in tube furnace in air atmosphere into
Row heat treatment, after being warming up to 450 DEG C with the heating rate of 5 DEG C/min, the calcining at constant temperature 1h at 450 DEG C, finally with 5 DEG C/min's
Rate of temperature fall is cooled to room temperature, finally obtains TiO2- Au NTPC electrode materials.
Fig. 2 is the photocurrent response figure of the embodiment of the present invention 1, embodiment 2 and embodiment 3, and the chart is bright with second step
The increase of anodising time, TiO2The photocurrent response of-Au NTPC electrode materials continuously decreases, and photoelectric catalytically active gradually subtracts
It is weak.
Embodiment 4：
The pretreatment of Ti-Au alloy sheets and anodization electrolyte solution are the same as embodiment 1.By Ti-Au alloy sheets in 10 DEG C of perseverances
Under tepidarium effect, in 120V constant voltage condition next step anodic oxidation 3h, then it is heat-treated.At heat after one step anodization
It manages same as Example 1, TiO is prepared2-Au NT。
Embodiment 5：
The pretreatment of Ti metallic plates is the same as embodiment 1.It is sun by pretreated Ti metallic plates under 10 DEG C of waters bath with thermostatic control
Pole, platinum plate electrode are used as to electrode, electrode spacing 1cm, using containing 0.25wt%NH4F and 1vol%H2The ethylene glycol solution of O
As anodization electrolyte solution, under magnetic agitation, the anodic oxidation 3h under the conditions of 30V constant voltages steams obtained electrode
After distilled water cleaning, 1h is infiltrated in ethanol, is then followed by drying in a nitrogen atmosphere, finally be placed in tube furnace in oxygen atmosphere
It is heat-treated, after being warming up to 500 DEG C with the heating rate of 5 DEG C/min, the calcining at constant temperature 3h at 500 DEG C, finally with 5 DEG C/min
Rate of temperature fall be cooled to room temperature, finally obtain TiO2NT。
Embodiment 6：
The pretreatment of Ti metallic plates is the same as embodiment 1.It is sun by pretreated Ti metallic plates under 10 DEG C of waters bath with thermostatic control
Pole, platinum plate electrode are used as to electrode, electrode spacing 1cm, using containing 0.25wt%NH4F and 1vol%H2The ethylene glycol solution of O
As anodization electrolyte solution, under magnetic agitation, the anodic oxidation 3h under the conditions of 30V constant voltages will then be prepared
Nanotube is ultrasonically treated in deionized water, and nanotube is removed from Ti plate surfaces, then Ti plates are permanent in 30V by treated
Voltage conditions anodic oxygen 10min.After treating two step anodizing process, after obtained electrode is cleaned with distilled water,
1h is infiltrated in ethyl alcohol, is then followed by drying in a nitrogen atmosphere, is finally placed in tube furnace and is heat-treated in oxygen atmosphere, with
After the heating rate of 5 DEG C/min is warming up to 500 DEG C, the calcining at constant temperature 3h at 500 DEG C is finally dropped with the rate of temperature fall of 5 DEG C/min
It warms to room temperature, finally obtains TiO2NTPC。
Fig. 3 is the photocurrent response figure of the embodiment of the present invention 1, embodiment 4, embodiment 5 and embodiment 6, the chart it is bright
Under the conditions of visible ray shines, TiO2The photocurrent response of-Au NTPC is apparently higher than TiO2NT and TiO2NTPC electrodes, this is because
TiO2Au in-Au NTPC has played surface plasma resonance effect under visible ray photograph, under the action of extra electric field,
The photoelectron of generation can be along Au and TiO2The Schottky barrier that contact interface is formed reaches TiO2Conduction band on, substantially increase
To the utilization ratio of light, so as to significantly improve visible light-responded current density.In addition, TiO2The photoelectric current of-Au NTPC is rung
It should be also higher than TiO2- Au NT electrodes, this is because TiO2The nano-pore of high-sequential can be used as photon in-Au NTPC structures
Crystal layer increases the capture to visible ray, and then can promote the photocurrent response of electrode material.
Embodiment 7
Before anodization, by Ti-Au (0.02at%Au) alloy sheets successively with 180 mesh, 320 mesh, 600 mesh and abrasive paper for metallograph
Polishing, makes its surface uniform and smooth and bright like a mirror face, is then respectively cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively
5min is finally dried in a nitrogen atmosphere.Under 5 DEG C of waters bath with thermostatic control, by pretreated Ti-Au alloy sheets be anode, platinized platinum
Electrode is used as to electrode, electrode spacing 1.5cm, using containing 0.3molL-1HF and 0.8molL-1H2The ethylene glycol of O
Solution is as anodization electrolyte solution, under 5 DEG C of waters bath with thermostatic control effects, the anodic oxidation 4h under the conditions of 110V constant voltages, then
The nanotube being prepared is ultrasonically treated in deionized water, nanotube is removed from Ti-Au alloys plate surface, then will
Ti-Au alloy sheets that treated are then in the case where 5 DEG C of waters bath with thermostatic control act on, the anodic oxidation 5min under the conditions of 110V constant voltages.It treats
After two step anodizing process, after obtained electrode is cleaned with distilled water, 0.5h is infiltrated in ethanol, is then followed by nitrogen
It is dry under gas atmosphere, it is finally placed in tube furnace and is heat-treated in air atmosphere, is warming up to the heating rate of 4 DEG C/min
After 400 DEG C, the calcining at constant temperature 2h at 400 DEG C is finally cooled to room temperature with the rate of temperature fall of 4 DEG C/min, finally obtains TiO2-Au
NTPC electrode materials.
Embodiment 8
Before anodization, by Ti-Au (0.4at%Au) alloy sheets successively with 180 mesh, 320 mesh, 600 mesh and abrasive paper for metallograph
Polishing, makes its surface uniform and smooth and bright like a mirror face, is then respectively cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively
30min is finally dried in a nitrogen atmosphere.Under 15 DEG C of waters bath with thermostatic control, by pretreated Ti-Au alloy sheets be anode, platinum
Plate electrode is used as to electrode, electrode spacing 0.5cm, using containing 0.1molL-1HF and 1.2molL-1H2The second two of O
Alcoholic solution is as anodization electrolyte solution, and under 15 DEG C of water bath with thermostatic control effects, anodic oxidation 2h, connects under the conditions of 130V constant voltages
It the nanotube that will be prepared to be ultrasonically treated in deionized water, nanotube is removed from Ti-Au alloys plate surface, then
Will treated Ti-Au alloy sheets then in the case where 15 DEG C of waters bath with thermostatic control act on, the anodic oxidation under the conditions of 130V constant voltages
10min.After treating two step anodizing process, after obtained electrode is cleaned with distilled water, 1.5h is infiltrated in ethanol, then
Then it dries in a nitrogen atmosphere, is finally placed in tube furnace and is heat-treated in air atmosphere, with the heating rate of 3 DEG C/min
After being warming up to 500 DEG C, the calcining at constant temperature 0.5h at 500 DEG C is finally cooled to room temperature with the rate of temperature fall of 5 DEG C/min, finally obtains
Obtain TiO2- Au NTPC electrode materials.
Embodiment 9
Before anodization, by Ti-Au (0.1at%Au) alloy sheets successively with 180 mesh, 320 mesh, 600 mesh and abrasive paper for metallograph
Polishing, makes its surface uniform and smooth and bright like a mirror face, is then respectively cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively
20min is finally dried in a nitrogen atmosphere.Under 15 DEG C of waters bath with thermostatic control, by pretreated Ti-Au alloy sheets be anode, platinum
Plate electrode is used as to electrode, electrode spacing 1.2cm, using containing 0.25molL-1HF and 1.1molL-1H2The second two of O
Alcoholic solution is as anodization electrolyte solution, under 12 DEG C of waters bath with thermostatic control effects, the anodic oxidation 3.5h under the conditions of 90V constant voltages,
Then the nanotube being prepared is ultrasonically treated in deionized water, nanotube is removed from Ti-Au alloys plate surface,
Again will treated Ti-Au alloy sheets then in the case where 12 DEG C of waters bath with thermostatic control act on, the anodic oxidation under the conditions of 90V constant voltages
15min.After treating two step anodizing process, after obtained electrode is cleaned with distilled water, 1.2h is infiltrated in ethanol, then
Then it dries in a nitrogen atmosphere, is finally placed in tube furnace and is heat-treated in air atmosphere, with the heating rate of 4 DEG C/min
After being warming up to 450 DEG C, the calcining at constant temperature 1.5h at 450 DEG C is finally cooled to room temperature with the rate of temperature fall of 5 DEG C/min, finally obtains
Obtain TiO2- Au NTPC electrode materials.
Embodiment 10
Before anodization, by Ti-Au (0.3at%Au) alloy sheets successively with 180 mesh, 320 mesh, 600 mesh and abrasive paper for metallograph
Polishing, makes its surface uniform and smooth and bright like a mirror face, is then respectively cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively
25min is finally dried in a nitrogen atmosphere.Under 8 DEG C of waters bath with thermostatic control, by pretreated Ti-Au alloy sheets be anode, platinized platinum
Electrode is used as to electrode, electrode spacing 0.8cm, using containing 0.15molL-1HF and 0.9molL-1H2The ethylene glycol of O
Solution is as anodization electrolyte solution, under 8 DEG C of waters bath with thermostatic control effects, the anodic oxidation 3h under the conditions of 100V constant voltages, then
The nanotube being prepared is ultrasonically treated in deionized water, nanotube is removed from Ti-Au alloys plate surface, then will
Ti-Au alloy sheets that treated are then in the case where 12 DEG C of waters bath with thermostatic control act on, the anodic oxidation 10min under the conditions of 110V constant voltages.
After treating two step anodizing process, after obtained electrode is cleaned with distilled water, 1h is infiltrated in ethanol, is then followed by nitrogen
It is dry under gas atmosphere, it is finally placed in tube furnace and is heat-treated in air atmosphere, is warming up to the heating rate of 5 DEG C/min
After 420 DEG C, the calcining at constant temperature 1h at 420 DEG C is finally cooled to room temperature with the rate of temperature fall of 5 DEG C/min, finally obtains TiO2-Au
NTPC electrode materials.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (7)
1. a kind of construction method with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes, the crystalline electrode
By TiO2With Uniform Doped in TiO2Au compositions in lattice, are formed by upper and lower two layers, wherein, upper strata is nano-pore composition
Stratum reticulare, lower floor are nano-tube array；
The preparation method includes the following steps：
（1）It is anode by pretreated Ti-Au alloy sheets, platinum plate electrode is used as to electrode, using fluoride and the second of water
Glycol solution is as anodization electrolyte solution, and under water bath with thermostatic control effect, anodic oxidation obtains being attached with the Ti-Au of nanotube
Alloy sheets；
（2）By step（1）The Ti-Au alloy sheets obtained for being attached with nanotube are ultrasonically treated the nanotube on removal surface, then will
Ti-Au alloy sheets that treated continue under water bath with thermostatic control effect, and anodic oxidation obtains electrode sample；
（3）By step（2）Obtained electrode sample is cleaned, and is infiltrated in ethanol, dry, is heat-treated to get to purpose product Ti-
Au alloy nanotube photonic crystal electrodes；
Step（1）In：
The temperature of water bath with thermostatic control is 5-15 DEG C；
The process conditions of anodic oxidation are：2 ~ 4 h of anodic oxidation under the conditions of 90 ~ 130 V constant voltages；
Step（2）In：
The temperature of water bath with thermostatic control is 5-15 DEG C；
The process conditions of anodic oxidation are：5 ~ 30min of anodic oxidation under the conditions of 90 ~ 130 V constant voltages.
2. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 1
Method, which is characterized in that the nano-pore is the hexagon nano-pore structure in periodic distribution.
3. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 2
Method, which is characterized in that the average diameter of the nano-pore is 100-200nm, pore wall thickness 20-40nm.
4. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 1
Method, which is characterized in that step（1）Anodic is 0.5-1.5cm with the spacing to electrode.
5. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 1
Method, which is characterized in that step（1）Middle fluorochemical is HF, a concentration of 0.1-0.3 mol in ethylene glycol solution
L-1；
A concentration of 0.8 ~ 1.2 molL of the water in ethylene glycol solution-1。
6. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 1
Method, which is characterized in that step（1）In pretreated Ti-Au alloy sheets refer to：The Ti-Au of the Au of at% containing 0.02-0.4 is closed
Golden plate is polishing to the uniform and smooth such as minute surface in surface, is then cleaned by ultrasonic in acetone, ethyl alcohol, isopropanol and distilled water successively, most
It is placed under nitrogen atmosphere dry.
7. a kind of constructing with high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes according to claim 1
Method, which is characterized in that step（3）In：
Process of thermal treatment condition is：In air atmosphere, after being warming up to 400-500 DEG C with the rate of 3-5 DEG C/min, constant temperature is forged
0.5-2h is burnt, then room temperature is cooled to the rate of 3-5 DEG C/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
| CN102297881A (en) * | 2011-05-26 | 2011-12-28 | 东南大学 | Preparation method of titanium dioxide nanotube based hydrogen sensor |
| BRPI1002220A2 (en) * | 2010-07-08 | 2012-06-05 | Univ Fed Do Rio Grande Do Sul | microstructures and nanostructures production process from anodizing alloys containing titanium and obtained product |
| CN102586834A (en) * | 2012-03-19 | 2012-07-18 | 北京航空航天大学 | Preparation method and application of transparent titanium dioxide nanotube film |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140119314A (en) * | 2013-03-28 | 2014-10-10 | 인텔렉추얼디스커버리 주식회사 | Electrode for photoelectrochemical cell, method of manufacturing the same and photoelectrochemical cell including the same |
-
2016
- 2016-05-06 CN CN201610296990.7A patent/CN105883715B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
| BRPI1002220A2 (en) * | 2010-07-08 | 2012-06-05 | Univ Fed Do Rio Grande Do Sul | microstructures and nanostructures production process from anodizing alloys containing titanium and obtained product |
| CN102297881A (en) * | 2011-05-26 | 2011-12-28 | 东南大学 | Preparation method of titanium dioxide nanotube based hydrogen sensor |
| CN102586834A (en) * | 2012-03-19 | 2012-07-18 | 北京航空航天大学 | Preparation method and application of transparent titanium dioxide nanotube film |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
Non-Patent Citations (4)
| Title |
|---|
| Au纳米粒子/双层TiO2周期结构的制备及其对乙醇的电催化性质;金朝等;《无机材料学报》;20160224;第31卷(第3期);第241-247页 * |
| Intrinsic Au Decoration of Growing TiO2 Nanotubes and Formation of a High-Efficiency Photocatalyst for H2 Production;Kiyoung Lee等;《Advanced Materials》;20130821;第25卷;第6133-6137页 * |
| Photocatalytic H2 production on self-decorated Au nanoparticles/TiO2 nanotubes under visible light;Kiyoung Lee等;《Electrochemistry Communications》;20140413;第43卷;第105-108页 * |
| 贵金属复合二氧化钛纳米管的制备及SERS与气敏效应研究;黄亮;《清华大学硕士学位论文》;20130215;第4、63-64页 * |
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