CN101509887A - Method for producing glass-based TiO2 nanometer tube array COD sensor - Google Patents
Method for producing glass-based TiO2 nanometer tube array COD sensor Download PDFInfo
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Abstract
The invention relates to a preparation method of a glass-based TiO2 nanotube array chemical oxygen demand (COD) sensor. The preparation method comprises the following steps of: firstly heating washed conductive glass for removing water molecules on the surface thereof, and after cooling, sputtering a layer of metallic titanium film on the surface of the conductive glass by a magnetron sputter in the protecting gas atmosphere of argon; then taking the conductive glass-based titanium film as an anode, and putting the titanium film in electrolyte solution containing fluorinions; carrying out anodic oxidation by taking a platinum electrode as a counter electrode; and after the completion of the anodic oxidation, sintering the obtained transparent glass-based TiO2 nanotube array film samples at high temperature, and obtaining the glass-based TiO2 nanotube array COD sensor. The sensor has high mechanical stability, long service life and high photoelectrocatalysis performance, and is suitable for bilateral illumination, and especially applicable to measure the COD in the water body by using a photoelectrocatalysis method in the water quality analysis.
Description
Technical field
The present invention relates to the preparation method of a kind of chemical oxygen demand (COD) (COD) sensor, relate in particular to a kind of glass-based TiO
2The preparation method of nanometer tube array COD sensor, the sensor of preparation can be used for measuring in the water analysis content of COD in the water.The invention belongs to the environmental monitoring technology field.
Background technology.
At present, the assay method of chemical oxygen demand (COD) (COD) mainly contains potassium dichromate method, Microwave Digestion, spectrophotometric method and coulometry etc.But above-mentioned these methods often need to consume a large amount of experimental drugs, poor accuracy, process in operating process loaded down with trivial details, time-consuming but also may cause secondary pollution to environment.In recent years, for addressing the above problem, people have proposed many COD and have measured new method, as Chinese invention patent (200510026208.1) " preparation method of nanometer tube array COD sensor and application thereof ", utilize Titanium base TiO
2The nano-tube array material carries out the mensuration of COD as the sensor of photoelectrocatalysis mensuration COD.Because at Titanium base TiO
2In the nano-tube array sensor material structure, photocatalyst TiO
2Nanotube is arranged on the metallic titanium matrix vertical, in good orderly, helps the separation and the transmission of photogenerated charge, thereby Titanium base TiO
2The nano-tube array sensor can show good photoelectrocatalysis and learn performance, help to realize COD measures fast, accurately, the characteristics of greenization.But, at titanium base TiO
2In the nano-pipe array thin film structure, TiO
2Nanotube directly is combined on the metallic titanium matrix surface, this combination is a semiconductor and the combining of two kinds of different materials of metal, when being subjected to mechanical external force, nanotube does the time spent, cracking or fracture between nanotube and matrix will take place, even cause peeling off of nano-pipe array thin film and substrate, influence titanium base TiO
2The separation efficiency of the photogenerated charge of nano-tube array material and transfer rate, these change can have a strong impact on titanium base TiO undoubtedly
2The photoelectrocatalysis performance and the stability of nano-tube array COD sensor.On the other hand, titanium base TiO
2Nano-pipe array thin film is light tight, can only shine into capable photoelectrocatalysis reaction by machine glazing, also can influence the photo-quantum efficiency of its COD sensor.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of glass-based TiO is provided
2The preparation method of nanometer tube array COD sensor, preparation has the sensor of higher photoelectrocatalysis performance and stability, is used for the content that COD in the water is measured in water analysis.
For realizing this purpose, the present invention is at first at the film of conductive glass surface sputter layer of metal titanium, then with electro-conductive glass base titanium film as anode, place the electrolyte solution of fluoride ion, with platinum electrode is to electrode, carry out anodic oxidation, again with the clear glass base TiO that obtains after the anodic oxidation
2The nano-pipe array thin film sample is through high temperature sintering, obtains mechanical stability height, glass-based TiO that the photoelectrocatalysis performance is high
2Nano-tube array COD sensor is used for measuring the COD of water body.
The present invention prepares glass-based TiO
2The method of nanometer tube array COD sensor is specifically:
1, with the electro-conductive glass of cleaning, adds its surperficial hydrone of heat abstraction, after the cooling,, under the argon shield atmosphere,, obtain electro-conductive glass base titanium membrane electrode at the film of conductive glass surface sputter layer of metal titanium by magnetic control sputtering device.
2, with electro-conductive glass base titanium membrane electrode as anode, place the electrolyte solution of fluoride ion, be to electrode with platinum electrode, carry out anodic oxidation, anodic oxidation voltage is controlled at 15-60V, anodizing time is 30min～24h.After anodic oxidation is finished, obtain transparent glass-based TiO
2The nano-pipe array thin film sample.
3, with glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, and to be cooled to room temperature, high temperature sintering can obtain glass-based TiO
2Nano-tube array COD sensor is used for the mensuration of COD.
Among the present invention, described film at conductive glass surface sputter layer of metal titanium, the thickness of the film of Titanium are 1-3 μ m.
The electrolyte solution of fluoride ion of the present invention can be the aqueous solution of fluoride ion, also can be the ethylene glycol solution of fluoride ion or the dimethyl sulphoxide solution of fluoride ion.In the electrolyte solution, the mass percent of fluorine ion is 0.1～0.3%, and the compound that constitutes fluorine ion can be hydrofluorite or ammonium fluoride.
Glass-based TiO of the present invention
2During nano-pipe array thin film sample sintering, its sintering temperature is 400～600 ℃, and sintering time is 1-6 hour, and sintering atmosphere can be that air atmosphere also can be an oxygen atmosphere.
The glass-based TiO of the present invention's preparation
2Nanometer tube array COD sensor, its TiO
2The pipe range scope of nano-tube array is 0.3-2 μ m.
The glass-based TiO of the present invention's preparation
2Nano-tube array COD sensor can be applicable to COD Determination on content in the water analysis, and its concrete grammar is with glass-based TiO
2Nano-tube array COD sensor is done anode, and ultraviolet lighting is incident upon glass-based TiO
2On the nano-tube array sensor, apply bias-voltage simultaneously, the organism in reactor in the photoelectrocatalysioxidization oxidization water sample by the variation of electrochemical properties in the organism photoelectrocatalysioxidization oxidization process, is determined the COD value of water sample.
Of the present invention ultraviolet lighting is incident upon glass-based TiO
2On the nano-tube array sensor, ultraviolet light can be exposed to glass-based TiO in a side
2On the nano-tube array sensor, also ultraviolet light can be exposed to glass-based TiO from both sides
2On the nano-tube array sensor.
Glass-based TiO of the present invention
2The preparation method of nanometer tube array COD sensor and titanium base TiO
2The preparation method of nanometer tube array COD sensor has compared tangible technical advantage: at glass-based TiO
2In the nano-tube array sensor, glass is rigidity, can avoid being similar to Titanium base TiO
2Nano-tube array is subjected to the mechanical external force effect and phenomenon that cracking between nanotube and matrix or fracture take place takes place, so glass-based TiO
2The good mechanical stability of nano-tube array COD sensor, photoelectrocatalysis performance height, the life-span of sensor is long; Glass-based TiO in addition
2The two-way printing opacity of nano-tube array material can two-sided absorbing light photograph, can improve the photoelectrocatalysis performance of COD sensor.
Description of drawings
Fig. 1 is the photo in kind of glass-based Nano tube array of titanium dioxide COD sensor, and top is glass-based transparent titanium dioxide nano pipe array film, and the bottom is the not anodised titanium film of glass-based.
Fig. 2 is the glass-based TiO of the embodiment of the invention 1 preparation
2The stereoscan photograph of nano-tube array material, (a) not anodised titanium film, (b) low power lower-glass base TiO
2The front elevation of nano-tube array, (c) the glass-based TiO under the high power
2Nano-tube array front elevation, (d) the glass-based TiO under the high power
2The nano-tube array side view.
Fig. 3 is reference examples titanium base TiO
2The stereoscan photograph of nano-tube array, (a) front elevation, (b) side view
Fig. 4 is the glass-based TiO of the embodiment of the invention 1 preparation
2The nano-pipe array thin film sensor (curve a) with titanium base TiO
2The photocurrent curve ratio of nano-pipe array thin film sensor (curve b) in the 0.1M metabisulfite solution be (curve c is a dark current).
Fig. 5 is the glass-based TiO of the embodiment of the invention 1 preparation
2Nano-pipe array thin film sensor (curve A) and titanium base TiO
2Nano-pipe array thin film sensor (curve B) is at the different degradation curves of degrade azo dyestuff acid orange.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1
Electro-conductive glass with cleaning adds its surperficial hydrone of heat abstraction, after the cooling, by magnetic control sputtering device, under the argon shield atmosphere, at the thick titanium film of conductive glass surface sputter one deck 2 μ m, obtains electro-conductive glass base titanium membrane electrode.
As anode, platinized platinum is as being assembled into the bipolar electrode system to electrode with electro-conductive glass base titanium membrane electrode, and adds ethylene glycol in reaction vessel, adds the ammonium fluoride solid then in ethylene glycol, makes that the fluorine ion mass percent reaches 0.15% in the solution.The adjusting anodic oxidation voltage is 30V, reacts after 1 hour, can obtain transparent glass-based TiO
2Nano-pipe array thin film sample, caliber are 80nm, and pipe range is 1 μ m (see figure 2).
With glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, to be cooled to room temperature, after 3 hours, can obtain glass-based TiO through 500 ℃ of sintering in air atmosphere
2Nano-tube array COD sensor is used for the mensuration of chemical oxygen demand (COD).
Adopt this sensor as anode, and ultraviolet lighting is incident upon on this sensor, apply bias-voltage simultaneously, the organism in a reactor in the photoelectrocatalysioxidization oxidization water sample to be measured, by the variation of electrochemical properties in the organism photoelectrocatalysioxidization oxidization process, determine the COD value of water sample.
In contrast, utilize metal titanium sheet with prior art for preparing Titanium base TiO
2Nano-tube array film electrode: the metal titanium sheet that will clean is as anode, the platinized platinum conduct is assembled into the bipolar electrode system to electrode, and the aqueous solution of adding hydrofluorite is done electrolyte in reaction vessel, and the mass percent of fluorine ion reaches 0.2% in the electrolyte, regulating pH is 4, anodic oxidation voltage is 20V, and whole anode oxidation process adopts magnetic agitation, behind the reaction 1h, take off sample, the water flushing is placed in the baking oven dry, to be cooled to room temperature, can obtain titanium base TiO
2Nano-pipe array thin film, pipe range are 1.2 μ m (see figure 3)s.In air atmosphere,, can obtain titanium base TiO through behind 500 ℃ of sintering 3
2Nano-tube array COD sensor is used for the mensuration of chemical oxygen demand (COD).
Fig. 1 is the photo in kind of the sensor of present embodiment preparation, and top is clear glass base TiO
2Nano-pipe array thin film, bottom are the not anodised titanium film of glass surface.
Fig. 2 is the stereoscan photograph of the sensor of present embodiment preparation, (a) not anodised titanium film, (b) clear glass base TiO
2The front elevation of nano-tube array, (c) the clear glass base TiO under the high power
2Nano-tube array front elevation, (d) the clear glass base TiO under the high power
2The nano-tube array side view.Scanning electron microscope adopts PHILIPS, Netherlands, Sirion200, accelerating potential 5kV.As seen from Figure 2, clear glass base TiO
2Nano-pipe array thin film is arranged high-sequential on conductive glass surface, caliber is 80nm, and pipe range is 1 μ m
That Fig. 3 provides is reference examples titanium base TiO
2Nano-pipe array thin film, caliber 90nm, pipe range 1.2 μ m.
Fig. 4 has provided clear glass base TiO of the present invention
2Nanometer tube array COD sensor (curve a) with reference examples titanium base TiO
2The photocurrent curve ratio of nano-pipe array thin film sensor (curve b) in the 0.1M metabisulfite solution be (curve c is a dark current).As seen from Figure 4, clear glass base TiO
2The nano-tube array sensor is than titanium base TiO
2The nano-tube array sensor has demonstrated higher photocurrent, thereby can show higher photoelectric catalytically active.
Fig. 5 has provided clear glass base TiO of the present invention
2Nanometer tube array COD sensor (curve A) and reference examples titanium base TiO
2Nano-tube array sensor (curve B) is at degrade azo dyestuff acid orange and percent of decolourization curve over time.As seen from Figure 5, the clear glass base TiO for preparing of the inventive method
2The nano-pipe array thin film sensor is than the titanium base TiO under the similarity condition
2The nano-pipe array thin film sensor sheet reveals high photoelectrocatalysis performance.
Embodiment 2
Electro-conductive glass with cleaning adds its surperficial hydrone of heat abstraction, after the cooling, by magnetic control sputtering device, under the argon shield atmosphere, at the thick titanium film of conductive glass surface sputter one deck 1 μ m, obtains electro-conductive glass base titanium membrane electrode.
With the electro-conductive glass base titanium membrane electrode that cleaned as anode, platinized platinum is as electrode is assembled into the bipolar electrode system, and the aqueous solution that adds hydrofluorite in reaction vessel is done electrolyte, the mass percent of fluorine ion reaches 0.1% in the electrolyte, the adjusting anodic oxidation voltage is 15V, behind the reaction 30min, can obtain caliber 50nm, the clear glass base TiO of pipe range 0.3 μ m
2The nano-pipe array thin film sample.
With glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, to be cooled to room temperature, after 3 hours, can obtain glass-based TiO through 400 ℃ of sintering in air atmosphere
2Nano-tube array COD sensor is used for the mensuration of chemical oxygen demand (COD).
Adopt this sensor as anode, and ultraviolet light exposed on this sensor from bilateral, apply bias-voltage simultaneously, the organism in a reactor in the photoelectrocatalysioxidization oxidization water sample to be measured, by the variation of electrochemical properties in the organism photoelectrocatalysioxidization oxidization process, determine the COD value of water sample.
Embodiment 3
Electro-conductive glass with cleaning adds its surperficial hydrone of heat abstraction, after the cooling, by magnetic control sputtering device, under the argon shield atmosphere, at the thick titanium film of conductive glass surface sputter one deck 2 μ m, obtains electro-conductive glass base titanium membrane electrode.
With the electro-conductive glass base titanium membrane electrode that cleaned as anode, platinized platinum is as electrode is assembled into the bipolar electrode system, and in reaction vessel, add ethylene glycol, and in ethylene glycol, add the ammonium fluoride solid then, make that the mass percent of fluorine ion reaches 0.15% in the solution.The adjusting anodic oxidation voltage is 60V, reacts after 3 hours, and can obtain caliber is 120nm, and pipe range is the clear glass base TiO of 1.8 μ m
2The nano-pipe array thin film sample.
With glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, to be cooled to room temperature, after 1 hour, can obtain glass-based TiO through 600 ℃ of sintering in air atmosphere
2Nano-tube array COD sensor is used for the mensuration of chemical oxygen demand (COD).
Embodiment 4
Electro-conductive glass with cleaning adds its surperficial hydrone of heat abstraction, after the cooling, by magnetic control sputtering device, under the argon shield atmosphere, at the thick titanium film of conductive glass surface sputter one deck 3 μ m, obtains electro-conductive glass base titanium membrane electrode.
With the electro-conductive glass base titanium membrane electrode that cleaned as anode, platinized platinum is as electrode is assembled into the bipolar electrode system, and in reaction vessel, add dimethyl sulfoxide (DMSO), and in dimethyl sulfoxide (DMSO), add hydrofluorite then, make that the mass percent of fluorine ion reaches 0.3% in the solution.The adjusting anodic oxidation voltage is 40V, reacts after 24 hours, can obtain caliber 120nm, the clear glass base TiO of pipe range 2.0 μ m
2The nano-pipe array thin film sample.
With glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, to be cooled to room temperature, after 6 hours, can obtain glass-based TiO through 550 ℃ of sintering in air atmosphere
2Nano-tube array COD sensor is used for the mensuration of chemical oxygen demand (COD).
Claims (6)
1, a kind of glass-based TiO
2The preparation method of nanometer tube array COD sensor is characterized in that comprising the steps:
1) with the electro-conductive glass of cleaning, adds its surperficial hydrone of heat abstraction, after the cooling,, under the argon shield atmosphere,, obtain electro-conductive glass base titanium membrane electrode at the film of conductive glass surface sputter layer of metal titanium by magnetic control sputtering device;
2) with electro-conductive glass base titanium membrane electrode as anode, place the electrolyte solution of fluoride ion, be to electrode with platinum electrode, carry out anodic oxidation, anodic oxidation voltage is controlled at 15-60V, anodizing time is 30min～24h; After anodic oxidation is finished, obtain transparent glass-based TiO
2The nano-pipe array thin film sample;
3) with glass-based TiO
2The flushing of nano-pipe array thin film samples with water is placed in the baking oven dry, and to be cooled to room temperature, high temperature sintering promptly obtains glass-based TiO
2Nanometer tube array COD sensor.
2, according to the glass-based TiO of claim 1
2The preparation method of nanometer tube array COD sensor, the film thickness that it is characterized in that described Titanium is 1-3 μ m.
3, according to the glass-based TiO of claim 1
2The preparation method of nanometer tube array COD sensor, the electrolyte solution that it is characterized in that described fluoride ion is the aqueous solution of fluoride ion, the ethylene glycol solution of fluoride ion or the dimethyl sulphoxide solution of fluoride ion; In the electrolyte solution, the mass percent of fluorine ion is 0.1～0.3%; The compound that constitutes fluorine ion is hydrofluorite or ammonium fluoride.
4, according to the glass-based TiO of claim 1
2The preparation method of nanometer tube array COD sensor is characterized in that described glass-based TiO
2During nano-pipe array thin film sample sintering, its sintering temperature is 400～600 ℃, and sintering time is 1-6 hour, and sintering atmosphere is air atmosphere or oxygen atmosphere.
5, according to the glass-based TiO of the method for claim 1 preparation
2Nanometer tube array COD sensor is characterized in that its TiO
2The pipe range scope of nano-tube array is 0.3-2 μ m.
6, according to the glass-based TiO of the method for claim 1 preparation
2The application of nanometer tube array COD sensor is characterized in that being used for water analysis chemical oxygen demand (COD) Determination on content.
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| CN104230180A (en) * | 2013-06-14 | 2014-12-24 | 中国科学院宁波材料技术与工程研究所 | Self-cleaning glass and preparation method thereof |
| CN104316581A (en) * | 2014-10-23 | 2015-01-28 | 华南理工大学 | Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof |
| CN106854755A (en) * | 2016-12-26 | 2017-06-16 | 北京工业大学 | A kind of preparation method of ultra-hydrophilic transparent titanium dioxide nano pipe array |
| RU2641017C1 (en) * | 2016-06-10 | 2018-01-15 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method of manufacturing multi-electrode gas-analytical chip based on titanium dioxide nanotube membranes |
| CN108445054A (en) * | 2018-03-07 | 2018-08-24 | 武汉理工大学 | Nano tube array of titanium dioxide BOD sensors and its preparation method and application |
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| CN1203212C (en) * | 2002-07-08 | 2005-05-25 | 中国科学院化学研究所 | Method for preparing titanium dioxide film under room temperature |
| CN100368798C (en) * | 2005-05-26 | 2008-02-13 | 上海交通大学 | Method for preparing sensor for chemical oxygen demand of Nano tube array and application |
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| CN104230180A (en) * | 2013-06-14 | 2014-12-24 | 中国科学院宁波材料技术与工程研究所 | Self-cleaning glass and preparation method thereof |
| CN104230180B (en) * | 2013-06-14 | 2016-09-07 | 中国科学院宁波材料技术与工程研究所 | A kind of self-cleaning glass and preparation method thereof |
| CN104316581A (en) * | 2014-10-23 | 2015-01-28 | 华南理工大学 | Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof |
| RU2641017C1 (en) * | 2016-06-10 | 2018-01-15 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method of manufacturing multi-electrode gas-analytical chip based on titanium dioxide nanotube membranes |
| EA033789B1 (en) * | 2016-11-21 | 2019-11-26 | Federal State Budget Educational Institution Of Higher Professional Education Yuri Gagarin State Tec | Method of manufacturing multi-electrode gas-analytical chip based on titanium dioxide nanotube membranes |
| CN106854755A (en) * | 2016-12-26 | 2017-06-16 | 北京工业大学 | A kind of preparation method of ultra-hydrophilic transparent titanium dioxide nano pipe array |
| CN108445054A (en) * | 2018-03-07 | 2018-08-24 | 武汉理工大学 | Nano tube array of titanium dioxide BOD sensors and its preparation method and application |
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