CN104049008A - Preparation method for micro redox potential sensor - Google Patents
Preparation method for micro redox potential sensor Download PDFInfo
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- CN104049008A CN104049008A CN201410273381.0A CN201410273381A CN104049008A CN 104049008 A CN104049008 A CN 104049008A CN 201410273381 A CN201410273381 A CN 201410273381A CN 104049008 A CN104049008 A CN 104049008A
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Abstract
The invention belongs to the technical field of electrochemical sensors, and in particular relates to a preparation method for a micro redox potential sensor. The preparation method comprises the following steps of respectively preparing a gold thin film micro electrode and a silver thin film micro electrode by taking a polyvinyl chloride film as a substrate material, electroplating the silver thin film micro electrode in a sodium chloride solution to prepare a silver chloride thin film micro electrode, connecting the gold thin film micro electrode serving as an indicating electrode to a positive electrode of an ion meter, connecting the silver chloride thin film micro electrode serving as a reference electrode to a cathode electrode of the ion meter, inserting the two electrodes into an ammonium ferrous sulfate-high ferric ammonium sulfate redox standard solution at normal temperature, and checking and calibrating a potential value by taking a potential value of redox potential, which is measured by the conventional platinum electrode method. The prepared redox potential sensor can easily realize automation, portability and real-time detection, and can facilitate the observation of changes of redox potentials of sealed space medium and gas phase medium as well as semi-solid and full-solid medium systems. The micro redox potential sensor is prepared from the polyvinyl chloride film, so that the material is low in cost.
Description
Technical field
The invention belongs to electrochemical sensor technical field, specifically relate to a kind of preparation method of miniature oxidation-reduction potential sensor.
Background technology
Electrochemical sensor is the electrochemical properties based on determinand and determinand chemical quantity is transformed into a kind of sensor that electrical quantities is carried out sensing detection.Along with microelectronic processing technique is widely used in electrochemical sensor, the application of microsensor (micro sensor refers to that those have a physical size at least at the sensor of submillimeter magnitude) in electrochemical analysis obtained development fast.Microsensor is easy to realize batch production, and analysis cost is low, and the response time is fast, detects lower limit low and be applicable to the advantages such as field quick detection.Because the electrode surface of microelectrode is minimum, its electrochemical properties has the unexistent distinct advantages of many conventional electrodes, is more suitable for the thermodynamics and kinetics research in electrochemical reaction process in theory than conventional electrodes.Except solution reaction system, the electrochemical properties that is also applicable to gas phase system, semisolid and all solid state system is studied.
Oxidation-reduction potential (Oxidation-Reduction Potential, ORP or Eh), measures the validity that changes character between chemical substance because of electron exchange.Oxidation-reduction potential is one of important parameter of water quality, as a composite target of medium (comprising soil, natural water, nutrient culture media etc.) environmental baseline, has continued to use for a long time the relative extent of its characterized medium oxidisability or reductibility.Although oxidation-reduction potential can not contribute to understand the electrochemical characteristic of aqueous medium as the index of certain oxidation material and reducing substances concentration, analyze the character of medium, be a composite target.The assay method of oxidation-reduction potential mainly contains two kinds of platinum electrode direct measuring methods and depolarization determination method at present.About how overcoming the research of the defect of conventional oxidation reduction potential assay method, it is the focus of scientific research group extensive concern, especially Fang Jianan proposes, after the two ten problems > > of < < about oxidation-reduction potential (ORP, Eh) depolarization determination method, more to have caused thinking how quick, easy, Accurate Determining oxidation-reduction potential problem.
At present, the preparation method of the microsensor of relevant polymorphic type purposes and technology be comparative maturity, for example, has announced a kind of for determining the micro sensing equipment of physical quantity in Chinese patent CN101258407.The assay method of oxidation-reduction potential is except traditional oxidation-reduction potential platinum electrode direct measuring method and depolarization determination method, also have relevant patent, for example, Chinese patent CN103293210A discloses a kind of on-line measuring device of oxidation-reduction potential of electrolyzed oxidizing water.Chinese patent CN101881748A discloses a kind of cannulate drill body glass bushing and by this glass bushing lower end closely parcel and the oxidation-reduction potential microelectrode that forms through platinum filament wherein.
The assay method reappearance of existing oxidation-reduction potential and less stable, complicated operation, can not easily realize robotization, portable, detect now, high and other media of inapplicable detection of testing cost are as the oxidation-reduction potential of solid state medium.In addition, utilize miniature thin-film material sensors to measure oxidation-reduction potential and also have no report.
Summary of the invention
In order to overcome the above-mentioned defect of the assay method existence of existing oxidation-reduction potential, the invention provides a kind of preparation method of miniature oxidation-reduction potential sensor, can realize the robotization of oxidation-reduction potential, portable, detection now.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of miniature oxidation-reduction potential sensor, and step is as follows:
1., the preparation of gold thin film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal chromium of first not sheltered by optical cement at substrate surface, then plate layer of gold, remove remaining optical cement, can be made into gold thin film microelectrode;
2., the preparation of silver chloride film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal copper of first not sheltered by optical cement at substrate surface, then plate one deck silver, remove remaining optical cement, can be made into silver-colored film microelectrode;
The silver-colored film microelectrode of preparation is placed in the NaCl solution of 0.1mol/L and is electroplated, and silver-colored film microelectrode is connected on positive pole, and platinum electrode is connected on negative pole, and plating current potential is 0.1V, and electroplating time is 2h, and the silver chloride film microelectrode of having electroplated is kept in Dark Place;
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicator electrode, the positive pole that connects ionometer, using silver chloride film microelectrode as contrast electrode, the negative pole that connects ionometer, under normal temperature, two electrodes are inserted in iron ammonium sulfate-ferric ammonium sulfate redox standard solution of 0.1mol/L, the potential value that its potential value is measured oxidation-reduction potential with traditional platinum electrode method is tested as reference and calibrates.
Preferably, described step 1. and the position of not sheltered by optical cement at substrate surface 2. deposition by thermal evaporation or vacuum sputtering, realize.
Preferably, described step in 2. silver-colored film microelectrode electroplate before through pretreated step, be specially: by the silver-colored film microelectrode preparing, with fine sandpaper, polish gently, then use acetone oil removing, then use the HNO of 1mol/L
3solution etch, finally cleans with intermediate water.
Preferably, described step 2. in silver-colored film microelectrode when electroplating, in stirring, make bubble cannot be enriched in electrode surface.
Preferably, the silver chloride film microelectrode that described step has been electroplated in is 2. placed in saturated KCl solution and keeps in Dark Place.
The preparation method of miniature oxidation-reduction potential sensor of the present invention, help to solve the technical limitation of conventional oxidation reduction potential assay method, easily realize robotization, portable, detection now, be convenient to observe the variation of seal cavity medium and gas phase media, semisolid and all solid state medium system oxidation-reduction potential.Meanwhile, what the making material of microelectrode adopted is Polyvinylchloride (PVC) film, and material price is cheap.
Embodiment
The preparation method of miniature oxidation-reduction potential sensor, step is as follows:
1., the preparation of gold thin film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal chromium of first not sheltered by optical cement at substrate surface by thermal evaporation or vacuum sputtering, then plate layer of gold, remove remaining optical cement, can be made into gold thin film microelectrode.
2., the preparation of silver chloride film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal copper of first not sheltered by optical cement at substrate surface by thermal evaporation or vacuum sputtering, then plate one deck silver, remove remaining optical cement, can be made into silver-colored film microelectrode.
By the silver-colored film microelectrode preparing, surface is slightly black, may be the result of silver oxidation, polishes gently, then use acetone oil removing with fine sandpaper, then uses the HNO of 1mol/L
3solution etch, finally cleans with intermediate water.
Silver-colored film microelectrode is placed in the NaCl solution of 0.1mol/L and electroplates, silver-colored film microelectrode is connected on positive pole, and platinum electrode is connected on negative pole, and plating current potential is 0.1V, and electroplating time is 2h.When electroplating, stir and make bubble cannot be enriched in silver electrode surface, the silver chloride film microelectrode of having electroplated is placed in saturated KCl solution and is kept in Dark Place.
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicator electrode, the positive pole that connects ionometer, using silver chloride film microelectrode as contrast electrode, the negative pole that connects ionometer, under normal temperature, two electrodes are inserted in iron ammonium sulfate-ferric ammonium sulfate redox standard solution of 0.1mol/L, the potential value that its potential value is measured oxidation-reduction potential with traditional platinum electrode method is tested as reference and calibrates.Microelectrode is put in the container of nutrient culture media, under air-proof condition, measured the nutrient culture media oxidation-reduction potential value of 7 days.
Above content is only made for the present invention giving an example and explanation; affiliated those skilled in the art make various modifications to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or surmount this scope as defined in the claims, all should belong to protection scope of the present invention.
Claims (5)
1. a preparation method for miniature oxidation-reduction potential sensor, is characterized in that step is as follows:
1., the preparation of gold thin film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal chromium of first not sheltered by optical cement at substrate surface, then plate layer of gold, remove remaining optical cement, can be made into gold thin film microelectrode;
2., the preparation of silver chloride film microelectrode
Take PVC film as base material, optical cement is coated on clean PVC substrate, then expose, develop and remove the optical cement of electrode bottom, the position deposition layer of metal copper of first not sheltered by optical cement at substrate surface, then plate one deck silver, remove remaining optical cement, can be made into silver-colored film microelectrode;
The silver-colored film microelectrode of preparation is placed in the NaCl solution of 0.1mol/L and is electroplated, and silver-colored film microelectrode is connected on positive pole, and platinum electrode is connected on negative pole, and plating current potential is 0.1V, and electroplating time is 2h, and the silver chloride film microelectrode of having electroplated is kept in Dark Place;
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicator electrode, the positive pole that connects ionometer, using silver chloride film microelectrode as contrast electrode, the negative pole that connects ionometer, under normal temperature, two electrodes are inserted in iron ammonium sulfate-ferric ammonium sulfate redox standard solution of 0.1mol/L, the potential value that its potential value is measured oxidation-reduction potential with traditional platinum electrode method is tested as reference and calibrates.
2. the preparation method of miniature oxidation-reduction potential sensor according to claim 1, is characterized in that: described step 1. and the position of not sheltered by optical cement at substrate surface 2. deposition by thermal evaporation or vacuum sputtering, realize.
3. the preparation method of miniature oxidation-reduction potential sensor according to claim 1, it is characterized in that: described step in 2. silver-colored film microelectrode electroplate before through pretreated step, be specially: by the silver-colored film microelectrode preparing, with fine sandpaper, polish gently, use again acetone oil removing, then use the HNO of 1mol/L
3solution etch, finally cleans with intermediate water.
4. the preparation method of miniature oxidation-reduction potential sensor according to claim 1, is characterized in that: described step 2. in silver-colored film microelectrode when electroplating, in stirring, make bubble cannot be enriched in electrode surface.
5. the preparation method of miniature oxidation-reduction potential sensor according to claim 1, is characterized in that: the silver chloride film microelectrode that described step has been electroplated in is 2. placed in saturated KCl solution and keeps in Dark Place.
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| CN201410273381.0A CN104049008B (en) | 2014-06-16 | 2014-06-16 | Preparation method for micro redox potential sensor |
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| CN104049008B CN104049008B (en) | 2017-02-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105628757A (en) * | 2015-12-30 | 2016-06-01 | 中国科学院电子学研究所 | ORP sensing chip based on MEMS and manufacturing method of ORP sensing chip |
| CN106596687A (en) * | 2016-12-14 | 2017-04-26 | 生益电子股份有限公司 | Standard solution for PCB etching redox potential detection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6014159A (en) * | 1983-07-05 | 1985-01-24 | Seiko Instr & Electronics Ltd | Ion sensor |
| JPH09292361A (en) * | 1996-04-26 | 1997-11-11 | Nec Corp | Method for manufacturing reference electrode |
| CN1460850A (en) * | 2002-05-21 | 2003-12-10 | 株式会社百利达 | Electrochemical sensor |
| CN101258407A (en) * | 2005-09-08 | 2008-09-03 | 皇家飞利浦电子股份有限公司 | Microsensor device |
| CN102495119A (en) * | 2011-11-23 | 2012-06-13 | 中国科学院上海微系统与信息技术研究所 | Multi-parameter water quality monitoring integrated microarray electrodes and preparation method |
-
2014
- 2014-06-16 CN CN201410273381.0A patent/CN104049008B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6014159A (en) * | 1983-07-05 | 1985-01-24 | Seiko Instr & Electronics Ltd | Ion sensor |
| JPH09292361A (en) * | 1996-04-26 | 1997-11-11 | Nec Corp | Method for manufacturing reference electrode |
| CN1460850A (en) * | 2002-05-21 | 2003-12-10 | 株式会社百利达 | Electrochemical sensor |
| CN101258407A (en) * | 2005-09-08 | 2008-09-03 | 皇家飞利浦电子股份有限公司 | Microsensor device |
| CN102495119A (en) * | 2011-11-23 | 2012-06-13 | 中国科学院上海微系统与信息技术研究所 | Multi-parameter water quality monitoring integrated microarray electrodes and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105628757A (en) * | 2015-12-30 | 2016-06-01 | 中国科学院电子学研究所 | ORP sensing chip based on MEMS and manufacturing method of ORP sensing chip |
| CN106596687A (en) * | 2016-12-14 | 2017-04-26 | 生益电子股份有限公司 | Standard solution for PCB etching redox potential detection |
| CN106596687B (en) * | 2016-12-14 | 2019-03-05 | 生益电子股份有限公司 | PCB etches oxidation-reduction potential examination criteria liquid |
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| CN104049008B (en) | 2017-02-01 |
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