CN102183568B - Formaldehyde electrochemical sensor - Google Patents
Formaldehyde electrochemical sensor Download PDFInfo
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- CN102183568B CN102183568B CN 201110035727 CN201110035727A CN102183568B CN 102183568 B CN102183568 B CN 102183568B CN 201110035727 CN201110035727 CN 201110035727 CN 201110035727 A CN201110035727 A CN 201110035727A CN 102183568 B CN102183568 B CN 102183568B
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Abstract
The invention relates to a formaldehyde electrochemical sensor which is a three-electrode electrochemical sensor. The formaldehyde electrochemical sensor comprises a working electrode, a reference electrode and an auxiliary electrode. A manufacture method for the working electrode comprises the following steps of: 1, mixing bismuth sulfide nanorods with a phosphate buffer solution in a certain percentage, and carrying out the ultrasonic dispersion on the mixed liquid to obtain bismuth sulfide nanorod dispersion liquid; 2, taking the bismuth sulfide nanorod dispersion liquid obtained in the step 1 to drop and smear on the surface of a blank glassy carbon electrode, drying at room temperature to obtain modified electrodes to be tested; and 3, detecting a volt-ampere characteristic curve of a potassium ferricyanide solution by using the modified electrode to be tested, which is obtained in the step 2, and picking out the modified electrode which can obtain a reversible oxidation-reduction peak to serve as the working electrode of the three-electrode electrochemical sensor. The surface of the electrode provided by the invention can not easily be contaminated and the sensor has a long service life and a high sensitivity; simultaneously, the formaldehyde electrochemical sensor can be used for measuring the methanol concentration precisely, and has the advantages of low manufacture cost and convenience for use.
Description
Technical field
The present invention relates to the electrochemical sensor field, more particularly, relate to a kind of formaldehyde electrochemical sensor based on bismuth sulfide nano-rod.
Background technology
Along with the raising of living standards of the people, interior decoration more and more has been applied to family and public place.Often contain the poisonous and harmful elements such as formaldehyde in various finishing materials and the furniture, the serious harm people's is healthy.Therefore the detection of these class objectionable constituent become the task of top priority.Detect the most effective approach of formaldehyde and adopt exactly sensing technology.The at present detection of people's PARA FORMALDEHYDE PRILLS(91,95) mainly contains semiconductor gas sensor, optical sensor and electrochemical sensor etc.Although wherein optical sensor is highly sensitive, since expensive, exceed general user's ability to bear, thereby can not get well popularizing.And most semiconductor gas sensor exists the alarm of not high, the easy generation of selectivity mistake, can not quantitatively detect and need the defective such as heating arrangement, thereby generally can only use as alarm.It is wide, low in energy consumption and can be used for the advantage such as field monitoring that electrochemical sensor has volume concentration range little, that detect, be used widely in fields such as industrial and agricultural production and routine testings, particularly have very important application potential aspect the detection formaldehyde content in indoor air.
The core component of electrochemical sensor often adopts platinum, gold, carbon etc. as electrode material.But, above-mentioned electrode material surperficial as easy as rolling off a log contaminated, thus seriously limited serviceable life and the sensitivity of traditional electrochemical sensor.In recent years, various nano particles such as carbon nano-tube and metal nanoparticle etc., have been introduced into electrochemical sensor as electrode modified material, have effectively improved the detection sensitivity of electrochemical sensor.Because the impact that the material of nano particle, pattern can produce on the electrochemical response signal of object outbalance.Therefore, in electrochemical sensor, introduce the nano material with good electric catalytic activity and might obtain better to detect effect.
Bismuth sulfide is a kind of important semiconductor material, has potential using value at aspects such as thermoelectricity, electronics and optoelectronic devices.In recent years, the bismuth sulfide of nanometer has shown good application prospect at aspects such as luminescent material, catalysis material, sensing materials especially.But, according to retrieval, utilize bismuth sulfide nano material to prepare the detection that electrochemical sensor also is used for formaldehyde, at home and abroad be not reported.
Summary of the invention
The problem to be solved in the present invention is, for the existing electrochemical sensor that detects formaldehyde, because electrode material surface is easily contaminated, and cause the defective of sensor life-time minimizing and sensitivity, a kind of long-life and highly sensitive formaldehyde electrochemical sensor are provided.
The present invention addresses the above problem and the technical scheme taked is, a kind of formaldehyde electrochemical sensor is provided, is the three-electrode electro Chemical sensor, comprise working electrode, contrast electrode and auxiliary electrode, described working electrode is the bismuth sulfide nano-rod modified electrode, and the method for making of described working electrode comprises:
Step 2 is got the bismuth sulfide nano-rod dispersion liquid 8 μ L that obtain in the described step 1～12 μ L and is dripped and be coated in blank glass-carbon electrode surface, after the drying at room temperature, obtains modified electrode to be tested;
Step 3, utilize the modified electrode described to be tested that obtains in the described step 2 to detect the volt-ampere characteristic of potassium ferricyanide solution, pick out the modified electrode that can access reversible redox peak as the working electrode of described three-electrode electro Chemical sensor.
In formaldehyde electrochemical sensor of the present invention, the ratio of weight and number of bismuth sulfide nano-rod and phosphate buffer solution described in the described step 1 is 1: 99.
In formaldehyde electrochemical sensor of the present invention, the concentration of phosphate buffer described in the described step 1 is 0.1mol/L.
In formaldehyde electrochemical sensor of the present invention, the time of carrying out ultrasonic dispersion in the described step 1 is 20 minutes.
In formaldehyde electrochemical sensor of the present invention, get described bismuth sulfide nano-rod dispersion liquid 10 μ L in the described step 2 and drip and be coated in blank glass-carbon electrode surface.
In formaldehyde electrochemical sensor of the present invention, in the described step 2 drip be coated with before, described blank glass-carbon electrode is polished and is cleaned.
In formaldehyde electrochemical sensor of the present invention, utilize the aluminum oxide polishing powder described blank glass-carbon electrode of polishing, after the polishing, clean described blank glass-carbon electrode at ethanol and deionized water for ultrasonic successively.
In formaldehyde electrochemical sensor of the present invention, described bismuth sulfide nano-rod is synthetic by hydro-thermal method.
In formaldehyde electrochemical sensor of the present invention, the contrast electrode of described formaldehyde electrochemical sensor is saturated calomel electrode.
In formaldehyde electrochemical sensor of the present invention, the auxiliary electrode of described formaldehyde electrochemical sensor is platinum plate electrode.
Implement methyl alcohol electrochemical sensor provided by the invention and have following beneficial effect: electrode surface is difficult for contaminated, sensor long service life and highly sensitive; Simultaneously, the methyl alcohol electrochemical sensor can accurately be measured methanol concentration, low cost of manufacture and easy to use.
Description of drawings
Fig. 1 is the working electrode method for making process flow diagram of methyl alcohol electrochemical sensor of the present invention;
Fig. 2 is the electron microscope scanning image of the working electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention;
When Fig. 3 is the methyl alcohol of cyclic voltammetry detection same concentrations, the working electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention and the Current-potential curve figure of blank glass-carbon electrode;
Fig. 4 is when detecting the methyl alcohol of same concentrations under the idiostatic condition, the electric current-time plot of methyl alcohol electrochemical sensor embodiment 1 working electrode of the present invention and blank glass-carbon electrode;
Fig. 5 is when detecting the methyl alcohol of variable concentrations under the idiostatic condition, the electric current-concentration curve of electrochemical sensor embodiment 1 working electrode of the present invention.
Embodiment
The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.
Formaldehyde electrochemical sensor of the present invention is three electrode sensors, and three electrodes are respectively working electrode, contrast electrode and auxiliary electrode.Three electrodes consist of two loops, a loop is comprised of working electrode and contrast electrode, be used for the electrochemical reaction process of test measured matter on working electrode, another loop is comprised of working electrode and auxiliary electrode, is used for the effect that transmission electronic forms the loop.
The inventive point of formaldehyde electrochemical sensor of the present invention is the glass-carbon electrode that working electrode adopts bismuth sulfide nano-rod to modify, namely in the glass-carbon electrode surface coverage bismuth sulfide nano-rod sensitive membrane of blank.See also Fig. 1, be the working electrode method for making process flow diagram of methyl alcohol electrochemical sensor of the present invention.As shown in Figure 1, bismuth sulfide nano-rod mixes by ultrasonic dispersion with phosphate buffer, obtains the bismuth sulfide dispersion liquid.Untreated blank glass-carbon electrode becomes the blank glass-carbon electrode for the treatment of titration after polishing and cleaning.Above-mentioned bismuth sulfide dispersant liquid drop is coated in the above-mentioned blank glass-carbon electrode for the treatment of titration, just obtains modified electrode to be tested.The modified electrode that is up to the standards is exactly the required working electrode of formaldehyde electrochemical sensor of the present invention.
The below will specifically set forth three specific embodiments of formaldehyde electrochemical sensor of the present invention.
Introduce first methyl alcohol electrochemical sensor embodiment 1 of the present invention
Step 1.1 is processed blank glass-carbon electrode
Use abrasive paper for metallograph, for example the Al of 0.05 μ m
2O
3Burnishing powder, the blank glass-carbon electrode of polishing diameter 3mm makes the substrate surface of blank glass-carbon electrode smooth smooth.Again should the blank glass-carbon electrode, in ethanol and deionized water, utilize ultrasonic the cleaning successively, obtain waiting to drip a blank glass-carbon electrode that is coated with.
Step 1.2, the preparation bismuth sulfide nano-rod
By the synthetic bismuth sulfide nano-rod of hydro-thermal method, concrete synthesis step is: directly synthesized BiCl take Bi powder and hydrochloric acid as raw material
3, with the BiCl of 1mmol
3In 50ml ethanol, be mixed to get black diethyldithiocar bamic acid bismuth precipitation (Bi (S with the sodium diethyldithiocarbamate of 3mmol
2CNEt
2)
3).With gained Bi (S
2CNEt
2)
3At room temperature clean for several times with distilled water and ethanol, and carry out centrifugal treating.With 0.4gBi (S
2CNEt
2)
3Mix to be placed on 50ml and to contain in the teflon-lined stainless steel cauldron with 30ml distilled water, and sealing, under 180 ℃ of conditions, be incubated 12h, then naturally cool to room temperature.In reactor, obtain black precipitate, cleaned for several times with distilled water and absolute ethyl alcohol, and centrifugal treating, in vacuum drying chamber, dried in 50 ℃, obtained bismuth sulfide nano-rod.The bismuth sulfide nano-rod diameter that obtains is 50 to 150nm, and length is 5 to 10 μ m.
Step 1.3, preparation bismuth sulfide nano-rod dispersion liquid
The phosphate buffer solution that the bismuth sulfide nano-rod that obtains in the 1g step 1.2 and 99g concentration are 0.1mol/L fully mixes, and this mixed liquor is carried out 20 minutes ultrasonic dispersion, obtains the black bismuth sulfide nano-rod dispersion liquid of homogeneous;
Step 1.4 prepares modified electrode to be tested
Get the bismuth sulfide nano-rod dispersion liquid that obtains in the 10 μ L steps 1.3, even is coated in treating of obtaining in the step 1.1 and after the drying at room temperature, obtains modified electrode to be tested on the blank glass-carbon electrode surface that is coated with.
Step 1.5 is selected qualified modified electrode
The modified electrode to be tested that obtains in the step 1.4 is detected the volt-ampere characteristic of potassium ferricyanide solution, pick out can access reversible redox peak modified electrode as qualified bismuth sulfide nano-rod modified electrode.
Step 1.6, the structure formaldehyde electrochemical sensor
As working electrode, saturated calomel electrode is as contrast electrode with the qualified modified electrode that obtains in the step 1.5, and platinum plate electrode is as auxiliary electrode, and concentration is that the potassium hydroxide solution of 0.01mol/L is as medium solution.Connectivity scenario according to prior art constructs formaldehyde electrochemical sensor.
See also Fig. 2, be the electron microscope scanning image of the working electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention.As shown in Figure 2, the surface distributed of the working electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention has bismuth sulfide nano-rod, and the diameter of bismuth sulfide nano-rod is 50 to 150nm, and length is 5 to 10 μ m.
See also Fig. 3, when detecting the methyl alcohol of same concentrations for cyclic voltammetry, the working electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention and the Current-potential curve figure of blank glass-carbon electrode.The bit scan scope is-1.0～1.0V, and sweep speed is 50mV/s.Dividing three groups tests: the working electrode of experiment a is blank glass-carbon electrode, and medium solution is the potassium hydroxide solution of 0.01mol/L, contains 1.0 * 10 in the medium solution
-4The formalin of mol/L; The working electrode of experiment b is the bismuth sulfide nano-rod modified electrode, and medium solution is the potassium hydroxide solution of 0.01mol/L, does not contain formaldehyde in the medium solution; The working electrode of experiment c is the bismuth sulfide nano-rod modified electrode, and medium solution is the potassium hydroxide solution of 0.01mol/L, contains 1.0 * 10 in the medium solution
-4The formalin of mol/L.Experiment a and experiment b are the contrasts of experiment c.
As shown in Figure 3, the result of experiment a, experiment b, experiment c is reflected by curve a, curve b, curve c respectively.Curve a for the experiment a the result, the response of blank glass-carbon electrode in the mixed solution of formaldehyde and potassium hydroxide, can find out that response signal very a little less than.Curve b is the result of experiment b, the response of bismuth sulfide nano-rod modified electrode in potassium hydroxide solution, can find out at-0.40V place one oxidation peak is arranged, electrochemical process corresponding to bismuth sulfide nano-rod, do not have the galvanochemistry peak at the positive potential place, illustrate that bismuth sulfide nano-rod does not have electrochemical reaction at the positive potential place.Curve c is the result of experiment c, the response of bismuth sulfide nano-rod modified electrode in the mixed solution of formaldehyde and potassium hydroxide, can find out-oxidation peak of the bismuth sulfide nano-rod at 0.40V place still exists, and a very strong oxidation peak occurred at the 0.40V place, corresponding to the oxidizing process of formaldehyde.The current value of the oxidation peak of formaldehyde has reached 485 microamperes, be far longer than the current value of formaldehyde on blank electrode, illustrate that bismuth sulfide nano-rod sensitive membrane PARA FORMALDEHYDE PRILLS(91,95) has extraordinary response, therefore, formaldehyde electrochemical sensor provided by the invention can detect formaldehyde delicately.
See also Fig. 4, when detecting the methyl alcohol of same concentrations under the idiostatic condition, the electric current-time plot of methyl alcohol electrochemical sensor embodiment 1 working electrode of the present invention and blank glass-carbon electrode.Because for cyclic voltammetry, electric current-time curve has higher sensitivity, therefore under the constant potential condition, study the current signal of formaldehyde on blank electrode and bismuth sulfide nano-rod modified electrode.Under the 0.4V constant potential, compare 1.0 * 10
-4Mol/L formaldehyde is the time dependent situation of current signal on bismuth sulfide nano-rod modified electrode and blank glass-carbon electrode.
As shown in Figure 4, curve d is the electric current-time curve of blank electrode, and curve e is the electric current-time curve of bismuth sulfide nano-rod modified electrode.In the formalin of same concentrations, and other condition determinations are when identical, and the response of formaldehyde on the bismuth sulfide nano-rod modified electrode of methyl alcohol electrochemical sensor embodiment 1 of the present invention is more than seven times of blank electrode.This explanation, methyl alcohol electrochemical sensor of the present invention can detect the methyl alcohol of low concentration effectively.
See also Fig. 5, when detecting the methyl alcohol of variable concentrations under the idiostatic condition, the electric current-concentration curve of electrochemical sensor embodiment 1 working electrode of the present invention.Under the constant potential 0.40V, working electrode is the bismuth sulfide nano-rod modified electrode, and medium solution is the potassium hydroxide solution of 0.01mol/L.When containing the formalin of 0.0001mol/L in the medium solution, the current value of surveying work electrode; When containing the formalin of 0.005mol/L in the medium solution, the current value of surveying work electrode; When containing the formalin of 0.01mol/L in the medium solution, the current value of surveying work electrode; When containing the formalin of 0.05mol/L in the medium solution, the current value of surveying work electrode; When containing the formalin of 0.10mol/L in the medium solution, the current value of surveying work electrode.
As shown in Figure 5, in the concentration range of 0.0001～0.10mol/L, present good linear relationship between concentration of formaldehyde and current signal, related coefficient reaches 0.995.
Introduce again methyl alcohol electrochemical sensor embodiment 2 of the present invention and embodiment 3
Embodiment 2 may further comprise the steps:
Step 2.1 is processed blank glass-carbon electrode
Use abrasive paper for metallograph, for example the Al of 0.05 μ m
2O
3Burnishing powder, the blank glass-carbon electrode of polishing diameter 3mm makes the substrate surface of blank glass-carbon electrode smooth smooth.Again should the blank glass-carbon electrode, in ethanol and deionized water, utilize ultrasonic the cleaning successively, obtain waiting to drip a blank glass-carbon electrode that is coated with.
Step 2.2, the preparation bismuth sulfide nano-rod
By the synthetic bismuth sulfide nano-rod of hydro-thermal method, concrete synthesis step is: directly synthesized BiCl take Bi powder and hydrochloric acid as raw material
3, with the BiCl of 1mmol
3In 50ml ethanol, be mixed to get black diethyldithiocar bamic acid bismuth precipitation (Bi (S with the sodium diethyldithiocarbamate of 3mmol
2CNEt
2)
3).With gained Bi (S
2CNEt
2)
3At room temperature clean for several times with distilled water and ethanol, and carry out centrifugal treating.With 0.4gBi (S
2CNEt
2)
3Mix to be placed on 50ml and to contain in the teflon-lined stainless steel cauldron with 30ml distilled water, and sealing, under 180 ℃ of conditions, be incubated 12h, then naturally cool to room temperature.In reactor, obtain black precipitate, cleaned for several times with distilled water and absolute ethyl alcohol, and centrifugal treating, in vacuum drying chamber, dried in 50 ℃, obtained bismuth sulfide nano-rod.The bismuth sulfide nano-rod diameter that obtains is 50 to 150nm, and length is 5 to 10 μ m.
Step 2.3, preparation bismuth sulfide nano-rod dispersion liquid
The phosphate buffer solution that the bismuth sulfide nano-rod that obtains in the 1g step 2.2 and 89g concentration are 0.1mol/L fully mixes, and this mixed liquor is carried out 20 minutes ultrasonic dispersion, obtains the black bismuth sulfide nano-rod dispersion liquid of homogeneous;
Step 2.4 prepares modified electrode to be tested
Get the bismuth sulfide nano-rod dispersion liquid that obtains in the 8 μ L steps 2.3, even is coated in treating of obtaining in the step 2.1 and after the drying at room temperature, obtains modified electrode to be tested on the blank glass-carbon electrode surface that is coated with.
Step 2.5 is selected qualified modified electrode
The modified electrode to be tested that obtains in the step 2.4 is detected the volt-ampere characteristic of potassium ferricyanide solution, pick out can access reversible redox peak modified electrode as qualified bismuth sulfide nano-rod modified electrode.
Step 2.6, the structure formaldehyde electrochemical sensor
As working electrode, saturated calomel electrode is as contrast electrode with the qualified modified electrode that obtains in the step 2.5, and platinum plate electrode is as auxiliary electrode, and concentration is that the potassium hydroxide solution of 0.01mol/L is as medium solution.Connectivity scenario according to prior art constructs formaldehyde electrochemical sensor.
Embodiment 3 may further comprise the steps:
Step 3.1 is processed blank glass-carbon electrode
Use abrasive paper for metallograph, for example the Al of 0.05 μ m
2O
3Burnishing powder, the blank glass-carbon electrode of polishing diameter 3mm makes the substrate surface of blank glass-carbon electrode smooth smooth.Again should the blank glass-carbon electrode, in ethanol and deionized water, utilize ultrasonic the cleaning successively, obtain waiting to drip a blank glass-carbon electrode that is coated with.
Step 3.2, the preparation bismuth sulfide nano-rod
By the synthetic bismuth sulfide nano-rod of hydro-thermal method, concrete synthesis step is: directly synthesized BiCl take Bi powder and hydrochloric acid as raw material
3, with the BiCl of 1mmol
3In 50ml ethanol, be mixed to get black diethyldithiocar bamic acid bismuth precipitation (Bi (S with the sodium diethyldithiocarbamate of 3mmol
2CNEt
2)
3).With gained Bi (S
2CNEt
2)
3At room temperature clean for several times with distilled water and ethanol, and carry out centrifugal treating.With 0.4gBi (S
2CNEt
2)
3Mix to be placed on 50ml and to contain in the teflon-lined stainless steel cauldron with 30ml distilled water, and sealing, under 180 ℃ of conditions, be incubated 12h, then naturally cool to room temperature.In reactor, obtain black precipitate, cleaned for several times with distilled water and absolute ethyl alcohol, and centrifugal treating, in vacuum drying chamber, dried in 50 ℃, obtained bismuth sulfide nano-rod.The bismuth sulfide nano-rod diameter that obtains is 50 to 150nm, and length is 5 to 10 μ m.
Step 3.3, preparation bismuth sulfide nano-rod dispersion liquid
The phosphate buffer solution that the bismuth sulfide nano-rod that obtains in the 1g step 3.2 and 109g concentration are 0.1mol/L fully mixes, and this mixed liquor is carried out 20 minutes ultrasonic dispersion, obtains the black bismuth sulfide nano-rod dispersion liquid of homogeneous;
Step 3.4 prepares modified electrode to be tested
Get the bismuth sulfide nano-rod dispersion liquid that obtains in the 12 μ L steps 3.3, even is coated in treating of obtaining in the step 3.1 and after the drying at room temperature, obtains modified electrode to be tested on the blank glass-carbon electrode surface that is coated with.
Step 3.5 is selected qualified modified electrode
The modified electrode to be tested that obtains in the step 3.4 is detected the volt-ampere characteristic of potassium ferricyanide solution, pick out can access reversible redox peak modified electrode as qualified bismuth sulfide nano-rod modified electrode.
Step 3.6, the structure formaldehyde electrochemical sensor
As working electrode, saturated calomel electrode is as contrast electrode with the qualified modified electrode that obtains in the step 3.5, and platinum plate electrode is as auxiliary electrode, and concentration is that the potassium hydroxide solution of 0.01mol/L is as medium solution.Connectivity scenario according to prior art constructs formaldehyde electrochemical sensor.
Also carry out the experiment carried out for embodiment 1 for embodiment 2, in the time of can obtaining respectively cyclic voltammetry and detect the methyl alcohol of same concentrations, the working electrode of methyl alcohol electrochemical sensor embodiment 2 of the present invention and the Current-potential curve figure of blank glass-carbon electrode; When detecting the methyl alcohol of same concentrations under the idiostatic condition, the electric current-time plot of methyl alcohol electrochemical sensor embodiment 2 working electrodes of the present invention and blank glass-carbon electrode; When detecting the methyl alcohol of variable concentrations under the idiostatic condition, the electric current-concentration curve of electrochemical sensor embodiment 2 working electrodes of the present invention.
Also carry out the experiment carried out for embodiment 1 for embodiment 3, in the time of can obtaining respectively cyclic voltammetry and detect the methyl alcohol of same concentrations, the working electrode of methyl alcohol electrochemical sensor embodiment 3 of the present invention and the Current-potential curve figure of blank glass-carbon electrode; When detecting the methyl alcohol of same concentrations under the idiostatic condition, the electric current-time plot of methyl alcohol electrochemical sensor embodiment 3 working electrodes of the present invention and blank glass-carbon electrode; When detecting the methyl alcohol of variable concentrations under the idiostatic condition, the electric current-concentration curve of electrochemical sensor embodiment 3 working electrodes of the present invention.
The above-mentioned experiment of doing for embodiment 2 and embodiment 3 respectively all can access the result close with embodiment 1, just repeats no more herein.Generally speaking, electrode surface provided by the invention is difficult for contaminated, sensor long service life and highly sensitive; Simultaneously, the methyl alcohol electrochemical sensor can accurately be measured methanol concentration, low cost of manufacture and easy to use.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure transformation that utilizes instructions of the present invention and accompanying drawing content to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (6)
1. formaldehyde electrochemical sensor, be the three-electrode electro Chemical sensor, comprise working electrode, contrast electrode and auxiliary electrode, it is characterized in that, described contrast electrode is saturated calomel electrode, described auxiliary electrode is platinum plate electrode, and described working electrode is the bismuth sulfide nano-rod modified electrode, and the method for making of described working electrode comprises:
Step 1 after the ratio mixing according to the parts by weight of 1:89 to 1:109, is carried out ultrasonic dispersion to mixed liquor with bismuth sulfide nano-rod and phosphate buffer solution, obtains the bismuth sulfide nano-rod dispersion liquid;
Step 2 is got the bismuth sulfide nano-rod dispersion liquid 8 μ L that obtain in the described step 1 ~ 12 μ L and is dripped and be coated in blank glass-carbon electrode surface, after the drying at room temperature, obtains modified electrode to be tested;
Step 3, utilize the modified electrode described to be tested that obtains in the described step 2 to detect the volt-ampere characteristic of potassium ferricyanide solution, pick out the modified electrode that can access reversible redox peak as the working electrode of described three-electrode electro Chemical sensor.
2. formaldehyde electrochemical sensor according to claim 1 is characterized in that, the ratio of weight and number of bismuth sulfide nano-rod and phosphate buffer solution described in the described step 1 is 1:99.
3. formaldehyde electrochemical sensor according to claim 2 is characterized in that, the concentration of phosphate buffer described in the described step 1 is 0.1mol/L.
4. formaldehyde electrochemical sensor according to claim 3 is characterized in that, the time of carrying out ultrasonic dispersion in the described step 1 is 20 minutes.
5. formaldehyde electrochemical sensor according to claim 4 is characterized in that, gets described bismuth sulfide nano-rod dispersion liquid 10 μ L in the described step 2 and drips and be coated in blank glass-carbon electrode surface.
6. formaldehyde electrochemical sensor according to claim 1 is characterized in that, described bismuth sulfide nano-rod is synthetic by hydro-thermal method.
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| CN104198706B (en) * | 2014-09-05 | 2016-03-30 | 扬州大学 | A kind of preparation method of tumor marker electrochemical immunosensor |
| CN104237347B (en) * | 2014-10-09 | 2016-08-24 | 无锡百灵传感技术有限公司 | Preparation method for the carbon nanotube electrode of formaldehyde examination |
| CN105203617B (en) * | 2015-09-11 | 2019-05-31 | 江苏大学 | A kind of electrochemical gas sensor and preparation method thereof for detecting ethyl alcohol |
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| CN101613882A (en) * | 2009-08-10 | 2009-12-30 | 重庆大学 | The method for preparing bismuth sulfide nano-rod crystalline material |
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| CN101613882A (en) * | 2009-08-10 | 2009-12-30 | 重庆大学 | The method for preparing bismuth sulfide nano-rod crystalline material |
Non-Patent Citations (6)
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| Juan Lu等.Preparation of Bi2S3 nanorods via a hydrothermal approach.《Materials Letters》.2006,(第61期),第3425-3428. |
| Lianshan Li等.Topotactic Transformation of Single-Crystalline Precursor Discs into Disc-Like Bi2S3 Nanorod Networks.《Advanced Functional Materials》.2008,(第18期),第1200页第2栏-1201页第1栏以及附图10. |
| Low temperature growth of bismuth sulfide nanorods by a hydrothermal method;Weixin Zhang等;《Solid State Communications》;20011231(第119期);第143-146页 * |
| Preparation of Bi2S3 nanorods via a hydrothermal approach;Juan Lu等;《Materials Letters》;20061208(第61期);第3425-3428 * |
| Topotactic Transformation of Single-Crystalline Precursor Discs into Disc-Like Bi2S3 Nanorod Networks;Lianshan Li等;《Advanced Functional Materials》;20081231(第18期);第1200页第2栏-1201页第1栏以及附图10 * |
| Weixin Zhang等.Low temperature growth of bismuth sulfide nanorods by a hydrothermal method.《Solid State Communications》.2001,(第119期),第143-146页. |
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