CN103007938A - Cu-doping modified TiO2 photocatalyst and preparation method thereof - Google Patents
Cu-doping modified TiO2 photocatalyst and preparation method thereof Download PDFInfo
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- CN103007938A CN103007938A CN201210499389XA CN201210499389A CN103007938A CN 103007938 A CN103007938 A CN 103007938A CN 201210499389X A CN201210499389X A CN 201210499389XA CN 201210499389 A CN201210499389 A CN 201210499389A CN 103007938 A CN103007938 A CN 103007938A
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Abstract
The invention discloses a Cu-doping modified TiO2 photocatalyst. The Cu-doping modified TiO2 photocatalyst grows on a copper-titanium alloy wire or bar base body and has a two-dimensional structure on the peripheral surface of the copper-titanium alloy wire or bar base body, and the structural unit of the Cu-doping modified TiO2 photocatalyst is a Cu-doping TiO2 nanotube. The invention also discloses a preparation method of the Cu-doping modified TiO2 photocatalyst. The preparation method can be used for directly growing a Cu-doping TiO2 nanotube array which has the two-dimensional structure and higher visible light response property on the copper-titanium alloy wire or bar base body through an electrochemical anode oxidation method. The Cu-doping TiO2 photocatalyst with the two-dimensional structure, which is disclosed by the invention, enlarges the specific area of a TiO2 photocatalyst and effectively extends the forbidden bandwidth of the TiO2 photocatalyst, thereby outstandingly enhancing the adsorptive capacity on a degradation product and obtaining the high-efficiency absorption on a solar spectrum; and the Cu-doping TiO2 photocatalyst is conductive to improving the visible light catalytic activity and has the advantages of good recoverability of the TiO2 photocatalyst, simple process, low cost and high controllable degree.
Description
Technical field
The present invention relates to a kind of titanium dioxide optical catalyst, relate in particular to a kind of Cu doping vario-property TiO with two dimension (2D) structure
2Nano-tube array and preparation method thereof.
Background technology
Titanium dioxide (TiO
2) nano-tube array is used widely in photocatalysis field with its excellent physics and chemistry performance.Yet, because TiO
2Energy gap wider, be about 3.0eV ~ 3.2eV so that only can be absorbed and used less than the solar spectrum in 5% ultraviolet light zone, therefore, seriously restricted its efficient absorption to sunshine.In order to overcome TiO
2This defective make it have better visible light-responded performance, the various countries researcher has launched extensive and deep research to this, wherein the most effective method then is to change its electronics and band structure by the doping means, such as transition metal (such as Cr, V and Cu) and nonmetalloid (such as N, S, F and P) etc., reduce the purpose that it absorbs band gap and improves its photoelectrochemical behaviour thereby reach.
TiO
2The preparation method of nanotube has sol-gel process, hydro-thermal method, template, electrochemistry anodic oxidation etc. usually.Preparing TiO by chemical method
2The TiO of nanotube and doping vario-property
2When nano-powder or nanotube, its complex process, apparatus expensive, controllable degree is low and the TiO for preparing
2The nanotube degree of order is lower.Compare with chemical method, electrochemistry anodic oxidation has then that technique is simple, with low cost, the length-controllable advantages of higher, therefore, has caused showing great attention to of various countries researchers.
In order to overcome chemical method synthesizing blender modification TiO
2The limitation that nanotube brings, also there is the researcher to pass through magnetron sputtering method, prepare Cu-Ti and Fe-Ti alloy firm at the electro-conductive glass matrix, then grow Cu mix Cu-Ti-O and Fe-Ti-O nano-tube array with the Fe doping vario-property by electrochemical anodic oxidation, but the method apparatus expensive and complex process, film quality are difficult to assurance.Also there is the researcher to prepare the TiO of one-dimensional nano structure at alloy flaky matrix such as TiTa, TiMn, TiZrNb
2Nano-pipe array thin film, yet, the one-dimensional nano structure of preparing by said method and the TiO of doping vario-property
2Nano-tube array, therefore the specific area less, still is unfavorable for the increase of catalytic degradation thing adsorbance and the efficient utilization of sunshine.
In addition, with the nanostructured TiO as wastewater through organic matter degradation such as nano-powder, nano thin-film
2During photochemical catalyst, also exist and reclaim complicated and the problem such as be difficult to reuse, therefore, limited the TiO with this type of nanostructured
2Range of application in the photochemical catalyst field.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of TiO of Cu doping vario-property
2Photochemical catalyst and preparation method thereof utilizes electrochemistry anodic oxidation directly to prepare at CuTi alloy wire or alloy bar matrix to have two-dimensional structure, high-sequential is arranged and the Cu doping vario-property TiO of stronger visible light-responded performance
2Photochemical catalyst can improve the adsorbance to the catalytic degradation thing, strengthens TiO
2Photochemical catalyst promotes TiO to the utilization ratio of solar spectrum
2Application in photocatalysis field.
Solving the technical scheme that technical problem of the present invention takes is: the TiO that a kind of Cu doping vario-property is provided
2Photochemical catalyst, this catalyst grow on copper-titanium alloy line or the alloy bar matrix, and have two-dimensional structure at the matrix periphery, and its construction unit is the TiO that Cu mixes
2Nanotube.
Preferably, the TiO of this Cu doping vario-property
2The crystal phase structure of photochemical catalyst is the compound crystal phase structure that Anatase and Rutile Type mix, and Rutile Type quality percentage composition is 1 ~ 10% in this compound crystal phase structure.
Preferably, described Cu doped Ti O with two-dimensional structure
2The Intrinsic Gettering band edge of nano-tube array is 350 ~ 500nm, and the absorption band edge in visible-range is 650 ~ 900nm.。
Solving another technical scheme that technical problem of the present invention takes is: the TiO that a kind of Cu doping vario-property is provided
2The preparation method of photochemical catalyst, the method may further comprise the steps:
Step 1, binary Cu-Ti alloy wire or alloy bar matrix are polished, polish, cleaned and drying for standby;
Step 4, described superficial growth there is Cu doped Ti O
2The Cu-Ti alloy wire of nano-tube array precursor thin-film or alloy bar ultrasonic wave in absolute ethyl alcohol is processed, and then uses washed with de-ionized water, dries up at last for subsequent use with inert gas;
Step 5, dried superficial growth in the step 4 there is Cu doped Ti O
2Cu-Ti alloy wire or the alloy bar of nano-tube array precursor thin-film are put into resistant to elevated temperatures pottery, then in stove it are carried out annealing in process.
Preferably, in step 1, the Ultrasonic Cleaning in acetone with binary Cu-Ti alloy wire or alloy bar matrix, then Ultrasonic Cleaning in absolute ethyl alcohol, use again distilled water flushing, dry up with inert gas at last and clean binary Cu-Ti alloy wire or alloy bar matrix afterwards.
Preferably, in step 1, be used for the TiO of growth Cu doping vario-property
2In the Cu-Ti alloy wire or alloy bar matrix of photochemical catalyst, the total mass fraction of Cu and Ti is that 100%, Cu quality percentage composition is that 5% ~ 50%, Ti quality percentage composition is 95% ~ 50%.
Preferably, in step 1, be used for the TiO of growth Cu doping vario-property
2The Cu-Ti alloy wire of photochemical catalyst or alloy bar matrix diameter are 1mm ~ 10mm, and length is 10mm ~ 50mm.
Preferably, in step 2, the consisting of of described formamido electrolyte: concentration is the NH of 0.1 ~ 0.8mol/L
4F, volume fraction is 3 ~ 10% H
2O and volume fraction are the formamide of 90-97%.
Preferably, in step 3, the voltage that applies when carrying out anodic oxidation is 5V ~ 50V constant voltage, anodizing time is 5min ~ 300min, distance is 1cm ~ 5cm between two electrodes, uses magnetic stirring apparatus to stir in the anodic oxidation reactions process, and mixing speed is 300 ~ 500 rev/mins.
Preferably, in step 4, ultrasonic treatment time is 5 ~ 15 seconds, uses washed with de-ionized water 3 ~ 5 times, adopts inert gas to dry up.
Preferably, in step 5, described dried superficial growth there is Cu doped Ti O
2Cu-Ti alloy wire or the alloy bar of nano-tube array precursor thin-film are put into the porcelain Noah's ark, and cover with onesize porcelain Noah's ark, then in tube-type atmosphere furnace it are carried out annealing in process.
Preferably, the annealing in process temperature is 300 ℃～600 ℃, and temperature retention time is 1h ~ 5h, and annealing atmosphere is 99.99% high purity oxygen gas atmosphere, and heating rate is 1 ~ 5 ℃/min, and rate of temperature fall is 1 ~ 10 ℃/min.
The present invention also provides a kind of TiO according to above-described Cu doping vario-property
2The TiO of the Cu doping vario-property of preparation method's preparation of photochemical catalyst
2Photochemical catalyst.
Cu doping vario-property TiO with two-dimensional structure of the present invention
2The nano-tube array photochemical catalyst is with the TiO that adopts the chemical method preparation
2Or doped Ti O
2Nano-powder or nano pipe light catalyst are compared, and adopt electrochemistry anodic oxidation at the photochemical catalyst that titanium alloy line or excellent matrix prepare, and have that recuperability is good, technique is simple, with low cost and controllable degree advantages of higher; With traditional titanium or the TiO of titanium alloy laminated structure Anodic oxidation preparation
2Nano-tube array is compared, and has larger specific area, thereby can increase significantly to the adsorption capacity of degradation product and adsorbance and to the efficient absorption ability of sunshine, is conducive to improve TiO
2The degradation rate of photochemical catalyst.
Description of drawings
Fig. 1 is the enlarged diagram of CuTi alloy wire matrix.
Fig. 2 is the enlarged diagram that the CuTi alloy wire matrix of Fig. 1 passes through the CuTi alloy wire that obtains after the electrochemical anodization reaction, and its surface is the Cu doping vario-property TiO of two-dimensional structure
2Nano-tube array.
Fig. 3 is the Cu doped Ti O that the embodiment of the invention 1 prepares
2The stereoscan photograph of nano-tube array surface topography.
The specific embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that instantiation described herein only in order to explain the present invention, does not limit the present invention.
The invention provides a kind of TiO of Cu doping vario-property
2Photochemical catalyst and preparation method thereof utilizes electrochemistry anodic oxidation directly to prepare at CuTi alloy wire or alloy bar matrix to have two-dimensional structure, high-sequential is arranged and the Cu doping vario-property TiO of stronger visible light-responded performance
2Photochemical catalyst can improve the adsorbance to the catalytic degradation thing, strengthens TiO
2Photochemical catalyst promotes TiO to the utilization ratio of solar spectrum
2Application in photocatalysis field.
TiO when in this application, term " crystallization " refers to anneal at a certain temperature
2The thaumatropy of nanotube from the amorphous state to the crystalline phase.Term " presoma " refers to TiO
2Sample when nano-pipe array thin film is processed without Annealing Crystallization.
Adopt two-dimensional structure of the present invention and Cu doped Ti O
2Photochemical catalyst has increased TiO
2The specific area of photochemical catalyst has effectively been expanded TiO
2The energy gap of photochemical catalyst, thus can significantly improve the adsorption capacity of degradation product and obtain efficient absorption to solar spectrum, be conducive to the improvement of visible light catalysis activity, and this TiO
2The recuperability of photochemical catalyst is good, technique is simple, with low cost and controllable degree is high.
Embodiment 1
In present embodiment 1, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
(1) seeing also Fig. 1, is that 3mm, length are the polishing of Cu5-Ti95 alloy wire matrix 1 usefulness abrasive paper for metallograph and the polishing of 20mm with diameter, and this matrix 1 is that the electric arc melting legal system is standby;
(2) with the alloy wire Ultrasonic Cleaning 15min in acetone that obtains in the step (1), then Ultrasonic Cleaning 5 ~ 15min in absolute ethyl alcohol, use at last distilled water flushing 3 ~ 5 times, the Cu5-Ti95 alloy wire after cleaning is purged drying for standby with inert gas (as: nitrogen or argon gas etc.).In present embodiment 1, inert gas adopts nitrogen;
(3) take by weighing 5.55gNH
4F is dissolved in the 15ml deionized water, makes NH with magnetic stirrer
4F all dissolves, and then mixes with the 485ml formamide and obtains electrolyte;
(4) at ambient temperature, Cu5-Ti95 alloy wire matrix immerses in the electrolyte of step (3) configuration as anode, electrode is adopted the platinum plate electrode that is of a size of 20mm * 10mm, obtain Cu5-Ti95 alloy wire 2 after the electrochemical anodization reaction, see also Fig. 2.Cu5-Ti95 alloy wire matrix 2 behind anodic oxidation reactions grows the Cu doped Ti O of two-dimensional structure
2Nano-tube array precursor thin-film, its structure component units are the TiO that Cu mixes
2Nanotube 3.In present embodiment 1, anodic oxidation voltage is 10V, and the time is 3h;
(5) superficial growth that obtains in the step (4) there is Cu doped Ti O
2Then the Cu-Ti alloy wire of nano-tube array precursor thin-film Ultrasonic Cleaning 5 ~ 10s in absolute ethyl alcohol uses distilled water flushing 3 ~ 5 times;
(6) superficial growth after will cleaning has Cu doped Ti O
2The Cu-Ti alloy wire of nano-tube array precursor thin-film adopts nitrogen to dry up for subsequent use;
(7) dried superficial growth there is Cu doped Ti O
2The Cu-Ti alloy wire of nano-tube array precursor thin-film is put into the porcelain Noah's ark, and covers with onesize porcelain Noah's ark, then carries out annealing in process in tube furnace.The temperature of annealing in process is 450 ℃, and temperature retention time is 1 ~ 3h, and annealing atmosphere is 99.99% high purity oxygen gas atmosphere, and heating rate is 1 ~ 5 ℃/min, and rate of temperature fall is 1 ~ 10 ℃/min.
The two-dimensional structure Cu doping vario-property TiO of present embodiment preparation
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy, its surface topography is as shown in Figure 3.In the large tracts of land black region, the TiO that Cu mixes
2Nano-tube array high-sequential and length are shorter, and nanotube length, caliber and pipe thickness are about respectively 150 ~ 200nm, 30 ~ 40nm, 5 ~ 10nm.And in the petal-shaped zone, the TiO that Cu mixes
2The nano-tube array degree of order descends but nanotube length increases, and nanotube length, caliber and pipe thickness are about respectively 400 ~ 500nm, 40 ~ 50nm, 5 ~ 8nm.The Cu doping vario-property TiO of this embodiment 1 preparation
2The absorption band edge of nano-tube array in the visible region is 720 ~ 750nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the TiO of the two-dimensional structure Cu doping vario-property of present embodiment 1 preparation
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 30% ~ 60%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
In present embodiment 2, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
Except the annealing in process temperature of the voltage of step (4) and step (7), other implementation step is identical with embodiment 1, and the voltage of step (4) is: the dc constant voltage of 30V; The annealing in process temperature of step (7) is 550 ℃.
The two-dimensional structure Cu doping vario-property TiO of present embodiment 2 preparations
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy, in the large tracts of land black region, the TiO that Cu mixes
2Nanotube length, caliber and pipe thickness are about respectively 200 ~ 300nm, 40 ~ 50nm, 5 ~ 10nm.And in the petal-shaped zone, the TiO that Cu mixes
2Nanotube length, caliber and pipe thickness are about respectively 500 ~ 800nm, 40 ~ 50nm, 5 ~ 10nm.The Cu doping vario-property TiO of embodiment 2 preparations
2The absorption band edge of nano-tube array in the visible region is 720 ~ 750nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the two-dimensional structure Cu doping vario-property TiO of present embodiment 2 preparations
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 30% ~ 60%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
In present embodiment 3, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
Step (1) is: be that 3mm, length are Cu30-Ti70 alloy wire matrix 1 usefulness abrasive paper for metallograph polishing and the polishing of 20mm with diameter, step (2) ~ step (7) is identical with embodiment 1, then carries out annealing in process in tube furnace.Wherein, the annealing in process temperature is 450 ℃, and temperature retention time is 1 ~ 3h, and annealing atmosphere is 99.99% high purity oxygen gas atmosphere, and heating rate is 1 ~ 5 ℃/min, and rate of temperature fall is 1 ~ 10 ℃/min.
The two-dimensional structure Cu doping vario-property TiO of present embodiment 3 preparations
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy.In the large tracts of land black region, the TiO that Cu mixes
2Nano-tube array high-sequential and length are shorter, and nanotube length, caliber and pipe thickness are about respectively 250 ~ 300nm, 40 ~ 60nm, 10 ~ 15nm.And in the petal-shaped zone, the TiO that Cu mixes
2The nano-tube array degree of order descends but nanotube length increases, and nanotube length, caliber and pipe thickness are about respectively 400 ~ 500nm, 50 ~ 60nm, 5 ~ 10nm.The Cu doping vario-property TiO of these embodiment 3 preparations
2The absorption band edge of nano-tube array in the visible region is 730 ~ 750nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the two-dimensional structure Cu doping vario-property TiO of present embodiment preparation
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 50% ~ 80%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
Embodiment 4
In present embodiment 4, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
Except the annealing in process temperature of the voltage of step (4) and step (7), other implementation step is substantially the same manner as Example 3, and difference is: the voltage of step (4) is the dc constant voltage of 30V; The annealing in process temperature of step (7) is 550 ℃.
The two-dimensional structure Cu doping vario-property TiO of present embodiment 4 preparations
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy.In the large tracts of land black region, the TiO that Cu mixes
2Nano-tube array high-sequential and length are shorter, and nanotube length, caliber and pipe thickness are about respectively 250 ~ 350nm, 40 ~ 60nm, 10 ~ 15nm.And in the petal-shaped zone, the TiO that Cu mixes
2The nano-tube array degree of order descends but nanotube length increases, and nanotube length, caliber and pipe thickness are about respectively 400 ~ 600nm, 40 ~ 60nm, 5 ~ 10nm.The Cu doping vario-property TiO of embodiment 4 preparations
2The absorption band edge of nano-tube array in the visible region is 730 ~ 750nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the two-dimensional structure Cu doping vario-property TiO of present embodiment 4 preparations
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 50% ~ 80%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
Embodiment 5
In present embodiment 5, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
Step (1) is: be that Cu50-Ti50 alloy wire or alloy bar matrix carry out the sanding and polishing preliminary treatment with specification, step (2) ~ step (7) is identical with embodiment 1, then carries out annealing in process in tube furnace.Wherein, the annealing in process temperature is 450 ℃, and temperature retention time is 1 ~ 3h, and annealing atmosphere is 99.99% high purity oxygen gas atmosphere, and heating rate is 1 ~ 5 ℃/min, and rate of temperature fall is 1 ~ 10 ℃/min.
The two-dimensional structure Cu doping vario-property TiO of present embodiment 5 preparations
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy.In the large tracts of land black region, the TiO that Cu mixes
2Nano-tube array high-sequential and length are shorter, and nanotube length, caliber and pipe thickness are about respectively 150 ~ 200nm, 50 ~ 80nm, 10 ~ 30nm.And in the petal-shaped zone, the TiO that Cu mixes
2The nano-tube array degree of order descends but nanotube length increases, and nanotube length, caliber and pipe thickness are about respectively 200 ~ 400nm, 30 ~ 80nm, 10 ~ 30nm.The Cu doping vario-property TiO of embodiment 5 preparations
2The absorption band edge of nano-tube array in the visible region is 700 ~ 730nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the two-dimensional structure Cu doping vario-property TiO of present embodiment 5 preparations
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 40% ~ 70%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
Embodiment 6
In present embodiment 6, has the Cu doped Ti O of two-dimensional structure
2The preparation method of nano-tube array may further comprise the steps:
Except the annealing in process temperature of the voltage of step (4) and step (7), other implementation step is substantially the same manner as Example 5, and difference is: the voltage of step (4) is the dc constant voltage of 30V; The annealing in process temperature of step (7) is 550 ℃.
The two-dimensional structure Cu doping vario-property TiO of present embodiment 6 preparations
2Nano-tube array, the TiO that its unit of structural units mixes for Cu
2Nanotube, and have hierarchy.In the large tracts of land black region, the TiO that Cu mixes
2Nano-tube array high-sequential and length are shorter, and nanotube length, caliber and pipe thickness are about respectively 100 ~ 150nm, 60 ~ 80nm, 10 ~ 30nm.And in the petal-shaped zone, the TiO that Cu mixes
2The nano-tube array degree of order descends but nanotube length increases, and nanotube length, caliber and pipe thickness are about respectively 300 ~ 500nm, 60 ~ 80nm, 10 ~ 30nm.The Cu doping vario-property TiO of these embodiment 6 preparations
2The absorption band edge of nano-tube array in the visible region is 700 ~ 730nm, the TiO of the ability of its photocatalytic degradation organic pollution of the same race and the undoped modification of one-dimensional nano structure
2Nano-tube array is compared and is greatly improved, and adopts the two-dimensional structure Cu doping vario-property TiO of present embodiment 6 preparations
2When nano-tube array ultraviolet catalytic degraded concentration was the 20mg/L methyl orange solution, the unit length degradation rate was 40% ~ 70%/μ m behind simulated solar illumination 4h, the one-dimensional nano structure TiO of undoped modification
2Nano-tube array unit length degradation rate 10% ~ 20%/μ m.
At the Cu doping vario-property TiO with two-dimensional structure of the present invention
2Among the preparation method of photochemical catalyst, by electrochemistry anodic oxidation, directly grow the TiO that Cu mixes at Cu-Ti alloy wire or alloy bar matrix
2Nano-tube array, technique is simple, with low cost and controllable degree is high.Cu mixes and has successfully expanded TiO
2Photochemical catalyst is at the absorption band edge of visible region, and two-dimensional structure has effectively increased TiO
2The specific area of photochemical catalyst, the increase and the photocatalysis performance that are conducive to catalytic degradation thing adsorbance improve.
Be understandable that; for the person of ordinary skill of the art; can make other various corresponding modifications, change and equivalent structure variation by technical conceive according to the present invention, and all these change the protection domain that all should belong to claim of the present invention with distortion.
Claims (13)
1. the TiO of a Cu doping vario-property
2Photochemical catalyst is characterized in that, this catalyst grows on copper-titanium alloy line or the alloy bar matrix, and has two-dimensional structure at the matrix periphery, and its construction unit is the TiO that Cu mixes
2Nanotube.
2. the TiO of Cu doping vario-property according to claim 1
2Photochemical catalyst is characterized in that, described TiO
2The crystal phase structure of photochemical catalyst is the compound crystal phase structure that Anatase and Rutile Type mix, and Rutile Type quality percentage composition is 1 ~ 10% in the described compound crystal phase structure.
3. the TiO of Cu doping vario-property according to claim 1
2Photochemical catalyst is characterized in that, described Cu doped Ti O with two-dimensional structure
2The Intrinsic Gettering band edge of nano-tube array is 350 ~ 500nm, and the absorption band edge in visible-range is 650 ~ 900nm.
4. the TiO of a Cu doping vario-property
2The preparation method of photochemical catalyst is characterized in that, said method comprising the steps of:
Step 1, binary Cu-Ti alloy wire or alloy bar matrix are polished, polish, cleaned and drying for standby;
Step 2, configuration formamido electrolyte;
Step 3, described Cu-Ti alloy wire or alloy bar matrix are immersed in the described formamido electrolyte as anode, adopt the high-purity platinum plate electrode as electrode is carried out anodic oxidation, obtain the TiO of Cu doping vario-property after certain reaction time at Cu-Ti alloy wire or alloy bar matrix
2The nano-tube array precursor thin-film;
Step 4, superficial growth in the step 3 there is Cu doped Ti O
2The Cu-Ti alloy wire of nano-tube array precursor thin-film or alloy bar ultrasonic wave in absolute ethyl alcohol is processed, and then uses washed with de-ionized water, the Cu doped Ti O after will cleaning again
2The nano-tube array precursor thin-film dries up for subsequent use;
Step 5, dried superficial growth in the step 4 there is Cu doped Ti O
2Cu-Ti alloy wire or the alloy bar of nano-tube array precursor thin-film are put into resistant to elevated temperatures pottery, then in stove it are carried out annealing in process.
5. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst, it is characterized in that, in step 1, the Ultrasonic Cleaning in acetone with binary Cu-Ti alloy wire or alloy bar matrix, then Ultrasonic Cleaning in absolute ethyl alcohol, use again distilled water flushing, dry up with inert gas at last and clean binary Cu-Ti alloy wire or alloy bar matrix afterwards.
6. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst is characterized in that, in step 1, is used for the TiO of growth Cu doping vario-property
2In the Cu-Ti alloy wire or alloy bar matrix of photochemical catalyst, the total mass fraction of Cu and Ti is that 100%, Cu quality percentage composition is that 5% ~ 50%, Ti quality percentage composition is 95% ~ 50%.
7. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst is characterized in that, in step 1, is used for the TiO of growth Cu doping vario-property
2The Cu-Ti alloy wire of photochemical catalyst or alloy bar matrix diameter are 1mm ~ 20mm, and length is 10mm ~ 100mm.
8. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst is characterized in that, in step 2, and the consisting of of described formamido electrolyte: the NH of 0.1 ~ 0.8mol/L
4F, volume fraction is 3 ~ 10% H
2O and volume fraction are the formamide of 90-97%.
9. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst, it is characterized in that, in step 3, the voltage that applies when carrying out anodic oxidation is 5V ~ 50V constant voltage, anodizing time is 5min ~ 300min, distance is 1cm ~ 5cm between two electrodes, uses magnetic stirring apparatus to stir in the anodic oxidation reactions process, and mixing speed is 300 ~ 500 rev/mins.
10. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst is characterized in that, in step 4, ultrasonic treatment time is 5 ~ 15 seconds, uses washed with de-ionized water 3 ~ 5 times, adopts inert gas to dry up.
11. the TiO of Cu doping vario-property according to claim 4
2The preparation method of photochemical catalyst is characterized in that, in step 5, described dried superficial growth is had Cu doped Ti O
2Cu-Ti alloy wire or the alloy bar of nano-tube array precursor thin-film are put into the porcelain Noah's ark, and cover with onesize porcelain Noah's ark, then in tube-type atmosphere furnace it are carried out annealing in process.
12. the TiO of Cu doping vario-property according to claim 11
2The preparation method of photochemical catalyst is characterized in that, the annealing in process temperature is 300 ℃～600 ℃, and temperature retention time is 1h ~ 5h, and annealing atmosphere is 99.99% high purity oxygen gas atmosphere, and heating rate is 1 ~ 5 ℃/min, and rate of temperature fall is 1 ~ 10 ℃/min.
13. TiO of the described Cu doping vario-property of any one according to claim 4-12
2The TiO of the Cu doping vario-property of preparation method's preparation of photochemical catalyst
2Photochemical catalyst.
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| CN107812521A (en) * | 2017-11-14 | 2018-03-20 | 江苏师范大学 | A kind of preparation method of bimetallic nano propane dehydrogenation catalyst |
| CN108506864A (en) * | 2018-03-29 | 2018-09-07 | 深圳大图科创技术开发有限公司 | A kind of Internet of Things solar energy intelligent road-lamp |
| CN108534377A (en) * | 2018-03-29 | 2018-09-14 | 深圳万智联合科技有限公司 | A kind of solar water heater intelligent monitor system based on Internet of Things |
| CN108634018A (en) * | 2018-03-29 | 2018-10-12 | 深圳万发创新进出口贸易有限公司 | Tea drier based on solar energy |
| CN111041523A (en) * | 2020-01-02 | 2020-04-21 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
| CN115895407A (en) * | 2022-12-29 | 2023-04-04 | 张红江 | Preparation method of high-performance water-based paint |
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