CN105734641B - A kind of preparation method of composite construction Nano tube array of titanium dioxide - Google Patents

A kind of preparation method of composite construction Nano tube array of titanium dioxide Download PDF

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CN105734641B
CN105734641B CN201610153266.9A CN201610153266A CN105734641B CN 105734641 B CN105734641 B CN 105734641B CN 201610153266 A CN201610153266 A CN 201610153266A CN 105734641 B CN105734641 B CN 105734641B
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titanium dioxide
tube array
nano tube
composite construction
preparation
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CN105734641A (en
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李耀刚
衡维新
王宏志
张青红
侯成义
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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Abstract

The present invention relates to a kind of preparation methods of composite construction Nano tube array of titanium dioxide, including：Using titanium foil as anode, platinized platinum obtains Nano tube array of titanium dioxide as cathode in ammonium fluoride electrolyte Anodic Oxidation；Nano tube array of titanium dioxide is heat-treated, TiCl is then immersed in3In solution, hydro-thermal process is carried out；The sample that hydro-thermal process obtains is cleaned, is dried, is then heat-treated, up to composite construction Nano tube array of titanium dioxide after cooling.The method of the present invention considerably increases the specific surface area of titania nanotube, improves the absorption rate to light, photoelectrocatalysis efficiency is doubled than ordinary titanium dioxide nano-tube array.

Description

A kind of preparation method of composite construction Nano tube array of titanium dioxide
Technical field
The invention belongs to the preparation field of Nano tube array of titanium dioxide, more particularly to a kind of composite construction titanium dioxide is received The preparation method of mitron array.
Background technology
With the fast development of world economy, water pollution problems getting worse, the organic pollution in water is to human body and life Object produces apparent toxic action, eliminates the important topic that organic pollutants have become field of environment protection.Photoelectricity is urged Change degradation technique is the hole generated under the irradiation of sunlight using semiconductor catalyst and hydroxyl radical free radical to be had difficult to degrade Machine object is decomposed into nontoxic carbon dioxide, water and other inorganic molecules, has efficient and advantages of environment protection, is a kind of reason The water pollution processing method thought.
TiO2As a kind of important inorganic material, have a wide range of applications in photocatalytic degradation organic matter field.Wherein TiO2Nano-tube array generates skin effect, quantum size effect etc. due to its special construction, make it have high stability, The features such as acid-fast alkali-proof is strong, PhotoelectrocatalytiPerformance Performance is good.But there are still some problems to constrain TiO2Nanotube it is further Using.TiO2The specific surface area of nanotube is smaller, improves the specific surface area of titania nanotube and can increase it to organic matter Adsorption capacity, to improve photocatalysis efficiency.Titania nanoparticles have larger specific surface area, make itself and titanium dioxide The compound specific surface area and electron transport ability that will improve titania nanotube of titanium nanotube, can significantly increase degradation has The ability of machine object.
Invention content
Technical problem to be solved by the invention is to provide a kind of preparation sides of composite construction Nano tube array of titanium dioxide Method, this method preparation process is simple, at low cost, in the nanometer that titania nanotube surface is evenly distributed and size is controllable Particle increases the specific surface area of titania nanotube, is effectively improved the catalytic performance to organic matter.
A kind of preparation method of composite construction Nano tube array of titanium dioxide of the present invention, including：
(1) using titanium foil as anode, platinized platinum obtains titanium dioxide as cathode in ammonium fluoride electrolyte Anodic Oxidation Nano-tube array；Wherein, the voltage of anodic oxidation is 40~60V, and oxidization time is 1~2h；
(2) Nano tube array of titanium dioxide obtained in step (1) is heat-treated, is then immersed in TiCl3In solution, Carry out hydro-thermal process；Wherein, the temperature of hydro-thermal process is 80~90 DEG C, and the time is 3~12h；
(3) sample that hydro-thermal process obtains in step (2) cleaned, dried, is then heat-treated, be after cooling Obtain composite construction Nano tube array of titanium dioxide.
The purity of titanium foil is 95~99wt% in the step (1), and thickness is 0.1~0.5mm, is cleaned before use.
The cleaning is：Titanium foil is immersed to acetone, isopropanol, second alcohol and water supersound washing 10~20 minutes successively.
Ammonium fluoride electrolyte is prepared using deionized water, ammonium fluoride and ethylene glycol in the step (1)；Wherein, ammonium fluoride Mass concentration be 0.2%~0.3%, the volumetric concentration of deionized water is 1%~5%, and ethylene glycol is solvent.
The temperature being heat-treated in the step (2) and step (3) is 400~500 DEG C, and soaking time is 2~3h.
TiCl in the step (2)3A concentration of 5~10mmol/L of solution.
Cleaning is that deionized water is cleaned by ultrasonic in the step (3).
Water used is the deionized water that resistivity is 18~18.2M Ω cm in the present invention.
Advantageous effect
(1) present invention uses the technique of anodic oxidation and hydro-thermal process, and composite construction titanium dioxide is prepared on titanium foil and is received Mitron array, the method preparation process is simple, at low cost, and effectively increases the specific surface of Nano tube array of titanium dioxide Product；
(2) the composite construction Nano tube array of titanium dioxide that method of the invention obtains has excellent electronics conduction energy Power, and the utilization ratio of light source can be improved, the efficiency of photoelectric catalysis degrading organic is improved, photoelectrocatalysis efficiency is than normal Rule Nano tube array of titanium dioxide is doubled.
Description of the drawings
Fig. 1 is the SEM figures of Nano tube array of titanium dioxide prepared by embodiment 1；
Fig. 2 is the section SEM figures of Nano tube array of titanium dioxide prepared by embodiment 1；
Fig. 3 is the SEM figures of composite construction Nano tube array of titanium dioxide prepared by embodiment 1；
Fig. 4 is the section SEM figures of composite construction Nano tube array of titanium dioxide prepared by embodiment 1；
Fig. 5 is Nano tube array of titanium dioxide in embodiment 1 and composite construction Nano tube array of titanium dioxide to ultraviolet light According to current-responsive curve, wherein (a) be ordinary titanium dioxide nano-tube array photocurrent curve, (b) be composite construction two The photocurrent curve of titanium oxide nanotubes.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
By titanium foil according to respective supersound washing in immersion acetone, isopropanol, ethyl alcohol and ultra-pure water 15 minutes.Using deionization Water, ammonium fluoride, ethylene glycol prepare electrolyte, and the mass concentration of ammonium fluoride is 0.25%, and the volumetric concentration of deionized water is 5%； Using processed titanium foil as anode, platinized platinum is cathode, and anodic oxidation is carried out under the conditions of voltage is the constant voltage mode of 40V, when Between be 1h, obtain Nano tube array of titanium dioxide.Titanium foil is taken out after anodic oxidation and is cleaned by ultrasonic with deionized water 15min calcines 2h after drying at 450 DEG C.Configure the TiCl of the 5mmol/L of 50ml3Aqueous solution obtains purple clear solution. By through Overheating Treatment sample and the TiCl for preparing3Solution is placed in water heating kettle and keeps the temperature 6h in 80 DEG C together, after hydro-thermal, uses Deionized water is cleaned by ultrasonic, dries, and is heat-treated, heat treatment process is identical as titania nanotube heat treatment process, cold But to room temperature, sample preparation is completed.Fig. 1 is the exterior view of untreated Nano tube array of titanium dioxide, and Fig. 2 is that titanium dioxide is received The sectional view of mitron array, it can be seen that the diameter of titania nanotube is in 55nm or so；Fig. 3 is the dioxy after hydro-thermal process Change the exterior view of titanium nano-tube array, Fig. 4 is the sectional view of the Nano tube array of titanium dioxide after hydro-thermal process；It can be seen that two TiOx nano pipe surface covers one layer of film being made of titania nanoparticles, and nano particle is also attached to simultaneously on tube wall And these nanoparticle aggregates make the diameter of titania nanotube wall become larger, and reach 100nm.
To contain the NaH of the 1mol/L of glucose (organic matter)2PO4Aqueous solution is right to examine working electrode (titanium dioxide) The PhotoelectrocatalytiPerformance Performance of glucose (organic matter).Using the composite construction Nano tube array of titanium dioxide of preparation as working electrode, Using Ag/AgCl as reference electrode, it is to connect three electrodes with electrochemical workstation to electrode with platinum filament, applies in working electrode Ultraviolet light (λ=365nm), and apply a bias (0.1~0.6V), titanium dioxide is can detect to the degradation of organic matter to purple The response condition of outer light.As shown in figure 5, under no illumination condition, the electric current that Nano tube array of titanium dioxide (a) detects is several It is zero；In the case where there is ultraviolet light, photoelectric current that nano composite structure Nano tube array of titanium dioxide (b) detects It doubles than original Nano tube array of titanium dioxide more.
Embodiment 2
Titanium foil is immersed to respective supersound washing 10 minutes in acetone, isopropanol, ethyl alcohol and ultra-pure water successively.Using deionization Water, ammonium fluoride, ethylene glycol prepare electrolyte, and the mass concentration of ammonium fluoride is 0.2%, and the volumetric concentration of deionized water is 3%；It will For processed titanium foil as anode, platinized platinum is cathode, and anodic oxidation, time are carried out under the conditions of voltage is the constant voltage mode of 40V For 1h, Nano tube array of titanium dioxide is obtained.Titanium foil is taken out after anodic oxidation and is cleaned by ultrasonic 10min with deionized water, After drying 2h is calcined at 400 DEG C.Configure the TiCl of the 10mmol/L of 50ml3Aqueous solution obtains purple clear solution.It will pass through The sample of heat treatment and the TiCl prepared3Solution is placed in water heating kettle and keeps the temperature 3h in 85 DEG C together, after hydro-thermal, uses deionization Water is cleaned by ultrasonic, dries, and is heat-treated, and heat treatment process is identical as Nano tube array of titanium dioxide heat treatment process, cooling To room temperature, sample preparation is completed.
Embodiment 3
Titanium foil is immersed to respective supersound washing 20 minutes in acetone, isopropanol, ethyl alcohol and ultra-pure water successively.Using deionization Water, ammonium fluoride, ethylene glycol prepare electrolyte, and the mass concentration of ammonium fluoride is 0.3%, and the volumetric concentration of deionized water is 5%；It will For processed titanium foil as anode, platinized platinum is cathode, and anodic oxidation, time are carried out under the conditions of voltage is the constant voltage mode of 40V For 1h, Nano tube array of titanium dioxide is obtained.Titanium foil is taken out after anodic oxidation and is cleaned by ultrasonic 20min with deionized water, After drying 2h is calcined at 500 DEG C.Configure the TiCl of the 8mmol/L of 50ml3Aqueous solution obtains purple clear solution.It will pass through The sample of heat treatment and the TiCl prepared3Solution is placed in together in water heating kettle keeps the temperature 12h in 90 DEG C, after hydro-thermal, spend from Sub- water is cleaned by ultrasonic, dries, and is heat-treated, heat treatment process is identical as Nano tube array of titanium dioxide heat treatment process, cold But to room temperature, sample preparation is completed.

Claims (6)

1. a kind of preparation method of composite construction Nano tube array of titanium dioxide, including：
(1) using titanium foil as anode, platinized platinum obtains nano titania as cathode in ammonium fluoride electrolyte Anodic Oxidation Pipe array；Wherein, the voltage of anodic oxidation is 40~60V, and oxidization time is 1~2h；The matter of ammonium fluoride in ammonium fluoride electrolyte Measure a concentration of 0.2%~0.3%；
(2) Nano tube array of titanium dioxide obtained in step (1) is heat-treated, is then immersed in TiCl3In solution, carry out Hydro-thermal process；Wherein, the temperature of hydro-thermal process is 80~90 DEG C, and the time is 3~12h；TiCl3A concentration of the 5 of solution~ 10mmol/L；
(3) sample that hydro-thermal process obtains in step (2) cleaned, dried, is then heat-treated, it is to obtain the final product multiple after cooling Close structure titanium dioxide nano-tube array.
2. a kind of preparation method of composite construction Nano tube array of titanium dioxide according to claim 1, which is characterized in that The purity of titanium foil is 95~99wt% in the step (1), and thickness is 0.1~0.5mm, is cleaned before use.
3. a kind of preparation method of composite construction Nano tube array of titanium dioxide according to claim 2, which is characterized in that The cleaning is：Titanium foil is immersed to acetone, isopropanol, second alcohol and water supersound washing 10~20 minutes successively.
4. a kind of preparation method of composite construction Nano tube array of titanium dioxide according to claim 1, which is characterized in that Ammonium fluoride electrolyte is prepared using deionized water, ammonium fluoride and ethylene glycol in the step (1)；Wherein, the volume of deionized water A concentration of 1%~5%, ethylene glycol is solvent.
5. a kind of preparation method of composite construction Nano tube array of titanium dioxide according to claim 1, which is characterized in that The temperature being heat-treated in the step (2) and step (3) is 400~500 DEG C, and soaking time is 2~3h.
6. a kind of preparation method of composite construction Nano tube array of titanium dioxide according to claim 1, which is characterized in that Cleaning is that deionized water is cleaned by ultrasonic in the step (3).
CN201610153266.9A 2016-03-17 2016-03-17 A kind of preparation method of composite construction Nano tube array of titanium dioxide Expired - Fee Related CN105734641B (en)

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CN106348620B (en) * 2016-08-30 2019-02-01 上海大学 The preparation method and applications of rutile titanium dioxide material with the three-dimensional flower-shaped structure of nanometer
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Citations (2)

* Cited by examiner, † Cited by third party
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CN103103596A (en) * 2013-01-14 2013-05-15 北京工业大学 Preparation method of coaxial titanium dioxide nanotube and nanorod composite array
CN104098134A (en) * 2014-07-07 2014-10-15 北京大学 Preparation method and application of TiO2 nanotube coated with amorphous layer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103103596A (en) * 2013-01-14 2013-05-15 北京工业大学 Preparation method of coaxial titanium dioxide nanotube and nanorod composite array
CN104098134A (en) * 2014-07-07 2014-10-15 北京大学 Preparation method and application of TiO2 nanotube coated with amorphous layer

Non-Patent Citations (1)

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Title
Meidan Ye等.Hierarchically Structured Nanotubes for Highly Efficient Dye-Sensitized Solar Cells.《advanced materials》.2013,第25卷(第22期),第1-6页. *

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