CN1384355A - Electrochemical sensor and its prepn and use - Google Patents
Electrochemical sensor and its prepn and use Download PDFInfo
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- CN1384355A CN1384355A CN 02115950 CN02115950A CN1384355A CN 1384355 A CN1384355 A CN 1384355A CN 02115950 CN02115950 CN 02115950 CN 02115950 A CN02115950 A CN 02115950A CN 1384355 A CN1384355 A CN 1384355A
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Abstract
The electrochemical sensor includes glass carbon electrode and sensitive film coated on the surface of the glass carbon electrode, and is prepared through dispersing carbon nanotube and hydrophobic cationic and/or anionic surfactant in deionized water to obtain dispersed carbon nanotube liquid, coating the dispersed liquid to the surface of glass carbon electrode and evaporating the solvent. It is solid, contains no toxic and environmental pollutant material, and has high stability, high sensitivity, good repeatability, and strong capacity of resisting the interference of other ions and is portable. It can be used in simultaneous detection of Pb and Cd ion at high sensitivity and with detection peak at 4E(-9) mol/L and 4 E(-9) mol/L separately and digesting peak potential difference greater than 250 mV.
Description
Technical field
The present invention relates to a kind of electrochemical sensor and its production and use.
Background technology
Heavy metal ion in the environment causes people's common concern owing to its toxicity.Can suppress red sanguinin synzyme as plumbous, protoheme is obstructed, hemoglobin level reduces; Lead poisoning also can cause the increase of erythrocyte membrane fragility and be easy to haemolysis, makes its lost of life and anaemia takes place.Modern medicine proves that the cadmium of low concentration level can cause the generation of many cancers.Therefore, the sensor of developing heavy metal ion in a kind of effectively testing environment has very significant meaning.
At present, measuring being operated in abroad of research plumbous in the water body, the cadmium ion sensor simultaneously carries out.But use mercury electrode more, environment is produced pollute; And all solid state transducer sensitivity is not high, and difficult the realization measured simultaneously.Also be in the exploratory stage in this research on the one hand both at home and abroad.Develop high sensitivity, all solid state, can detect lead simultaneously, the cadmium ion electrochemical sensor becomes the unremitting pursuit of people.
Carbon nano-tube because of its unique mechanical, characteristic electron and chemical stability, has become one of worldwide research focus since 1991 are found.It can think graphite linings is folded into the cylindrical result of carbon, is divided into multi-walled carbon nano-tubes (MWNT) and Single Walled Carbon Nanotube (SWNT).According to its atomic structure difference, carbon nano-tube will show as metal or semiconductor, and the characteristic electron of this uniqueness will make it be expected to become the novel sensor device.Though carbon nano-tube has many unique advantages, because very stable, the water insoluble and general organic solvent of its character, it especially is restricted in the utilization aspect the electrochemical sensor at electroanalysis.
Summary of the invention
The present invention provides a kind of highly sensitive all solid state electrochemical sensor and the method for making and purposes that can detect lead, cadmium ion simultaneously at the problems referred to above.
Technical scheme provided by the invention is: a kind of electrochemical sensor, comprise glass-carbon electrode, and its special character is that the surface-coated of glass-carbon electrode has sensitive membrane.
Or/and anionic surfactant is formed, above percentage is mass percent to above-mentioned sensitive membrane by the hydrophobic cations surfactant of 2.4～75% carbon nano-tube and 25～97.6%.
Above-mentioned hydrophobic cations surfactant is or/and anionic surfactant is that to contain chain length be that the double-stranded cationic surfactant of C12～20 is or/and anionic surfactant.
Above-mentioned carbon nano-tube is a multi-walled carbon nano-tubes.
The preparation method of above-mentioned electrochemical sensor, with carbon nano-tube and hydrophobic cations surfactant or/and anionic surfactant adds in the deionized water is uniformly dispersed, obtain the carbon nano-tube dispersion liquid, the carbon nano-tube dispersion liquid is coated to the glass-carbon electrode surface, and evaporating solvent promptly gets required sensor.
Content of carbon nanotubes is 1～15 grams per liter in the above-mentioned carbon nano-tube dispersion liquid, and the hydrophobic cations surfactant is or/and the content of anionic surfactant is 5～40 grams per liters.
The carbon nano-tube dispersion liquid that is coated to the glass-carbon electrode surface in said method is 1～30 microlitre.
Above-mentioned electrochemical sensor is used for detecting plumbous, cadmium ion.
Electrochemical sensor of the present invention is all solid state material poisonous to human body, contaminated environment that do not contain, good stability, highly sensitive, favorable reproducibility, and other common ion interference capability is strong in the anti-environment, and sensor is easy to carry.The present invention passes through conventional solid electrode surperficial MOLECULE DESIGN, to have the carbon nano-tube of good electric chemical property and some other molecule that the good electric chemical property arranged, polymkeric substance, metal oxide etc. and be fixed on conventional Solid Electrode Surface in Voltammetric Measurement, realize that high sensitivity plumbous in the environment, cadmium ion measures simultaneously; Make its detected peaks reach 4 * 10 respectively
-9Mol/L and 6 * 10
-9Mol/L; Difference＞the 250mV of stripping spike potential.
Description of drawings
Fig. 1 is the structural representation of electrochemical sensor of the present invention;
Fig. 2 is plumbous, the stripping voltammogram of cadmium ion on sensor.
Embodiment
Referring to Fig. 1, electrochemical sensor of the present invention comprises glass-carbon electrode 1, and glass-carbon electrode 1 is made of glass carbon substrate 3, the contact conductor 4 that is electrically connected with glass carbon substrate 3 and insulation course 5, and glass carbon substrate 3 surface-coated have sensitive membrane 2.Or/and anionic surfactant (as double hexadecyl phosphoric acid) is formed, above percentage is mass percent to sensitive membrane 2 by 2.4～75% single wall or the hydrophobic cations surfactant (as didodecyldimethylammbromide bromide or two octadecyl dimethyl ammonium bromides etc.) of multi-walled carbon nano-tubes and 25～97.6%.
The preparation method of above-mentioned electrochemical sensor, 1～15 gram carbon nano-tube and 5～40 is restrained the hydrophobic cations surfactants or/and anionic surfactant adds in 1000 ml deionized water, ultrasonic dispersion is until the carbon nano-tube dispersion liquid that obtains homogeneous, light/dark balance, 1～30 microlitre carbon nano-tube dispersion liquid is coated to the glass-carbon electrode surface, and infrared lamp promptly gets required sensor according to roasting evaporating solvent down.
What above-mentioned electrochemical sensor was used to detect lead, cadmium ion the results are shown in Figure 2, and concentration plumbous, cadmium ion is 1 * 10
-7Mol/L, stripping spike potential plumbous, cadmium be respectively-641.4mV and-900.0mV; Stripping peak current plumbous, cadmium is respectively 1.387 μ A and 1.191 μ A.Measure the condition of plumbous cadmium ion: measure medium 0.1mol/L KI, pH=1.50; Accumulating potential :-1.20V (vs.SCE); Enrichment time: 5 minutes.Differentiated pulse stripping voltammetry location parameter: pulse-response amplitude 0.1V; Duration of pulse 40ms; Sweep velocity 50Mv/s.
Embodiment 1: a kind of electrochemical sensor, comprise glass-carbon electrode, insulation course, and the surface-coated of glass-carbon electrode has sensitive membrane.Sensitive membrane is made up of 2.4% carbon nano-tube and two octadecyl dimethyl ammonium bromides of 97.6%.
The preparation method of above-mentioned electrochemical sensor, 1 gram carbon nano-tube and the two octadecyl dimethyl ammonium bromides of 40 grams are added in 1000 ml deionized water, ultrasonic dispersion is until the carbon nano-tube dispersion liquid that obtains homogeneous, light/dark balance, 30 microlitre carbon nano-tube dispersion liquids are coated to the glass-carbon electrode surface, and infrared lamp promptly gets required sensor according to roasting evaporating solvent down.
Embodiment 2: a kind of electrochemical sensor, comprise glass-carbon electrode, insulation course, and the surface-coated of glass-carbon electrode has sensitive membrane.Sensitive membrane is made up of 75% multi-walled carbon nano-tubes and 25% double hexadecyl phosphoric acid.
The preparation method of above-mentioned electrochemical sensor, 15 gram carbon nano-tube and 5 gram double hexadecyl phosphoric acid are added in 1000 ml deionized water, ultrasonic dispersion is until the carbon nano-tube dispersion liquid that obtains homogeneous, light/dark balance, 15 microlitre carbon nano-tube dispersion liquids are coated to the glass-carbon electrode surface, and infrared lamp promptly gets required sensor according to roasting evaporating solvent down.
Embodiment 3: a kind of electrochemical sensor, comprise glass-carbon electrode, insulation course, and the surface-coated of glass-carbon electrode has sensitive membrane.Sensitive membrane is made up of 50% carbon nano-tube, 25% didodecyldimethylammbromide bromide and 25% double hexadecyl phosphoric acid.
The preparation method of above-mentioned electrochemical sensor, 20 gram carbon nano-tube, 10 gram didodecyldimethylammbromide bromides and 10 gram double hexadecyl phosphoric acid are added in 1000 ml deionized water, ultrasonic dispersion is until the carbon nano-tube dispersion liquid that obtains homogeneous, light/dark balance, 2 microlitre carbon nano-tube dispersion liquids are coated to the glass-carbon electrode surface, and infrared lamp promptly gets required sensor according to roasting evaporating solvent down.
Claims (8)
1. an electrochemical sensor comprises glass-carbon electrode, it is characterized in that: the surface-coated of glass-carbon electrode has sensitive membrane.
2. sensor according to claim 1 is characterized in that: or/and anionic surfactant is formed, above percentage is mass percent to sensitive membrane by the hydrophobic cations surfactant of 2.4～75% carbon nano-tube and 25～97.6%.
3. sensor according to claim 2 is characterized in that: the hydrophobic cations surfactant is or/and anionic surfactant is that to contain chain length be C
12～20Double-stranded cationic surfactant or/and anionic surfactant.
4. according to claim 2 or 3 described sensors, it is characterized in that: carbon nano-tube is a multi-walled carbon nano-tubes.
5. the preparation method of the described electrochemical sensor of claim 1, it is characterized in that: with carbon nano-tube and hydrophobic cations surfactant or/and anionic surfactant adds in the deionized water is uniformly dispersed, obtain the carbon nano-tube dispersion liquid, the carbon nano-tube dispersion liquid is coated to the glass-carbon electrode surface, and evaporating solvent promptly gets required sensor.
6. preparation method according to claim 5 is characterized in that: content of carbon nanotubes is 1～15 grams per liter in the carbon nano-tube dispersion liquid, and the hydrophobic cations surfactant is or/and the content of anionic surfactant is 5～40 grams per liters.
7. preparation method according to claim 6 is characterized in that: the carbon nano-tube dispersion liquid that is coated to the glass-carbon electrode surface is 1～30 microlitre.
8. the described electrochemical sensor of claim 1 is used for detecting plumbous, cadmium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021159505A CN1187607C (en) | 2002-06-10 | 2002-06-10 | Electrochemical sensor and its prepn and use |
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|---|---|---|---|
| CNB021159505A CN1187607C (en) | 2002-06-10 | 2002-06-10 | Electrochemical sensor and its prepn and use |
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| CN1384355A true CN1384355A (en) | 2002-12-11 |
| CN1187607C CN1187607C (en) | 2005-02-02 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346156C (en) * | 2003-12-15 | 2007-10-31 | 富士施乐株式会社 | Electrode for electrochemical measurement and method for manufacturing the same |
| CN100406879C (en) * | 2003-12-15 | 2008-07-30 | 富士施乐株式会社 | Electrode for electrochemical measurement |
| CN100417938C (en) * | 2005-11-11 | 2008-09-10 | 河北科技大学 | Testing apparatus for water anionics and producing method thereof |
| CN100498321C (en) * | 2004-03-29 | 2009-06-10 | 中国科学院长春应用化学研究所 | Preparation method for polyer/carbon nanotube composite membrane electrochemical luminous sensor |
| CN101046461B (en) * | 2006-03-29 | 2011-04-13 | 福建医科大学 | Electrochemical sensor and its preparation process and use |
| CN1982887B (en) * | 2005-12-16 | 2012-05-09 | 天津市食品加工工程中心 | Anionic surfactant electrochemical sensor and its manufacture method |
| CN102478539A (en) * | 2010-11-19 | 2012-05-30 | 中国科学院海洋研究所 | Application of hydroxypropyl chitosan/carbon nanotube modified electrochemical sensor |
| CN102654476A (en) * | 2012-05-29 | 2012-09-05 | 叶健 | Lead-ion-selective electrode with self-repairing function and preparation method thereof |
| CN101706471B (en) * | 2008-12-12 | 2012-10-03 | 中国科学院烟台海岸带研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN101424693B (en) * | 2008-12-08 | 2012-12-26 | 盛青松 | Portable plumbum ion concentration analyzer using disposable sensor |
| CN101015025B (en) * | 2004-06-03 | 2013-03-13 | 南泰若股份有限公司 | Spin-coatable liquid for use in electronic fabrication processes |
| CN103954667A (en) * | 2014-05-20 | 2014-07-30 | 上海第二工业大学 | Electrochemical sensor modified by nitrogen-doped carbon nano-tube and application of electrochemical sensor |
| CN104280448A (en) * | 2014-10-17 | 2015-01-14 | 扬州大学 | Method for measuring concentration of lead ions in PM2.5 |
-
2002
- 2002-06-10 CN CNB021159505A patent/CN1187607C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346156C (en) * | 2003-12-15 | 2007-10-31 | 富士施乐株式会社 | Electrode for electrochemical measurement and method for manufacturing the same |
| CN100406879C (en) * | 2003-12-15 | 2008-07-30 | 富士施乐株式会社 | Electrode for electrochemical measurement |
| CN100498321C (en) * | 2004-03-29 | 2009-06-10 | 中国科学院长春应用化学研究所 | Preparation method for polyer/carbon nanotube composite membrane electrochemical luminous sensor |
| CN101015025B (en) * | 2004-06-03 | 2013-03-13 | 南泰若股份有限公司 | Spin-coatable liquid for use in electronic fabrication processes |
| CN100417938C (en) * | 2005-11-11 | 2008-09-10 | 河北科技大学 | Testing apparatus for water anionics and producing method thereof |
| CN1982887B (en) * | 2005-12-16 | 2012-05-09 | 天津市食品加工工程中心 | Anionic surfactant electrochemical sensor and its manufacture method |
| CN101046461B (en) * | 2006-03-29 | 2011-04-13 | 福建医科大学 | Electrochemical sensor and its preparation process and use |
| CN101424693B (en) * | 2008-12-08 | 2012-12-26 | 盛青松 | Portable plumbum ion concentration analyzer using disposable sensor |
| CN101706471B (en) * | 2008-12-12 | 2012-10-03 | 中国科学院烟台海岸带研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN102478539A (en) * | 2010-11-19 | 2012-05-30 | 中国科学院海洋研究所 | Application of hydroxypropyl chitosan/carbon nanotube modified electrochemical sensor |
| CN102654476A (en) * | 2012-05-29 | 2012-09-05 | 叶健 | Lead-ion-selective electrode with self-repairing function and preparation method thereof |
| CN102654476B (en) * | 2012-05-29 | 2014-04-23 | 叶健 | Lead-ion-selective electrode with self-repairing function and preparation method thereof |
| CN103954667A (en) * | 2014-05-20 | 2014-07-30 | 上海第二工业大学 | Electrochemical sensor modified by nitrogen-doped carbon nano-tube and application of electrochemical sensor |
| CN103954667B (en) * | 2014-05-20 | 2016-11-02 | 上海第二工业大学 | The electrochemical sensor of a kind of nitrogen-doped carbon nanometer pipe modification and application thereof |
| CN104280448A (en) * | 2014-10-17 | 2015-01-14 | 扬州大学 | Method for measuring concentration of lead ions in PM2.5 |
| CN104280448B (en) * | 2014-10-17 | 2016-08-24 | 扬州大学 | A kind of measure the method for plumbum ion concentration in PM2.5 |
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| Publication number | Publication date |
|---|---|
| CN1187607C (en) | 2005-02-02 |
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