CN104089995A - Sulfur dioxide sensor based on anodic alumina nanowire and preparation method thereof - Google Patents
Sulfur dioxide sensor based on anodic alumina nanowire and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulfur dioxide sensor based on an anodic alumina nanowire and a preparation method thereof. The sulfur dioxide sensor electrode is coated with the anodic alumina nanowire, which undergoes surface modification by a mixed solution of palladium chloride, anhydrous cobalt chloride and thiourea or titanium dioxide. The preparation method includes pretreatment, oxidation, surface modification, and sensor preparation. The sensor provided by the invention has the characteristics of low cost, rapid response, short desorption time, good repeatability and high accuracy. Preparation of the sensor has the advantages of simple process, low material consumption, high process repeatability and controllability, and is convenient for batch production.
Description
Technical field
The present invention relates to sensor technical field, particularly a kind ofly respond fast, accuracy is high, the SO 2 sensor based on anodised aluminium nano wire and the preparation method of favorable repeatability.
Background technology
Sulphuric dioxide chemical formula: SO
2,it is modal oxysulfide.Colourless gas, has intense stimulus smell.One of Air Pollutant Discharge.During volcanic explosion, this gas can be sprayed, in many industrial processs, also sulphuric dioxide can be produced.Because coal and oil all contain sulphur compound conventionally, while therefore burning, can generate sulphuric dioxide.Soluble in water when sulphuric dioxide, can form sulphurous acid, the principal ingredient of acid rain.
SO
2by human body, sucked after respiratory tract, because of soluble in water, therefore major part is arrested in the upper respiratory tract.On moistening mucous membrane, generate and have corrosive sulphurous acid, a part and then be oxidized to sulfuric acid, strengthens spread effect, if human body inhaled concentration every day is the SO of 100 ppm
2, after 8 h will there is obvious irritation in bronchus and lung, and lung tissue is come to harm.In nonferrous metallurgical process, not only produce SO
2gas, also can produce a large amount of dust.SO
2with the synergy of dust, to the industrial healthy great infringement that caused.Because SO
2with floating dust aerosol particles, enter human lung's deep layer, toxicity will increase by 3～4 times, cause alveolus wall fibroplasia.If hyperplasia scope involves extensively, form lung stringiness and become, development goes down to make lung fibre breakage to form pulmonary emphysema.
SO
2also can be absorbed by the body and enter blood, whole body is produced to toxic action, the vigor of its energy destructive enzyme, affects human body metabolism, and liver is caused to certain infringement.The chronic toxicity test of animal is shown to SO
2there is general toxic action, occur the downtrod phenomenon of immune response.Therefore Long Term Contact person is difficult for recovery from illness after may having the increase of the breathing problem incidence of disease or flu, removes due to SO
2direct spread effect outside, still may be suppressed relevant with immune response.
SO
2also have short carcinous.During calomel poisoning, shed tears, photophobia, cough, pharynx, larynx cusalgia etc.; Serious poisoningly can within a few hours, there is pulmonary edema; High concentration sucks and can cause reflectivity glottidospasm and cause and suffocate.Skin or eye contact are inflamed or burn.Chronic Effect: long-term low concentration contact, can have headache, giddy, constitutional symptom and rhinitis chronic, sphagitis, bronchitis, sense of smell and the hypogeusia etc. such as weak.Fewer workers has tooth erosion disease [3].To atmosphere, can cause severe contamination.Easily by airborne dust catalytic oxidation, and then form sulfate type acid rain, Chemical formula 2 SO
2+ 2H
2o+O
2=2H
2sO
4particularly serious to the harm of plant.
For low-concentration sulfur dioxide detection method, mainly rely at present the method for instrumental analysis, as vapor-phase chromatography etc.Although these detections are the concentration of trace sulfur dioxide in testing environment accurately, the deficiencies such as but these method ubiquity sense cycle are long, cost is expensive, and need to, through those of skill in the art's operating instrument equipment of professional training, cannot realize the accurate fast detecting in the scene of trace sulfur dioxide in environment.
Chinese patent publication No. CN102021219A, date of publication on April 20th, 2011, name is called the Microbial cell-based biosensors that detects toluene class organic contaminant, this application case discloses a kind of Microbial cell-based biosensors that detects toluene class organic contaminant, utilize regulating and controlling sequence and the regulatory protein gene of pseudomonas putida degrading genes to follow commercialization reporter plasmid sequence, build the Microbial cell-based biosensors and the detection method that detect toluene class organic contaminant, bacterial host is Escherichia coli.Its weak point is, this detection method sense cycle is long, cost is expensive.
Summary of the invention
The object of the invention is in order to solve that the method sense cycle of existing detection sulphuric dioxide is long, cost is expensive and need to be through those of skill in the art's operating instrument equipment of professional training, cannot realize trace sulfur dioxide in environment the accurate fast detecting in scene defect and provide a kind of and respond fast, accuracy is high, the SO 2 sensor based on anodised aluminium nano wire of favorable repeatability.
Another object of the present invention is to provide and a kind ofly responds fast, accuracy is high, the preparation method of the SO 2 sensor based on anodised aluminium nano wire of favorable repeatability.
To achieve these goals, the present invention is by the following technical solutions:
A kind of SO 2 sensor based on anodised aluminium nano wire, on described SO 2 sensor electrode, be coated with anodised aluminium nano wire, described anodised aluminium nano wire is modified through mixed solution or the titanium dioxide surface of palladium bichloride, waterless cobaltous chloride and thiocarbamide.In the technical program, anodised aluminium nano-material own wt is light, and therefore the sensor of preparation has superiority in weight, compared with the sensor of lightweight, is conducive to be fixed on different positions, is easy to use; Anodised aluminium nano-material is not yielding and broken, can keep the shape maintains of sensor constant; Anodised aluminium nano-material has the feature of porous, is therefore conducive to tested gas permeation and enters, and increases anodised aluminium nano-material for the suction-operated of tested gas molecule, increases and detects effect; Anodised aluminium nano-material has good compatibility, can and be plated between its surperficial metal and produces affinity, is therefore plated in its surperficial metal difficult drop-off, has increased the stability of sensor construction; Anodised aluminium nano-material also has fabulous electrical insulating property, it is hereby ensured that electrode normally works in a good dielectric base; Anodised aluminium nano-material is easy to preparation, and favorable repeatability, is convenient to large quantities of preparations.
As preferably, described anodised aluminium nano wire is by following steps system:
A) pre-treatment: 6-8h that aluminium sheet is annealed at 220-320 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 35-50 ℃, and soak time is 10-30min; Taking-up is carried out electrochemical polish after cleaning;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, in oxidation solution, be oxidized, oxidation voltage 40V, oxidization time 15-25min, before oxidation finishes in 20s by the near 16-18V of oxidation voltage, after taking-up, putting into massfraction is the phosphoric acid solution reaming of 7-10%, obtains anodic oxidation aluminium sheet;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 5-10min; Electroplate rear taking-up, at 600-700 ℃, dried 25-35min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 8-10h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, the mixed solution or the titania that in anode alumina nanowires suspension, add palladium bichloride, waterless cobaltous chloride and thiocarbamide, ultrasonic concussion, then drying for standby when adding.
In the technical program, step b) adopts step-down to process before the end of oxidation, can reduce the thickness of anodised aluminium surface barrier, if not taking step-down processes, barrier layer thickness is 50 microns of left and right, and takes step-down of the present invention to process, and the thickness on restraining barrier is 18 microns of left and right;
Reaming is in order to increase the diameter of the hole on alumina formwork, also makes the diameter homogenization more of hole simultaneously, is conducive to improve the dielectricity of anodic oxidation aluminium formwork, thereby improves sensitivity and the accuracy detecting, and increases the stability of sensor construction; If not reaming, the hole diameter on alumina formwork is not of uniform size, and this must reduce stability and the dielectricity of sensor construction, reduces detection sensitivity and accuracy; Pore-enlargement is too short, falls flat, and via hole overlong time, can reduce the degree of adhering to of noble metal on porous anodic alumina template.
As preferably, in step a), cleaning degrease solution used is the mixed liquor of acetone and cyclohexanol, and the volume ratio of acetone and cyclohexanol is 1:2-4, uses vibration of ultrasonic wave cleansing solution in the time of cleaning; Soak solution is the sodium carbonate of massfraction 5-8% and the potassium hydroxide mixed solution that massfraction is 2-4%, and the volume ratio of sodium carbonate and potassium hydroxide is 1:3-4.
As preferably, in step b), oxidation solution is that mass concentration is the tartrate of 8-10% and the mixed solution of the potassium permanganate that mass concentration is 0.9-1.5%.
As preferably, in step b), pore-enlargement is 30-45min, and the temperature of phosphoric acid solution is 50-55 ℃.
As preferably, in step c), strong acid solution is hydrochloric acid, perchloric acid or sulfuric acid; The mixed solution or the titania that in every 1mL anodised aluminium nanowire suspension, add 1mg palladium bichloride, waterless cobaltous chloride and thiocarbamide, in mixed solution, the mass concentration of waterless cobaltous chloride and thiocarbamide is 1.2-2.3%, waterless cobaltous chloride is 1:1 with the ratio of thiocarbamide; The composition of copper plating bath is: the rare earth gadolinium of 1-butyl-3-methylimidazole paratoluenesulfonic acid sodium salt of 20-24g/L cupric chloride, 0.1-0.8g/L nickel chloride, 45-65mg/L polyglycol, 1.2-3.6g/L, chlorination 1-benzyl-3 methylimidazole, 33-38g/L potassium tartrate and the 1.1-2.7g/L of 0.5-1.1g/L.
A preparation method for SO 2 sensor based on anodised aluminium nano wire, described preparation method comprises the following steps:
A) pre-treatment: 6-8h that aluminium sheet is annealed at 220-320 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 35-50 ℃, and soak time is 10-30min; Taking-up is carried out electrochemical polish after cleaning;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, in oxidation solution, be oxidized, oxidation voltage 40V, oxidization time 15-25min, before oxidation finishes in 20s by the near 16-18V of oxidation voltage, after taking-up, putting into massfraction is the phosphoric acid solution reaming of 7-10%, obtains anodic oxidation aluminium sheet;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 5-10min; Electroplate rear taking-up, at 600-700 ℃, dried 25-35min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 8-10h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, the mixed solution or the titania that in anode alumina nanowires suspension, add palladium bichloride, waterless cobaltous chloride and thiocarbamide, ultrasonic concussion, then drying for standby when adding;
D) prepare sensor: the anodised aluminium nano wire after step c) is modified is coated on sensor electrode, and the number of plies that anodised aluminium nano wire applies is 3-7 layer.
As preferably, ultrasonic processing 55-65W.
As preferably, aluminium sheet adopts high-purity aluminium sheet of purity >=99.999%.
As preferably, during electroplating processes, adopt two electrolytic tanks, utilize three-electrode system, auxiliary electrode is iridium tantalum titanium electrode, and contrast electrode is saturated calomel electrode SCE, and working electrode is the anodic oxidation aluminium sheet of bottom spray platinum.
The invention has the beneficial effects as follows:
1) sensor cost of the present invention is low, and fast, desorption time is short in response, favorable repeatability, and accuracy is high;
2) preparation process of sensor of the present invention is simple, and material consumption is few, and the repeatability of technique and controllability are very high, is convenient to batch production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the anodic oxidation aluminium sheet of embodiment 1 preparation.
Fig. 2 is the scanning electron microscope (SEM) photograph of the anodised aluminium nano wire of embodiment 1 preparation.
Fig. 3 is sulfur dioxide concentration detection model.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention will be further explained:
Embodiment 1
A preparation method for SO 2 sensor based on anodised aluminium nano wire, described preparation method comprises the following steps:
A) pre-treatment: by high-purity aluminium sheet of purity >=99.999% 8h that anneals at 220 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 35 ℃, and soak time is 30min; After taking-up is cleaned, in the ethanol that is 2:1 in volume ratio and perchloric acid mixed solution, (Ra≤0.01 μ m) carries out electrochemical polish 5min; Cleaning degrease solution used is the mixed liquor of acetone and cyclohexanol, and the volume ratio of acetone and cyclohexanol is 1:2, uses vibration of ultrasonic wave cleansing solution in the time of cleaning; Soak solution is the sodium carbonate of massfraction 5% and the potassium hydroxide mixed solution that massfraction is 2%, and the volume ratio of sodium carbonate and potassium hydroxide is 1:3; Ultrasonic processing 55W;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, is oxidized oxidation voltage 40V in oxidation solution, oxidization time 15min, before oxidation finishes in 20s by the near 18V of oxidation voltage, after taking-up, put into massfraction and be 7% phosphoric acid solution reaming, obtain anodic oxidation aluminium sheet; Oxidation solution is that mass concentration is the mixed solution of 8% tartrate and the mass concentration potassium permanganate that is 0.9%; Pore-enlargement is 30min, and the temperature of phosphoric acid solution is 55 ℃;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 5min; Electroplate rear taking-up, at 600 ℃, dried 35min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 8h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, in anode alumina nanowires suspension, add palladium bichloride, ultrasonic concussion, then drying for standby when adding; Wherein, strong acid solution is hydrochloric acid; In every 1mL anodised aluminium nanowire suspension, add 1mg palladium bichloride; The composition of copper plating bath is: the gadolinium of 1-butyl-3-methylimidazole paratoluenesulfonic acid sodium salt of 20g/L cupric chloride, 0.1g/L nickel chloride, 45mg/L polyglycol, 1.2g/L, chlorination 1-benzyl-3 methylimidazole, 33g/L potassium tartrate and the 1.1g/L of 0.5g/L; During electroplating processes, adopt two electrolytic tanks, utilize three-electrode system, auxiliary electrode is iridium tantalum titanium electrode, and contrast electrode is saturated calomel electrode SCE, and working electrode is the anodic oxidation aluminium sheet of bottom spray platinum; Ultrasonic processing 55W;
D) prepare sensor: the anodised aluminium nano wire after step c) is modified is coated on sensor electrode, once, the number of plies that the anodised aluminium nano wire after modification applies is 3 layers to every coating first drying.
Embodiment 2
A preparation method for SO 2 sensor based on anodised aluminium nano wire, described preparation method comprises the following steps:
A) pre-treatment: by high-purity aluminium sheet of purity >=99.999% 7h that anneals at 280 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 45 ℃, and soak time is 20min; After taking-up is cleaned, in the ethanol that is 2:1 in volume ratio and perchloric acid mixed solution, (Ra≤0.01 μ m) carries out electrochemical polish 5min; Cleaning degrease solution used is the mixed liquor of acetone and cyclohexanol, and the volume ratio of acetone and cyclohexanol is 1:3, uses vibration of ultrasonic wave cleansing solution in the time of cleaning; Soak solution is the sodium carbonate of massfraction 7% and the potassium hydroxide mixed solution that massfraction is 3%, and the volume ratio of sodium carbonate and potassium hydroxide is 1:3; Ultrasonic processing 60W;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, is oxidized oxidation voltage 40V in oxidation solution, oxidization time 20min, before oxidation finishes in 20s by the near 16V of oxidation voltage, after taking-up, put into massfraction and be 8.5% phosphoric acid solution reaming, obtain anodic oxidation aluminium sheet; Oxidation solution is that mass concentration is the mixed solution of 9% tartrate and the mass concentration potassium permanganate that is 1.2%; Pore-enlargement is 35min, and the temperature of phosphoric acid solution is 52 ℃;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 7min; Electroplate rear taking-up, at 650 ℃, dried 30min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 9h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, in anode alumina nanowires suspension, adding mass concentration is the mixed solution of 1.2% waterless cobaltous chloride and thiocarbamide, waterless cobaltous chloride is 1:1 with the ratio of thiocarbamide, in every 1mL anodised aluminium nanowire suspension, adds 1mg mixed solution; Ultrasonic concussion, then drying for standby when adding; Wherein, strong acid solution is perchloric acid; The composition of copper plating bath is: the gadolinium of 1-butyl-3-methylimidazole paratoluenesulfonic acid sodium salt of 22g/L cupric chloride, 0.5g/L nickel chloride, 50mg/L polyglycol, 2.4g/L, chlorination 1-benzyl-3 methylimidazole, 35g/L potassium tartrate and the 1.9g/L of 0.95g/L; During electroplating processes, adopt two electrolytic tanks, utilize three-electrode system, auxiliary electrode is iridium tantalum titanium electrode, and contrast electrode is saturated calomel electrode SCE, and working electrode is the anodic oxidation aluminium sheet of bottom spray platinum; Ultrasonic processing 55W;
D) prepare sensor: the anodised aluminium nano wire after step c) is modified is coated on sensor electrode, once, the number of plies that the anodised aluminium nano wire after modification applies is 5 layers to every coating first drying.
Embodiment 3
A preparation method for SO 2 sensor based on anodised aluminium nano wire, described preparation method comprises the following steps:
A) pre-treatment: by high-purity aluminium sheet of purity >=99.999% 6h that anneals at 320 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 50 ℃, and soak time is 10min; After taking-up is cleaned, in the ethanol that is 2:1 in volume ratio and perchloric acid mixed solution, (Ra≤0.01 μ m) carries out electrochemical polish 5min; Cleaning degrease solution used is the mixed liquor of acetone and cyclohexanol, and the volume ratio of acetone and cyclohexanol is 1:4, uses vibration of ultrasonic wave cleansing solution in the time of cleaning; Soak solution is the sodium carbonate of massfraction 8% and the potassium hydroxide mixed solution that massfraction is 4%, and the volume ratio of sodium carbonate and potassium hydroxide is 1:4; Ultrasonic processing 65W;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, is oxidized oxidation voltage 40V in oxidation solution, oxidization time 25min, before oxidation finishes in 20s by the near 18V of oxidation voltage, after taking-up, put into massfraction and be 10% phosphoric acid solution reaming, obtain anodic oxidation aluminium sheet; Oxidation solution is that mass concentration is the mixed solution of 10% tartrate and the mass concentration potassium permanganate that is 1.5%; Pore-enlargement is 30min, and the temperature of phosphoric acid solution is 50 ℃;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 10min; Electroplate rear taking-up, at 700 ℃, dried 25min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 10h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, in anode alumina nanowires suspension, add titania, ultrasonic concussion, then drying for standby when adding; Wherein, strong acid solution is sulfuric acid; In every 1mL anodised aluminium nanowire suspension, add 1mg titania; The composition of copper plating bath is: the gadolinium of 1-butyl-3-methylimidazole paratoluenesulfonic acid sodium salt of 24g/L cupric chloride, 0.8g/L nickel chloride, 65mg/L polyglycol, 3.6g/L, chlorination 1-benzyl-3 methylimidazole, 38g/L potassium tartrate and the 2.7g/L of 1.1g/L; During electroplating processes, adopt two electrolytic tanks, utilize three-electrode system, auxiliary electrode is iridium tantalum titanium electrode, and contrast electrode is saturated calomel electrode SCE, and working electrode is the anodic oxidation aluminium sheet of bottom spray platinum; Ultrasonic processing 65W;
D) prepare sensor: the anodised aluminium nano wire after step c) is modified is coated on sensor electrode, once, the number of plies that the anodised aluminium nano wire after modification applies is 7 layers to every coating first drying.
Anodic oxidation aluminium sheet to embodiment 1 preparation is done electron-microscope scanning, the results are shown in Figure 1; Anodised aluminium nano wire to embodiment 1 preparation is done electron-microscope scanning, the results are shown in Figure 2;
Select electric current-time (i-t) analytic function under the constant voltage of CHI660 electrochemical analyser, by the reference electrode of CHI electrochemical analyser with electrode is connect to one end of sensor electrode, working electrode connects the other end of sensor electrode, and test voltage is constant is 0.1V.It is stable to sensor response that the response time of sensor is set as being exposed to sulfur dioxide gas from sensor, and secondary response is stable to be again set as being blown into sensor from drying nitrogen release time.All experiments are all at room temperature carried out.Adopt successively sensor prepared by embodiment 1-3 to concentration be respectively 180,150,120,90,60, the sulfur dioxide gas of 30ppm detects, between every two concentration in testing process, all pass into high pure nitrogen sensor air chamber is cleaned, make sensor response return to baseline value.Then adopt the response of electric current-time curve method survey sensor to sulfur dioxide gas, prepared sensor all has sensitive response to the sulfur dioxide gas of variable concentrations, pass into sulfur dioxide gas in air chamber after, its electric conductivity has been produced to impact, and the electric current that concentration of SO 2 gas passes through is more greatly less.Relation between detection electric current and concentration of SO 2 gas as shown in Figure 3, obtains sensor according to Fig. 3 through linear fit and detects the relation between electric current and concentration of SO 2 gas, and physical relationship formula is:
, R=0.94755, utilizes this formula, and we just can detect electric current according to sensor and realize the detection to tested sulphuric dioxide sample.
Claims (10)
1. the SO 2 sensor based on anodised aluminium nano wire, it is characterized in that, on described SO 2 sensor electrode, be coated with anodised aluminium nano wire, described anodised aluminium nano wire is modified through mixed solution or the titanium dioxide surface of palladium bichloride, waterless cobaltous chloride and thiocarbamide.
2. a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 1, is characterized in that, described anodised aluminium nano wire is by following steps system:
A) pre-treatment: 6-8h that aluminium sheet is annealed at 220-320 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 35-50 ℃, and soak time is 10-30min; Taking-up is carried out electrochemical polish after cleaning;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, in oxidation solution, be oxidized, oxidation voltage 40V, oxidization time 15-25min, before oxidation finishes in 20s by the near 16-18V of oxidation voltage, after taking-up, putting into massfraction is the phosphoric acid solution reaming of 7-10%, obtains anodic oxidation aluminium sheet;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 5-10min; Electroplate rear taking-up, at 600-700 ℃, dried 25-35min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 8-10h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, the mixed solution or the titania that in anode alumina nanowires suspension, add palladium bichloride, waterless cobaltous chloride and thiocarbamide, ultrasonic concussion, then drying for standby when adding.
3. a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 2, it is characterized in that, in step a), cleaning degrease solution used is the mixed liquor of acetone and cyclohexanol, the volume ratio of acetone and cyclohexanol is 1:2-4, uses vibration of ultrasonic wave cleansing solution in the time of cleaning; Soak solution is the sodium carbonate of massfraction 5-8% and the potassium hydroxide mixed solution that massfraction is 2-4%, and the volume ratio of sodium carbonate and potassium hydroxide is 1:3-4.
4. a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 2, is characterized in that, in step b), oxidation solution is that mass concentration is the tartrate of 8-10% and the mixed solution of the potassium permanganate that mass concentration is 0.9-1.5%.
5. a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 2, is characterized in that, in step b), pore-enlargement is 30-45min, and the temperature of phosphoric acid solution is 50-55 ℃.
6. a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 2, is characterized in that, in step c), strong acid solution is hydrochloric acid, perchloric acid or sulfuric acid; The mixed solution or the titania that in every 1mL anodised aluminium nanowire suspension, add 1mg palladium bichloride, waterless cobaltous chloride and thiocarbamide, in mixed solution, the mass concentration of waterless cobaltous chloride and thiocarbamide is 1.2-2.3%, waterless cobaltous chloride is 1:1 with the ratio of thiocarbamide; The composition of copper plating bath is: the rare earth gadolinium of 1-butyl-3-methylimidazole paratoluenesulfonic acid sodium salt of 20-24g/L cupric chloride, 0.1-0.8g/L nickel chloride, 45-65mg/L polyglycol, 1.2-3.6g/L, chlorination 1-benzyl-3 methylimidazole, 33-38g/L potassium tartrate and the 1.1-2.7g/L of 0.5-1.1g/L.
7. a preparation method for the SO 2 sensor based on anodised aluminium nano wire as claimed in claim 1 or 2, is characterized in that, described preparation method comprises the following steps:
A) pre-treatment: 6-8h that aluminium sheet is annealed at 220-320 ℃, cooling rear cleaning degrease, then immerses in soak solution, and soak solution temperature is 35-50 ℃, and soak time is 10-30min; Taking-up is carried out electrochemical polish after cleaning;
B) oxidation: the aluminium sheet that step a) is obtained carries out anodic oxidation, in oxidation solution, be oxidized, oxidation voltage 40V, oxidization time 15-25min, before oxidation finishes in 20s by the near 16-18V of oxidation voltage, after taking-up, putting into massfraction is the phosphoric acid solution reaming of 7-10%, obtains anodic oxidation aluminium sheet;
C) finishing: the anodic oxidation aluminium sheet that step b) is obtained is washed till pH for neutral, then carries out electroplating processes in copper plating bath, time 5-10min; Electroplate rear taking-up, at 600-700 ℃, dried 25-35min; Anodic oxidation aluminium sheet after copper facing is placed in to strong acid solution 8-10h, obtain anodised aluminium nano-material, then with deionized water, be configured to 5mg/mL anodised aluminium nanowire suspension, the mixed solution or the titania that in anode alumina nanowires suspension, add palladium bichloride, waterless cobaltous chloride and thiocarbamide, ultrasonic concussion, then drying for standby when adding;
D) prepare sensor: the anodised aluminium nano wire after step c) is modified is coated on sensor electrode, and the number of plies that anodised aluminium nano wire applies is 3-7 layer.
8. the preparation method of a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 7, is characterized in that, ultrasonic processing 55-65W.
9. the preparation method of a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 7, is characterized in that, aluminium sheet adopts high-purity aluminium sheet of purity >=99.999%.
10. the preparation method of a kind of SO 2 sensor based on anodised aluminium nano wire according to claim 7, it is characterized in that, during electroplating processes, adopt two electrolytic tanks, utilize three-electrode system, auxiliary electrode is iridium tantalum titanium electrode, and contrast electrode is saturated calomel electrode SCE, and working electrode is the anodic oxidation aluminium sheet of bottom spray platinum.
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