CN107957440A - Plane ammine selective sensing electrode and its preparation method - Google Patents
Plane ammine selective sensing electrode and its preparation method Download PDFInfo
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Abstract
This disclosure relates to a kind of plane ammine selective sensing electrode and its preparation method applied to water quality monitoring.Its structure includes electrically insulating base, conductive layer, ammonium ion sensed layer, hydroxide ion sensed layer and a dielectric substrate.Electrically insulating base has an at least plane.Conductive layer is arranged at least in a plane of electrically insulating base.Wherein conductive layer has at least one first conductive part and at least one second conductive part, the first conductive part and the isolation insulated from each other of the second conductive part, and is assembled with one first reaction zone and a second reaction zone respectively.Ammonium ion sensed layer is arranged at the first reaction zone of the first conductive part.Hydroxide ion sensed layer is arranged at the second reaction zone of the second conductive part.Dielectric substrate sets and is covered on ammonium ion sensed layer and hydroxide ion sensed layer.The plane ammine selective sensing electrode preparation method that the disclosure provides can significantly reduce sensing electrode volume, plane ammine selective sensing electrode is had high selectivity and sensitivity.
Description
Technical field
This disclosure relates to a kind of sensing electrode applied to water quality monitoring, more particularly to a kind of plane ammine selective sensing
Electrode and its preparation method.
Background technology
The sampling of traditional water quality monitoring often needs to expend many times and manpower with analysis, also can not effectively react at once
Go out the problems such as wastewater treatment is ineffective or processing water water quality is abnormal, and then waste discharge is influenced the water quality in rivers and creeks.For
Meet actual demand, water monitoring device must be able to analyze water quality in real time, effectively to grasp water process effect and water quality variation
Situation, and then improve the operation of reply processing routine.On the other hand, the demand recycled for Water Sproading, also makes water quality monitoring
The demand that device must be able to monitor in real time on line is substantially improved.
But traditional water monitoring device is as its ion sense electrode using glass electrode.Although glass electrode can
Ion concentration in stable measure water quality, but its is complicated, costly, is also unfavorable for minimizing.In addition, it is limited to water
The glass electrode of matter monitoring device and the structure of reference electrode, also can not effectively lift the sensitivity of sensing.
In view of aforementioned need and problem, it is really necessary to provide a kind of plane ammine selective sensing electrode and its preparation method,
With applied to water quality monitoring.
The content of the invention
The purpose of the disclosure is to provide a kind of plane ammine selective sensing electrode and its preparation method.Coated by drop
Method, sputtering method, electrodeposition process or wire mark thick film technology set ammonium ion sensed layer and hydroxide ion sensing planarizing layers
It is placed on a conductive layer, to lift accuracy, and significantly reduces sensing electrode volume.Make plane ammine selective sensing electricity at the same time
Has high selectivity and sensitivity, applied to fields such as medicine, biochemistry, chemistry, agricultural, environment, to be such as applied to monitoring
Water plough planting process ammonia nitrogen concentration change, human sweat ammonia nitrogen concentration change, aquaculture water quality monitoring or
Particular organisms index (being, for example, that creatine is intoxicated) etc. can be detected with reference to specific ferment.
Disclosure another object is to provide a kind of plane ammine selective sensing electrode and its preparation method.Its compact structure essence
Letter, processing procedure are simple, of low cost, more conducively realize the purpose for providing disposal type sensing electrode.
For up to object defined above, the disclosure provides a kind of plane ammine selective sensing electrode, including electrically insulating base, conduction
Layer, ammonium ion sensed layer, hydroxide ion sensed layer and a dielectric substrate.Electrically insulating base has an at least plane.It is conductive
Layer is arranged at least in a plane of electrically insulating base.Wherein conductive layer is led with least one first conductive part and at least 1 second
Electric portion, the first conductive part and the isolation insulated from each other of the second conductive part, and one first reaction zone and one second reaction are assembled with respectively
Area.Ammonium ion sensed layer is arranged at the first reaction zone of the first conductive part.Hydroxide ion sensed layer is arranged at the second conductive part
Second reaction zone.Dielectric substrate sets and is covered on ammonium ion sensed layer and hydroxide ion sensed layer.
For up to object defined above, the disclosure separately provides a kind of preparation method of plane ammine selective sensing electrode, including step：
(a) providing an electrically insulating base has an at least plane, and a conductive layer is at least formed in a plane in electrically insulating base, its
Middle conductive layer is insulated from each other with least one first conductive part and at least one second conductive part, the first conductive part and the second conductive part
Isolation, and one first reaction zone and a second reaction zone are assembled with respectively；(b) monoammonium ion sense layer and a hydrogen-oxygen are formed respectively
Radical ion sensed layer is covered in the first reaction zone of the first conductive part and the second reaction zone of the second conductive part；And (c) formation
One dielectric substrate, is covered on ammonium ion sensed layer and hydroxide ion sensed layer.
Brief description of the drawings
Fig. 1 is the structure decomposition figure of the plane ammine selective sensing electrode of disclosure preferred embodiment.
Fig. 2 is an exemplary sensing voltage response curves of disclosure plane ammine selective sensing electrode.
Fig. 3 is the sensing number of the plane ammine selective sensing electrode and traditional ammonia sensing electrode of disclosure preferred embodiment
According to voltage and ammonia density relation calibration curve.
Fig. 4 is the preparation flow chart of the plane ammine selective sensing electrode of disclosure preferred embodiment.
Description of reference numerals：
1：Plane ammine selective sensing electrode (abbreviation sensing electrode)
10：Electrically insulating base 11：Plane
20：Conductive layer 21：First conductive part
22：Second conductive part 23：First reaction zone
24：Second reaction zone 25：Working electrode join domain
26：To electrode connecting region domain 30：Insulating waterproof layer
40：Ammonium ion sensed layer 50：PH sensed layers
60：Middle partition 61：Opening
70：Dielectric substrate 80：Gas air-permeable layer
S1~S5：Step
Embodiment
Embodying some exemplary embodiments of disclosure features and advantages will describe in detail in the explanation of back segment.It should be understood that
It is that the disclosure can have various changes in different embodiments, it does not all depart from the scope of the present disclosure, and therein
Illustrate and attached drawing inherently is illustrated as being used, not for the limitation disclosure.
The disclosure discloses a kind of plane ammine selective sensing electrode (planar ammonia selective sensing
Electrode), its structure mainly includes electrically insulating base (insulating base plate), conductive layer (electric-
Conductive layer), ammonium ion sensed layer (ammonium ion sensing layer), hydroxide ion sensed layer
(hydroxide ion sensing layer) and dielectric substrate (electrolyte layer).In the disclosure, hydrogen-oxygen
Radical ion sensed layer can be for example but be not only restricted to an acid-base value sensed layer or pH sensed layers (pH sensing layer).It is conductive
Layer is arranged in the plane of electrically insulating base, and wherein conductive layer has at least one first conductive part and at least one second conductive part,
First conductive part and the isolation insulated from each other of the second conductive part, and the first reaction zone and second reaction zone are assembled with respectively.Ammonium ion
Sensed layer is arranged at the first reaction zone of the first conductive part.Hydroxide ion sensed layer is arranged at the second reaction of the second conductive part
Area.Dielectric substrate sets and is covered on ammonium ion sensed layer and hydroxide ion sensed layer.Utilize drop cladding process, sputter
Method, electrodeposition process or wire mark thick film technology set plane ammonium ion sensed layer and plane hydroxide ion sensed layer
In on conductive layer, and can be in the case of exactness without misalignment, significantly reduced plan type ammine selective sensing electrode volume, and
Make plane ammine selective sensing electrode that there is high selectivity and sensitivity.
Referring to Fig. 1, it is the structure decomposition figure of the plane ammine selective sensing electrode of disclosure preferred embodiment.Such as
Shown in figure, disclosure plane ammine selective sensing electrode (in rear abbreviation sensing electrode) 1, including electrically insulating base 10, conduction
Layer 20, insulating waterproof layer 30, ammonium ion sensed layer 40, pH sensed layers 50, middle partition 60, dielectric substrate 70 and gas air-permeable layer
80.Wherein electrically insulating base 10 has an at least plane 11.Conductive layer 20 includes the first conductive part 21 and the second conductive part 22, point
At least in a plane 11, and isolation insulated from each other of electrically insulating base 10 is not arranged at.In this present embodiment, the first conductive part 21
And second conductive part 22 to be arranged at same plane 11 be preferable.First conductive part 21 and the second conductive part 22 have first respectively
Reaction zone 23 and second reaction zone 24.Insulating waterproof layer 30 is arranged on conductive layer 20, at least partly covers the of conductive layer 20
One conductive part 21 and the second conductive part 22, and the first conductive part 21 and the second conductive part 22 is distinguished Partial exposure, wherein first
The part that 21 and second conductive part 22 of conductive part is exposed to outside insulating waterproof layer 30 assemble respectively as the first reaction zone 23 and
Second reaction zone 24.Preferably, the first conductive part 21 and the first reaction zone 23 of the second conductive part 22 and second reaction zone 24 are more
With a fine interval, neighbour relatively sets, so as to be beneficial to integrally-built miniaturization.Better, the first reaction zone 23 and the second reaction
Area 24 is each end for being located at the first conductive part 21 and the second conductive part 22 respectively.Ammonium ion sensed layer 40 and pH sensed layers 50 are divided
The part that the first conductive part 21 and the second conductive part 22 are not covered and exposed to the open air by insulating waterproof layer 30 is not arranged at, i.e., corresponds to respectively
It is arranged at the first reaction zone 23 and second reaction zone 24.In other words, insulating waterproof layer 30, ammonium ion sensed layer 40 and pH sensed layers
50 collectively cover on conductive layer 20, and wherein insulating waterproof layer 30, ammonium ion sensed layer 40 and pH sensed layers 50 can be but not
It is limited to copline setting.In a preferred embodiment, except the first reaction zone 23 and second reaction zone 24 are to be led respectively positioned at first
Outside each end of electric 21 and second conductive part 22 of portion, the first conductive part 21 and the second conductive part 22 are relative to the first reaction zone 23
And the other end of second reaction zone 24 also has a working electrode join domain 25 and a pair of electrodes join domain 26 respectively, not by
Insulating waterproof layer 30 is covered and exposed to the open air, and is connected to measurement connection circuit (not shown), to form sensing circuit.In addition, electrolysis
Matter layer 70 is arranged on ammonium ion sensed layer 40 and pH sensed layers 50, and is covered in ammonium ion sensed layer 40 and pH sensings at the same time
On layer 50.In this present embodiment, sensing electrode 1 also includes middle partition 60, have one opening 61, middle partition 60 be located on ammonium from
Around sub- sensed layer 40, pH sensed layers 50 and dielectric substrate 70, so that dielectric substrate 70 is through opening 61 and is placed in out
Contacted in the inner peripheral surface of mouth 61 and with ammonium ion sensed layer 40 and pH sensed layers 50.In addition, sensing electrode 1 is also breathed freely comprising gas
Layer 80, is arranged on dielectric substrate 70, and is bonded with middle partition 60, so that dielectric substrate 70 is held in gas air-permeable layer 80
Between ammonium ion sensed layer 40 and pH sensed layers 50, the object sensing ion produced from gas air-permeable layer 80 to be passed through
Dielectric substrate 70 is transferred to ammonium ion sensed layer 40 and pH sensed layers 50 respectively.
In this present embodiment, the object sensing ion of ammonium ion sensed layer 40 and pH sensed layers 50 is respectively ammonium ion (NH4 +) and hydroxide ion (OH-).Ammonium ion (NH can be produced since ammonia is soluble in water4 +) and hydroxide ion (OH-), its chemistry
Reaction equation is such as shown in (formula 1).Amino molecule in a water corpse or other object for laboratory examination and chemical testing is diffused in dielectric substrate 70 by gas air-permeable layer 80 makes electrolyte
In ammonium ion (NH4 +) and hydroxide ion (OH-) concentration changes, then is transferred to ammonium ion sensed layer 40 and pH sensed layers respectively
50.Wherein ammonium ion (NH4 +) change for producing electrochemical membrane voltage can be reacted with ammonium ion conversion zone 40, when the ammonium in aqueous solution
Ion concentration is higher, then the membrane voltage produced at ammonium ion conversion zone 40 is bigger.On the other hand, when being dissolved in aqueous solution due to ammonia
Also hydroxide ion (OH can be generated-) and cause aqueous solution to change in alkalescence, pH sensed layers 50 sense hydroxide ion at this time
(OH-) voltage in negative growth.In other words, when aqueous solution is in itself more in alkalescence, then pH sensed layers 50 sense hydroxide ion
(OH-) voltage it is smaller.Therefore, in the presence of having ammonia in aqueous solution, sensed at ammonium ion sensed layer 40 and pH sensed layers 50
Signal have an addition, therefore sensing electrode 1 proposed by the invention can increase substantially Conventional electrochemical measurement ammonia density
Sensitivity.
Fig. 2 is an exemplary sensing voltage response curves of disclosure plane ammine selective sensing electrode.Fig. 3 is this public affairs
The sensing data voltage of the plane ammine selective sensing electrode and traditional ammonia sensing electrode of opening preferred embodiment is closed with ammonia density
It is calibration curve.As shown in the figure, when Ammonia In Aqueous Solution/ammonium concentration improves, the mode of traditional measurement film potential all only with respect to
Reference electrode silver/silver chlorate, i.e. ammonia ammonium concentration sensing voltage ENH4+=EWorking(NH4+)-EReference.When ammonia ammonium concentration is higher
When relative to reference electrode silver/silver chlorate ammonia ammonium concentration sensing voltage ENH4+Can be higher, and its change only may conform to electrochemistry
59.2 ± 2mV/ of slope variation (10 multiple) of energy scholar's special formula formula.But in this present embodiment, due to being at the same time by aqueous solution
The change of middle pH value also calculates at the same time, that is, the pH sensing voltages E relative to reference electrode silver/silver chloratepH=
EWorking(pH)-EReference, reaction can be produced as shown in Equation 1 when being influenced in aqueous solution be subject to ammonia dissolving, cause aqueous solution
PH rises, that is, pH sensing voltages EpHCan be lower.Therefore, in this present embodiment, the measurement method of sensing electrode 1 is to utilize
Ammonia ammonium concentration sensing voltage ENH4+With pH sensing voltages EpHDifference, i.e. ENH4+-EpH=EWorking(NH4+)-EWorking(pH)So that
The sensitivity slope change of disclosure plane ammine selective sensing electrode 1 is in 132 ± 3mV/ (10 multiple), than aforementioned conventional ammonia
59.2 ± 2mV/ of sensitivity (10 multiple) of sensing electrode is high, as shown in Fig. 3 and following table 1.
Table 1：The performance ratio of the plane ammine selective sensing electrode of disclosure preferred embodiment and traditional ammonia sensing electrode
Compared with table.
| Disclosure plane ammine selective sensing electrode | Traditional ammonia sensing electrode | |
| The range of linearity | 0.01~1400ppm | 0.01~1400ppm |
| The linearity | R2=0.9901 | R2=0.9954 |
| Sensitivity | 132mV/10 multiples | 59.2mV/10 multiples |
On the other hand, according to the plane ammine selective sensing electrode structure of aforementioned preferred embodiments, the disclosure is at the same time
A kind of preparation method of plane ammine selective sensing electrode is disclosed.Fig. 4 is the plane ammine selective sense of disclosure preferred embodiment
Survey the preparation flow chart of electrode.1 and Fig. 4 is refer to, first in step S1, there is provided electrically insulating base 10 has an at least plane
11, and conductive layer 20 is formed at least in a plane 11 in electrically insulating base 10.Conductive layer 20 includes the first conductive part 21 and the
Two conductive parts 22, are utilized respectively e.g. but are not only restricted to screen painting or the mode of sputtering process is arranged at electrically insulating base 10
At least in a plane 11, and isolation insulated from each other.First conductive part 21 and the second conductive part 22 have the first reaction zone respectively
23 and second reaction zone 24.Then, in step S2, in forming insulating waterproof layer 30 on conductive layer 20, part covers conductive layer
20 the first conductive part 21 and the second conductive part 22, and the first conductive part 21 and the second conductive part 22 is distinguished Partial exposure, its
In the part that is exposed to outside insulating waterproof layer 30 of the first conductive part 21 and the second conductive part 22 assemble framework respectively as first
Reaction zone 23 and second reaction zone 24.In this present embodiment, insulating waterproof layer 30 be using be, for example, but be not only restricted to wire mark or
It is the mode of chemical vapour deposition technique and is covered on conductive layer 20, and makes unlapped 20 part of conductive layer assemble to be formed
First reaction zone 23 of the first conductive part 21 and the second reaction zone 24 of the second conductive part 22.Wherein, the of the first conductive part 21
The second reaction zone 24 of one reaction zone 23 and the second conductive part 22 also with a fine interval and neighbour relatively sets so that beneficial to overall knot
The miniaturization of structure.In a preferred embodiment, except the first reaction zone 23 and second reaction zone 24 are to be located at the first conductive part respectively
21 and second conductive part 22 each end outside, the first conductive part 21 and the second conductive part 22 are relative to the first reaction zone 23 and
The other end of two reaction zones 24 is not also covered by insulating waterproof layer 30, and it is a working electrode join domain to assemble framework respectively
25 with a pair of electrodes join domain 26, to form sensing circuit, and the essential features of its unrestricted disclosure, in this not
Repeat again.Thereafter, in step S3, respectively at the first reaction zone 23 and the second conductive part of the first conductive part 21 of conductive layer 20
Ammonium ion sensed layer 40 and pH sensed layers 50 are formed on 22 second reaction zone 24.In this present embodiment, insulating waterproof layer 30,
Ammonium ion sensed layer 40 and pH sensed layers 50 are collectively covered on conductive layer 20, therefore insulating waterproof layer 30, ammonium ion sense
The order that layer 40 and pH sensed layers 50 are formed at conductive layer 20 is not limited, visual practical application request and carry out optimization tune
It is whole, repeated no more in this.Then, in step S4, form dielectric substrate 70 and be covered in ammonium ion sensed layer 40 and pH sensed layers
On 50.In this present embodiment, or with the opening 61 of middle partition 60 electrolyte fill area is defined, wherein 60 ring of middle partition is set
Around ammonium ion sensed layer 40, pH sensed layers 50 and dielectric substrate 70, so that dielectric substrate 70 is through opening 61 and holds
It is placed in the inner peripheral surface of opening 61 and is contacted with ammonium ion sensed layer 40 and pH sensed layers 50.Middle partition 60 can be by e.g. but not
The material for being limited to polyethylene terephthalate (polyethylene terephthalate, PET) is formed.It is in addition, electric
Solution matter layer 70 then may, for example, be but be not only restricted to the opening that 0.01M trishydroxymethylaminomethane aqueous solutions are filled in middle partition 60
Define electrolyte fill area in 61 inner peripheral surface and form.Finally, in step S5, gas air-permeable layer 80 is formed in electrolysis
On matter layer 70, and it is bonded with middle partition 60, so that dielectric substrate 70 is held in gas air-permeable layer 80 and ammonium ion sensed layer 40
And between pH sensed layers 50, i.e., dielectric substrate 70 is placed in the electrolyte defined in the inner peripheral surface of the opening 61 of middle partition 60
In fill area.In this present embodiment, gas air-permeable layer 80 can be for example but be not only restricted to the polytetrafluoroethylene (PTFE) gas of 10 μm of thickness
Air-permeable layer.
In this present embodiment, conductive layer 20 can be for example, by being but being not only restricted to the mode shape such as screen painting or sputtering process
Into in the plane 11 of electrically insulating base 10.Wherein the first conductive part 21 of conductive layer 20 and the second conductive part 22 respectively by ammonium from
The first reaction zone 23 and second reaction zone 24 that sub- sensed layer 40 and pH sensed layers 50 are covered are respectively ammonium ion (NH4 +) anti-
Answer electrode district and hydroxide ion (OH-) reaction electrode area, and remainder is then 30 covering protections of insulating waterproof layer.Yu Yi
In preferred embodiment, the first conductive part 21 and the second conductive part 22 are covered opposite by ammonium ion sensed layer 40 and pH sensed layers 50
First reaction zone 23 of lid and the other end of second reaction zone 24 also have a working electrode join domain 25 and a pair of electricity respectively
Pole join domain 26, and measurement connection circuit (not shown) is connected to, to form sensing circuit.In this present embodiment, conductive layer
20 can be for example but be not only restricted to jet-plating metallization film, its material may be selected from wire mark silver carbonaceous conductive mixed slurry, gold size, platinum
Glue, elargol, conductive carbon paste, gold, palladium, platinum, rhotanium, silver or its combination.Electrically insulating base 10 can by be, for example, but from
It is limited to polyethylene terephthalate (PET) or ceramic substrate is formed.In an embodiment, conductive layer 20 is with mode of printing shape
It is made into after electrically insulating base 10, then to dry at such as 60 DEG C to 140 DEG C.
In this present embodiment, the first reaction zone 23 of the first conductive part 21 of conductive layer 20 is covered by ammonium ion sensed layer 40
Lid, and the second reaction zone 24 of the second conductive part 22 is covered by pH sensed layers 50, then the first reaction zone 23 and second reaction zone
24 form ammonium ion (NH respectively4 +) and hydroxide ion (OH-) reaction electrode area, to transmit the ammonium ion sensed layer 40 and
Voltage change caused by measured electrochemical membrane current potential between pH sensed layers 50, and it is conductive via the first of conductive layer 20 respectively
Electric signal is transferred to measurement by 25 and second conductive part 22 of working electrode join domain in portion 21 to electrode connecting region domain 26
Connect circuit.In an embodiment, measurement connection circuit is additionally coupled to a measuring instrument (not shown), this measuring instrument can show and count
The ammonia density of corresponding sensing voltage change is calculated, so that follow-up user is easy to use.
In addition, in this present embodiment, insulating waterproof layer 30 can be by for example but being not only restricted to electric insulation and waterproof
Material, as the materials such as xylylene po1ymer, wire mark insulating cement, wire mark UV insulating cements are formed.In an embodiment, insulation is anti-
Water layer 30 is to be coated with to be formed by a wire mark insulating cement, and dries and be made at such as 60 DEG C to 140 DEG C, 30 meeting portion of insulating waterproof layer
Divide the first conductive part 21 and the second conductive part 22 for covering the conductive layer 20, and divide the first conductive part 21 and the second conductive part 22
Other Partial exposure and form the first reaction zone 23 and second reaction zone 24, to supply ammonium ion sensed layer 40 and pH sensed layers 50 respectively
Covered.It is respectively ammonium ion sensed layer 40 and pH in preferred embodiment, in the first conductive part 21 and the second conductive part 22
The first reaction zone 23 and second reaction zone 24 that sensed layer 50 is covered are isolation insulated from each other, and with small spacing and each other phase
Neighbour is set, in favor of the miniaturization of sensing electrode 1.
In the embodiment of the present disclosure, ammonium ion sensed layer 40 and pH sensed layers 50 can be for example, by being but being not only restricted to drop
Cladding process, sputtering method, electrodeposition process or wire mark thick film technology are formed.In this present embodiment, the first of conductive layer 20 is conductive
The ammonium ion sensed layer 40 formed on first reaction zone 23 in portion 21 is monoammonium ion-selective membrane, its constituent material is included for example
Be but be not only restricted to ionophore, plasticiser, heat stable resin or its combination.In a preferred embodiment, ammonium ion sensed layer 40
Cation-exchanger is also included, and each component configuration weight can be for example but be not only restricted to include ion in ammonium ion sensed layer 40
The percentage by weight of carrier between 0.2wt% between 5wt%, the percentage by weight of plasticiser between 50wt% to 70wt% it
Between, the percentage by weight of heat stable resin between 30wt% between 60wt% and cation-exchanger percentage by weight between
0.1wt% is between 2.5wt%.Foregoing ion carrier, plasticiser, heat stable resin and cation-exchanger are formed mixed
Liquid is closed, with drop rubbing method drop is overlying on ammonium ion sensed layer 40 to be formed on the first conductive part 21 of conductive layer 20 and exposes to the open air
Part, wherein droplet size between 10 μ L between 50 μ L, be placed at such as 30 DEG C to 60 DEG C dry 2 to 10 it is small when after, then
When vacuum drying 6 to 18 is small at such as 40 DEG C to 60 DEG C, that is, complete the making of the ammonium ion sensed layer 40.
On the other hand, pH sensed layers 50 are then available is, for example, but is not only restricted to electrochemistry chronoamperometry or circulates volt
The electro-deposition such as peace method mode is by yttrium oxide (IrO2) it is deposited on pH sensed layers 50 to be formed on the second conductive part 22 of conductive layer 20
And the second reaction zone 24 exposed to the open air.In an embodiment, pH sensed layers 50 are to utilize chronoamperometry by yttrium oxide (IrO2) heavy
Product is in the second reaction zone 24 that pH sensed layers 50 to be formed on the second conductive part 22 of conductive layer 20 expose to the open air, wherein current density
Scope is between 0.2mA/cm2To 5mA/cm2Between.In another embodiment, pH sensed layers 50 are then using cyclic voltammetry by oxygen
Change iridium (IrO2) second reaction zone 24 that is deposited on pH sensed layers 50 to be formed on the second conductive part 22 of conductive layer 20 and exposes to the open air,
Then voltage range can be between -0.2V between 1.3V, and sweep speed between 10mV/s between 100mV/s, then may be used by the scanning number of turns
Between 10 circles between 100 circles.In an embodiment, the pH sensed layers 50 of electro-deposition completion, can also first be incited somebody to action with deionized water again
After unnecessary plating solution cleans up, it is placed at 80 DEG C, when drying 1 is small, excessive moisture is dried, that is, completes the pH sensed layers 50
Make.In this present embodiment, used plating solution composition can be for example but be not only restricted to include chlorination when forming pH sensed layers 50
Iridium (IrClx) wherein X is made of 3-4,30wt% hydrogen peroxide, oxalic acid, 3M potassium carbonate and deionized water, wherein iridium chloride
(IrClx) percentage by weight between 0.05wt% between 0.18wt%, the percentage by weight of 30wt% hydrogen peroxide between
0.5wt% between 1wt%, the percentage by weight of oxalic acid between 0.2wt% between 0.6wt%, the weight hundred of 3M potassium carbonate
Point than between 6wt% between 12wt%, and deionized water percentage by weight between 80wt% between 90wt%.
In previous embodiment, middle partition 60 is located on ammonium ion sensed layer 40 and the periphery of pH sensed layers 50, middle partition
Also assembled in the inner peripheral surface of 60 opening 61 and be defined as an electrolyte fill area, to fill dielectric substrate 70.In an embodiment,
Middle partition 60 can be for example but be not only restricted to by the material such as polyethylene terephthalate (PET) or polyvinyl chloride (PVC) institute
Form.In a preferred embodiment, middle partition 60 is formed with polyethylene terephthalate (PET), thickness 0.35mm, and
Gum is coated in its back side, is fitted in the plane 11 of electrically insulating base 10, and is located on ammonium ion sensed layer 40 and pH
The periphery of sensed layer 50, after pressed with roller press and place 12 it is small when, make its stickup more firm, and the opening of middle partition 60
Assembled in 61 inner peripheral surface and define an electrolyte filling region, to fill dielectric substrate 70.
In previous embodiment, the material of dielectric substrate 70 is made of liquid electrolyte, be can be for example but is not only restricted to
Aqueous hydrochloric acid solution, potassium chloride solution, potassium hydroxide aqueous solution, sodium-chloride water solution, phosphate-buffered aqueous solution, trihydroxy methyl
Aminomethane (Tris (hydroxymethyl) aminomethane, Tris) aqueous solution or aqueous ammonium chloride solution, concentration range are situated between
In 0.01M between 1M.In an embodiment, it can be made in a manner of solid electrolyte, using being, for example, but be not only restricted to fine jade
Fat candy gel (Agarose), polyacrylamide gel (Polyacrylamide), gelatin (Gelatin) or calcium alginate
(Calcium alginate) isogel material attachment removal liquid electrolyte.In a preferred embodiment, tri- hydroxyls of 0.01M are also utilized
Aminomethane aqueous solution, and accumulated with dispenser fixing point colloid as 500 μ L, by 61 (the i.e. electrolyte of opening of middle partition 60
Filling region) fill up after, you can complete the making of the dielectric substrate 70.
In addition, the material of gas air-permeable layer 80 can be by being, for example, but being not only restricted to cellulose acetate, silicon in previous embodiment
Rubber, polytetrafluoroethylene (PTFE) (PTFE), fluorinated ethylene propylene copolymer (FEP), poly bis methylsiloxane (PDMS), polyvinyl chloride
(PVC), natural rubber or its combination are formed.In this present embodiment, the thickness of gas air-permeable layer 80 can be between 0.1 μm to 30 μm
Between.In preferred embodiment, gas air-permeable layer 80 is to be made of using thickness 10 μm of polytetrafluoroethylene film, is carried on the back
Gum is coated in face, and polytetrafluoroethylene film is covered on the middle top of partition 60 with joint tool and covers dielectric substrate 70, will
Dielectric substrate 70 is packaged in the opening 61 of middle partition 60, that is, forms the sensing electrode 1 of the disclosure.
In conclusion the disclosure provides a kind of plane ammine selective sensing electrode and its preparation method.By drop cladding process,
Ammonium ion sensed layer and hydroxide ion sensing planarizing layers are arranged at by sputtering method, electrodeposition process or wire mark thick film technology
In on a conductive layer, to lift accuracy, and sensing electrode volume is significantly reduced.Make plane ammine selective sensing electrode at the same time
With high selectivity and sensitivity, applied to fields such as medicine, biochemistry, chemistry, agricultural, environment, to be such as applied to monitoring water
Plough ammonia nitrogen concentration change, ammonia nitrogen concentration change, the water quality monitoring of aquaculture or the knot of human sweat of planting process
Particular organisms index (being, for example, that creatine is intoxicated) etc. can be detected by closing specific ferment.And its compact structure is simplified, processing procedure is simple, into
This is cheap, more conducively realizes the purpose for providing disposal type sensing electrode.
Claims (11)
1. a kind of plane ammine selective sensing electrode, including：
One electrically insulating base, has an at least plane；
One conductive layer, be arranged at the electrically insulating base this at least on a plane, wherein the conductive layer have at least one first
Conductive part and at least one second conductive part, first conductive part and the second conductive part isolation insulated from each other, and be assembled with respectively
One first reaction zone and a second reaction zone；
Monoammonium ion sense layer, is arranged on first reaction zone；
One hydroxide ion sensed layer, is arranged on the second reaction zone；And
One dielectric substrate, set and be covered in the ammonium ion sensed layer and the hydroxide ion sensed layer on.
2. plane ammine selective sensing electrode as claimed in claim 1, also comprising an insulating waterproof layer, is arranged at the conduction
On layer, first conductive part and second conductive part are partly covered, and distinguishes first conductive part and second conductive part
Assemble and form first reaction zone and the second reaction zone.
3. plane ammine selective sensing electrode as claimed in claim 1, also comprising partition in one, the electric insulation base is arranged at
This of plate is at least in a plane, and partition has an opening wherein in this, and partition is arranged at the ammonium ion sensed layer and is somebody's turn to do in this
The periphery of hydroxide ion sensed layer, and the dielectric substrate is placed in the inner peripheral surface of the opening.
4. plane ammine selective sensing electrode as claimed in claim 3, also comprising a gas air-permeable layer, sets and is covered in
On the dielectric substrate, and it is bonded with partition in this, so that the dielectric substrate is held in the gas air-permeable layer and the ammonium ion
Between sensed layer and the hydroxide ion sensed layer.
5. plane ammine selective sensing electrode as claimed in claim 1, wherein hydroxide ion sensed layer are an acid-base value
Sensed layer.
6. a kind of preparation method of plane ammine selective sensing electrode, including step：
Step a：There is provided an electrically insulating base has an at least plane, and this in the electrically insulating base is at least formed in a plane
One conductive layer, the wherein conductive layer have at least one first conductive part and at least one second conductive part, first conductive part and should
The isolation insulated from each other of second conductive part, and one first reaction zone and a second reaction zone are assembled with respectively；
Step b：Formed respectively monoammonium ion sense layer and a hydroxide ion sensed layer be covered on first reaction zone with
On the second reaction zone；And
Step c：A dielectric substrate is formed, is covered on the ammonium ion sensed layer and the hydroxide ion sensed layer.
7. the preparation method of plane ammine selective sensing electrode as claimed in claim 6, wherein step b is further included：
Step b1：An insulating waterproof layer is formed on the conductive layer, partly covers first conductive part and second conductive part,
And first conductive part and second conductive part is set to assemble form first reaction zone and the second reaction zone respectively.
8. the preparation method of plane ammine selective sensing electrode as claimed in claim 6, wherein step c is further included：
Step c1：Partition has an opening in providing one, and partition in this is conformed to this of the electrically insulating base at least one is flat
Face, makes partition in this be arranged at the ammonium ion sensed layer and the periphery of the hydroxide ion sensed layer, and the dielectric substrate holds
It is placed in the inner peripheral surface of the opening.
9. the preparation method of plane ammine selective sensing electrode as claimed in claim 8, further includes：
Step d：Form a gas air-permeable layer to be bonded on the dielectric substrate, and with partition in this, keep the dielectric substrate
In this in inner peripheral surface of opening of partition.
10. the preparation method of plane ammine selective sensing electrode as claimed in claim 6, wherein hydroxide ion sensed layer are one
Acid-base value sensed layer.
11. ammonium ion in the preparation method of plane ammine selective sensing electrode as claimed in claim 6, wherein step b
Sensed layer and the hydroxide ion sensed layer are by drop cladding process, sputtering method, electrodeposition process or wire mark thick film technology
Formed.
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| US15/641,940 US10473610B2 (en) | 2016-10-17 | 2017-07-05 | Planar ammonia selective sensing electrode and manufacturing method thereof |
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| CN110044984B (en) * | 2019-04-10 | 2021-10-15 | 华东师范大学 | Preparation technology of coplanar flexible electrochemical sensor electrode and array |
| CN111855754B (en) * | 2019-04-29 | 2021-12-03 | 深圳安吉尔饮水产业集团有限公司 | Water hardness detection probe, sensor, detection method and water softener |
| CN113916954A (en) * | 2021-09-30 | 2022-01-11 | 上海交通大学 | On-chip in-situ micro silver chloride reference electrode and preparation method thereof |
| CN115684304B (en) * | 2022-11-03 | 2024-05-28 | 中国科学院长春应用化学研究所 | Potential method dissolved oxygen sensor based on antimony-based electrode |
| CN115739110B (en) * | 2022-11-04 | 2024-01-30 | 湖州美奇医疗器械有限公司 | Preparation method and application of platinum-based catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6666963B1 (en) * | 2002-08-14 | 2003-12-23 | Industrial Scientific Corporation | Oxygen sensor |
| US20050252790A1 (en) * | 2002-04-09 | 2005-11-17 | Dobson John V | Electrochemical sensor system and sensing method |
| US20100252428A1 (en) * | 2002-12-02 | 2010-10-07 | Epocal Inc. | Heterogeneous membrane electrodes |
| CN103592162A (en) * | 2013-11-06 | 2014-02-19 | 安徽皖仪科技股份有限公司 | Sample treatment method for testing chloride ions in cement through ion selective electrode method |
| US20140209485A1 (en) * | 2011-08-01 | 2014-07-31 | Omron Healthcare Co., Ltd. | Sensor head, electrochemical sensor, and method for using electrochemical sensor |
| CN104316584A (en) * | 2014-10-31 | 2015-01-28 | 深圳市希莱恒医用电子有限公司 | Sensor for measuring concentration of various ions and manufacturing method for sensor |
| CN104330449A (en) * | 2014-10-31 | 2015-02-04 | 深圳市希莱恒医用电子有限公司 | Sodium ion sensor and preparation method thereof |
| CN105548306A (en) * | 2014-10-22 | 2016-05-04 | 爱科来株式会社 | ELECTROCHEMICAL SENSOR,METHOD FOR PRODUCING ELECTROCHEMICAL SENSOR, and Ag/AgCl electrode |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100358933B1 (en) * | 2000-03-27 | 2002-10-31 | 차근식 | Planar reference electrode |
| US6761817B2 (en) * | 2001-12-19 | 2004-07-13 | Honeywell International Inc. | Smart determination of dissolved oxygen probe operating bias |
| TWI314211B (en) * | 2006-04-14 | 2009-09-01 | Univ Tamkang | Method and electrochemical sensing strip with screen-printed three electrodes for determining concentration of dissolved oxygen in a solution |
| US8357662B2 (en) * | 2006-09-08 | 2013-01-22 | Worcester Polytechnic Institute | Surface-based ammonium ion sensor and methods of making thereof |
| WO2013081443A1 (en) * | 2011-12-02 | 2013-06-06 | Mimos Berhad | Ammonium selective electrode and method of preparing it |
| TWI539153B (en) * | 2014-04-09 | 2016-06-21 | Univ Nat Kaohsiung 1St Univ Sc | Flexible dissolved oxygen sensor |
| CN104155355A (en) * | 2014-08-20 | 2014-11-19 | 黄崇艺 | Oxygen sensor |
-
2017
- 2017-05-25 CN CN201710377336.3A patent/CN107957440B/en not_active Expired - Fee Related
- 2017-05-25 CN CN201710411401.XA patent/CN107957439A/en active Pending
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050252790A1 (en) * | 2002-04-09 | 2005-11-17 | Dobson John V | Electrochemical sensor system and sensing method |
| US6666963B1 (en) * | 2002-08-14 | 2003-12-23 | Industrial Scientific Corporation | Oxygen sensor |
| US20100252428A1 (en) * | 2002-12-02 | 2010-10-07 | Epocal Inc. | Heterogeneous membrane electrodes |
| US20140209485A1 (en) * | 2011-08-01 | 2014-07-31 | Omron Healthcare Co., Ltd. | Sensor head, electrochemical sensor, and method for using electrochemical sensor |
| CN103592162A (en) * | 2013-11-06 | 2014-02-19 | 安徽皖仪科技股份有限公司 | Sample treatment method for testing chloride ions in cement through ion selective electrode method |
| CN105548306A (en) * | 2014-10-22 | 2016-05-04 | 爱科来株式会社 | ELECTROCHEMICAL SENSOR,METHOD FOR PRODUCING ELECTROCHEMICAL SENSOR, and Ag/AgCl electrode |
| CN104316584A (en) * | 2014-10-31 | 2015-01-28 | 深圳市希莱恒医用电子有限公司 | Sensor for measuring concentration of various ions and manufacturing method for sensor |
| CN104330449A (en) * | 2014-10-31 | 2015-02-04 | 深圳市希莱恒医用电子有限公司 | Sodium ion sensor and preparation method thereof |
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| CN107957439A (en) | 2018-04-24 |
| TW201816396A (en) | 2018-05-01 |
| TWI625522B (en) | 2018-06-01 |
| TWI631329B (en) | 2018-08-01 |
| CN107957440B (en) | 2020-06-26 |
| TW201816397A (en) | 2018-05-01 |
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