CN104250828A - Preparation method for CuS titanium dioxide nanotube composite membrane electrode capable of degrading phosphor-series scale inhibitors - Google Patents
Preparation method for CuS titanium dioxide nanotube composite membrane electrode capable of degrading phosphor-series scale inhibitors Download PDFInfo
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- CN104250828A CN104250828A CN201410449498.XA CN201410449498A CN104250828A CN 104250828 A CN104250828 A CN 104250828A CN 201410449498 A CN201410449498 A CN 201410449498A CN 104250828 A CN104250828 A CN 104250828A
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Abstract
The invention relates to a preparation method for a CuS titanium dioxide nanotube composite membrane electrode capable of degrading phosphor-series scale inhibitors. The preparation method is characterized by comprising early-stage processing of a titanium sheet, preparation of a titanium dioxide nanotube, hydro-thermal reaction and the like. The large specific surface area of the titanium dioxide nanotube is fully utilized, thus the titanium sheet as a matrix is relatively stable, and also the characteristic of relatively strong photoelectric conversion capability of CuS is utilized. The preparation cost is low, the process is simple, and operation is convenient. The prepared CuS titanium dioxide nanotube composite membrane electrode is of a tubular structure with the diameter of about 50 nm, and the nanotube membrane is directly grown on a titanium foil. By taking the titanium foil as the matrix, the prepared titanium dioxide nanotube composite membrane electrode has extremely good photocatalytic effect on the phosphor-series scale inhibitors. Light energy is scientifically reasonably utilized to remove the phosphor-series scale inhibitors, pollution does not exist, and operation is simple and feasible.
Description
Technical field
The invention belongs to polymer compound film field of material technology, there is the preparation method of the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors.
Background technology
TiO
2it is the semiconductor material of a kind of character very stable inorganic, nontoxic pollution-free, easy acquisition and the hazardous and noxious substances can effectively removed in air and water body, and become the focus solving the energy and environmental problem. in sun power sensitized cells and photocatalytic degradation, there is the TiO of application very widely and other forms
2compare, nanotube has better transmittability, higher adsorptive power, larger specific surface area, and tubular structure is conducive to catching of light induced electron.But due to TiO
2energy gap be 3.2eV(anatase octahedrite), can only absorb the light of λ <387.5nm, only have optical responsivity at ultraviolet region, this part light accounts for 5% greatly in visible ray, and therefore energy gap is too wide strongly limit it in light-catalysed effect.Solar energy utilization ratio is very low, in order to more reasonably utilize solar energy, attempts shortening TiO as far as possible
2energy gap.On the other hand, due to the easy and Lacking oxygen compound by light activated electronics, quantum yield reduces.The methods such as transition metal deposition, doped with non-metals element are used to shorten TiO
2energy gap.Although aforesaid method can improve TiO to a certain extent
2photocatalytic activity, but the material doped rear instability had, crystal deforms, and improves the recombination rate in electronics and hole, thus causes the reduction of photocatalytic activity.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors, it is low that it has preparation cost, and process is simple, easy to operate; The tubular structure of the CuS titania nanotube composite film electrode diameter 50nm of preparation, and be that direct growth forms nano-tube film on titanium foil; Using titanium foil as matrix, the CuS titania nanotube composite film electrode of preparation has good photocatalysis effect to phosphorus system Scale inhibitors; The scientific and reasonable luminous energy that make use of removes catalysis phosphorus system Scale inhibitors, and pollution-free, operation is simple and feasible; The CuS titanium dioxide nanotube composite electrode of preparation can complete degraded at normal temperatures and pressures and measure, and operational safety is reliable, and improves 10% than the titania nanotube catalytic efficiency of sizing.
The object of the invention is to be realized by following technical scheme: a kind of preparation method with the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors, it is characterized in that, it comprises the following steps:
1) process in early stage of titanium sheet
With the titanium sheet of 20mm × 15mm × 0.5mm, purity 99.6% for anode material, through the sand papering of different meshes to titanium plate surface no marking, successively in deionized water, acetone, ultrasonic vibration 15min in dehydrated alcohol, removes the spot of titanium plate surface, then, at HF:HNO
3: H
2in the etching liquid of O=1:4:5, chemical rightenning 30s, rinses post-drying with a large amount of water;
2) preparation of titania nanotube
Under the DC voltage-stabilizing condition of 30V, by 0.2996g NH
4f and 95ml ethylene glycol mixed dissolution, take copper sheet as anode, titanium sheet is fixed on copper sheet, and graphite flake is as negative electrode, and electrolysis obtains unformed TiO in 8 hours
2nanotube, unformed TiO
2nanotube is ultrasonic vibration 1min in ethylene glycol, rinses with large water gaging, dries, is finally placed on by sample in 450 DEG C of retort furnaces, naturally cools to room temperature after constant temperature l h, obtains the TiO shaped
2nanotube, prepares nano titania array by anonizing;
3) hydro-thermal reaction
The CuCl of 20ml, 0.003mol/L is added in autoclave
2, then add the Na of 30ml, 0.02mol/L
2s
2o
3, regulate pH=3.0 to put into baking oven and be adjusted to temperature 130 DEG C of hydro-thermal reaction 15h, obtain CuS titania nanotube composite film electrode.
The preparation method with the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors of the present invention passes through preparation CuS titania nanotube composite film electrode, and be by direct growing nano-tube array on titanium-base, by hydrothermal method, CuS is successfully loaded to titania nanotube surface, compared to granular matrix, highly stable as matrix using titanium plate, reusable, degrading organic phosphor in the photocatalysis apparatus of self-assembly, CuS titanium dioxide nanotube composite electrode makes anode, platinized platinum is as to electrode, compared with single sizing membrane electrode, phosphorus system Scale inhibitors catalytic efficiency can be brought up to 65% by CuS titanium dioxide nanotube composite electrode, phosphorus system Scale inhibitors catalytic efficiency under UV-light only has 30%, by the granular CuS titanium dioxide nanotube composite electrode that tetrabutyl titanate is obtained, the catalytic efficiency of phosphorus system Scale inhibitors catalytic efficiency only has 48%, so CuS titanium dioxide nanotube composite electrode prepared by the present invention has very strong use value.
The present invention compared with prior art had outstanding substantive distinguishing features and marked improvement is embodied in:
(1) preparation cost is low, and process is simple, easy to operate;
(2) the CuS titania nanotube composite film electrode diameter prepared is about the tubular structure of 50nm, and is that direct growth forms nano-tube film on titanium foil;
(3) using titanium foil as matrix,
(4) the CuS titania nanotube composite film electrode prepared has good photocatalysis effect to phosphorus system Scale inhibitors;
(5) the scientific and reasonable luminous energy that make use of removes catalysis phosphorus system Scale inhibitors, and pollution-free, operation is simple and feasible.
Accompanying drawing explanation
Fig. 1 is the SEM figure of titania nanotube of the present invention;
Fig. 2 is the TEM figure before titania nanotube hydro-thermal reaction of the present invention;
Fig. 3 is the TEM figure after titania nanotube hydro-thermal reaction of the present invention;
Fig. 4 is the XRD figure of titania nanotube of the present invention.
Embodiment
Below by drawings and Examples, the invention will be further described.
With reference to Fig. 1-Fig. 3, as can be seen from the figure TiO
2the pattern of nanotube is better, is 50nm by diameter, the even pipe array composition of height about 300nm.Closely, specific surface area is larger, is conducive to photoelectronic transmission in arrangement.As can be seen from Figures 2 and 3, CuS even particle distribution.
With reference to Fig. 4, analyze and draw from figure, diffraction peak is at 38.3 °, and 46.2 °, 53.2 ° is the matrix peak of titanium, Anatase TiO
2diffraction peak appear at 25.1 °, 37.5 °, Rutile Type diffraction peak appears at 54.8 °.Before and after compound, characteristic peak has considerable change, and in Fig. 4, the diffraction peak of CuS appears in b at 29.5 °, illustrates that semi-conductor CuS is successfully doped in nano titania array.
The preparation method with the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors of the present invention, comprises the following steps:
1) process in early stage of titanium sheet
With the titanium sheet of 20mm × 15mm × 0.5mm, purity 99.6% for anode material, through the sand papering of different meshes to titanium plate surface no marking, successively in deionized water, acetone, ultrasonic vibration 15min in dehydrated alcohol, removes the spot of titanium plate surface, then, at HF:HNO
3: H
2in the etching liquid of O=1:4:5 mass parts ratio, chemical rightenning 30s, rinses post-drying with a large amount of water;
2) preparation of titania nanotube
Under the DC voltage-stabilizing condition of 30V, by 0.2996g NH
4f and 95ml ethylene glycol mixed dissolution, take copper sheet as anode, titanium sheet is fixed on copper sheet, and graphite flake is as negative electrode, and electrolysis obtains unformed TiO in 8 hours
2nanotube, unformed TiO
2nanotube is ultrasonic vibration 1min in ethylene glycol, rinses with large water gaging, dries, is finally placed on by sample in 450 DEG C of retort furnaces, naturally cools to room temperature after constant temperature l h, obtains the TiO shaped
2nanotube, prepares nano titania array by anonizing;
3) hydro-thermal reaction
The CuCl of 20ml, 0.003mol/L is added in autoclave
2, then add the Na of 30ml, 0.02mol/L
2s
2o
3, regulate pH=3.0 to put into baking oven and be adjusted to temperature 130 DEG C of hydro-thermal reaction 15h, obtain CuS titania nanotube composite film electrode.
Specific embodiment:
With the titanium sheet of 20mm × 15mm × 0.5mm purity 99.6% for anode material, through the sand papering of different meshes to titanium plate surface no marking.Successively in deionized water, acetone, ultrasonic vibration 15min in dehydrated alcohol, removes the spot of titanium plate surface, then at HF:HNO
3: H
2chemical rightenning 30s in O=1:4:5 etching liquid, a large amount of water rinses post-drying, under the DC voltage-stabilizing condition of 30V, by 0.2996g NH
4f and 95ml ethylene glycol mixed dissolution, take copper sheet as anode, titanium sheet is fixed on copper sheet, and graphite flake is as negative electrode, and electrolysis obtains unformed TiO in 8 hours
2nanotube.Unformed TiO
2nanotube is ultrasonic vibration 1min in ethylene glycol, and large water gaging rinses, and dries.Finally sample is placed in 450 DEG C of retort furnaces, after constant temperature l h, naturally cools to room temperature.Obtain the TiO shaped
2nanotube.Nano titania array is prepared by anonizing.20ml0.003mol/L CuCl is added in autoclave
2add the 0.02mol/L Na of 30ml again
2s
2o
3, regulate pH=3.0 to put into baking oven and be adjusted to temperature 120 DEG C of hydro-thermal reaction 15h, obtain CuS titania nanotube composite film electrode.
The specific embodiment of the present invention is also non exhaustive, and those skilled in the art, without the simple copy of creative work and improvement, should belong to the protection domain of the claims in the present invention.
Claims (1)
1. have a preparation method for the CuS titania nanotube composite film electrode of degradable phosphorus system Scale inhibitors, it is characterized in that, it comprises the following steps:
The process in early stage of titanium sheet
With the titanium sheet of 20mm × 15mm × 0.5mm, purity 99.6% for anode material, through the sand papering of different meshes to titanium plate surface no marking, successively in deionized water, acetone, ultrasonic vibration 15min in dehydrated alcohol, removes the spot of titanium plate surface, then, at HF:HNO
3: H
2in the etching liquid of O=1:4:5, chemical rightenning 30s, rinses post-drying with a large amount of water;
2) preparation of titania nanotube
Under the DC voltage-stabilizing condition of 30V, by 0.2996g NH
4f and 95ml ethylene glycol mixed dissolution, take copper sheet as anode, titanium sheet is fixed on copper sheet, and graphite flake is as negative electrode, and electrolysis obtains unformed TiO in 8 hours
2nanotube, unformed TiO
2nanotube is ultrasonic vibration 1min in ethylene glycol, rinses with large water gaging, dries, is finally placed on by sample in 450 DEG C of retort furnaces, naturally cools to room temperature after constant temperature l h, obtains the TiO shaped
2nanotube, prepares nano titania array by anonizing;
3) hydro-thermal reaction
The CuCl of 20ml, 0.003mol/L is added in autoclave
2, then add the Na of 30ml, 0.02mol/L
2s
2o
3, regulate pH=3.0 to put into baking oven and be adjusted to temperature 130 DEG C of hydro-thermal reaction 15h, obtain CuS titania nanotube composite film electrode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506710A (en) * | 2015-12-15 | 2016-04-20 | 天津理工大学 | Method for preparing titanium dioxide nanotube arrays with CuS nanoparticles sensitized |
| CN107670673A (en) * | 2017-09-27 | 2018-02-09 | 湖北工业大学 | A kind of TiO2The preparation method of/CuS composite Nano array photoelectrics pole material |
| JP2019518869A (en) * | 2016-04-27 | 2019-07-04 | パリ・シアンス・エ・レットゥル−カルチエ・ラタン | Metal / metal chalcogenide electrode with high specific surface area |
| 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 |
| CN115041235A (en) * | 2022-06-22 | 2022-09-13 | 湖南师范大学 | Titanium metal organic framework loaded copper sulfide composite photocatalyst and preparation method and application thereof |
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| CN101899701A (en) * | 2010-07-19 | 2010-12-01 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
| CN102776513A (en) * | 2012-07-13 | 2012-11-14 | 西南交通大学 | Preparation process of TiO2 nanotube/PbS/CuS nanocomposite |
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2014
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| CN101899701A (en) * | 2010-07-19 | 2010-12-01 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
| CN102776513A (en) * | 2012-07-13 | 2012-11-14 | 西南交通大学 | Preparation process of TiO2 nanotube/PbS/CuS nanocomposite |
| CN102776513B (en) * | 2012-07-13 | 2014-11-12 | 西南交通大学 | Preparation process of TiO2 nanotube/PbS/CuS nanocomposite |
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| 俞娥: "半导体纳米二氧化钛光电催化降解乙草胺及相关分析问题研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506710A (en) * | 2015-12-15 | 2016-04-20 | 天津理工大学 | Method for preparing titanium dioxide nanotube arrays with CuS nanoparticles sensitized |
| JP2019518869A (en) * | 2016-04-27 | 2019-07-04 | パリ・シアンス・エ・レットゥル−カルチエ・ラタン | Metal / metal chalcogenide electrode with high specific surface area |
| CN107670673A (en) * | 2017-09-27 | 2018-02-09 | 湖北工业大学 | A kind of TiO2The preparation method of/CuS composite Nano array photoelectrics pole material |
| 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 |
| CN111041523B (en) * | 2020-01-02 | 2021-09-07 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
| CN115041235A (en) * | 2022-06-22 | 2022-09-13 | 湖南师范大学 | Titanium metal organic framework loaded copper sulfide composite photocatalyst and preparation method and application thereof |
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Application publication date: 20141231 |