CN107367542A - Portable flow field type electrode heavy metal ion detection device and electrode card - Google Patents
Portable flow field type electrode heavy metal ion detection device and electrode card Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/416—Systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract
The embodiments of the invention provide a kind of by electrode card and the portable flow field type electrode heavy metal ion detection device of laminar flows pond assembling, electrode card face has an all solid-state electrode of three pure-surfaces, i.e., working electrode, to electrode and reference electrode;In the neck in the electrode card pluggable closely sealed insertion laminar flows pond, microchannel that the workspace of electrode card face is stretched into laminar flows pond, Flow Field Distribution of three electrodes in the workspace interior edge solution to be measured.Shape of the invention by analyzing three distribution of electrodes of flow Field Design in microchannel, longer action time and more satisfactory stability can be obtained in the enrichment process that ASV is analyzed, be favorably improved sensitivity and the reappearance of detection.The embodiment of the present invention additionally provides the electrode card with flow field type electrode for above-mentioned detection device.
Description
Technical field
The present invention relates to technical field of environmental detection, more particularly to a kind of portable flow field type electrode detection of heavy metal ion
Device, available for trace heavy metal ion in Anodic stripping voltammetry Rapid Detection solution.Present invention also offers one kind to use
In the electrode card with flow field type electrode of the detection means.
Background technology
A large amount of electronic wastes cause serious problem of environmental pollution caused by the development of global electronic electrical industry, to the whole world
Ecological environment bring stern challenge.In recent years, various countries actively take measures to control electronic product to ecological ring one after another
Pollute and destroy caused by border.Such as the RoHS instructions that European Union issues, make in being limited in into the electronic and electrical equipment of EU market
With some harmful substances, all electronic electric equipment classifications that may be used in daily life are substantially covered, are limited
Harmful substance include lead(Pb)﹑ cadmiums(Cd)And mercury(Hg)Deng heavy metal.
At present, although the pretreatment technology of electric equipment products is highly developed, for example realized using microwave digestion technology
While batch processing, its equipment is less demanding to environment place, can be used for Site Detection;Electric equipment products resolution after, it is necessary to
Content of beary metal in solution is tested and analyzed, traditional element test method has atomic absorption spectrophotometry and inductance
Coupled plasma-atomic emission spectrometry, but the detecting instrument of these methods needs larger working space and suitable work
Environment is higher to power requirement, it is necessary to which the corollary apparatus such as ventilating system, gas cylinder, some also need to recirculating cooling water system.It is above-mentioned
Detection means is mostly large-scale instrument, with high costs in general, and detection sample consumption is big, and labor intensive, is not suitable for scene
Quick detection, heavy metal ion on site detection efficiency is caused to be difficult to improve.Anodic stripping voltammetry(Anodic Stripping
Voltammetry, ASV)As a kind of electrochemical analysis method, its detection limit up to ppb-ppt levels, fully meet heavy metal from
The sensitivity of son detection needs, and it is the technology development side that can be expected that heavy metal ion on site quick detection is realized based on ASV
To.
Traditional ASV heavy metal ion detection devices are the three-electrode system in beaker, and three electrodes are by working electrode(Mostly
Outstanding mercury or mercury film electrode), to electrode(Mostly strip platinum electrode)And reference electrode(Mostly bar-shaped calomel electrode or silver-chlorination
Silver electrode)Form, heavy metal ion solution to be measured is held in beaker;During detection, by applying voltage between electrode, pre- electricity is first carried out
Solution, reducing heavy metal ion in solution, to separate out be metal enrichment in working electrode surface;Dissolution is carried out again, makes to be deposited on work
Make heavy metal oxidation to be measured dissolution for ion of electrode surface, can be determined by the current peak obtained on Stripping Voltammetry curve
The concentration of heavy metal ion to be measured;Although the trace in sample solution is also can detect using the progress ASV analyses of above-mentioned conventional apparatus
Heavy metal ion, but detection process is present that sample solution consumption is big, the preelectrolysis time is long, testing result poor reproducibility lacks
Point.
Zhiwei Zou and Am Jang et al. research discloses a kind of laboratory for detection of heavy metal ion in situ
Two groups of small-sized sensor electrodes are arranged in series in microchannel by chip sensor, the sensor;Microchannel is a saddle type
Thin layer cavity, straight-through solution inlet port to be measured and outlet are set respectively at two-end-point;Every group of electrode is three-electrode system, wherein
Working electrode is bismuth pole, is gold electrode to electrode, and reference electrode is silver-silver chloride electrode, connects the Pin arrangement of each electrode
Form contact regions.Said chip sensor detecting device utilizes micro electro mechanical system (MEMS) technology, the theory based on chip lab, realizes
The miniaturization of ASV detecting instruments, the use that avoids mercury electrode pollute to environment;But above-mentioned detection device two arrays of electrodes string
The design of connection, Flow Field Distribution and electrode are not accounted for completely and is effectively worked relation of plane, when not only more extending enrichment procedure
Between, also increase the link for producing error.
For insufficient existing for the above-mentioned heavy metal ion detection device with thin layer microcell, preferably to realize high-volume
The heavy metal ion on site quick detection of sample to detection means, it is necessary to be improved, to improve ASV analysis heavy metals in process
In the efficiency of detection means electrode surface enrichment.
The content of the invention
The present invention existing gold during ASV analyses for the existing heavy metal ion detection device with microchannel
A kind of category not high technical problem of bioaccumulation efficiency on electrode, there is provided new portable flow field type electrode heavy metal ion inspection
Device and electrode card are surveyed, by forming flow field type electrode to electrode optimization, the enrichment effect of electrode surface metal can be effectively improved
Rate.
In order to solve the above technical problems, embodiments of the invention provide a kind of portable flow field type electrode heavy metal ion inspection
Device, including microchannel and three electrodes stretched into the microchannel are surveyed, three electrodes are respectively working electrode, to electricity
Pole and reference electrode, wherein:
The microchannel is a lamelliform cavity being arranged in laminar flows pond;Three electrodes are to be arranged on an electricity
Plane all solid-state electrode on the substrate of pole card;Laminar flows pond being provided at both ends with outside connection in the microchannel
Input duct and drain pipe road, the laminar flows pond also include the lamelliform cavity below set the matching electrode
Card-like neck;In the neck in the pluggable closely sealed insertion laminar flows pond of electrode card, the electricity
The region that pole card face falls into the microchannel is workspace, and three electrodes are in the workspace interior edge solution to be measured
Flow Field Distribution, the contact feet of three electrodes are stretched out outside the neck.The pluggable design of electrode card, can be according to continuous
Need of work realizes freely changing for electrode card, avoids the cross pollution of sample room;By contact feet it is electrode card during work
Three electrodes on piece apply voltage, while the electric current between detecting electrode.
Preferably, the lamelliform cavity of the microchannel is arranged to saddle type, the input duct and drain pipe road edge respectively
Tangential direction is connected to two tops of the lamelliform cavity;Now, the flow field of the solution to be measured in the microchannel
For S-shaped, three electrodes are in S-shaped Flow Field Distribution described in the workspace interior edge.The shape of the lamelliform cavity of the microchannel
Shape can make multiple choices as needed, and the shapes such as rectangle, ellipse or circle also can be selected in addition to saddle type.
It is further preferred that three electrodes are distributed in the first half area, later half in the S-shaped flow field in the workspace
Area or whole region;Wherein, three electrodes can be set in tandem in the workspace, can also be in parallel
Set.
As the preferred of preceding solution, the wedge angle of three electrode edges is subjected to cavetto processing, optionally, three
The edge of individual electrodes conduct coupling part is also configured as round and smooth curve.
As the preferred of preceding solution, the width of the working electrode and reference electrode is more than to electrode.
As the preferred of preceding solution, the input duct and drain pipe road have the pipeline opening protruded.
The embodiment of the present invention additionally provides a kind of electrode card, is used in preceding solution, with the laminar flows
Pond assembles to form the portable flow field type electrode heavy metal ion detection device.
The technical scheme of the above embodiment of the present invention, the flow field in microchannel by analyzing thin layer microcell type fill to detection
Three electrodes in putting are transformed, and electrode, along the Flow Field Distribution, is formed the weight with flow field type electrode in microchannel
Metal ion detection device, its advantage are as follows:
1. in the detection means of the embodiment of the present invention, three electrode designs of electrode card are the shape with Flow Field Distribution, such as S-shaped,
Traditional distribution of electrodes shape such as linear or circle is different from, longer effect can be obtained in the enrichment process that ASV is analyzed
Time and more satisfactory stability, it is favorably improved sensitivity and the reappearance of detection;
2. needed due to this electrode under two working conditions of dissolution under the enrichment and inactive state being operated under flow regime,
The embodiment of the present invention increases the area of working electrode and reference electrode, can improve the operating efficiency under flow regime;
3. the embodiment of the present invention is sharply located to have carried out cavetto processing to the electrode of electrode card in detection means, tip can be avoided
The generation of effect;Round and smooth curve is revised as in the part that is conductively connected on electrode card again, can be in silk-screen printing manufacture craft
The middle dosage for saving electrically conductive ink, reduces cost of manufacture.
Brief description of the drawings
Fig. 1 is ASV analysis principle schematic diagrames;
Fig. 2 is the ASV detection means schematic diagrames of traditional three-electrode system;
Fig. 3 is the stereogram of the portable flow field type electrode heavy metal ion detection device of the embodiment of the present invention;
Fig. 4 is the stereochemical structure perspective view of Fig. 3 detection means;
Fig. 5 is the structural representation in the laminar flows pond of Fig. 3 detection means, wherein, Fig. 5 a are the stereochemical structure in laminar flows pond
Perspective view, Fig. 5 b are the A-A sectional views in laminar flows pond in Fig. 5 a;
Fig. 6 is the structural representation of the electrode card in Fig. 3 detection means with three electrodes, wherein, Fig. 6 a are electrode card
Stereogram, Fig. 6 b be electrode card top view;
Fig. 7 is the assembly structure diagram of Fig. 3 detection means;
Fig. 8 is the structural representation of three electrodes of conventional shape;
Fig. 9 is the Flow Field Distribution schematic diagram at the A directions visual angle in the saddle type thin layer cavity of detection means shown in Fig. 5 a;
Figure 10 is the structural representation of the flow field type electrode of the tandem of the embodiment of the present invention, and three electrodes are arranged in parallel and along S
Shape Flow Field Distribution, wherein, electrode shape is the S-shaped first half in Figure 10 a, and electrode shape is S-shaped lower half in Figure 10 b, in Figure 10 c
Electrode shape is whole S-shaped;
Figure 11 is the structural representation of the parallel flow field type electrode of the embodiment of the present invention, and three electrodes are arranged in series and along S
Shape Flow Field Distribution, wherein, electrode shape is the S-shaped first half in Figure 11 a, and electrode shape is S-shaped lower half in Figure 11 b, in Figure 11 c
Electrode shape is whole S-shaped;
Figure 12 be the embodiment of the present invention cavetto after flow field type electrode structural representation, wherein, Figure 12 a to 12c are tandem
Electrode, Figure 12 d to 12f are parallel electrode;
Figure 13 is hierarchy schematic diagram of the electrode card of the embodiment of the present invention in silk-screen printing.
[ main element symbol description ]
C1- beakers;C2- cover plates;C3- solution to be measured;WE- Steel Work electrodes;CE- stainless steel plate auxiliary electrodes;RE- references electricity
Pole;C4- non-woven fabrics;
1- laminar flows pond;11- microchannels;12- input ducts;13- drain pipes road;14- necks;2- electrode cards;21- bases
Piece;22- workspaces;23- reference electrodes;24- working electrodes;25- is to electrode;26- contact feets;Z-S shapes flow field;Z1- first is managed
Think area;Z2- secondary ideals area.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
The present invention belongs to electrochemistry using anodic stripping voltammetry detection heavy metal ions concentration in solution, the detection method
One kind of voltammetry in analysis, controlled potential eletrolysis enrichment is combined on the basis of voltammetry and forms stripping voltammetry, it is examined
Rising limit is applicable to the analysis detection of 30 multiple elements up to ppb ~ ppt levels.Stripping voltammetry analysis process is divided into enrichment
(Preelectrolysis)With two parts of dissolution, reacted according to the dissolution occurred on Different electrodes, be divided into anodic stripping voltammetry(ASV)With
Cathodic Stripping Voltammetry(CSV).Wherein, ASV is suitable to measure metal ion, with its extremely low cost and high sensitivity, turns into weight
The common method of metal detection.
Common ASV Cleaning Principles volt-ampere curve as shown in Figure 1, preelectrolysis is carried out first using working electrode as negative electrode,
Cathode potential is controlled in heavy metal ion M to be measuredn+Limiting diffusion current potential range in(Typically compare half wave potentialE 1/2Minus 0.2
~ 0.3V, corresponding to the D positions in Fig. 1), make Mn+Metal is reduced to be enriched with the working electrode (s;After the completion of preelectrolysis, to electricity
In the case that pole continues to voltage, stop stirring, dissolution is proceeded by after standing, the current potential of working electrode is square by negative sense
To constant-speed scanning, the M metals now deposited on the working electrode (s are anodized into ion M againn+Into solution;In dissolution
Cheng Jilu Stripping Currents, and current potential is mapped, metallics to be measured can determine that according to the peak height of volt-ampere curve during dissolution
Concentration.
A kind of existing ASV devices are as shown in Fig. 2 by Steel Work electrode WE, reference electrode RE and parcel non-woven fabrics c4
The three-electrode system insertions of stainless steel plate auxiliary electrode CE compositions fill the burning of the solution c3 to be measured containing trace heavy metal ion
Detected in cup c1;During detection, the first making alive between working electrode and reference electrode, when working electrode potential is more than to be measured
During the evolution or deposition potential of heavy metal ion, the heavy metal ion in solution reduces in working electrode surface to be separated out(Similar to electrolysis or
Electroplating process), potential application time is longer on working electrode, restore be deposited on its surface metal it is more, obtain in Fig. 1
The enrichment volt-ampere curve of electric current negative area;When there is enough metal enrichments, after solution to be measured is kept for certain time stand,
Carry out process in leaching:Increase forward voltage to working electrode, dissolution will be aoxidized by being deposited on the metal of working electrode surface, lasting to survey
Measure working electrode during this and the corresponding current potential of the electric current and writing task electrode in loop is formed to electrode, obtain Fig. 1
The Stripping Voltammetry curve of middle electric current positive area, a μ A level or smaller peak point current can be measuredi p If control all operations
Condition is highly consistent, then the peak point currenti p Concentration linear positive correlation of the size only with metal ion to be measured in solution, lead to
Cross and draw concentration to be measured with the standard liquid contrast under the same terms.Sample is can detect using above-mentioned traditional ASV detection means
Trace heavy metal ion in solution, there is higher sensitivity.But it is molten sample to be present in the detection carried out generally in beaker
Many defects such as liquid dosage is big, preelectrolysis time length, poor reproducibility.
With the demand that the development of microflow control technique and detection means minimize, occur being used for heavy metal ion ASV inspections
The micro-fluidic detection device of survey, it can effectively overcome aforementioned conventional ASV devices existing segmental defect in the detection;The micro-fluidic inspection
Survey device to be combined microchannel with chip sensor, chip sensor of each set of procedures of detection in microchannel will be analyzed
Upper completion;The small yardstick of microchannel not only causes analytical equipment to be miniaturized on overall dimensions, also brings many microns and receives
Meter Xiao Ying, making it, analytical performance has significant raising compared with traditional analysis system.But current micro-fluidic detection dress
Put, electrode design is simple, does not take into full account the relation of electrode shape and detection efficiency, when not only more extending enrichment procedure
Between, also increase the link for producing error.
Technical solution of the present invention deficiency existing for existing ASV detection means, by analyzing the micro- of thin layer microcell type
Three electrodes on electrode card of the flow field to forming detection means in passage are transformed, and make electrode in microchannel along institute
State Flow Field Distribution.
In order to realize above-mentioned technical proposal, as shown in Fig. 3 to Fig. 7, the embodiment provides a kind of portable stream
Field pattern electrode heavy metal ion detection device.The detection means is assembled by electrode card 2 and the two parts of laminar flows pond 1,
The detection means being illustrated in figure 3 after assembling, is illustrated in figure 4 its internal structure, the detection means after assembling includes microchannel
11 and three electrodes stretching into microchannel 11, microchannel 11 be a lamelliform cavity being arranged in laminar flows pond 1;It is thin
Laminar flow pond 1 is provided at both ends with the input duct 12 outside connecting and drain pipe road 13 microchannel 11, and laminar flows pond 1 is also
Including the neck 14 of the shape of matched electrodes card 2 set below lamelliform cavity, shaping mechanism such as Fig. 5 a in laminar flows pond 1
Shown in Fig. 5 b;
As shown in figures 6 a and 6b, three electrodes are the base for being arranged on an electrode card 2 to a kind of embodiment of electrode card 2
Plane all solid-state electrode on piece 21, the electrode of three strips is followed successively by electrode 25, work electricity from left to right in the present embodiment
Pole 24 and reference electrode 23;Electrode card 2 can be in the neck 14 in pluggable closely sealed insertion laminar flows pond 1, electrode card 2
After fully-inserted neck 14, the region that the surface of electrode card 2 is located in microchannel 11 is workspace 22, and three electrodes are in workspace
The Flow Field Distribution of 22 interior edges solution to be measured, the contact feet 26 of three electrodes are stretched out outside microchannel 11, electrode card 2 and Thin Film Flows
The assembling fit system in dynamic pond 1 is as shown in Figure 7.
The monnolithic case of laminar flows pond 1 is typically designed to cuboid, may be designed in other shapes, as long as inside it just
In structures such as receiving microchannels 11;For ease of controlling fluid flow inside in detection process, Thin Film Flows in the present embodiment
Dynamic pond 1 is made using transparent material, also can select nontransparent material according to being actually needed.
In the present embodiment, as shown in Figure 4 and Figure 5, the cavity stage casing of microchannel 11 is rectangle, two ends be it is semicircular,
It is overall that saddle type is presented;The microchannel of detection means of the present invention is not limited to described saddle type, on the basis of lamelliform cavity structure
On, the various shapes such as rectangle, circle, ellipse are can also be designed as, wherein the most commonly used with rectangle and saddle type.
Input duct 12 and drain pipe road 13 are connected to two tops of the saddle type cavity of the microchannel 11, tie point pipe
Mouth direction and the cavity edge of the point are tangent, and two pipelines are led to the outside in laminar flows pond 1 by microchannel 11, on the outer wall shape
Into the pipeline opening of protrusion, the internal diameter of pipeline is less than or equal to the thickness of microchannel 11;Input duct and the company of drain pipe road and microchannel
Connecing position and mouth of pipe direction also has multiple choices, and usual input duct and drain pipe road are connected to the cavity length of microchannel
The both ends in direction are spent, swimmingly flow through whole microchannel to be advantageous to solution, mouth of pipe direction is typically designed to cavity at tie point
The normal or tangential direction at edge, other directions can also be selected according to being actually needed.
When the cavity of microchannel 11 is saddle type, input duct 12 and drain pipe road 13 are connected to two tops of saddle type cavity
When cavity edge at end and mouth of pipe direction and tie point is tangent, it is moderate that solution to be measured flows smooth and flow velocity in microchannel,
The thickness of diffusion layer of heavy metal ion to be measured is larger in solution, and reactant has the sufficient time to be deposited in electrode surface, beneficial to weight
Metal ion is reduced to metal and is enriched with the working electrode (s, and therefore, the structure of above-mentioned microchannel and pipeline detects for the present invention
The preferable embodiment of device, illustrated by basic microchannel shape of saddle type in following examples.
In the present embodiment, the lower section of microchannel 11 has the neck of a rectangular sheet for leading to the outer wall of laminar flows pond 1
14, electrode card 2 used matches in the geomery and the present embodiment of the neck 14, when electrode card 2 inserts neck 14
It can be formed closely sealed, the electrode card 2 of insertion can easily extract realization and change;When electrode card 2 inserts neck 14 on earth, work
Make area 22 to be fully located in microchannel 11, three electrodes, microchannel 11 and these three electrodes are contained in the region of workspace 22
Core work region when forming detection of heavy metal ion;The length of electrode card 2 is slightly larger than the depth of neck 14, electrode card after insertion
2 one end is stayed in outside neck 14, and this one end has a contact feet 26 of three electrodes, during detection as with electrochemical workstation electricity
The interface of connection.
In the detection means of the present embodiment, electrode card 2 and laminar flows pond 1 constitute complete microfluidic system.
Using the portable flow field type electrode heavy metal ion detection device described in above example, carried out by ASV methods in solution
The flow of detection of heavy metal ion is:
1. the preparation of solution to be measured:Bismuth ion is added in the solution to be measured containing heavy metal ion(Bi3+)Solution and acid bottom
Liquid;
2. the assembling of detecting system:The input duct 12 in the laminar flows pond and drain pipe road 13 are connected into feed liquor flexible pipe respectively
With go out liquid flexible pipe, feed liquor flexible pipe is stretched into the solution to be measured, and peristaltic pump is set on feed liquor flexible pipe, by the electrode card 2
Contact feet 26 is connected with the corresponding interface of electrochemical analysis work station;
3. enrichment process:Electrochemical analysis work station is adjusted, applies negative voltage between working electrode 24 and reference electrode 23;Open
Peristaltic pump, drives solution to be measured preelectrolysis since input duct 12 flows into microchannel 11, and waste liquid is discharged from drain pipe road 13;In advance
After electrolysis terminates, peristaltic pump is closed, stands solution to be measured;
4. process in leaching:The voltage that regulation electrochemical analysis work station makes to apply between working electrode 24 and reference electrode 23 is by negative sense
Heavy metal to be measured dissolution again that is positive to scan, being enriched with working electrode 24;
5. detect data acquisition:Record process in leaching working electrode 24 and to electric current and working electrode potential in the loop of electrode 25,
Obtain Stripping Voltammetry curve.
The peak point current of solution to be measured is obtained by Stripping Voltammetry curvei p , willi p Standard specimen with concentration known is in phase
Obtained peak current value comparing calculation is detected with the conditions of, you can draw solution concentration to be measured.
It is as shown in Figure 8 as the electrode card 2 being applied in combination with laminar flows pond 1, its conventional structure:Electrode card 2
Three electrodes are arranged in workspace 22 on substrate 21, are followed successively by reference electrode 23, working electrode 24 from top to bottom and to electricity
Pole 25, the three-electrode system of the tandem of composition.During the preelectrolysis of ASV detections, surface has the flat of solution laminar motion
The Faradaic current of face electrode is:
In above formula,LFor the electrode size parallel to laminar flow direction;bFor perpendicular to the electrode size in laminar flow direction;uFor solution
Flow velocity;νFor the kinematic viscosity of solution.According to the formula, increase flow velocity and increase electrode area can increase Faradaic current, to improving
Preelectrolysis efficiency is favourable, but electrode area cross conference cause current density diminish and ambient noise increase, to quantitative analysis extremely
It is unfavorable, therefore consider on the premise of electrode area is not increased as far as possible, design electrode shape makes its effective workspace position as far as possible
In the region that solution flow rate is larger.By taking the electrode card 2 shown in Fig. 8 as an example, if the microchannel 11 of itself and saddle type, which is coordinated, to be made
With then workspace 22 overlaps with microchannel 11, and the part that three electrodes are located in workspace 22 is effective work department of electrode.
To make three electrodes that there is more effective work department in saddle type microchannel 11, to the electrode card 2 shown in Fig. 8
Conventional electrodes are improved.First, the Flow Field Distribution in fluid dynamic theory and software calculating simulation microchannel 11,
Connected using the saddle type microchannel 11 in embodiment as shown in Figure 5 and pipeline, with Fig. 5 same view angles, its microchannel 11
S-shaped distribution as shown in Figure 9 is substantially presented in interior whole flow field, as shown in Figure 9;Have two flow velocitys relatively steady in the Z of S-shaped flow field
Fixed ideal zone, the region flow velocity positioned at the S-shaped first half close to the mouth of pipe of input duct 12 is most fast, is the first ideal area Z1,
The region flow velocity positioned at the S-shaped lower half of close drain pipe road 13 mouth of pipe is slow but tends to be steady, and is secondary ideal area Z2;
Based on above-mentioned Flow Field Distribution state, three electrodes on electrode card 2 in workspace 22 are improved, made it have along flow field
The shape of distribution, the flow field type electrode designed and produced out are different from common shape electrode, and a huge sum of money is carried out using the electrode of the type
Belong to ion detection, it is contemplated that longer action time and more satisfactory stability can be obtained, be favorably improved the sensitive of detection
Degree and reappearance.
In view of the consideration that flow field effectively utilizes, the flow field type electrode after improvement can be whole flow field type electrode, i.e. distribution of electrodes
In the whole S-shaped flow field including the first ideal area Z1 and secondary ideal area Z2;Meanwhile the flow field type electrode after improvement is alternatively
Semi-fluid field pattern electrode, i.e. distribution of electrodes are in the first ideal area Z1(S-shaped flow field Z first half area, i.e. the S-shaped first half)Or secondary ideal
Area Z2(S-shaped flow field Z later half area, i.e. S-shaped lower half);On the electrode base of electrode card shown in Fig. 82 after above-mentioned improvement
Block flow field type electrode as shown in Figure 10 a to Figure 10 c, in figure electrode be distributed in respectively the first half of flow field S-shaped, lower half and
Whole S-shaped region, three electrodes tandem arrangement in workspace 22 of electrode card 2, such as figure are followed successively by reference from top to bottom
Electrode 23, working electrode 24 and to electrode 25.
As another preferable embodiment, the flow field type electricity after being improved on the electrode base of electrode card shown in Fig. 82
The extremely strip of arranged in parallel, as shown in Figure 11 a to Figure 11 c, electrode is distributed in the first half of flow field S-shaped, lower half respectively in figure
Portion and whole S-shaped region, three electrodes of electrode card 2 are parallel in workspace 22 to be arranged parallel to each other, and such as figure is certainly left extremely
The right side is followed successively by electrode 25, working electrode 24 and reference electrode 23.
Using three electrodes after above-mentioned improvement shape, can be obtained more preferably in the case where not increasing electrode entire area
Action time and preferable stability, it is favorably improved sensitivity and the reappearance of detection.
There is wedge angle in above-mentioned block and strip shaped electric poles, can produce point effect, wedge angle is more sharp, caused physical effect
(Such as charge density)It is stronger, therefore a kind of more preferably embodiment is used as, cavetto processing can be carried out to electrode sharp corner, with
Avoid the generation of point effect;In addition cost of manufacture is considered, the edge for being conductively connected part is also revised as to round and smooth curve,
Take a shortcut as far as possible, save electrode material to greatest extent;By the improved flow field type electrode of above-mentioned cavetto as shown in Figure 12 a to 12f,
The improvement of electrode shown in corresponding diagram 10a to Figure 10 c, Figure 11 a to Figure 11 c respectively.
Three electrodes in the present invention on electrode card have two working conditions in detection:Solution stream in enrichment process
Under dynamic state, making alive is electrolysed between working electrode and reference electrode;Under solution stand state in process in leaching,
Working electrode and to detecting electric current between electrode.To improve the electrolysis bioaccumulation efficiency under solution flow regime, it is necessary to increase work
The area of electrode and reference electrode, and solution remains static when working electrode, to area and shape and insensitive, therefore
Further improvement can be made on the basis of above-mentioned electrode shape is improved, the area of working electrode and reference electrode is increased, such as schemes
Shown in 12a to Figure 12 c, in figure in three electrodes of strip, the width of working electrode 24 and reference electrode 23 is more than to electrode 25.
There is the limitation in terms of use range in traditional ISE, its root knot is to have used the interior of liquid
Fill reference electrolyte;Electrode card described in the above embodiment of the present invention employs all solid state electrode of pure-surface, has enrichment
Time is short, voltage scan rate is fast, automatic compensation iR drops, reduces the advantages that foreign ion interference, can solve traditional liquid from
Sub- electrodes selective is inconvenient to carry, can not be inverted, the problem of non-refractory high pressure;
Screen printing technique is the main method for preparing disposable electrochemical sensor electrodes at present, the electrode in present invention implementation
Card can use silk-screen printing technique to make.Silk-screen printing makees mould, the size of made sensor electrode with screen printing forme
It can change with shape, it is easy to accomplish the miniaturization of sensor electrode and integrated;Using silk-screen printing technique can easily by
Three electrode prints produce the pure flat of electrode card face of the embodiment of the present invention on the base material of same electrode card
The all solid state electrode in face.
Below according to requirements of the ASV to three electrode characteristics, and the characteristics of combination screen printing electrode, it specify that each electricity
The material and structure of pole:
For working electrode, it is desirable to which resistance is smaller, bigger than surface, therefore the silver that bottom selection electric conductivity is stronger, in conductive silver layer
On cover one layer of carbon again, form the working electrode surface of naked carbon-coating;Reference electrode requires that resistance is larger, and current potential is stable, is divided into work
Make area and nonclient area, bottom selects the silver of electric conductivity, and silver layer has certain distance between workspace and nonclient area
Tomography, workspace top layer use silver-silver chloride, and nonclient area top layer uses carbon, and carbon-coating is directly contacted and covered with silver-silver chloride layer
Base layer fault region, by the resistance for changing bottom tomography distance regulation electrode;Resistance is small to be required to electrode, surface nature is steady
It is fixed, bottom selection silver, top layer selection carbon;Finally, non-active area selection dielectric ink is covered.With reference to each layer of three electrodes
Material requested, electrode print level is designed, as shown in figure 13, the print primer conductive silver layer first on substrate material, secondly printed
Brush silver-silver chloride layer, then prints carbon-coating, finally prints insulating barrier.
The general knowledge such as known concrete structure and characteristic does not describe excessively herein in scheme described above;Each embodiment is adopted
Described with progressive mode, what each embodiment stressed is the difference with other embodiment, each embodiment it
Between identical similar portion mutually referring to involved technical characteristic does not form conflict among each other in each embodiment
Under the premise of can be mutually combined.
In the description of the invention, it is necessary to the orientation or position of the instruction such as explanation, term " on ", " under ", "front", "rear"
Put relation to be based on shown in accompanying drawing, be for only for ease of the description present invention and simplify description, rather than instruction or the dress for implying meaning
Put or element there must be specific orientation, with specific azimuth configuration and operation, therefore it is not intended that to limit of the invention
System;In addition, term " first ", " second " are only used for describing purpose, and it is not intended that instruction or hint relative importance.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of portable flow field type electrode heavy metal ion detection device, including microchannel(11)With stretch into the microchannel
(11)In three electrodes, three electrodes are respectively working electrode(24), to electrode(25)And reference electrode(23), it is special
Sign is, the microchannel(11)To be arranged at laminar flows pond(1)In a lamelliform cavity;Three electrodes are flat
Face all solid-state electrode, it is arranged on an electrode card(2)Substrate(21)On;Wherein:
The laminar flows pond(1)In the microchannel(11)Be provided at both ends with connection outside input duct(12)With go out liquid
Pipeline(13), the laminar flows pond(1)Also include the matching electrode card set below the lamelliform cavity(2)Shape
The neck of shape(14);
The electrode card(2)The pluggable closely sealed insertion laminar flows pond(1)On the neck(14)In, the electricity
Pole card(2)Surface falls into the microchannel(11)Region be workspace(22);Three electrodes are in the workspace
(22)The Flow Field Distribution of interior edge solution to be measured;When the electrode card(2)The fully-inserted neck(14)When, three electricity
The contact feet of pole(26)Stretch out the neck(14)Outside.
2. detection means according to claim 1, it is characterised in that the microchannel(11)Lamelliform cavity be saddle
Shape, the input duct(12)With drain pipe road(13)Two tops of the lamelliform cavity are tangentially connected to respectively
End.
3. detection means according to claim 2, it is characterised in that the microchannel(11)Interior solution to be measured it is described
Flow field is S-shaped, and three electrodes are in the workspace(22)S-shaped Flow Field Distribution described in interior edge.
4. detection means according to claim 3, it is characterised in that three electrodes are in the workspace(22)Interior point
It is distributed in the first half area, later half area or whole region in the S-shaped flow field.
5. detection means according to claim 4, it is characterised in that three electrodes are in the workspace(22)Interior
Part is set in tandem.
6. detection means according to claim 4, it is characterised in that three electrodes are in the workspace(22)Interior
Part is in parallel setting.
7. detection means according to claim 3, it is characterised in that the wedge angle of three electrode edges is subjected to cavetto
Processing.
8. according to the detection means described in any one of claim 1 to 7, it is characterised in that the working electrode(24)And reference
Electrode(23)Width be more than to electrode(25).
9. according to the detection means described in any one of claim 1 to 7, it is characterised in that the input duct(12)With go out liquid
Pipeline(13)Pipeline opening with protrusion.
A kind of 10. electricity of portable flow field type electrode heavy metal ion detection device for described in any one of claim 1 to 9
Pole card(2).
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CN112763555A (en) * | 2019-10-21 | 2021-05-07 | 上海交通大学 | Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof |
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