CN100422727C - Electrochemical sensor - Google Patents
Electrochemical sensor Download PDFInfo
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- CN100422727C CN100422727C CNB2005100991039A CN200510099103A CN100422727C CN 100422727 C CN100422727 C CN 100422727C CN B2005100991039 A CNB2005100991039 A CN B2005100991039A CN 200510099103 A CN200510099103 A CN 200510099103A CN 100422727 C CN100422727 C CN 100422727C
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Abstract
Disclosed is an electrochemical sensor comprising a work electrode and a reference electrode, said sensor adapted to measure the characteristics of a liquid under test, based on the relative electric potential difference and electric current between the work electrode and the reference electrode both immersed in the liquid under test, said work electrode comprising a substrate that reacts to the liquid under test for generating an electric potential according to the concentration of the liquid under test, and said reference electrode comprising a substrate that reacts to the liquid under test for generating a fixed electric potential. According to the present invention, at least one of the work electrode and the reference electrode comprises said substrate coated with a function film for serving to generate the electric potential through the intervention of the film between said substrate and the liquid under test.
Description
The application be that May 21, application number in 2003 are 03136843.3 the applying date, denomination of invention divides an application for the application for a patent for invention of " electrochemical sensor ".
Technical field
The present invention relates to a kind of electrochemical sensor that comprises working electrode and reference electrode, described sensor is applicable to the characteristic of measuring tested liquid, it carries out described measurement according to immersing paired working electrode in the tested liquid and the relative potential difference (PD) between the reference electrode and electric current, described working electrode comprises the matrix of being made by platinum, gold, platinum black etc., and described reference electrode comprises matrix of being made by the silver that is coated with the chlorination silverskin or the matrix that is made of gold.
Background technology
Electrochemical sensor in routine, for example in pH (hereinafter referred to as " the PH ") sensor, working electrode constitutes by this way, the pipe that is filled with as the solution with known pH value of internal liquid wherein is provided, the matrix that constitutes working electrode is immersed in the interior solution of pipe, and an end that is set at the pipe adjacent with tested liquid has thin glass-film, described glass-film has the hydrogen ion selective power, by described glass-film internal liquid is contacted with tested liquid.On the other hand, reference electrode constitutes by this way, the pipe that is filled with as the salt bridge solution of the neutral ion concentration of internal reference liquid wherein is provided, the matrix that constitutes reference electrode is immersed in the interior solution of pipe, and a part that immerses the pipe in the tested solution when measuring has the fluid connection part of being made by porous ceramics, porous resin etc., by described connected component internal reference liquid contacted with tested liquid.
For example, a kind of such conventional structure can find in the open No.11-258197 (hereinafter referred to as " patent documentation 1 ") of Jap.P., and particularly, this structure is shown in Fig. 5 of this patent documentation.Correspondence between being referred to as with reference to the element names of the title of element among Fig. 5 of patent documentation 1 and above-mentioned PH sensor as seen, glass electrode " a " is a working electrode, glass electrode body " c " is the pipe of working electrode, glass electrode internal liquid " f " is an internal liquid, the interior utmost point " e " of glass electrode is the matrix of working electrode, responsive glass " d " is a thin glass film, relatively electrode " b " is a reference electrode, relatively electrode body " h " is the pipe of reference electrode, relatively the internal liquid " j " of electrode is an internal reference liquid, relatively the interior utmost point " i " of electrode is the body of reference electrode, and fluid connection spare " m " is the fluid connection part.
In addition, in oxidation-reduction potential (hereinafter referred to as " ORP ") sensor, working electrode is so constructed, and makes the matrix that constitutes working electrode directly immerse in the tested liquid, and this makes no longer needs internal liquid, glass tube etc.But, reference electrode is to constitute with the identical mode of above-mentioned PH sensor.
In addition, in counting, comprise amplifier with higher input impedance in conjunction with the PH meter of the electrochemical sensor of said structure and ORP.
The open No.11-258197 (patent documentation 1) of Jap.P. is incorporated herein by reference.
But, above-mentioned previous PH sensor has many shortcomings: described sensor is difficult to handle or make, and this is because wherein relate to liquid, for example internal liquid, internal reference liquid etc.; And described sensor is being restricted aspect the miniaturization of the pipe that is filled with liquid continuously.In addition,, use the glass tube that when sintering, can connect because the fluid connection part that is made of thin glass-film or pottery need be provided an end of pipe always, but its extremely difficult processing.For working electrode, the thickness of the thin glass-film that contacts with tested liquid is very little, thereby breaks easily.For reference electrode, internal reference liquid is easy to leak slightly by the fluid connection part.Therefore, if do not take measures, just have on the surface that some crystal of internal reference liquid of the moisture of evaporation are deposited on the fluid connection part, this makes must clean the fluid connection surface partly that contacts with tested liquid before measuring.In addition, for inner reference fluids is replenished the amount of being leaked, need provide the other internal liquid source that is used for replenishing internal liquid.In addition, have the possibility of tested liquid reversed flow in the fluid connection part, thereby reduce the concentration of internal reference liquid, cause the change of the current potential between the liquid, this causes measuring error.
The ORP sensor also is difficult to handle, and because of the liquid catalyst that uses in reference electrode miniaturization is restricted.
Because the electrode that is formed by thin glass-film or liquid catalyst has the internal resistance of increase, so need to use the amplifier with higher input impedance, so that improve the magnitude of voltage that is used to measure, this increases the cost of this device.
Summary of the invention
By as seen above-mentioned, the object of the present invention is to provide a kind of electrochemical sensor, wherein internal liquid is no longer needed by utilizing polytype film that electrode is solidified, this sensor is handled easily, and can miniaturization.
For achieving the above object; according to one aspect of the present invention; a kind of electrochemical sensor is provided; comprise working electrode and reference electrode; according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode; described sensor is suitable for measuring the characteristic of tested liquid; described working electrode comprises the matrix of being made by platinum or gold or platinum black; described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin; wherein this reference electrode is included in the salt bridge that applies on the chlorination silverskin surface in the described matrix of being made by the silver that is coated with the chlorination silverskin and keeps film; and the fixing hydrophobic membrane that on described salt bridge maintenance film surface, applies; the salt bridge that is used to protect and be stabilized on the described matrix of being made by the silver that is coated with the chlorination silverskin keeps film; described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer; described salt bridge maintenance film is the perfluoro alkyl sulfonic acid film with the salt bridge dipping of potassium chloride or sodium chloride; or carrying out the salt bridge crystal film that crystallization is made by the salt bridge of potassium chloride or sodium chloride, described working electrode includes only the described matrix of being made by platinum or gold or platinum black.
According to another aspect of the present invention; a kind of electrochemical sensor is provided; comprise working electrode and reference electrode; according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode; described sensor is suitable for measuring the characteristic of tested liquid; described working electrode comprises the matrix of being made by platinum or gold or platinum black; described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin; wherein this reference electrode is included in the salt bridge that applies on the chlorination silverskin surface in the described matrix of being made by the silver that is coated with the chlorination silverskin and keeps film; and the fixing hydrophobic membrane that on described salt bridge maintenance film surface, applies; the salt bridge that is used to protect and be stabilized on the described matrix of being made by the silver that is coated with the chlorination silverskin keeps film; described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer; described salt bridge maintenance film is the perfluoro alkyl sulfonic acid film with the salt bridge dipping of potassium chloride or sodium chloride; or carry out the salt bridge crystal film that crystallization is made by the salt bridge of potassium chloride or sodium chloride; described working electrode comprises and being coated on the described matrix of being made by platinum or gold or platinum black; have the plasma polymerization film of selective material through ability; and be coated in and have the lip-deep fixing hydrophobic membrane that selective material sees through the described plasma polymerization film of ability; be used to protect and be stabilized in the described plasma polymerization film on the described matrix of being made by platinum or gold or platinum black, described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer.
According to a third aspect of the present invention; a kind of electrochemical sensor is provided; comprise working electrode and reference electrode; according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode; described sensor is suitable for measuring the characteristic of tested liquid; described working electrode comprises the matrix of being made by platinum or gold or platinum black; described reference electrode comprises the matrix that is made of gold; wherein said reference electrode is included in NaOH or the potassium hydroxide base solution impregnation film that applies on the described matrix that is made of gold; described working electrode comprises and being coated on the described matrix of being made by platinum or gold or platinum black; have the plasma polymerization film of selective material through ability; and be coated in and have the lip-deep fixing hydrophobic membrane that selective material sees through the described plasma polymerization film of ability; be used to protect and be stabilized in the described plasma polymerization film on the described matrix of being made by platinum or gold or platinum black, described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer.
Description of drawings
Describe the present invention with reference to the accompanying drawings in detail, wherein:
Fig. 1 is the view of explanation according to the PH sensor of first embodiment of the invention;
Fig. 2 is the view of explanation according to the ORP sensor of second embodiment of the invention;
Fig. 3 is the view of explanation according to the PH sensor of the monolithic devices of third embodiment of the invention;
Fig. 4 is the view of explanation according to the PH sensor of the monolithic devices of fourth embodiment of the invention;
Fig. 5 is the view of explanation according to the PH meter of fifth embodiment of the invention; And
Fig. 6 is the view of explanation according to the PH meter of sixth embodiment of the invention.
Embodiment
The present invention relates to a kind of electrochemical sensor that comprises working electrode and reference electrode, described sensor is applicable to the characteristic of measuring tested liquid, it carries out described measurement according to the working electrode that immerses in the tested liquid with reference electrode relative potential difference (PD) and electric current between the two, thereby described working electrode comprises and is used for producing the matrix of a current potential with tested liquid reactions according to the concentration of tested liquid, thereby described reference electrode comprises the matrix that is used for producing with tested liquid reactions a set potential.According to the present invention, at least one in described working electrode and the reference electrode comprises the described matrix that is coated with a kind of functional membrane, by getting involved described functional membrane to produce this current potential between described matrix and tested liquid.As a result, the present invention advantageously makes the internal liquid that no longer need use in electrochemical sensor, thereby makes described sensor make easily and handle, and makes this sensor can miniaturization.
The invention still further relates to a kind of electrochemical sensor that comprises working electrode and reference electrode, described sensor is applicable to the characteristic of measuring tested liquid, it carries out described measurement according to the working electrode that immerses in the tested liquid with reference electrode relative potential difference (PD) and electric current between the two, described working electrode comprises the matrix of being made by platinum, gold, platinum black etc., and described reference electrode comprises matrix of being made by the silver that is coated with the chlorination silverskin or the matrix that is made of gold.According to the present invention, described reference electrode comprises the described matrix that is coated with functional membrane (i.e. matrix of being made by the silver that is coated with the chlorination silverskin or the matrix that is made of gold), by getting involved described functional membrane to produce this current potential between described matrix and tested liquid.As a result, the invention enables described electrochemical sensor to make easily and handle, and make the described sensor can miniaturization.
In addition, the present invention relates to a kind of electrochemical sensor that comprises working electrode and reference electrode, described sensor is applicable to the characteristic of measuring tested liquid, it carries out described measurement according to immersing working electrode in the tested liquid and the relative potential difference (PD) between the reference electrode and electric current, described working electrode comprises the matrix of being made by platinum, gold, platinum black etc., and described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin.According to the present invention, described reference electrode comprises the described matrix (more particularly, this reference electrode comprises that described matrix of being made by the silver that is coated with the chlorination silverskin and the salt bridge that is provided on the described matrix as functional membrane keep film) that is coated with salt bridge maintenance film.This structure of the present invention advantageously makes no longer needs internal liquid, and makes electrode to solidify.As a result, because the voltage between liquid does not change, make it possible to improve measuring accuracy.In addition, make described electrochemical sensor handle easily, and make the sensor can miniaturization.
In addition, this reference electrode can comprise the matrix of described gold and be provided on the described auri body as the non-plasma polymerization film that sees through ability of the material with selection of functional membrane that described plasma polymerization film is made of at least a compound in aromatics, fluorinated compound, the alcoholic compound etc.As a result, advantageously making no longer needs internal liquid, and makes electrode to solidify.In addition, because the voltage between liquid does not change, make it possible to improve measuring accuracy.In addition, make described electrochemical sensor handle easily, and make this sensor can miniaturization.
In addition, this reference electrode can comprise described auri body and be provided at aqueous slkali impregnated membranes on the described auri body by described auri body being immersed in the aqueous slkali such as NaOH, potassium hydroxide for example as functional membrane.Thereby making no longer needs internal liquid, and this electrode can be solidified.Because the voltage between liquid does not change, so make it possible to improve measuring accuracy.In addition, make described electrochemical sensor handle easily, and make this sensor can miniaturization.
In electrochemical sensor of the present invention, electrode is solidified by coated film.Therefore, compare with the electrode that uses thin glass film or liquid catalyst, can reduce the interior resistance of electrode, this makes does not need to be used to improve the amplifier than high input impedance of having of magnitude of voltage when measuring potential difference (PD).Thereby, can use the measurement mechanism that comprises common potentiometric cheapness to measure.
In addition, working electrode can comprise the described matrix of being made by platinum, gold, platinum black etc., and being provided on the described matrix and material with selection sees through the plasma polymerization film of ability, described plasma polymerization film is made of at least a compound in aromatics, fluorinated compound, the alcoholic compound etc.Specifically, the material of the described selection of the described plasma polymerization film of working electrode sees through ability and makes it possible to selectively see through hydrogen ion.Thereby, for example, on matrix, apply P-xylene, aromatics if utilize plasma polymerization to handle, then can form and can selectively see through hydrionic film.In addition, the advantage of this plasma polymerization film is, it has higher near adhesion to described matrix, and it can stop sneaks into bubble, perhaps stops tested liquid to enter, and can remove any other material outside the hydrogen ion in the tested liquid.If change the condition of described combination of compounds or change plasma polymerization, then can form and be applicable to any plasma polymerization film that selectively sees through the material of any particular type.In addition, if on matrix, form a plurality of plasma polymerization films concurrently, then can measure a plurality of characteristics of liquids with different qualities.
Described working electrode and described reference electrode can be coated with the fixing hydrophobic membrane that is made of alkane polymer and cyclic olefin polymer.In this case, because can suppress peeling off and gaining in strength of film, can prolong the serviceable life of electrode.
In addition, described working electrode and described reference electrode can be assembled into an integral body, but mutually insulated.Therefore, can make the further miniaturization of electrochemical sensor of the present invention.In addition, because two electrodes are closely close, so can reduce the interior resistance of measuring system.
In addition, it can be the perfluoroalkyl sulfonate film that utilizes the salt bridge dipping of potassium chloride, sodium chloride etc. that described salt bridge keeps film, or by by the salt bridge by potassium chloride, sodium chloride etc. is carried out the salt bridge crystal film that crystallization forms.In this case, the film of wherein any maintenance salt bridge all can reach electrobalance by chlorion in the salt bridge and tested liquid in film.Thereby, stop tested liquid to contact and etched the matrix with matrix, this can prolong the serviceable life of sensor.
In addition, described salt bridge is the potpourri that also is added with silver chloride.In this case, matrix can be made from silver simply and not had argentine chloride coating.
PH with reference to electricity counts first embodiment of explanation according to electrochemical sensor of the present invention below.
Fig. 1 is the view of the PH sensor (or the PH of electricity meter) according to first embodiment of the invention.Described PH sensor comprises working electrode 1 and reference electrode 5.Working electrode 1 comprises by the thread matrix 2 of platinum black metal, is provided at that matrix 2 is lip-deep to have the plasma polymerization film 3 that selectively sees through hydrionic ability, and be used to protect with stabilized matrix 2 on the fixing hydrophobic membrane 4 of plasma polymerization film 3.
It is one to have the film of several micron thickness that salt bridge keeps film 8.Specifically, it is a kind of Nafion film, promptly a kind of perfluoroalkyl sulfonate film with the potassium chloride dipping, and it utilizes casting method to form.
Between two electrodes, provide conventional pot 13, make the platinum black line 2 of working electrode 1 and the silver-colored line 6 of reference electrode 5 link to each other, thereby constitute the PH meter of electricity by pot 13.
When operation, two electrodes are immersed in the tested liquid of wanting measured PH.At first, in working electrode, tested liquid is by fixedly film 4 infiltrations.Then, in plasma polymerization film 3, except the various materials that mix in the tested liquid (chlorion (Cl for example
-), urea, protein, vitamin etc., if tested liquid is living specimen for example to be urinated, saliva etc.) outside, have only hydrogen ion selectively to be seen through.Thereby on the surface of platinum black line 2, hydrogen ion remains on electrobalance.This " Nernst " reaction produces the electromotive force relevant with the pH value of tested liquid.
In the aforesaid operations that carries out working electrode 1, in reference electrode 5, tested liquid keeps film 8 to permeate by fixing film 4 to salt bridge.Then, salt bridge keeps hydrogen ion in film 8 and the chlorination silverskin 7 to be equivalent to tested liquid remaining on electrobalance.Thereby, the irrelevant constant current potential of the pH value of generation and tested liquid in reference electrode 5, this constant potential is called as reference potential.
Because the migration by the positive and negative ion that provides in the tested liquid of being reflected at of two electrodes produces electric coupling between two electrodes, and the potential difference (PD) of measuring between two electrodes by conventional pot 13.Thereby, by using the PH meter of known pH value computing formula and known electricity,, can calculate the pH value of tested liquid according to the measurement of described potential difference (PD).
ORP with reference to electricity counts second embodiment of explanation according to electrochemical sensor of the present invention below.
Fig. 2 is the view of the ORP sensor (or the ORP of electricity meter) according to second embodiment of the invention.Working electrode comprises by the thread matrix 2 of platinum black, and reference electrode 5 forms in the mode identical with the reference electrode of above-mentioned first embodiment.This ORP sensor comprises working electrode and reference electrode 5.Between two electrodes, provide conventional pot 13, make the platinum black line 2 of working electrode 1 and the silver-colored line 6 of reference electrode 5 link to each other, thereby constitute the ORP meter of electricity by pot 13.
In working electrode,, and in reference electrode, produce reference potential in the mode identical with first embodiment owing to redox reaction produces oxidation-reduction potential.By the potential difference (PD) between two electrodes of pot 13 measurements of routine.Thereby, by using the ORP meter of known ORP value computing formula and known electricity,, can calculate the ORP value of tested liquid according to the measurement of described potential difference (PD).
PH below with reference to monolithic devices counts three embodiment of explanation according to electrochemical sensor of the present invention, and it has working electrode and reference electrode, and they are installed in the relative both sides of an insulcrete.
Fig. 3 is the view of explanation monolithic devices PH sensor (or monolithic devices PH meter).Described PH sensor comprises working electrode 1, reference electrode 5 and glass plate (insulcrete) 9.Working electrode 1 comprises by electrolytic method at the matrix 10 that is made of the platinum black film that a side of glass plate 9 provides, and is used to cover the plasma polymerization film 3 on the surface of matrix 10, and the fixedly film 4 that is used to cover the surface of plasma polymerization film 3.Reference electrode comprise by electrolytic method be provided at glass plate 9 opposite side by silverskin 11 and be provided at the matrix that the chlorination silverskin 7 on the silverskin 11 constitutes, the salt bridge that is used to cover the surface of matrix keeps film 8, and is used to cover the fixedly film 4 that salt bridge keeps the surface of film 8.Conventional pot 13 is provided between two electrodes, makes the platinum black film 10 of working electrode 1 and the silverskin 11 of reference electrode 5 link to each other by pot 13, thereby constitutes monolithic devices PH meter.
Use the both sides of glass plate in this embodiment, but also can only use a side of glass plate to form two electrodes thereon, if do not make them overlapping.This insulcrete is not limited to glass plate.Can use any suitable insulation plate for example ceramic wafer, resin plate, glass mat etc.
In the 3rd above-mentioned embodiment, the monolithic devices PH meter of the working electrode that has on the relative both sides that are formed on insulcrete and reference electrode has been described.Another kind of monolithic devices PH meter will be described below, and it has working electrode and the reference electrode that forms coaxially, as the 4th embodiment according to electrochemical sensor of the present invention.
Fig. 4 is the view of explanation without any need for the another kind of monolithic devices PH sensor (or monolithic devices PH meter) of insulcrete.This PH sensor comprises working electrode 1, reference electrode 5 and glass part (insulator) 12.The silver-colored line 6 that forms axle is coated with chlorination silverskin 7, is used for any part that part covers silver-colored line 6, then, provides a salt bridge to keep fixedly film 4 of film 8 and successively, thereby forms reference electrode 5.In addition, in order to separate, provide glass part 12 to cover another part of silver-colored line 6 with reference electrode 5.Glass part 12 is in order coated with platinum black film 10, plasma polymerization film 3 and fixing film 4, to form working electrode.Conventional pot 13 is provided between two electrodes, makes the platinum black film 10 of working electrode 1 and the silver-colored line 6 of reference electrode 5 link to each other by pot 13, thereby constitutes monolithic devices PH meter.
Below with reference to five embodiment of the PH meter explanation with reference electrode different according to electrochemical sensor of the present invention with first embodiment.
Fig. 5 is the view that explanation has the PH meter of the reference electrode different with first embodiment.This PH meter comprises working electrode 1 and reference electrode 5.The structure of working electrode 1 is identical with first embodiment's.Therefore, omission is to the explanation of working electrode 1.
When operation, two electrodes are dipped in the tested liquid that will measure pH value.At first, in reference electrode 5, tested liquid is by fixedly film 4 infiltrations.Then, in plasma polymerization film 15, some compositions in the tested liquid are not selectively seen through, and make tested liquid remain on electrobalance on the surface of gold thread 14.Thereby, the irrelevant constant potential (or reference potential) of the pH value of generation and tested liquid in reference electrode 5.
Because the migration by the positive and negative ion that provides in the tested liquid of being reflected at of two electrodes produces electric coupling between two electrodes, and the potential difference (PD) of measuring between two electrodes by conventional pot 13.Thereby, by using known pH value computing formula,, can calculate the pH value of tested liquid with the mode identical with first embodiment according to the measurement of described potential difference (PD).
Below with reference to six embodiment of the PH meter explanation with reference electrode different according to electrochemical sensor of the present invention with first embodiment.
Fig. 6 is the view that explanation has the PH meter of the reference electrode different with first embodiment.This PH meter comprises working electrode 1 and reference electrode 5.The structure of working electrode 1 is identical with first embodiment's.Therefore, omission is to the explanation of working electrode 1.
When operation, two electrodes are dipped in the tested liquid that will measure pH value.At first, in reference electrode 5, tested liquid is by 16 infiltrations of aqueous slkali impregnated membranes.Then, tested liquid is maintained at electrobalance on the surface of gold thread 14.Thereby, the irrelevant constant potential (or reference potential) of the pH value of generation and tested liquid in reference electrode 5.
Because the migration by the positive and negative ion that provides in the tested liquid of being reflected at of two electrodes produces electric coupling between two electrodes, and the potential difference (PD) of measuring between two electrodes by conventional pot 13.Thereby, by using known pH value computing formula,, can calculate the pH value of tested liquid with the mode identical with first embodiment according to the measurement of described potential difference (PD).
Top reference first to the 6th embodiment describes the present invention, but other embodiment can also be arranged, and is as described below:
The chlorination silverskin 7 in first to the 4th embodiment and the platinum black film 10 of the working electrode 1 in the three or four embodiment and the silverskin 11 of reference electrode 5 are made with electrolytic method as mentioned above.But, the formation method of these films is not limited to electrolytic method, but can use any other method, for example non-electrolytic method, sputtering method, ion plating method, paper tinsel sticks method, and the method for printing screen owing to the paste material uses uses the direct plotting method of ink-jet etc.
As the matrix of working electrode, in first and second embodiment, use the platinum black line, in third and fourth embodiment, use the platinum black film.But, also can use any other line and film, for example platinum line and gold thread and platinum film and golden film.In the 5th and the 6th embodiment, use the matrix of gold thread as working electrode.But, also can use platinum line and platinum black line.In addition, can use the element of paper tinsel or other adequate types to replace described line.
Illustrated above by P-xylene, aromatics being carried out the plasma polymerization film 3 that plasma treatment forms.But can be by at least a plasma treatment of carrying out in aromatics, fluorinated compound and the alcoholic compound is formed the plasma polymerization film.
Illustrated that above it is a kind of Nafion films that salt bridge keeps film 8, promptly a kind of perfluoroalkyl sulfonate film that is used as the potassium chloride dipping of salt bridge.In addition, can use any perfluoroalkyl sulfonate film of utilization as the sodium chloride dipping of salt bridge.In addition, salt bridge maintenance film can be the salt bridge crystal film that forms by this way: make the salt bridge crystallization on the surface of matrix, thereby cover described matrix.In addition, illustrated that above the reference electrode use is coated with the silver of silver chloride as matrix.But, if use the potpourri formation salt bridge maintenance film that wherein salt bridge is added with silver chloride, then can save the chlorination silverskin 7 of matrix this moment.
Illustrated above that fixedly film 4 is formed by alkane polymer.But, it also can be formed by cyclic olefin polymer.
In the above-described embodiment, electrochemical sensor is made into linear or tabular.But, it can be designed to any other shape, and is for example columniform or paper tinsel shape, as long as can form film.
In the 6th embodiment, the aqueous slkali impregnated membranes is to form by impregnation matrix in sodium hydroxide solution.But, also can form by impregnation matrix in potassium hydroxide solution.
The plasma polymerization film of working electrode or reference electrode, salt bridge keep film and aqueous slkali impregnated membranes to be not limited to these above-mentioned types, can use other any suitable type, be used between matrix and the tested liquid producing current potential by described matrix as long as they get involved.
Electrochemical sensor of the present invention can use with the measurement mechanism of any kind, for example electric, polarography, coulometric analysis etc., as long as it is suitable for measuring relative current potential or electric current between pair of electrodes.
Can clearly be seen that by above-mentioned, in according to electrochemical sensor of the present invention, in working electrode and the reference electrode at least one comprises the matrix that is coated with functional membrane, by get involved described film between described matrix and tested liquid, is used to produce current potential.As a result, the present invention has advantageously eliminated the needs to the internal liquid that uses in sensor, makes described sensor make easily and handle, and makes that described sensor can miniaturization.
In addition, in according to electrochemical sensor of the present invention, reference electrode comprises the matrix that is coated with functional membrane, by get involved described film between described matrix and tested liquid, is used to produce current potential.As a result, the present invention advantageously makes described sensor make easily and handle, and makes that described sensor can miniaturization.
In addition, the invention provides a kind of electrochemical sensor that is used to measure the characteristic of tested liquid, it is measured according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode, described working electrode comprises the matrix of being made by platinum, gold, platinum black etc., and described reference electrode comprises the matrix that is made of gold.According to the present invention, reference electrode comprises the auri body, and it is coated with the plasma polymerization film or the aqueous slkali impregnated membranes of the non-handling capacity of material with selection.As a result, advantageously making no longer needs internal liquid, and makes electrode to solidify.In addition, because the voltage between the liquid does not change, make measuring accuracy improve.In addition, help the processing of described electrochemical sensor, and make that described sensor can miniaturization.
In addition, the invention provides a kind of electrochemical sensor that is used to measure the characteristic of tested liquid, it is measured according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode, described working electrode comprises the matrix of being made by platinum, gold, platinum black etc., and described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin.According to the present invention, this reference electrode comprises the matrix that is coated with salt bridge maintenance film.This structure of the present invention advantageously makes no longer needs internal liquid, and makes described electrode to solidify.Thereby, owing to there is not the change of the voltage between the liquid, make it possible to improve measuring accuracy.In addition, help the processing of described electrochemical sensor, and make that described sensor can miniaturization.
In electrochemical sensor of the present invention, electrode is cured by coated film.Therefore, compare with the electrode that uses thin glass film or liquid catalyst, can reduce the interior resistance of electrode, this makes no longer needs to have high input impedance so that improve the amplifier of magnitude of voltage when measuring potential difference (PD).Thereby, can utilize the measurement mechanism that comprises common potentiometric cheapness to measure.
In addition, working electrode can comprise the described matrix that is coated with the plasma polymerization film, and the material that described polymeric membrane has selection sees through ability, and is made of at least a compound in aromatics, fluorinated compound, the alcoholic compound etc.Thereby, for example, on matrix, apply P-xylene, aromatics if use plasma polymerization to handle, then can form and can selectively see through hydrionic film.In addition, the advantage of this plasma polymerization film is, it has higher near adhesion to described matrix, and it can stop sneaks into bubble, perhaps stops tested liquid to enter, and can remove any other material outside the hydrogen ion in the tested liquid.If change the condition of described combination of compounds or change plasma polymerization, then can form and be applicable to the plasma polymerization film that selectively sees through any specific type of material.In addition, if on matrix, form a plurality of plasma polymerization films concurrently, then can measure a plurality of characteristics of liquids with different qualities.
Described working electrode and described reference electrode can apply the fixing hydrophobic membrane that is made of alkane polymer and cyclic olefin polymer.In this case, because can suppress peeling off and gaining in strength of film, can prolong the serviceable life of electrode.
In addition, the matrix of working electrode and reference electrode can integrally be configured on the surface of an insulcrete, makes them not contact each other.Therefore, can make the further miniaturization of electrochemical sensor of the present invention.In addition, because two electrodes are very close, so can make the internal resistance minimum of measuring system.
In addition, it can be perfluoroalkyl sulfonate film with the salt bridge dipping of potassium chloride, sodium chloride etc. that described salt bridge keeps film, or by by the salt bridge by potassium chloride, sodium chloride etc. is carried out the salt bridge crystal film that crystallization forms.In this case, the film of wherein any maintenance salt bridge can reach electrobalance by chlorion in the salt bridge and tested liquid in film.Thereby, stop tested liquid to contact and etched the matrix with matrix, this can prolong the serviceable life of sensor.
In addition, described salt bridge can be the potpourri that also is added with silver chloride.In this case, matrix can be made from silver and simply without any argentine chloride coating.
Claims (6)
1. electrochemical sensor, comprise working electrode and reference electrode, according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode, described sensor is suitable for measuring the characteristic of tested liquid, described working electrode comprises the matrix of being made by platinum or gold, described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin, wherein
This reference electrode is included in the salt bridge that applies on the chlorination silverskin surface in the described matrix of being made by the silver that is coated with the chlorination silverskin and keeps film; and the fixing hydrophobic membrane that on described salt bridge maintenance film surface, applies; the salt bridge that is used to protect and be stabilized on the described matrix of being made by the silver that is coated with the chlorination silverskin keeps film; described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer; described salt bridge maintenance film is the perfluoro alkyl sulfonic acid film with the salt bridge dipping of potassium chloride or sodium chloride; or carrying out the salt bridge crystal film that crystallization is made by the salt bridge of potassium chloride or sodium chloride, described working electrode includes only the described matrix of being made by platinum or gold.
2. according to the electrochemical sensor of claim 1, the matrix of wherein said working electrode is made by platinum black.
3. according to the electrochemical sensor of claim 1, wherein said salt bridge is to the potpourri that wherein further adds silver chloride.
4. electrochemical sensor, comprise working electrode and reference electrode, according to working electrode in the tested liquid of immersion and relative potential difference (PD) and the electric current between the reference electrode, described sensor is suitable for measuring the characteristic of tested liquid, described working electrode comprises the matrix of being made by platinum or gold, described reference electrode comprises the matrix of being made by the silver that is coated with the chlorination silverskin, wherein
This reference electrode is included in the salt bridge that applies on the chlorination silverskin surface in the described matrix of being made by the silver that is coated with the chlorination silverskin and keeps film; and the fixing hydrophobic membrane that on described salt bridge maintenance film surface, applies; the salt bridge that is used to protect and be stabilized on the described matrix of being made by the silver that is coated with the chlorination silverskin keeps film; described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer; described salt bridge maintenance film is the perfluoro alkyl sulfonic acid film with the salt bridge dipping of potassium chloride or sodium chloride; or carry out the salt bridge crystal film that crystallization is made by the salt bridge of potassium chloride or sodium chloride
Described working electrode comprise be coated in by on platinum or the described matrix made of gold, have a plasma polymerization film that selective material sees through ability; and be coated in and have the lip-deep fixing hydrophobic membrane that selective material sees through the described plasma polymerization film of ability; be used to protect and be stabilized in the described plasma polymerization film on the described matrix of being made by platinum or gold, described fixing hydrophobic membrane is made by alkane polymer or cyclic olefin polymer.
5. according to the electrochemical sensor of claim 4, the matrix of wherein said working electrode is made by platinum black.
6. according to the electrochemical sensor of claim 4, wherein said salt bridge is to the potpourri that wherein further adds silver chloride.
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| JP145586/2002 | 2002-05-21 | ||
| JP2002145586 | 2002-05-21 | ||
| JP050297/2003 | 2003-02-27 |
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| CN100422727C true CN100422727C (en) | 2008-10-01 |
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| CN103114911B (en) * | 2011-11-16 | 2015-03-25 | 深圳职业技术学院 | Early warning system of engine |
| JP6312396B2 (en) * | 2013-09-30 | 2018-04-18 | 株式会社日立ハイテクノロジーズ | Ion selective electrode |
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