CN104049008B - Preparation method for micro redox potential sensor - Google Patents
Preparation method for micro redox potential sensor Download PDFInfo
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- CN104049008B CN104049008B CN201410273381.0A CN201410273381A CN104049008B CN 104049008 B CN104049008 B CN 104049008B CN 201410273381 A CN201410273381 A CN 201410273381A CN 104049008 B CN104049008 B CN 104049008B
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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 technology field, it is specifically related to a kind of miniature oxidation-reduction potential sensor
Preparation method.
Background technology
Electrochemical sensor is electrochemical properties based on determinand and determinand chemical quantity is transformed into electrical quantities carries out
A kind of sensor of sensing detection.It is widely used in electrochemical sensor with microelectronic processing technique, microsensor
(micro sensor refers to the sensor in submillimeter magnitude for those at least one physical sizes) answering in electro chemical analysis
With achieving quick development.Microsensor is easily achieved batch production, and analysis cost is low, and response time is fast, Monitoring lower-cut
Low and the advantages of be applied to field quick detection.Because the electrode surface of microelectrode is minimum, its electrochemical properties has many normal
The rule unexistent particular advantages of electrode, are more suitable for thermodynamics in electrochemical reaction process and dynamic than conventional electrodes in theory
Mechanics study.In addition to solution reaction system, the electrochemical properties being also applied for gas phase system, semisolid and all solid state system enter
Row research.
Oxidation-reduction potential (oxidation-reduction potential, orp or eh), measure chemical substance between because
Electron exchange and change the effectiveness of property.Oxidation-reduction potential is one of important parameter of water quality, (includes soil as medium
Earth, natural water, culture medium etc.) environmental condition a composite target, continued to use for a long time, it characterizes medium oxidizing property or reduction
The relative extent of property.Although oxidation-reduction potential cannot function as the index of certain oxidation material and reducing substances concentration, help
In the electrochemical characteristic understanding aqueous medium, the property of analysis medium, is a composite target.The mensure side of oxidation-reduction potential
Method mainly has two kinds of platinum electrode direct measuring methods and depolarization algoscopy at present.With regard to how overcoming conventional oxidation reduction potential to survey
The research determining the defect of method is the focus of scientific research group extensive concern, and especially Fang Jianan proposes " with regard to oxidation-reduction potential
Two ten problems of (orp, eh) depolarization algoscopy " after, more cause and how quick, easy, Accurate Determining oxidation are gone back
The thinking of former current potential problem.
At present, the preparation method about the microsensor of polymorphic type purposes and technology comparative maturity, for example, in
A kind of micro sensing equipment for determining physical quantity is disclosed in state's patent cn101258407.The mensure side of oxidation-reduction potential
Method, in addition to traditional oxidation-reduction potential platinum electrode direct measuring method and depolarization algoscopy, also has related patent, example
As Chinese patent cn103293210a discloses a kind of on-line measuring device of the oxidation-reduction potential of electrolyzed oxidizing water.China
Patent cn101881748a discloses a kind of tubular tapered body glass bushing and by this glass bushing lower end tight and runs through
The oxidation-reduction potential microelectrode constituting in platinum filament therein.
The assay method repeatability of existing oxidation-reduction potential and less stable, complex operation are it is impossible to easy realize certainly
Dynamicization, portable, current detection, testing cost high and inapplicable detection other media such as solid state medium oxidation-reduction potential.Separately
Outward, measure oxidation-reduction potential using miniature thin-film material sensors and also have no report.
Content of the invention
The drawbacks described above existing for the assay method overcoming existing oxidation-reduction potential, the invention provides a kind of miniature
The preparation method of oxidation-reduction potential sensor, the automatization of achievable oxidation-reduction potential, portable, current detection.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is: a kind of miniature oxidation-reduction potential passes
The preparation method of sensor, step is as follows:
1., the preparation of gold thin film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode bottom
The optical cement in portion, the site deposition layer of metal chromium first do not sheltered by optical cement in substrate surface, then plates one layer of gold, removes residual light
Glue, you can make gold thin film microelectrode；
2., the preparation of silver chloride film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode bottom
The optical cement in portion, the site deposition layer of metal copper first do not sheltered by optical cement in substrate surface, then plates one layer of silver, removes residual light
Glue, you can make Ag films microelectrode；
The Ag films microelectrode of preparation is placed on plating in the nacl solution of 0.1mol/l, Ag films microelectrode is just connected on
Pole, platinum electrode is connected on negative pole, and plating current potential is 0.1v, and electroplating time is 2h, by the silver chloride electroplated film microelectrode lucifuge
Preserve；
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicating electrode, connect the positive pole of ion meter, using silver chloride film microelectrode as ginseng
Ratio electrode, connects the negative pole of ion meter, and two electrodes insert under room temperature the Ferrous ammonium sulfate-ferric ammonium sulfate oxidation of 0.1mol/l
In reduction standard solution, the potential value that its potential value measures oxidation-reduction potential with traditional platinum electrode method is tested as reference
With calibration.
Preferably, described step 1. and 2. in the site deposition do not sheltered by optical cement in substrate surface be by thermal evaporation
Or vacuum sputtering realization.
Preferably, 2. middle Ag films microelectrode electroplates the front step through pretreatment, particularly as follows: will prepare to described step
Ag films microelectrode, gently polished with fine sandpaper, then use acetone oil removing, then use 1mol/l hno3Solution etch, finally
Cleaned with secondary water.
Preferably, 2. middle Ag films microelectrode is in stirring and makes bubble cannot be enriched in electricity in plating described step
Pole surface.
Preferably, 2. the middle silver chloride film microelectrode electroplated is placed in saturation kcl solution and keeps in Dark Place described step.
The preparation method of the miniature oxidation-reduction potential sensor of the present invention, helps solve conventional oxidation reduction potential mensure
The technical limitations of method, easily realize automatization, portable, current detection, be easy to observe sealing space medium and gas phase media, half
Solid-state and the change of all solid state medium system oxidation-reduction potential.Meanwhile, the making material of microelectrode uses polrvinyl chloride
(pvc) thin film, material price is cheap.
Specific embodiment
The preparation method of miniature oxidation-reduction potential sensor, step is as follows:
1., the preparation of gold thin film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode bottom
The optical cement in portion, the site deposition layer of metal first do not sheltered by optical cement in substrate surface by thermal evaporation or vacuum sputtering
Chromium, then plates one layer of gold, removes remaining optical cement, you can make gold thin film microelectrode.
2., the preparation of silver chloride film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode bottom
The optical cement in portion, the site deposition layer of metal first do not sheltered by optical cement in substrate surface by thermal evaporation or vacuum sputtering
Copper, then plates one layer of silver, removes remaining optical cement, you can make Ag films microelectrode.
By the Ag films preparing microelectrode, surface, is gently beaten it may be possible to the result of silver oxidation with fine sandpaper slightly in black
Mill, then use acetone oil removing, then use the hno of 1mol/l3Solution etch, is finally cleaned with secondary water.
Ag films microelectrode is placed on plating in the nacl solution of 0.1mol/l, Ag films microelectrode is connected on positive pole, platinum electricity
Pole is connected on negative pole, and plating current potential is 0.1v, and electroplating time is 2h.It is stirred while plating making bubble cannot be enriched in silver electricity
Pole surface, the silver chloride electroplated film microelectrode is placed in saturation kcl solution and keeps in Dark Place.
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicating electrode, connect the positive pole of ion meter, using silver chloride film microelectrode as ginseng
Ratio electrode, connects the negative pole of ion meter, and two electrodes insert under room temperature the Ferrous ammonium sulfate-ferric ammonium sulfate oxidation of 0.1mol/l
In reduction standard solution, the potential value that its potential value measures oxidation-reduction potential with traditional platinum electrode method is tested as reference
With calibration.Microelectrode is put in the container of culture medium, under air-proof condition, measure the culture medium oxidation reduction potential value of 7 days.
Above content is only citing made for the present invention and illustrates, affiliated those skilled in the art are to being retouched
The specific embodiment stated is made various modifications or supplements or substituted using similar mode, without departing from the design of invention
Or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.
Claims (5)
1. a kind of preparation method of miniature oxidation-reduction potential sensor, is characterized in that step is as follows:
1., the preparation of gold thin film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode base
Optical cement, the site deposition layer of metal chromium first do not sheltered by optical cement in substrate surface, then plate one layer of gold, remove remaining optical cement,
Can be made into gold thin film microelectrode；
2., the preparation of silver chloride film microelectrode
With pvc film as base material, optical cement is coated on the pvc substrate of cleaning, then exposure, development removes electrode base
Optical cement, the site deposition layer of metal copper first do not sheltered by optical cement in substrate surface, then plate one layer of silver, remove remaining optical cement,
Can be made into Ag films microelectrode；
The Ag films microelectrode of preparation is placed on plating in the nacl solution of 0.1mol/l, Ag films microelectrode is connected on positive pole, platinum
Electrode is connected on negative pole, and plating current potential is 0.1v, and electroplating time is 2h, and the silver chloride electroplated film microelectrode is kept in Dark Place；
3., the preparation of miniature oxidation-reduction potential sensor
Using gold thin film microelectrode as indicating electrode, connect the positive pole of ion meter, using silver chloride film microelectrode as reference electricity
Pole, connects the negative pole of ion meter, and two electrodes insert under room temperature the Ferrous ammonium sulfate-ferric ammonium sulfate oxidoreduction of 0.1mol/l
In standard solution, the potential value that its potential value measures oxidation-reduction potential with traditional platinum electrode method is tested as reference and school
Accurate.
2. miniature oxidation-reduction potential sensor according to claim 1 preparation method it is characterised in that: described step
1. the site deposition do not sheltered by optical cement in substrate surface in and 2. is to be realized by thermal evaporation or vacuum sputtering.
3. miniature oxidation-reduction potential sensor according to claim 1 preparation method it is characterised in that: described step
2. through the step of pretreatment before middle Ag films microelectrode plating, particularly as follows: by the Ag films preparing microelectrode, using fine sandpaper
Gently polish, then use acetone oil removing, then use the hno of 1mol/l3Solution etch, is finally cleaned with secondary water.
4. miniature oxidation-reduction potential sensor according to claim 1 preparation method it is characterised in that: described step
2. middle Ag films microelectrode is in stirring in plating makes bubble cannot be enriched in electrode surface.
5. miniature oxidation-reduction potential sensor according to claim 1 preparation method it is characterised in that: described step
2. the middle silver chloride film microelectrode electroplated is placed in saturation 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 true CN104049008B (en) | 2017-02-01 |
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| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6014159A (en) * | 1983-07-05 | 1985-01-24 | Seiko Instr & Electronics Ltd | Ion sensor |
| JP2970534B2 (en) * | 1996-04-26 | 1999-11-02 | 日本電気株式会社 | Manufacturing method of reference electrode |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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