CN103424438A - Palladium plating multi-wall carbon nanotube smell sensor suitable for prawns - Google Patents
Palladium plating multi-wall carbon nanotube smell sensor suitable for prawns Download PDFInfo
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Abstract
The invention relates to the technical field of sensors, in particular to a palladium plating multi-wall carbon nanotube smell sensor suitable for prawns. The palladium plating multi-wall carbon nanotube smell sensor suitable for the prawns comprises a sensor sensitive film layer, a first electrode and a second electrode, wherein the sensor sensitive film layer, the first electrode and the second electrode are distributed in sequence from top to bottom. The second electrode is made of an aluminum plate through anodic oxidation. The first electrode is made of precious metal on the surface of the second electrode through the direct current magnetron sputtering technology. The sensor sensitive film layer is formed in the mode that palladium plating is conducted on the surface of a multi-wall nanotube after acid treatment and the surface of the first electrode is coated with the sensor sensitive film layer. The smell sensor has the advantages of being high in sensitivity, short in responding time, low in testing temperature and simple in structure.
Description
Technical field
The present invention relates to sensor technical field, be specifically related to a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn.
Background technology
Traditional gas sensor has numerous species, as galvanochemistry type gas sensor, frequency type gas sensor, doping method improve gas sensor, organic coordination compound gas sensor etc., in producing and living, is widely used.Traditional air-sensitive detection system ubiquity response speed slow, detect gaseous species few, repeatable low, easily be subject to the unfavorable factors such as such environmental effects such as temperature and air pressure, some detection systems are even huge because comprising the instrument mechanism such as microcomputer, and the Site Detection that has restricted the gas sensing system is used.
Prawn is more common a kind of shrimps, after fishing for, As time goes on, shrimp can produce rotten, the quality of shrimp quality is directly connected to people's health problem, but does not but have suitable sensor tip to monitor fast and effectively the quality of prawn at present.
Summary of the invention
The objective of the invention is for the problem for above-mentioned existence, solve at present not specially for prawn and sensor can quick and precisely the shrimp quality is detected over the ground, a kind of olfactory sensor that is applicable to prawn is provided.
In order to reach the foregoing invention purpose, the present invention by the following technical solutions:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The concentration change of tested gas can cause the conductivity variations of sensor sensing rete prepared by carbon nano-tube, dominant mechanism is that the sensor sensing rete is after adsorbed gas, variation has occurred in its electron energy band, and the variation by conductivity just can detect the size of gas concentration.
Anodic oxidation aluminum own wt is light, and therefore the sensor of preparation has superiority on weight, than the sensor of lightweight, is conducive to be fixed on different positions, is easy to use; The anodic oxidation aluminum has higher hardness simultaneously, not yielding and broken, can keep the shape maintains of sensor constant; Therefore the anodic oxidation aluminum has the characteristics of porous, is conducive to tested gas permeation enter, and increases the suction-operated for tested gas molecule of the carbon nano-tube that is attached on the anodic oxidation aluminum, increases and detects effect; The anodic oxidation aluminum has compatibility preferably, can and be plated between its surperficial metal and produces affinity, therefore is plated in its surperficial metal difficult drop-off, has increased the stability of sensor construction; The anodic oxidation aluminum also has fabulous electrical insulating property, it is hereby ensured that the first electrode works on a good dielectric base; The anodic oxidation aluminum is easy to preparation, and favorable repeatability, be convenient to large quantities of preparations.Therefore the sensor sensing rete is combined with anodised aluminium and prepares gas sensor and compare with other and there is more advantage.
The second electrode is prepared from by following steps: getting thickness is high-purity aluminium sheet of 1-5mm, at first ultrasonic cleaning 15-30min in the acetone that is 1-2:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 5-15min in the ethanol that is then 2-4:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.25-0.35mol/L, is anodic oxidation 0.5-1h under 25-40V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 45-50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 10-30min that 0.25-0.35mol/L, volume ratio are 1-3:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 20-40min, the anodic aluminum oxide film that is 3-10 μ m in high-purity aluminium sheet plated surface a layer thickness again, after taking-up, in temperature, be reaming 10-20min in 45-50 ℃, the mass percent phosphoric acid solution that is 3-6%, obtain porous anodic alumina template, be the second electrode.
Acetone and alcohol mixed solution can be removed the grease that surface of aluminum plate is adhered to preferably, guarantee the successful preparation of alumina formwork.If scavenging period is too short, high-purity surface of aluminum plate meeting residual impurity, scavenging period is too short, and the aluminium oxide of high-purity surface of aluminum plate reacts not exclusively with mixed solution, causes cleaning losing efficacy.Ethanol and perchloric acid mixed liquor have oxidation effectiveness preferably, can be by the surface of aluminum plate oxidizing polishing to minute surface, the purpose of polishing is to eliminate the surface scratch that aluminium sheet produces in process of production etc., and these cuts can cause the alumina formwork preparation to be subject to irreversible destruction.If roughness is excessive, so prepared alumina formwork flatness variation even ftractures, so just can't be on alumina formwork the sputter noble metal, can't prepare final sensor.At first high-purity aluminium sheet is carried out to anodic oxidation and the anodic aluminum oxide film obtained is removed, carry out again two-step anodization, because aluminium sheet is placed in air for a long time, some alumina compositions are contained on its surface, get rid of oxide layer after adopting once oxidation again, so newly expose whole are pure aluminums, the composition of the aluminium oxide produced after two-step anodization again is single, and purer, formed alumina layer is dense, thereby make the hole after reaming be not easy to subside.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 detected; The degree of adhering to of noble metal on alumina formwork that also is conducive to sputter, the stability of increase 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 the via hole overlong time, can reduce the degree of adhering to of noble metal on porous anodic alumina template.
The first electrode is prepared from by following steps: adopting the gold target of purity 5N is target, and the control base vacuum is 5.5-7 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 8-10W, and the thickness of finally controlling the first electrode is 30-50nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, add successively 65-70ml red fuming nitric acid (RFNA) and the 175-185ml concentrated sulphuric acid, under 35-45 ℃, ultrasonic continuous processing 7-8h, then use that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, by the multi-walled carbon nano-tubes after acidification, by washed with de-ionized water, to pH, be 6.8 ± 0.2 again, filtration is also dried in electric dry oven, obtains the acidifying multi-walled carbon nano-tubes;
Multi-walled carbon nano-tubes is after nitration mixture is processed, structure changes, the reactive group of surfaces externally and internally increases, air-sensitive response for organic gas strengthens, wherein 8 hours mixed acid-treated multi-walled carbon nano-tubes show than the more significant gas-sensitive property of many walls in other processing times carbon pipe: under normal temperature and pressure, in the organic gas low strength range, its responsive rate is along with gas concentration increases and the approximately linear increase.Due to Tilapia mossambica, the escaping gas concentration ratio in process is larger on the turn, so the multi-walled carbon nano-tubes of acidification just can have enough sensitivity to be detected.
2) at first get the palladium bichloride powder of 35-40mg, even with the deionized water dissolving vibration of 35-40mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 13-17 mC, then will plate the electrode that palladium is disposed and dry 30-60min under 600-650 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
The Pd particle has demonstrated good catalytic effect, and electronics and tested gas that Pd tends to capture the carbon pipe have formed Pd
δ+(CH
4)
δ-The weak bond compound.With regard to the hole that makes carbon nano-tube, increase like this, electricity is led and is become large.The carbon nano-tube of doping Pd has gradient response preferably to the gas of low concentration, thereby makes the highly sensitive of sensor sensing rete, and energy consumption is less.
Due to prawn on the turn the escaping gas in process do not have the concentration of fish large, be plated palladium on therefore will the carbon nano-tube after acidification to process, thus the sensitivity that improves the sensor sensing rete.
3) using deionized water as solvent, by step 2) the plating palladium multi-walled carbon nano-tubes that obtains is mixed with the suspension that mass percent is 10-20%, this suspension is evenly dripped and is applied on the first electrode, then under 50-80 ℃ through vacuum drying, the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 5-10 μ m.
As preferably, the internal diameter of described porous anodic alumina template reaming metapore is 20-60nm, and the spacing in hole is 40-60nm, and the degree of depth in hole is 2 ± 0.5 μ m.
As preferably, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 20-200nm.
As preferably, when will plate the palladium multi-walled carbon nano-tubes in step 3) and be mixed with suspension, add cupric oxide or silver oxide in suspension, cupric oxide or silver oxide add the 30-50% that weight is plating palladium multi-walled carbon nano-tubes.Cupric oxide or silver oxide add the sensitivity that can improve the sensor sensing rete, after interpolation, sensitivity improves 10-30%.
As preferably, when will plate the palladium multi-walled carbon nano-tubes in step 3) and be mixed with suspension, add oxide nano rare earth in suspension, oxide nano rare earth add the 20-40% that weight is plating palladium multi-walled carbon nano-tubes.Rare earth oxide add the sensitivity that can improve the sensor sensing rete, after interpolation, sensitivity improves 10-30%.
As preferably, described oxide nano rare earth is lanthana, cerium oxide or praseodymium oxide.
As preferablyIn the preparation of described sensor sensing rete, step 3) is: get step 2) carbon nano-tube 5-10g and polyglycol 0.5-2g, with ethanol, 100ml is mixed with mixed liquor, after ultrasonic being uniformly dispersed, at the first electrode surface, evenly apply, then heat 1-3h under 100-150 ℃, obtain the sensor sensing rete.After adopting polyglycol and carbon nano-tube to be mixed with solution with ethanol, apply film forming at the first electrode surface, then after drying, the polyglycol volatilization of being heated, thereby form cavity in become film, can increase the contact area of sensor sensing rete and gas like this, also being convenient to the inside that gas is deep into film enters in carbon nano-tube, improve the adsorbance of sensor sensing rete to gas, thereby improve the sensitivity of sensor sensing rete, adsorbance improves 5-15%, and sensitivity improves 5-10%.
As preferably, the molecular weight of described polyglycol is 600-900.Low-molecular-weight polyglycol is liquid, can better in solution, with carbon nano-tube, form mixed liquor, be convenient to apply film forming, also be convenient to the volatilization in later stage, thereby impel in become film and form cavity, and then the contact area of increase gas and institute's film forming, increase the sensitivity of sensor sensing rete.
The present invention is compared with prior art: olfactory sensor of the present invention, mainly for be prawn rotten after the comparatively complicated and more difficult problem be detected of the composition of gas, with other sensors, compare, have highly sensitive, response time is short, and probe temperature is low, and test condition is simpler, simple in structure, the advantage such as easily manufactured and with low cost.It is firm in structure in addition, and production cost is low, and favorable repeatability is convenient to batch production, and material source is extensive, and the preparation method is simple, and specificity is good.
The accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
The scanning electron microscope (SEM) photograph that Fig. 2 is the porous anodic alumina template surface;
Electric current-time plot that Fig. 3 is olfactory sensor;
Fig. 4 is the olfactory sensor response model of olfactory sensor to different cold preservation time prawn samples.
In figure: 1 sensor sensing rete, 2 first electrodes, 3 second electrodes, 4 aluminium sheets, 5 anodic aluminum oxide films.
Embodiment
Below by specific embodiment, technical scheme of the present invention is further described to explanation.
Embodiment 1:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, as shown in Figure 1, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The second electrode is prepared from by following steps:
Getting thickness is high-purity aluminium sheet of 1mm, ultrasonic cleaning 15min in the acetone that is at first 2:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 5min in the ethanol that is then 4:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.35mol/L, is anodic oxidation 1h under 25V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 45 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 30min that 0.35mol/L, volume ratio are 1:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 20min, the anodic aluminum oxide film that is 10 μ m in high-purity aluminium sheet plated surface a layer thickness again, be reaming 10min in 45 ℃, the mass percent phosphoric acid solution that is 6% in temperature after taking-up, obtain porous anodic alumina template, be the second electrode.Wherein the internal diameter of porous anodic alumina template reaming metapore is 60nm, and the spacing in hole is 40nm, and the degree of depth in hole is 2 ± 0. 5 μ m.
The first electrode is prepared from by following steps:
Adopting the gold target of purity 5N is target, and controlling base vacuum is 7 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 8W, and the thickness of finally controlling the first electrode is 50nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 200nm, add successively 65ml red fuming nitric acid (RFNA) and the 185ml concentrated sulphuric acid, under 35 ℃, ultrasonic continuous processing 8h, then used that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, then by the multi-walled carbon nano-tubes after acidification with washed with de-ionized water to pH be 6.8 ± 0.2, filter and dry in electric dry oven, obtaining the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 35mg, even with the deionized water dissolving vibration of 40mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 13mC, then will plate the electrode that palladium is disposed and dry 30min under 650 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) using deionized water as solvent, by step 2) the plating palladium multi-walled carbon nano-tubes that obtains is mixed with the suspension that mass percent is 20%, and add cupric oxide or silver oxide and oxide nano rare earth (lanthana, cerium oxide or praseodymium oxide) in suspension, the weight that adds of cupric oxide or silver oxide is 30% of plating palladium multi-walled carbon nano-tubes, and the weight that adds of oxide nano rare earth is 40% of plating palladium multi-walled carbon nano-tubes; This suspension is evenly dripped and is applied on the first electrode, then under 50 ℃ through vacuum drying, obtain the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 10 μ m.
Embodiment 2:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, as shown in Figure 1, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The second electrode is prepared from by following steps:
Getting thickness is high-purity aluminium sheet of 5mm, ultrasonic cleaning 30min in the acetone that is at first 1:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 15min in the ethanol that is then 2:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.25mol/L, is anodic oxidation 0.5h under 40V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 10min that 0.25mol/L, volume ratio are 3:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 40min, the anodic aluminum oxide film that is 3 μ m in high-purity aluminium sheet plated surface a layer thickness again, be reaming 20min in 50 ℃, the mass percent phosphoric acid solution that is 3% in temperature after taking-up, obtain porous anodic alumina template, be the second electrode.Wherein the internal diameter of porous anodic alumina template reaming metapore is 20nm, and the spacing in hole is 60nm, and the degree of depth in hole is 2 ± 0. 5 μ m.
The first electrode is prepared from by following steps:
Adopting the gold target of purity 5N is target, and controlling base vacuum is 5.5 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 10W, and the thickness of finally controlling the first electrode is 30nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 20nm, add successively 70ml red fuming nitric acid (RFNA) and the 175ml concentrated sulphuric acid, under 45 ℃, ultrasonic continuous processing 7h, then used that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, then by the multi-walled carbon nano-tubes after acidification with washed with de-ionized water to pH be 6.8 ± 0.2, filter and dry in electric dry oven, obtaining the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 40mg, even with the deionized water dissolving vibration of 35mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 17 mC, then will plate the electrode that palladium is disposed and dry 60min under 600 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) using deionized water as solvent, by step 2) the plating palladium multi-walled carbon nano-tubes that obtains is mixed with the suspension that mass percent is 10%, and add cupric oxide or silver oxide and oxide nano rare earth (lanthana, cerium oxide or praseodymium oxide) in suspension, the weight that adds of cupric oxide or silver oxide is 50% of plating palladium multi-walled carbon nano-tubes, and the weight that adds of oxide nano rare earth is 20% of plating palladium multi-walled carbon nano-tubes; This suspension is evenly dripped and is applied on the first electrode, then under 80 ℃ through vacuum drying, obtain the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 5 μ m.
Embodiment 3:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, as shown in Figure 1, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The second electrode is prepared from by following steps:
Getting thickness is high-purity aluminium sheet of 5mm, ultrasonic cleaning 30min in the acetone that is at first 1:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 15min in the ethanol that is then 2:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.25mol/L, is anodic oxidation 0.5h under 40V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 10min that 0.25mol/L, volume ratio are 3:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 40min, the anodic aluminum oxide film that is 3 μ m in high-purity aluminium sheet plated surface a layer thickness again, be reaming 20min in 50 ℃, the mass percent phosphoric acid solution that is 3% in temperature after taking-up, obtain porous anodic alumina template, be the second electrode.Wherein the internal diameter of porous anodic alumina template reaming metapore is 20nm, and the spacing in hole is 60nm, and the degree of depth in hole is 2 ± 0. 5 μ m.
The first electrode is prepared from by following steps:
Adopting the gold target of purity 5N is target, and controlling base vacuum is 5.5 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 10W, and the thickness of finally controlling the first electrode is 30nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 20nm, add successively 70ml red fuming nitric acid (RFNA) and the 175ml concentrated sulphuric acid, under 45 ℃, ultrasonic continuous processing 7h, then used that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, then by the multi-walled carbon nano-tubes after acidification with washed with de-ionized water to pH be 6.8 ± 0.2, filter and dry in electric dry oven, obtaining the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 40mg, even with the deionized water dissolving vibration of 35mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 17 mC, then will plate the electrode that palladium is disposed and dry 60min under 600 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) get step 2) carbon nano-tube 10g and the molecular weight polyglycol 0.5g that is 900, with ethanol, 100ml is mixed with mixed liquor, after ultrasonic being uniformly dispersed, at the first electrode surface, evenly apply, then heat 1h under 150 ℃, the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 5 μ m.
Embodiment 4:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, as shown in Figure 1, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The second electrode is prepared from by following steps:
Getting thickness is high-purity aluminium sheet of 3mm, ultrasonic cleaning 15min in the acetone that is at first 2:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 8min in the ethanol that is then 3:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.3mol/L, is anodic oxidation 1h under 25V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 30min that 0.35mol/L, volume ratio are 2:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 30min, the anodic aluminum oxide film that is 8 μ m in high-purity aluminium sheet plated surface a layer thickness again, after taking-up, in temperature, be reaming 10min in 50 ℃, the mass percent phosphoric acid solution that is 3-6%, obtain porous anodic alumina template, be the second electrode.Wherein the internal diameter of porous anodic alumina template reaming metapore is 40nm, and the spacing in hole is 60nm, and the degree of depth in hole is 2 ± 0. 5 μ m.
The first electrode is prepared from by following steps:
Adopting the gold target of purity 5N is target, and controlling base vacuum is 6 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 10W, and the thickness of finally controlling the first electrode is 50nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 100nm, add successively 70ml red fuming nitric acid (RFNA) and the 178ml concentrated sulphuric acid, under 45 ℃, ultrasonic continuous processing 8h, then used that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, then by the multi-walled carbon nano-tubes after acidification with washed with de-ionized water to pH be 6.8 ± 0.2, filter and dry in electric dry oven, obtaining the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 40mg, even with the deionized water dissolving vibration of 35mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 15mC, then will plate the electrode that palladium is disposed and dry 60min under 630 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) using deionized water as solvent, by step 2) the plating palladium multi-walled carbon nano-tubes that obtains is mixed with the suspension that mass percent is 13%, and add cupric oxide or silver oxide and oxide nano rare earth (lanthana, cerium oxide or praseodymium oxide) in suspension, the weight that adds of cupric oxide or silver oxide is 40% of plating palladium multi-walled carbon nano-tubes, and the weight that adds of oxide nano rare earth is 25% of plating palladium multi-walled carbon nano-tubes; This suspension is evenly dripped and is applied on the first electrode, then under 60 ℃ through vacuum drying, obtain the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 8 μ m.
Embodiment 5:
A kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, as shown in Figure 1, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment.
The second electrode is prepared from by following steps:
Getting thickness is high-purity aluminium sheet of 3mm, ultrasonic cleaning 15min in the acetone that is at first 2:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 8min in the ethanol that is then 3:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.3mol/L, is anodic oxidation 1h under 25V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 30min that 0.35mol/L, volume ratio are 2:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 30min, the anodic aluminum oxide film that is 8 μ m in high-purity aluminium sheet plated surface a layer thickness again, after taking-up, in temperature, be reaming 10min in 50 ℃, the mass percent phosphoric acid solution that is 3-6%, obtain porous anodic alumina template, be the second electrode.Wherein the internal diameter of porous anodic alumina template reaming metapore is 40nm, and the spacing in hole is 60nm, and the degree of depth in hole is 2 ± 0. 5 μ m.
The first electrode is prepared from by following steps:
Adopting the gold target of purity 5N is target, and controlling base vacuum is 6 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 10W, and the thickness of finally controlling the first electrode is 50nm.
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 100nm, add successively 70ml red fuming nitric acid (RFNA) and the 178ml concentrated sulphuric acid, under 45 ℃, ultrasonic continuous processing 8h, then used that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, then by the multi-walled carbon nano-tubes after acidification with washed with de-ionized water to pH be 6.8 ± 0.2, filter and dry in electric dry oven, obtaining the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 40mg, even with the deionized water dissolving vibration of 35mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 15mC, then will plate the electrode that palladium is disposed and dry 60min under 630 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) get step 2) carbon nano-tube 5g and the molecular weight polyglycol 2g that is 700, with ethanol, 100ml is mixed with mixed liquor, after ultrasonic being uniformly dispersed, at the first electrode surface, evenly apply, then heat 3h under 100 ℃, the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 8 μ m.
The Performance Detection of olfactory sensor characterizes:
Select prawns meat that 4 ℃ of cold preservation times are 0 day, 2 days, 4 days, 6 days, 8 days as testing sample.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 an 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 the sensor response that the response time of sensor is set as being exposed to gas to be measured from sensor, and secondary response is stable again to be set as being blown into sensor from drying nitrogen release time.All experiments are all at room temperature carried out.
Sensor resistance relative change rate's calculating formula is:
Wherein,
Sheet resistance value for sensor in drying nitrogen,
For the sheet resistance value of sensor in gas to be measured.By comparing
Size just can understand the air-sensitive response of sensor, therefore also can by
Be considered as the sensitivity of sensor.
Electric current-the time curve of Fig. 3 olfactory sensor, all can be observed out by Fig. 3, after each sensor adsorbs gas to be measured, adopts to pass into nitrogen purge and can not make its complete desorption, and this trend is later more obvious sensor follow-on test 3 times.If directly by the curent change value before and after sensor contact gas, than the electric current initial value of upper sensor, characterize, just be difficult to react accurately the graded situation in follow-on test.
Because electric current-time test carries out under constant voltage, due to
, therefore
Calculating formula after deriving, can all with the Electrochemical Detection reometer, show:
In formula,
Initial current value for sensor.
For sensor is exposed to the stationary value again that detects electric current in the sample bottle that fills the prawn sample.This value is closely related with the adsorption-desorption characteristic of sensor air-sensitive film.Therefore, can reflect more accurately the sensor sensing response of certain cold preservation time prawn sample with the current change quantity of sensor than the stationary value again of sensor current in upper each test.
Obtain the linear functional relation formula between sensor resistance variation and prawn cold preservation time according to the many experiments data fitting, be shown below:
，
The olfactory sensor response model of olfactory sensor to different cold preservation time prawn samples, as shown in Figure 4.
Claims (8)
1. a plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn, it is characterized in that, comprise the sensor sensing rete, the first electrode and the second electrode that distribute successively from top to bottom, the second electrode is prepared from through anodic oxidation by aluminium sheet, the first electrode is for adopting magnetically controlled DC sputtering technique to be prepared from the second electrode surface noble metal, and then the sensor sensing rete is applied and form at the first electrode surface after the plated surface palladium by the multi-walled carbon nano-tubes after peracid treatment;
The second electrode is prepared from by following steps:Getting thickness is high-purity aluminium sheet of 1-5mm, ultrasonic cleaning 15-30min in the acetone that is at first 1-2:1 by it in volume ratio and alcohol mixed solution, polishing (Ra≤0.01 μ m) 5-15min in the ethanol that is then 2-4:1 in volume ratio and perchloric acid mixed solution; Then, with deionized water, cleaning and insert in the oxalic acid solution of 0.25-0.35mol/L, is anodic oxidation 0.5-1h under 25-40V in DC voltage, at high-purity aluminium sheet plated surface anodic aluminum oxide film; Then being placed in temperature and being 45-50 ℃, volumetric molar concentration is phosphoric acid and the chromic acid mixed solution 10-30min that 0.25-0.35mol/L, volume ratio are 1-3:1, removes anodic aluminum oxide film; Then under the same conditions after two-step anodization 20-40min, the anodic aluminum oxide film that is 3-10 μ m in high-purity aluminium sheet plated surface a layer thickness again, after taking-up, in temperature, be reaming 10-20min in 45-50 ℃, the mass percent phosphoric acid solution that is 3-6%, obtain porous anodic alumina template, be the second electrode;
The first electrode is interdigital electrode,By following steps, be prepared from: adopting the gold target of purity 5N is target, and the control base vacuum is 5.5-7 * 10
-3Pa, starting voltage are that the power that 0.26kV, electric current are 25mA, d.c. sputtering process is 8-10W, and the thickness of finally controlling the first electrode is 30-50nm;
The preparation of sensor sensing rete comprises the steps:
1) get respectively the multi-walled carbon nano-tubes of 200mg, add successively 65-70ml red fuming nitric acid (RFNA) and the 175-185ml concentrated sulphuric acid, under 35-45 ℃, ultrasonic continuous processing 7-8h, then use that hydro-extractor is centrifugal separates multi-walled carbon nano-tubes, by the multi-walled carbon nano-tubes after acidification, by washed with de-ionized water, to pH, be 6.8 ± 0.2 again, filtration is also dried in electric dry oven, obtains the acidifying multi-walled carbon nano-tubes;
2) at first get the palladium bichloride powder of 35-40mg, even with the deionized water dissolving vibration of 35-40mL, be mixed with palladium chloride solution, then get the 15mL palladium chloride solution, the electric current of employing CHI660 electrochemical analyser-time method is carried out electroplating processes, be made as-0.48V of recovery voltage, working electrode connects the electrode that scribbles the acidifying multi-walled carbon nano-tubes, contrast electrode connects mercurous chloride electrode, electrode is connect to platinum electrode, by controlling electroplating time, make the plating quantity of electric charge be respectively 13-17 mC, then will plate the electrode that palladium is disposed and dry 30-60min under 600-650 ℃, obtain plating the palladium multi-walled carbon nano-tubes,
3) using deionized water as solvent, by step 2) the plating palladium multi-walled carbon nano-tubes that obtains is mixed with the suspension that mass percent is 10-20%, this suspension is evenly dripped and is applied on the first electrode, then under 50-80 ℃ through vacuum drying, the sensor sensing rete, and the thickness of finally controlling the sensor sensing rete is 5-10 μ m.
2. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 1, it is characterized in that, the internal diameter of described porous anodic alumina template reaming metapore is 20-60nm, and the spacing in hole is 40-60nm, and the degree of depth in hole is 2 ± 0.5 μ m.
3. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 1, is characterized in that, the diameter of many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is 20-200nm.
4. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 1, it is characterized in that, when will plate the palladium multi-walled carbon nano-tubes in step 3) and be mixed with suspension, add cupric oxide or silver oxide in suspension, the weight that adds of cupric oxide or silver oxide is to plate the 30-50% of palladium multi-walled carbon nano-tubes.
5. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 1, it is characterized in that, when will plate the palladium multi-walled carbon nano-tubes in step 3) and be mixed with suspension, add oxide nano rare earth in suspension, the weight that adds of oxide nano rare earth is to plate the 20-40% of palladium multi-walled carbon nano-tubes.
6. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 5, is characterized in that, described oxide nano rare earth is lanthana, cerium oxide or praseodymium oxide.
7. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 1, it is characterized in that, in the preparation of described sensor sensing rete, step 3) is: get step 2) carbon nano-tube 5-10g and polyglycol 0.5-2g, with ethanol, 100ml is mixed with mixed liquor, after ultrasonic being uniformly dispersed, evenly apply at the first electrode surface, then under 100-150 ℃, heat 1-3h, obtain the sensor sensing rete.
8. a kind of plating palladium multi-walled carbon nano-tubes olfactory sensor that is applicable to prawn according to claim 7, is characterized in that, the molecular weight of described polyglycol is 600-900.
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