CN102586872A - Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array - Google Patents
Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array Download PDFInfo
- Publication number
- CN102586872A CN102586872A CN2012100623944A CN201210062394A CN102586872A CN 102586872 A CN102586872 A CN 102586872A CN 2012100623944 A CN2012100623944 A CN 2012100623944A CN 201210062394 A CN201210062394 A CN 201210062394A CN 102586872 A CN102586872 A CN 102586872A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nano tube
- tube array
- titanium sheet
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a low-temperature crystallization manufacturing method and an application of a titanium dioxide nanotube array, belonging to the technical field of manufacturing of polycrystalline titanium dioxide nanotubes. The low-temperature crystallization manufacturing method of the titanium dioxide nanotube array comprises the following steps of: (1) preparing samples; and (2) crystallizing at low temperature. The application of the titanium dioxide nanotube array is application of the titanium dioxide nanotube array to hydrogen production through water photolysis. According to the invention, the titanium dioxide nanotube array is manufactured through low-temperature crystallization in a sealed reactor by a gas-solid interface crystallization method, the low-temperature crystallization manufacturing method of the titanium dioxide nanotube array has much lower crystal-form transforming temperature of 110-180 DEG C in a process of manufacturing the titanium dioxide nanotube array compared with a traditional calcining method; in addition, the titanium dioxide nanotube array is applied to hydrogen production through water photolysis by combining electrochemical anode oxidation technology with electrochemical devices so that the titanium dioxide can be widely applied to solar cells and hydrogen production through water photolysis.
Description
Technical field
The invention belongs to the technical field of preparation polycrystalline titania nanotube, be specifically related to a kind of low temperature crystallization preparation method and application thereof of Nano tube array of titanium dioxide.
Background technology
The energy is that human society is able to one of important substance of survival and development.The continuous growth of the high speed development of global economy and population will consume a large amount of energy.Hydrogen is a kind of ideal, high Efficiency and Clean Energy Resources carrier.Consider that from the energy and environment two aspects utilizing sun power from water, to produce hydrogen is one of following the most attractive hydrogen manufacturing approach.Consider polycrystalline TiO from angle of practical application
2[Nature 1972 owing to its less cost, high specific surface area and the electrode area that is prone to amplify become one of the most attractive solar photoelectric catalyzing manufacturing of hydrogen material for nanoparticle electrode; 238:37-8].But, at traditional T iO
2In the nanoparticle electrode, a large amount of edges potential barrier that exists between the particle has increased the recombination probability in light induced electron and hole, has influenced the charge collection efficiency of electrode.The Nano tube array of titanium dioxide of electrochemistry anodic oxidation preparation is keeping polycrystalline TiO
2In the time of the electrode high-specific surface area, unidirectional electricity passage is provided, thereby has reduced TiO
2Edge potential barrier between the particle has improved the charge collection efficiency of electrode, shows high photoelectrocatalysis hydrogen production by water decomposition efficient.Grimes etc. are through the orderly TiO of preparation
2Nano-tube array structure has significantly improved the speed [Nano Lett.2005,5,191-195.] of electrode photo electrocatalysis water of decomposition generation hydrogen.Under UV-irradiation, hydrogen is 80mL/h W cm at the dissolution rate on nanometer pipe array electrode surface
2Yet, in order to make TiO
2Nano-tube array has high photoelectric catalytically active, must carry out crystallization to it and handle.Unformed titania nanotube is converted into that Detitanium-ore-type is temperature required for 450-500 ℃, and energy consumption is high, needs in retort furnace, accomplish.The Tc that how to reduce titania nanotube is a urgent problem.
Summary of the invention
To the problem that exists in the prior art; The present invention proposes a kind of low temperature crystallization preparation method and application thereof of Nano tube array of titanium dioxide; The low temperature crystallization preparation method of this Nano tube array of titanium dioxide is simple to operate, the crystal formation conversion temp is low, further develops the application of titanium dioxide nano material aspect sun power.
The present invention proposes a kind of low temperature crystallization preparation method of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: specimen preparation process:
(1) the titanium sheet is put into acetone, Virahol and deionized water for ultrasonic successively and clean, dry up;
(2) to put into massfraction be 0.2～0.5% hydrofluoric acid solution to the titanium sheet after under the room temperature cleaning being dried up, and carries out anodic oxidation, during anodic oxidation; Clamp the upper end of titanium sheet with clip; The lower end is immersed in the hydrofluoric acid solution, stirs simultaneously, and wherein oxidation voltage is 12～30V; Oxidization time is 20～40min; When carrying out anodic oxidation and the platinized platinum facing surfaces for positive, be reverse side back to the platinized platinum facing surfaces, the both side surface that oxidation finishes titanium sheet lower end, back all forms unbodied Nano tube array of titanium dioxide;
(3) place deionized water to clean the titanium sheet and dry up, obtain the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after placing 100～120 ℃ baking oven to dry 1～3h the titanium sheet after the anodic oxidation, be cooled to room temperature;
(2) the titanium sheet lower end with anodic oxidation makes progress; The upper end of not carrying out the oxidation of titanium sheet is downward; Place closed reaction vessel, and inject 0.1～1ml deionized water, put into baking oven; Carry out the gas-solid interface low temperature crystallization in 110～180 ℃ of reaction 1～12h, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
The present invention also proposes a kind of application of Nano tube array of titanium dioxide, uses Nano tube array of titanium dioxide and carries out photolysis water hydrogen, comprises following step:
Step 1: electrode set-up procedure:
Adopt epoxy resin parcel sample with the fixed sample area with utilizing closed reaction vessel to carry out the Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares, dry behind the parcel;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is that concentration is the KOH solution of 0.1～1M, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the Nano tube array of titanium dioxide of epoxy resin parcel as working electrode; Three-electrode system is linked to each other with electrochemical workstation, and initial voltage is an open circuit voltage, directly reads through electrochemical workstation; Final voltage is 0.6～0.8V, and the use light intensity is 8～12mW/cm
2The light source vertical irradiation have the front surface of Nano tube array of titanium dioxide titanium sheet; After beginning to shine uv lamp, produce hydrogen, and use electrochemical workstation to measure current-voltage linear time base sweep curve; Accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy.
The invention has the advantages that:
(1) the present invention proposes a kind of low temperature crystallization preparation method and application thereof of Nano tube array of titanium dioxide, and the calcination method that temperature is more traditional when the crystalline titania nano-tube array is much lower, only needs 110-180 ℃.
(2) the present invention proposes a kind of low temperature crystallization preparation method and application thereof of Nano tube array of titanium dioxide; Under uniform temp, the density of photocurrent that the electrode that adopts the gas-solid interface crystallization process to prepare produces is apparently higher than the density of photocurrent that utilizes the electrode generation for preparing after the crystallizing dish crystallization.
Description of drawings
Fig. 1-A: the scanned photograph of the Nano tube array of titanium dioxide that 110 ℃ of crystallization 12h prepare in closed reaction vessel;
Fig. 1-B: the scanned photograph of the Nano tube array of titanium dioxide that 160 ℃ of crystallization 12h prepare in closed reaction vessel;
Fig. 2: the XRD curve of the Nano tube array of titanium dioxide that under different crystallization temperature condition, prepares;
Fig. 3: unglazed according to crystallization in closed reaction vessel under the condition, in closed reaction vessel crystallization is arranged under the illumination condition and has under the illumination condition in crystallizing dish crystalline Nano tube array of titanium dioxide continue the current-voltage linear time base sweep curve of generation;
Fig. 4: the electric current-time curve of crystalline Nano tube array of titanium dioxide in crystalline Nano tube array of titanium dioxide and the closed reaction vessel in crystallizing dish;
Fig. 5: three-electrode system synoptic diagram.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
The present invention proposes a kind of low temperature crystallization preparation method of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: specimen preparation process:
(1) be more than 99.7% with purity; Thickness is the titanium sheet of 0.20～0.25cm, resquaring titanium sheet sample, and the width of square titanium sheet is 1.00～2.00cm; Length is 3.00～4.00cm; To shear good titanium sheet sample then and put into acetone, Virahol and deionized water ultrasonic cleaning 15～20min respectively successively, dry up, remove the impurity and the organism of titanium plate surface;
(2) it is 0.2～0.5% hydrofluoric acid solution that (20～25 ℃) under the room temperature, the titanium sheet after cleaning dried up are put into massfraction, carries out anodic oxidation; During anodic oxidation, with the upper end that clip is clamped the titanium sheet, the lower end is immersed in the hydrofluoric acid solution; Stir simultaneously; Wherein oxidation voltage is 12～30V, and oxidization time is 20～40min, when carrying out anodic oxidation and the platinized platinum facing surfaces be designated as the front; Back to the platinized platinum facing surfaces is reverse side, and the pros and cons that oxidation finishes to immerse the titanium sheet lower end of solution in the back all forms unbodied Nano tube array of titanium dioxide;
(3) the titanium sheet of step (2) being handled takes out, and places deionized water to clean and dries up, and obtains the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after placing 100～120 ℃ baking oven to dry 1～3h the titanium sheet after the anodic oxidation, be cooled to room temperature.
(2) the titanium sheet lower end with anodic oxidation makes progress; The titanium sheet upper end of not carrying out oxidation is downward, places closed reaction vessel, and injects 0.10～1.00ml deionized water; Put into baking oven; Carry out the gas-solid interface low temperature crystallization in 110～180 ℃ of reaction 1～12h, when injecting deionized water, avoid the deionized water sputter to touch sample, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
Compare experiment simultaneously, the titanium sheet after step (1) is handled is placed in the crystallizing dish, places 110～180 ℃ baking oven to react 1～12h and carries out crystallization, accomplishes the contrast experiment.
Place the titanium sheet behind closed reaction vessel and the crystallizing dish low temperature crystallization to be transformed into Detitanium-ore-type, but place closed reaction vessel crystalline titanium sheet percent crystallinity to be higher than crystallizing dish crystalline titanium sheet by unformed Nano tube array of titanium dioxide.
As shown in Figure 1; The scanned photograph of the Nano tube array of titanium dioxide for preparing under the gas-solid interface low temperature crystallization 12h is as shown in Figure 1, wherein the scanned photograph of the Nano tube array of titanium dioxide for preparing for 110 ℃ of following crystallization 12h in closed reaction vessel of Fig. 1-A; The scanned photograph of the Nano tube array of titanium dioxide that Fig. 1-B prepares for 160 ℃ of following crystallization 12h in closed reaction vessel; Can find out that from Fig. 1-A and Fig. 1-B the titania nanotube of 110 ℃ of crystallization 12h keeps tubulose pattern preferably, though the part mouth of pipe has the whole tubular structure that subsides not destroyed under 160 ℃ of temperature.
The XRD curve of the Nano tube array of titanium dioxide for preparing under the different crystallization temperature condition as shown in Figure 2, TiO when wherein a curve is for crystallization not
2The XRD virgin curve; The b curve is in closed reaction vessel, the XRD curve of the Nano tube array of titanium dioxide that obtains after the crystallization under 110 ℃ of Tcs; The c curve is in closed reaction vessel, the XRD curve of the Nano tube array of titanium dioxide that obtains after the crystallization under 130 ℃ of Tcs; The d curve is in closed reaction vessel, the XRD curve of the Nano tube array of titanium dioxide that obtains after the crystallization under 160 ℃ of Tcs; The e curve is in closed reaction vessel, the XRD curve of the Nano tube array of titanium dioxide that obtains after the crystallization under 180 ℃ of Tcs.Curve b, c, d, e compare with curve a; Anatase octahedrite phase (101) diffraction peak appears during ° left and right sides in 2 θ=25; Explanation is to be all the Detitanium-ore-type crystallization under the Nano tube array of titanium dioxide that obtains of 110 ℃, 130 ℃, 160 ℃ and 180 ℃ of crystallizations in Tc in closed reaction vessel.
The present invention also proposes a kind of application of Nano tube array of titanium dioxide, is specially the application Nano tube array of titanium dioxide and carries out the photolysis water hydrogen method, specifically comprises following step:
Step 1: electrode set-up procedure:
With utilizing closed reaction vessel to carry out the middle part that Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares adopts epoxy resin parcel sample; Nano tube array of titanium dioxide behind the parcel vertically is divided into three parts; Be respectively not by the middle part and the anodised bottom of anodised top, epoxy resin parcel; Wherein be not preferably 0.30～0.50cm by anodised upper height, anodised lower height is preferably 1～1.5cm, and area is preferably 1 * 1cm
2, be used for the preparation work electrode.Dry after parcel is good, connect not by anodised titanium sheet top the preparation of the electrode of finishing the work with copper rod;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is that (concentration is 0.1～1M) solution to KOH, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the electrode for preparing in the step 1 is working electrode, and three-electrode system is linked to each other with electrochemical workstation, as shown in Figure 3; Initial voltage is an open circuit voltage; Can directly read through electrochemical workstation, final voltage is made as 0.6～0.8V, and the use light intensity is 8～12mW/cm
2Uv lamp be light source; Vertical irradiation has the front of Nano tube array of titanium dioxide titanium sheet, after beginning to shine uv lamp, produces hydrogen; And use electrochemical workstation to measure current-voltage linear time base sweep curve; Can calculate its photoelectrocatalysis hydrogen production efficiency according to Faraday's law, accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy with this.
Nano tube array of titanium dioxide that 80 ℃ of continuous crystallisation 12h of application 1 prepare and TiO during crystallization not
2Carry out the photolysis water hydrogen reaction; As can be seen from Figure 4; Curve a is continuing the unglazed current density that produces under the condition of shining for crystalline Nano tube array of titanium dioxide in closed reaction vessel; Curve b is the current density that the crystalline Nano tube array of titanium dioxide produces under the continuous illumination condition in crystallizing dish; Curve c can find out from curve a, curve b and curve c, under the continuous illumination condition for the current density that the crystalline Nano tube array of titanium dioxide produces under the continuous illumination condition in closed reaction vessel; The current density of the current density that Nano tube array of titanium dioxide produced through closed reaction vessel preparation under the no optical condition; The Nano tube array of titanium dioxide that low temperature crystallization is described can produce tangible electric current having under the illumination condition, and Nano tube array of titanium dioxide can be converted into electric energy with luminous energy, accomplishes photolysis water hydrogen; And the current density that the crystalline titania nano-tube array in the crystallizing dish that passes through of the current density that Nano tube array of titanium dioxide produced through closed reaction vessel preparation is produced is arranged under the optical condition.
Simultaneously, in step 2, can also utilize electrochemical workstation to measure electric current-time curve (I-t), voltage is made as 0.2～0.4V; Every separated 10s gives light (the vertical titanium sheet of direction of illumination is positive) or is in the light (unglazed photograph) once; Add the light or the 10s that is in the light at every turn, change continuously, 10s gives that light, 10s are in the light, 10s is in the light for light, 10s ... It is as shown in Figure 5 to obtain electric current-time curve (I-t), and wherein curve a is the electric current-time curve of crystalline Nano tube array of titanium dioxide in the crystallizing dish; Curve b is the electric current-time curve of crystalline Nano tube array of titanium dioxide in the closed container, and wherein 0～10s, 20～30s, 40～50s...... are for interval to light; 10～20s, 30～40s, 50～60s...... are between light-blocking region; Can find out all that from curve a, b electric current is 0 basically when unglazed the photograph, moment produces the high current value when illumination is arranged; The present invention can accomplish the photolysis water hydrogen process when illumination is arranged, realize the conversion of luminous energy to electric energy.And can find out the density of photocurrent value that the density of photocurrent value that the crystalline Nano tube array of titanium dioxide produces in closed reaction vessel produces apparently higher than crystalline Nano tube array of titanium dioxide in crystallizing dish from the contrast of curve a and curve b.
Utilize closed reaction vessel, employing gas-solid interface crystallization process to carry out low temperature crystallization and prepare Nano tube array of titanium dioxide among the present invention; And combine the electrochemical anodic oxidation technology and the electrochemical apparatus of shortcut and simple that Nano tube array of titanium dioxide is carried out the application of photolysis water hydrogen, titanium oxide is being used widely aspect solar cell, the photolysis water hydrogen.
Embodiment 1:
Present embodiment proposes a kind of low temperature crystallization preparation method of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: specimen preparation process:
(1) be that 99.7% thickness is the titanium sheet resquaring titanium sheet sample of 0.20cm with purity; Width is 1.00cm; Length is 3.00cm; To shear good titanium sheet sample then and put into acetone, Virahol and deionized water ultrasonic cleaning 15min respectively successively, dry up, remove the impurity and the organism of titanium plate surface;
(2) it is 0.2% hydrofluoric acid solution that (20 ℃) under the room temperature, the titanium sheet after cleaning dried up are put into massfraction, carries out anodic oxidation; During anodic oxidation, with the upper end that clip is clamped the titanium sheet, the lower end is immersed in the hydrofluoric acid solution; Stir simultaneously; Wherein oxidation voltage is 12V, and oxidization time is 20min, when carrying out anodic oxidation and the platinized platinum facing surfaces be designated as the front; Back to the platinized platinum facing surfaces is reverse side, and the pros and cons that oxidation finishes to immerse the titanium sheet lower end of solution in the back all forms unbodied Nano tube array of titanium dioxide;
(3) the titanium sheet of step (2) being handled takes out, and places deionized water to clean and dries up, and obtains the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after the titanium sheet after the anodic oxidation is placed 100 ℃ baking oven oven dry 1h, be cooled to room temperature.
(2) the titanium sheet lower end with anodic oxidation makes progress; The titanium sheet upper end of not carrying out oxidation is downward, places closed reaction vessel, and injects the 0.10ml deionized water; Put into baking oven; Carry out the gas-solid interface low temperature crystallization in 110 ℃ of reaction 1h, when injecting deionized water, avoid the deionized water sputter to touch sample, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
Present embodiment also proposes a kind of application of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: electrode set-up procedure:
With utilizing closed reaction vessel to carry out the middle part that Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares adopts epoxy resin parcel sample; Nano tube array of titanium dioxide behind the parcel vertically is divided into three parts; Be respectively not by the middle part and the anodised bottom of anodised top, epoxy resin parcel; Be not 0.30cm by anodised upper height wherein, anodised lower height is preferably 1cm, and area is 1 * 1cm
2, be used for the preparation work electrode.Dry after parcel is good, connect not by anodised titanium sheet top the preparation of the electrode of finishing the work with copper rod;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is KOH (concentration is a 0.1M) solution, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the electrode for preparing in the step 1 is working electrode, and three-electrode system is linked to each other with electrochemical workstation, and initial voltage is an open circuit voltage; Directly read through electrochemical workstation, final voltage is made as 0.6V, uses light intensity to be 8mW/cm
2Uv lamp be light source; Vertical irradiation has the front of Nano tube array of titanium dioxide titanium sheet, after beginning to shine uv lamp, produces hydrogen; And use electrochemical workstation to measure current-voltage linear time base sweep curve; Can calculate its photoelectrocatalysis hydrogen production efficiency according to Faraday's law, accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy with this.
Embodiment 2:
Present embodiment proposes a kind of low temperature crystallization preparation method of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: specimen preparation process:
(1) be 99.7% with purity; Thickness is the titanium sheet of 0.25cm, resquaring titanium sheet sample, and the width of square titanium sheet is 2.00cm; Length is 4.00cm; To shear good titanium sheet sample then and put into acetone, Virahol and deionized water ultrasonic cleaning 20min respectively successively, dry up, remove the impurity and the organism of titanium plate surface;
(2) it is 0.5% hydrofluoric acid solution that (25 ℃) under the room temperature, the titanium sheet after cleaning dried up are put into massfraction, carries out anodic oxidation; During anodic oxidation, with the upper end that clip is clamped the titanium sheet, the lower end is immersed in the hydrofluoric acid solution; Stir simultaneously; Wherein oxidation voltage is 30V, and oxidization time is 40min, when carrying out anodic oxidation and the platinized platinum facing surfaces be designated as the front; Back to the platinized platinum facing surfaces is reverse side, and the pros and cons that oxidation finishes to immerse the titanium sheet lower end of solution in the back all forms unbodied Nano tube array of titanium dioxide;
(3) the titanium sheet of step (2) being handled takes out, and places deionized water to clean and dries up, and obtains the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after the titanium sheet after the anodic oxidation is placed 120 ℃ baking oven oven dry 3h, be cooled to room temperature.
(2) the titanium sheet lower end with anodic oxidation makes progress; The titanium sheet upper end of not carrying out oxidation is downward, places closed reaction vessel, and injects the 1.00ml deionized water; Put into baking oven; Carry out the gas-solid interface low temperature crystallization in 180 ℃ of reaction 12h, when injecting deionized water, avoid the deionized water sputter to touch sample, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
Present embodiment also proposes a kind of application of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: electrode set-up procedure:
With utilizing closed reaction vessel to carry out the middle part that Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares adopts epoxy resin parcel sample; Nano tube array of titanium dioxide behind the parcel vertically is divided into three parts; Be respectively not by the middle part and the anodised bottom of anodised top, epoxy resin parcel; Wherein be not preferably 0.50cm by anodised upper height, anodised lower height is preferably 1.5cm, is used for the preparation work electrode.Dry after parcel is good, connect not by anodised titanium sheet top the preparation of the electrode of finishing the work with copper rod;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is KOH (concentration is a 1M) solution, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the electrode for preparing in the step 1 is working electrode, and three-electrode system is linked to each other with electrochemical workstation, and initial voltage is an open circuit voltage; Can directly read through electrochemical workstation, final voltage is made as 0.8V, uses light intensity to be 12mW/cm
2Uv lamp be light source; Vertical irradiation has the front of Nano tube array of titanium dioxide titanium sheet, after beginning to shine uv lamp, produces hydrogen; And use electrochemical workstation to measure current-voltage linear time base sweep curve; Can calculate its photoelectrocatalysis hydrogen production efficiency according to Faraday's law, accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy with this.
Embodiment 3:
Present embodiment proposes a kind of low temperature crystallization preparation method of Nano tube array of titanium dioxide, specifically comprises following step:
Step 1: specimen preparation process:
(1) be 99.7% with purity; Thickness is the titanium sheet of 0.22cm, resquaring titanium sheet sample, and the width of square titanium sheet is 1.50cm; Length is 3.50cm; To shear good titanium sheet sample then and put into acetone, Virahol and deionized water ultrasonic cleaning 18min respectively successively, dry up, remove the impurity and the organism of titanium plate surface;
(2) it is 0.4% hydrofluoric acid solution that (22 ℃) under the room temperature, the titanium sheet after cleaning dried up are put into massfraction, carries out anodic oxidation; During anodic oxidation, with the upper end that clip is clamped the titanium sheet, the lower end is immersed in the hydrofluoric acid solution; Stir simultaneously; Wherein oxidation voltage is 20V, and oxidization time is 30min, when carrying out anodic oxidation and the platinized platinum facing surfaces be designated as the front; Back to the platinized platinum facing surfaces is reverse side, and the pros and cons that oxidation finishes to immerse the titanium sheet lower end of solution in the back all forms unbodied Nano tube array of titanium dioxide;
(3) the titanium sheet of step (2) being handled takes out, and places deionized water to clean and dries up, and obtains the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after the titanium sheet after the anodic oxidation is placed 110 ℃ baking oven oven dry 2h, be cooled to room temperature.
(2) the titanium sheet lower end with anodic oxidation makes progress; The titanium sheet upper end of not carrying out oxidation is downward, places closed reaction vessel, and injects the 0.50ml deionized water; Put into baking oven; Carry out the gas-solid interface low temperature crystallization in 150 ℃ of reaction 6h, when injecting deionized water, avoid the deionized water sputter to touch sample, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
Present embodiment also proposes a kind of application of Nano tube array of titanium dioxide, comprises following step:
Step 1: electrode set-up procedure:
With utilizing closed reaction vessel to carry out the middle part that Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares adopts epoxy resin parcel sample; Nano tube array of titanium dioxide behind the parcel vertically is divided into three parts; Be respectively not by the middle part and the anodised bottom of anodised top, epoxy resin parcel; Be not 0.40cm by anodised upper height wherein, anodised lower height is preferably 1.2cm, is used for the preparation work electrode.Dry after parcel is good, connect not by anodised titanium sheet top the preparation of the electrode of finishing the work with copper rod;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is KOH (concentration is a 0.5M) solution, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the electrode for preparing in the step 1 is working electrode; Three-electrode system is linked to each other with electrochemical workstation, and initial voltage is an open circuit voltage, can directly read through electrochemical workstation; Final voltage is made as 0.7V, uses light intensity to be 10mW/cm
2Uv lamp be light source; Vertical irradiation has the front of Nano tube array of titanium dioxide titanium sheet, after beginning to shine uv lamp, produces hydrogen; And use electrochemical workstation to measure current-voltage linear time base sweep curve; Can calculate its photoelectrocatalysis hydrogen production efficiency according to Faraday's law, accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy with this.
Embodiment 4:
Carry out the gas-solid interface low temperature crystallization in 160 ℃ of reaction 8h in the step 1 that the difference of the low temperature crystallization preparation method of Nano tube array of titanium dioxide and embodiment 3 only is to prepare in the present embodiment, other preparation process and embodiment 3 are identical.
Embodiment 5:
Carry out the gas-solid interface low temperature crystallization in 120 ℃ of reaction 10h in the step 1 that the difference of the low temperature crystallization preparation method of Nano tube array of titanium dioxide and embodiment 3 only is to prepare in the present embodiment, other preparation process and embodiment 3 are identical.
Embodiment 6:
Carry out the gas-solid interface low temperature crystallization in 140 ℃ of reaction 3h in the step 1 that the difference of the low temperature crystallization preparation method of Nano tube array of titanium dioxide and embodiment 3 only is to prepare in the present embodiment, other preparation process and embodiment 3 are identical.
Claims (3)
1. the low temperature crystallization preparation method of a Nano tube array of titanium dioxide is characterized in that: specifically comprise following step:
Step 1: specimen preparation process:
(1) the titanium sheet is put into acetone, Virahol and deionized water for ultrasonic successively and clean, dry up;
(2) to put into massfraction be 0.2～0.5% hydrofluoric acid solution to the titanium sheet after under the room temperature cleaning being dried up, and carries out anodic oxidation, during anodic oxidation; Clamp the upper end of titanium sheet with clip; The lower end is immersed in the hydrofluoric acid solution, stirs simultaneously, and wherein oxidation voltage is 12～30V; Oxidization time is 20～40min; When carrying out anodic oxidation and the platinized platinum facing surfaces for positive, be reverse side back to the platinized platinum facing surfaces, the both side surface that oxidation finishes titanium sheet lower end, back all forms unbodied Nano tube array of titanium dioxide;
(3) place deionized water to clean the titanium sheet and dry up, obtain the titanium sheet after the anodic oxidation;
Step 2: low temperature crystallization process:
(1) takes out after placing 100～120 ℃ baking oven to dry 1～3h the titanium sheet after the anodic oxidation, be cooled to room temperature;
(2) the titanium sheet lower end with anodic oxidation makes progress; The upper end of not carrying out the oxidation of titanium sheet is downward; Place closed reaction vessel, and inject 0.1～1ml deionized water, put into baking oven; Carry out the gas-solid interface low temperature crystallization in 110～180 ℃ of reaction 1～12h, obtain the Nano tube array of titanium dioxide of low temperature crystallization.
2. the application of a Nano tube array of titanium dioxide is characterized in that: use Nano tube array of titanium dioxide and carry out photolysis water hydrogen, comprise following step:
Step 1: electrode set-up procedure:
Adopt epoxy resin parcel sample with the fixed sample area with utilizing closed reaction vessel to carry out the Nano tube array of titanium dioxide that the gas-solid interface low temperature crystallization prepares, dry behind the parcel;
Step 2: photolysis water hydrogen process:
Adopt the electrochemical workstation principle to measure current-voltage linear time base sweep curve process, accomplish the photolysis water hydrogen process, utilize quartz cell to measure photoelectric properties; Ionogen is that concentration is the KOH solution of 0.1～1M, is supporting electrode with the platinum filament, is reference electrode with Ag/AgCl; With the Nano tube array of titanium dioxide of epoxy resin parcel as working electrode; Three-electrode system is linked to each other with electrochemical workstation, and initial voltage is an open circuit voltage, directly reads through electrochemical workstation; Final voltage is 0.6～0.8V, and the use light intensity is 8～12mW/cm
2The light source vertical irradiation have the front surface of Nano tube array of titanium dioxide titanium sheet; After beginning to shine uv lamp, produce hydrogen, and use electrochemical workstation to measure current-voltage linear time base sweep curve; Accomplish the photolysis water hydrogen process, and realize that luminous energy is converted into electric energy.
3. the application of a kind of Nano tube array of titanium dioxide according to claim 2; It is characterized in that: the titanium sheet in the step 1 behind the epoxy resin parcel vertically is divided into three parts; Be respectively not by the middle part and the anodised bottom of anodised top, epoxy resin parcel; Be not 0.2～0.3cm by anodised upper height; Anodised lower height is 1～1.5cm, and area is 1 * 1cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210062394.4A CN102586872B (en) | 2012-03-12 | 2012-03-12 | Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210062394.4A CN102586872B (en) | 2012-03-12 | 2012-03-12 | Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102586872A true CN102586872A (en) | 2012-07-18 |
| CN102586872B CN102586872B (en) | 2015-03-25 |
Family
ID=46476082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210062394.4A Active CN102586872B (en) | 2012-03-12 | 2012-03-12 | Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102586872B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817062A (en) * | 2012-09-13 | 2012-12-12 | 桂林理工大学 | Method of preparing double-wall TiO2 nanotube array with good photocatalytic performance through three-electrode technique |
| CN107138111A (en) * | 2017-05-23 | 2017-09-08 | 郑州轻工业学院 | A kind of carbon dioxide catalytic reduction reaction device |
| CN116328768A (en) * | 2023-03-16 | 2023-06-27 | 上海电力大学 | Cuprous oxide quantum dot/titanium dioxide nanotube structure and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101016637A (en) * | 2007-01-12 | 2007-08-15 | 清华大学 | Method of preparing TiO2 nano pipe array by anodic oxidation method |
| US20100078066A1 (en) * | 2008-09-30 | 2010-04-01 | Uchicago Argonne, Llc | Hybrid solar cells via uv-polymerization of polymer precursor |
| WO2010036289A9 (en) * | 2008-04-30 | 2010-05-20 | University Of Florida Research Foundation, Inc. | Nanorod materials and methods of making and using same |
| CN101844804A (en) * | 2010-05-19 | 2010-09-29 | 西南交通大学 | Preparation method of crystallized TiO2 nanotube array |
| US20100269894A1 (en) * | 2009-04-28 | 2010-10-28 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada | Titanium dioxide nanotubes and their use in photovoltaic devices |
| US20110189081A1 (en) * | 2008-03-25 | 2011-08-04 | Gao Qing Lu | Crystalline inorganic species having optimised reactivity |
| CN102145917A (en) * | 2011-04-22 | 2011-08-10 | 西安交通大学 | Low-temperature crystallization method of titanium oxide nanotube array or titanium oxide nanotube powder |
-
2012
- 2012-03-12 CN CN201210062394.4A patent/CN102586872B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101016637A (en) * | 2007-01-12 | 2007-08-15 | 清华大学 | Method of preparing TiO2 nano pipe array by anodic oxidation method |
| US20110189081A1 (en) * | 2008-03-25 | 2011-08-04 | Gao Qing Lu | Crystalline inorganic species having optimised reactivity |
| WO2010036289A9 (en) * | 2008-04-30 | 2010-05-20 | University Of Florida Research Foundation, Inc. | Nanorod materials and methods of making and using same |
| US20100078066A1 (en) * | 2008-09-30 | 2010-04-01 | Uchicago Argonne, Llc | Hybrid solar cells via uv-polymerization of polymer precursor |
| US20100269894A1 (en) * | 2009-04-28 | 2010-10-28 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada | Titanium dioxide nanotubes and their use in photovoltaic devices |
| CN101844804A (en) * | 2010-05-19 | 2010-09-29 | 西南交通大学 | Preparation method of crystallized TiO2 nanotube array |
| CN102145917A (en) * | 2011-04-22 | 2011-08-10 | 西安交通大学 | Low-temperature crystallization method of titanium oxide nanotube array or titanium oxide nanotube powder |
Non-Patent Citations (1)
| Title |
|---|
| JIAGUO YU: "effect of crystllization methods on morphology and photocatalytic activity of anodized TiO2 nanotube array films", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》, vol. 114, no. 45, 22 October 2010 (2010-10-22), pages 19378 - 19385 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817062A (en) * | 2012-09-13 | 2012-12-12 | 桂林理工大学 | Method of preparing double-wall TiO2 nanotube array with good photocatalytic performance through three-electrode technique |
| CN107138111A (en) * | 2017-05-23 | 2017-09-08 | 郑州轻工业学院 | A kind of carbon dioxide catalytic reduction reaction device |
| CN107138111B (en) * | 2017-05-23 | 2019-02-22 | 郑州轻工业学院 | A kind of carbon dioxide catalytic reduction reaction device |
| CN116328768A (en) * | 2023-03-16 | 2023-06-27 | 上海电力大学 | Cuprous oxide quantum dot/titanium dioxide nanotube structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102586872B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Photoelectrochemical water splitting on highly smooth and ordered TiO2 nanotube arrays for hydrogen generation | |
| Sun et al. | TiO2 nanotubes for hydrogen generation by photocatalytic water splitting in a two-compartment photoelectrochemical cell | |
| CN102774883B (en) | Rutile type titanium dioxide nanowire film and preparation method and applications thereof | |
| Kmentova et al. | Photoelectrochemical and structural properties of TiO2 nanotubes and nanorods grown on FTO substrate: Comparative study between electrochemical anodization and hydrothermal method used for the nanostructures fabrication | |
| CN106521547B (en) | A kind of TiO2/RGO/C3N4The Preparation method and use of combination electrode | |
| CN104752071B (en) | A kind of cobaltosic oxide, cobalt molybdate nucleocapsid heterogeneous structural nano linear array, preparation method and applications | |
| Liu et al. | Electrodeposition of ZnO nanoflake-based photoanode sensitized by carbon quantum dots for photoelectrochemical water oxidation | |
| CN103700829B (en) | Titanium dioxide (B)-Graphene is from the preparation method of winding nano composite material | |
| Ahmad et al. | Enhanced photoelectrochemical water splitting using gadolinium doped titanium dioxide nanorod array photoanodes | |
| CN105347694A (en) | Branched heterogeneous hydrogenated titanium dioxide nanorod array electrode and preparation method thereof | |
| CN102162127A (en) | Method for preparing rutile single crystal superfine titanium dioxide nano wire array grown vertical to substrate | |
| Cao et al. | Current characterization and growth mechanism of anodic titania nanotube arrays | |
| CN104313637A (en) | Metal sulfide electrode with hydrogen reduction activity and preparation method of metal sulfide electrode | |
| CN103872174B (en) | A kind of Au modifies TiO2The preparation method of nanometer stick array light anode | |
| CN109806902A (en) | A kind of W18O49/NiWO4The preparation method of/NF self-supporting electrocatalysis material | |
| CN102703952A (en) | Method for preparing carbon boron nitrogen doped double-tube TiO2 nanotube array from ionic liquid on titanium base and application thereof | |
| CN109289890A (en) | Efficient self-supporting titanium nitride/nitrogen-doped titanium dioxide light electro catalytic electrode material and preparation method | |
| CN110508291A (en) | A kind of Au-ZnIn2S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material | |
| Zhu et al. | Electrochemically etched triangular pore arrays on GaP and their photoelectrochemical properties from water oxidation | |
| Li et al. | Effects of geometric and crystal structures on the photoelectrical properties of highly ordered TiO2 nanotube arrays | |
| CN107680816B (en) | Preparation method of the porous Ti load hollow needle NiCo2S4 to electrode | |
| CN102586872B (en) | Low-temperature crystallization manufacturing method and application of titanium dioxide nanotube array | |
| CN103390507A (en) | Graphene/ platinum nano particle complex fiber electrode material and preparation method thereof | |
| CN101853973A (en) | Photo-electrochemical cell with nanostructure for solar hydrogen production and preparation method thereof | |
| CN109821559A (en) | A kind of preparation method and applications of core-shell structure composite photoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |