CN108318543A - A kind of heavy metal ion sensor and its operating method based on grapheme material - Google Patents
A kind of heavy metal ion sensor and its operating method based on grapheme material Download PDFInfo
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- CN108318543A CN108318543A CN201810088014.1A CN201810088014A CN108318543A CN 108318543 A CN108318543 A CN 108318543A CN 201810088014 A CN201810088014 A CN 201810088014A CN 108318543 A CN108318543 A CN 108318543A
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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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/128—Microapparatus
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a kind of heavy metal ion sensors based on grapheme material, including the first microelectrode array, second microelectrode array, upper cover plate, lower cover slip and multi-stage micro-fluidic chamber, there is microelectrode gap between first microelectrode array and the second microelectrode array, multi-stage micro-fluidic chamber is installed on first, the upper surface of second microelectrode array, upper cover plate and first, first is accompanied between second microelectrode array, second draws winding displacement, graphene microchip aggregation microelectrode gap location respectively with the first microelectrode array, second microelectrode array is combined closely, also disclose its operating method simultaneously；The present invention has that high sensitivity, sample size is few for consumption, detection speed is fast, it is simple to replace component, it is convenient to draw winding displacement setting, and operating procedure is simple, detection links up degree is high and the characteristics of have a wide range of application.
Description
Technical field
The invention belongs to micro-nano sensory fields, and in particular to a kind of heavy metal ion sensor based on grapheme material
And its operating method.
Background technology
Metal is divided into heavy metal and light metal according to the density of metal, density is often more than 5g/cm3Metal be known as weight
Metal, such as：About 45 kinds of gold, silver, copper, lead, zinc, nickel, cobalt, chromium, mercury, cadmium etc..It is more next with the continuous acceleration of Progress in industrialization
More heavy metal particles such as lead, cadmium, mercury, copper, zinc, vanadium are disposed in water, not only generate harm to aquatic animals and plants, and
Enter biological chain cycle by enrichment, causes entire ecological environment to all suffer from and seriously threaten.Wherein, harm to the human body is maximum
Have 5 kinds：Such as lead, mercury, chromium, arsenic, cadmium.These heavy metals cannot be decomposed in water, and life is combined with other toxin in water
At the organic matter of toxicity bigger.Other also have to what is be hazardous to the human body：Aluminium, cobalt, vanadium, calcium halophosphate activated by antimony andmanganese, tin, thallium etc..Heavy metal is to people
The injury of body common are：Lead injures the brain cell of people, carcinogenic mutagenesis etc.；Mercury directly sinks to liver after being eaten, to brain
Neural eyesight is destroyed very big.Contain 0.01 milligram of mercury in every liter of water of natural water, will be poisoned strongly；Chromium can cause numb limb, essence
Gods and spirits are normal；Cadmium can lead to hypertension, cause cardiovascular and cerebrovascular disease, destroy bone calcium, cause renal dysfunction；It is right when aluminium accumulation is more
Children cause feeblemindedness, artificial at failure of memory to the middle age, and dementia etc. is caused to the elderly.Inspection to above-mentioned metallics
It surveys, usual way has：It is ultraviolet can spectrophotometry (UV), atomic absorption spectrography (AAS) (AAS), atomic fluorescence spectrometry (AFS),
Inductively coupled plasma method (ICP), X fluorescence spectrum (XRF), Inductively coupled plasma-mass spectrometry (ICP-MS).Although above-mentioned
All kinds of methods can realize the detection of metal ion, however it is prominent in the detection of super low concentration (ion concentration is less than 1nM), reply
Contact scar object incident of leakage is sent out then to need when sample size seldom (is less than 10 microlitres) or continuously monitors a region
Using hypersensitive, fast and efficiently detection instrument.Therefore, it designs and manufactures the metal ion oversoul that disclosure satisfy that the demand
Quick detecting micro element is of great significance.
Graphene is one kind by single layer sp2Hydbridized carbon atoms it is tightly packed at the two dimension in hexangle type honeycomb lattice structure
Carbon nanomaterial, grapheme material is ultra-thin (thickness of single layer of carbon atom), has big specific surface area, high electric conductivity and room temperature
Electron mobility, and excellent mechanical mechanics property, in materialogy, micro-nano technology, the energy, biomedicine and drug delivery etc.
Aspect is with important application prospects, it is considered to be a kind of future revolutionary material.Graphene also has electrochemical window mouth width,
Electrochemical stability is good, the small feature of charge-transfer resistance, and the attraction characteristic of graphene makes it basic research and dives
In the ideal material of application, such as circuit, chemistry and biosensor and composite material etc..
Reduction is carried out to graphene oxide and provides a kind of graphene oxide (reduced of mass production reduction
Graphene oxide, RGO) method, mechanical stripping method can be substituted to a certain extent.Due to material handling ease,
Synthesis cost is low, good mechanical property, and flexibility is high, and redox graphene piece is made to become a good time of electric circuit manufacture
Material selection.In addition, RGO is very sensitive to the reaction of external environment.Therefore, to the sharp reaction of external environment and incited somebody to action using RGO
It is this to react the variation that electrical characteristic is converted by engineering technology, then it is to have actively to the application in terms of its microenvironment sensing
Meaning.
RGO is prepared by electronation graphene oxide, can be scattered in the water for being added to surfactant
Or in ethanol solution, by the way that RGO suspension is randomly dropped on preformed electrode, you can prepare graphene-based chip circuit.
This method for preparing some microcircuit structures with drop coating suspension, although easy to operate, controllability is very low, is not suitable for
Internal element assembly precision requires high microcircuit to manufacture.
Currently, heavy metal ion or substance detection process exist to the super low concentration amount less than 1nM in the prior art
Detection result is bad or high expensive；Table top type expensive instrument must be used；Inaccurate problem is detected in the case of sample size is few.
Invention content
To solve above-mentioned the technical problems existing in the prior art, the present invention provides one kind by using not by completely also
The defect of former graphene oxide itself adsorbs all kinds of metal ions, is passed to influence the electronics in graphene microchip
It is defeated, then convert the influence to the metal ion sensor based on grapheme material of current signal variable quantity in senser element
And its operating method.
The present invention solves its technical problem and is achieved through the following technical solutions：
A kind of heavy metal ion sensor based on grapheme material, including the first microelectrode array, the second microelectrode battle array
Row, upper cover plate, lower cover slip and multi-stage micro-fluidic chamber, first microelectrode array and the second microelectrode array may be contained within upper cover
Between piece and lower cover slip, and it is in the same plane, and there are micro- between first microelectrode array and the second microelectrode array
Electrode gap, the bottom transverse of the multi-stage micro-fluidic chamber across and be installed on the upper of the first microelectrode array and the second microelectrode array
Surface, and expose microelectrode gap and graphene microchip aggregation, the upper cover plate and the first microelectrode array accompany first
Winding displacement is drawn, the upper cover plate and the second microelectrode array accompany the second extraction winding displacement, and the graphene microchip aggregation is micro-
It combines closely respectively with the first microelectrode array, the second microelectrode array at electrode gap.
It should be noted that the bottom of the miniflow body cavity described in above-mentioned technical proposal be ion samples solution directly with reduction
The position of physics chemical action occurs for graphene oxide composite material.
As further improved technical scheme of the present invention, first microelectrode array, the second microelectrode array are under
Substrate of glass is accompanied between cover plate.
As further improved technical scheme of the present invention, clamped by trip bolt between the upper cover plate and lower cover slip
Fixed, the quantity of the trip bolt is 4.
As further improved technical scheme of the present invention, first microelectrode array and the second microelectrode array are adopted
With identical strip microelectrode, the strip microelectrode of first microelectrode array and the strip microelectrode of the second microelectrode array
Dislocation and parallel arranged opposite.
As further improved technical scheme of the present invention, first microelectrode array has circular arc by single or multiple
Portion, the first microelectrode parallel to each other composition, second microelectrode array have round plate, parallel to each other by single or multiple
The second microelectrode composition, the corresponding arc sections for being enclosed with the first microelectrode outside the round plate of second microelectrode, every group of institute
It states the first microelectrode and the second microelectrode is placed on same straight line.
It should be noted that using above-mentioned improved technical solution, every microelectrode can individually apply excitation telecommunications
Number or in groups apply excitation electric signal；First microelectrode array and the second microelectrode array are due between the corner angle of comparative electrode
It is also easy to produce highfield so that graphene microchip assembles to form graphene microchip aggregation in the opposite corner angle gap location of comparative electrode
Body.For another example, when having wrapped up the technical solution of the round plate of the second microelectrode of central area using the arc sections of the first microelectrode,
Graphene microchip is gathered in two microelectrode gap areas under dielectrophoretic force effect and forms aggregation, further increases single pair electricity
The aggregation zone of extremely corresponding graphene microchip, improves the utilization rate of Single lead.It is not single electricity in practical operation
The amount for the graphene film assembled at pole is the bigger the better, because graphene film aggregation excessive at electrode gap can make oxygen reduction
The electric current of graphite alkene microplate aggregation is excessive, it is possible to which the disturbance of the ion pair of the low concentration electric current can be by big electric current radix
It is flooded, is unfavorable for measuring.So structure must be according to specific measurement demand and electric current radix model to Electrode form size
It encloses to be adjusted, the width of every electrode in strip microelectrode array and interval is adjusted, or by packaging type electrode
Include radian increase or reduce with adaption demand.
As further improved technical scheme of the present invention, the multi-stage micro-fluidic chamber is coaxial by several, etc. outer diameters
Hollow cylinder is stacked, and from top to the bottom of the multi-stage micro-fluidic chamber, the internal diameter of the hollow cylinder becomes successively
It is small, bottom centre's face microelectrode gap center of the multistage miniflow chamber, and microelectrode clearance distance≤multistage miniflow chamber
1.5 times of bottom inner diameter≤microelectrode clearance distance.
It should be noted that the structure of multi-stage micro-fluidic chamber is mainly while examining in above-mentioned further improved technical solution
Worry can reduce the contact area of sample solution and bottom surface microelectrode array and be conveniently operated personnel as far as possible uses macroscopic view
Tool, such as pipettor add sample into the device.The contact area for reducing sample solution and bottom surface microelectrode array be in order to
Make the redox graphene microplate aggregation between the electric current gap as much as possible by microelectrode in sample solution, and
Less passes through this conductive path of solion.It, will be compared with if the electric current by solion this paths is relatively excessive
The precision of the big redox graphene microplate aggregation detecting ion concentration influenced between microelectrode gap, or even affect
By the current signal of the redox graphene microplate aggregation between microelectrode gap, then, detect various concentration from
The current signal size obtained when sub- solution is just no longer proportional to concentration, and it is not normal to eventually lead to working sensor；Multistage miniflow
The capacity bigger of body cavity additionally aids the detection for realizing continuous concentration, you can first to detect a kind of sample of low solubility, detection electricity
Stream signal measurement and then be directly added into the solion sample of the same race of high concentration, detect the corresponding current signal of the sample it
Afterwards, the solion sample of the same race of higher concentration is then added into miniflow body cavity again；Each hollow cylinder all can serve as
The measurement mark of sample solution amount, suggesting effect is played to survey crew, is substantially reduced sample size injection when measurement and is measured not
Accurate problem, and be monotonically changed step by step if obtaining current signal, demonstrate the magnitude relationship of above-mentioned several concentration.
As further improved technical scheme of the present invention, the material of the multi-stage micro-fluidic chamber uses poly dimethyl
Siloxanes, organic glass or off-stoichiometry thiol-ene polymer.
As further improved technical scheme of the present invention, the inner surface of the multi-stage micro-fluidic chamber is coated with molecular weight model
Enclose the polyethylene glycol liquid for 200-400.
It should be noted that using above-mentioned improved technical solution, be in order to be 200-400 with molecular weight ranges poly- second
Glycolic liquids are to multi-stage micro-fluidic chamber hydrophilicity-imparting treatment.
A kind of operating method of the heavy metal ion sensor based on grapheme material, including step in detail below：
Step 1:The multistage miniflow after inner wall is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400
Body cavity, which is placed in baking oven, carries out heating, drying；
Step 2:The multi-stage micro-fluidic chamber that completion is dried in the step 1 is mounted on described based on grapheme material
In heavy metal ion sensor, and by the heavy metal ion sensor based on grapheme material and Conventional electrochemical work station
Connection；
Step 3:On the basis of the step 2, apply between the first extraction winding displacement and the second extraction winding displacement
The sine voltage signal of 1-3V, and signal frequency is adjusted to 1M-3MHz, using positive dielectrophoresis technology by the oxidation of partial reduction
Graphene microchip manipulates the microelectrode gap location for being moved to the first microelectrode array and the first microelectrode array, and it is micro- to form graphene
Piece aggregation, meanwhile, by microscopic observation so that the graphene microchip aggregation reaches setting density；
Step 4：On the basis of the step 3, the metal ion solution to be measured of 5 μ L-100 μ L will be taken to instill described more
Grade miniflow body cavity；
Step 5：On the basis of the step 4, the electricity of the graphene microchip aggregation after adsorbing metal ions is tested
Conductance, and the computer connected by the electrochemical workstation generates current break under constant voltage and C-V characteristic is bent
Line；
Step 6：The current break and VA characteristic curve that are obtained in the step 5 are recorded into knowledge base, and
It is compared and analyzed according to the opposite variation of the conductivity of the graphene microchip aggregation after adsorbing metal ions, and then differentiates and work as
The concentration or type of preceding sample；
Step 7:When continuing the sample of a kind of concentration or next metal ion species under measuring, step 4 is repeated to step 6.
As further improved technical scheme of the present invention, the temperature of the baking oven heating, drying process in the step 1 is
60-70 °, when a length of 1h.
It is first by that will have the microelectrode battle array of specific pattern structure it should be noted that using above-mentioned technical proposal
Row assemble to form specific micro- detection circuit with graphene microchip, then utilize the graphene oxide not being completely reduced itself
Defect adsorbs all kinds of metal ions, is passed to influence the electronics in graphene microchip or graphene microchip aggregation
It is defeated, so that the current signal in detection microcircuit occurs quickly, significantly to change；By measuring variation of the electric current with voltage
The different variable quantities of electric current in sensing chip circuit caused by the metal ion solution of various concentration can be obtained in curve, and thus
Realize the sensing to different ions and its various concentration and analysis.Also, directional assembly of the graphene film in precalculated position is must
It needs.Dielectrophoresis is a kind of internal element mounting technology of controllable nano electron device, can be in the effect of inhomogeneous field
Under, apply certain dielectrophoretic force on polarized object.Dielectrophoresis provides a kind of simple, expansible, inexpensive method
To position graphene film.So it is a kind of pole to assemble micro-nano element using dielectrophoresis technology and then build corresponding senser element
Has the technical method of application value.Compared with the one-dimensional sensing material such as nano wire, nanotube, nanobelt, the two dimension for detection
Graphene platelet has unique advantage, because it is moved with high specific surfaces area, uniform functional group, high charge
Shifting rate and carrier concentration.Since surface is directly exposed in environment, the electrical characteristics of graphene film have height to external interference
Sensibility, if such as RGO can be adsorbed onto corresponding protein molecular, peptide chain, other macromoleculars or ion, flow through this
The quantity of electric charge of grapheme material is then likely occurred significant changes.
Beneficial effects of the present invention are：
This metal ion sensor part based on grapheme material proposed by the invention, (1) can complete metal ion
Concentration is less than the detection of 1nM, high sensitivity；(2) minimum required of sample capacity needs 5-10 μ L when detecting, and consumes sample size
It is few；(3) time detected every time can ensure that within 2 seconds, detection speed is very fast；(4) device is dismantled and assembled, replaces component letter
Easily, it draws winding displacement setting and facilitates advantage；(5) operating procedure is simple, and accuracy is high, and it is high to detect the degree that links up；(6) application range
Extensively, in addition to the detection to metal ion, portable micro-fluidic heavy metal analysis device can also be made, for water environment scene
And the detection occasion of pollutant variation suddenly.
Description of the drawings
Fig. 1 is the structural front view of the metal ion sensor based on grapheme material of the present invention；
Fig. 2 is the structure top view of the metal ion sensor based on grapheme material of the present invention；
Fig. 3 is strip microelectrode array in the metal ion sensor part based on grapheme material in the embodiment of the present invention 1
In schematic shapes；
Circular arc wraps up the electricity that declines in the metal ion sensor part based on grapheme material in the embodiment of the present invention 2 in Fig. 4
Schematic shapes in the array of pole；
Fig. 5 is the operating method schematic diagram of the metal ion sensor part based on grapheme material of the present invention；
Reference sign：1, lower cover slip；2, upper cover plate；3, trip bolt；4, multi-stage micro-fluidic chamber；51, first micro- electricity
Pole array；52, the second microelectrode array；61, first winding displacement is drawn；62, second winding displacement is drawn；7, substrate of glass；8, microelectrode
Gap；41, hollow cylinder one；42, hollow cylinder two, 81, graphene microchip aggregation；31, trip bolt one；32, tight
Gu screw two；33, trip bolt three；34, trip bolt four；511, strip microelectrode one；512, strip microelectrode two；513, item
Shape microelectrode three；514, strip microelectrode four；521, strip microelectrode five；522, strip microelectrode six；523, strip microelectrode
Seven；811, graphene microchip one；515, the first microelectrode one；516, the first microelectrode two；517, the first microelectrode three；524,
Two microelectrodes one；525, the second microelectrode two；526, the second microelectrode three；812, graphene microchip two.
Specific implementation mode
Below by specific embodiment, the invention will be further described, and following embodiment is descriptive, is not limit
Qualitatively, protection scope of the present invention cannot be limited with this.
Embodiment 1
As shown in Figure 1, a kind of heavy metal ion sensor based on grapheme material, including the first microelectrode array 51,
Second microelectrode array 52, upper cover plate 2, lower cover slip 1 and multi-stage micro-fluidic chamber 4, the first microelectrode array 51 and the second microelectrode
Array 52 may be contained between upper cover plate 2 and lower cover slip 1, and in the same plane, and the first microelectrode array 51 and second is micro-
There are microelectrode gap 8 between electrod-array 52, the bottom transverse of multi-stage micro-fluidic chamber 4 across and be installed on the first microelectrode array 51
With the upper surface of the second microelectrode array 52, and expose microelectrode gap 8 and graphene microchip aggregation 81, upper cover plate 2 with
First microelectrode array 51 accompanies the first extraction winding displacement 61, and upper cover plate 2 and the second microelectrode array 52 accompany the second extraction winding displacement
62, graphene microchip aggregation 81 is tight with the first microelectrode array 51, the second microelectrode array 52 respectively at microelectrode gap 8
Close combination.
Substrate of glass 7 is accompanied between first microelectrode array 51, the second microelectrode array 52 and lower cover slip 1.
As shown in Fig. 2, being fixedly clamped by trip bolt 3 between upper cover plate 2 and lower cover slip 1
As shown in figure 3, the first microelectrode array 51 and the second microelectrode array 52 are all made of identical strip microelectrode, the
One microelectrode array 51 includes strip microelectrode 1, strip microelectrode 2 512, strip microelectrode 3 513 and strip microelectrode
4 514, the second microelectrode array 52 includes strip microelectrode 5 521, strip microelectrode 6 522 and strip microelectrode 7 523,
Middle strip microelectrode 1, strip microelectrode 2 512, strip microelectrode 3 513 and the alignment of 4 514 both ends of strip microelectrode are put down
Row arrangement, strip microelectrode 5 521, strip microelectrode 6 522 and the alignment of 7 523 both ends of strip microelectrode, arranged in parallel, strip
Microelectrode 1, strip microelectrode five, strip microelectrode 2 512, strip microelectrode 6 522, strip microelectrode 3 513, strip
Microelectrode 7 523 and strip microelectrode 4 514 are staggered successively, are graphene microchip aggregation 8 in microelectrode gap 8,
Graphene microchip aggregation 8 is made of several graphene microchips 1.
As shown in Figure 1 and Figure 2, multi-stage micro-fluidic chamber 4 it is coaxial by several, etc. the hollow cylinders of outer diameters be stacked, from
The internal diameter of the top of multi-stage micro-fluidic chamber 4 to bottom, hollow cylinder becomes smaller successively, bottom centre's face of multistage miniflow chamber 4
8 center of microelectrode gap, and bottom inner diameter=microelectrode clearance distance of multistage miniflow chamber 4.
The material of multi-stage micro-fluidic chamber 4 uses organic glass.
The material of multi-stage micro-fluidic chamber 4 is poly- using dimethyl silicone polymer or off-stoichiometry thiol-ene
Close object material.
The inner surface of multi-stage micro-fluidic chamber 4 is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400.
Operating method
As shown in figure 5, the operating method of the heavy metal ion sensor based on grapheme material, including walk in detail below
Suddenly：
Step 1:The multistage miniflow after inner wall is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400
Body cavity 4 is placed in baking oven, under the conditions of temperature is 60-70 °, carries out heating, drying 1h；
Step 2:The multi-stage micro-fluidic chamber that completion is dried in the step 1 is mounted on described based on grapheme material
In heavy metal ion sensor, and by the heavy metal ion sensor based on grapheme material and Conventional electrochemical work station
Connection；
Step 3:On the basis of the step 2, apply between the first extraction winding displacement and the second extraction winding displacement
The sine voltage signal of 1-3V, and signal frequency is adjusted to 1M-3MHz, using positive dielectrophoresis technology by the oxidation of partial reduction
Graphene microchip manipulates the microelectrode gap location for being moved to the first microelectrode array and the first microelectrode array, and it is micro- to form graphene
Piece aggregation, meanwhile, by microscopic observation so that the graphene microchip aggregation reaches setting density；
Step 4：On the basis of the step 3, the metal ion solution to be measured of 5 μ L-100 μ L will be taken to instill described more
Grade miniflow body cavity；
Step 5：On the basis of the step 4, the electricity of the graphene microchip aggregation after adsorbing metal ions is tested
Conductance, and the computer connected by the electrochemical workstation generates current break under constant voltage and C-V characteristic is bent
Line；
Step 6：The current break and VA characteristic curve that are obtained in the step 5 are recorded into knowledge base, and
It is compared and analyzed according to the opposite variation of the conductivity of the graphene microchip aggregation after adsorbing metal ions, and then differentiates and work as
The concentration or type of preceding sample；
Step 7:When continuing the sample of a kind of concentration or next metal ion species under measuring, step 4 is repeated to step 6.
It should be noted that the conductivity G=I/U of the graphene microchip aggregation after adsorbing metal ions, wherein voltage U
It is the current value under current voltage to take any one value in 0.5-1V, I.
The relative variation of G is Δ G=G-G0, and wherein G0 is the graphene of the unadsorbed metal ion under pure solvent environment
The conductivity of microplate aggregation；A kind of metal ion solution of concentration is often measured, just obtaining a Δ Gi, (i=1,2,3 ... n).
By comparing Δ G1, the numerical value difference between Δ G2, Δ G3 ..., you can judge the corresponding metal ion of each data concentration and
Type.
Embodiment 2
As shown in Figure 1, a kind of heavy metal ion sensor based on grapheme material, including the first microelectrode array 51,
Second microelectrode array 52, upper cover plate 2, lower cover slip 1 and multi-stage micro-fluidic chamber 4, the first microelectrode array 51 and the second microelectrode
Array 52 may be contained between upper cover plate 2 and lower cover slip 1, and in the same plane, and the first microelectrode array 51 and second is micro-
There are microelectrode gap 8 between electrod-array 52, multi-stage micro-fluidic chamber 4 across and be installed on the first microelectrode array 51 and second
The upper surface of microelectrode array 52, and microelectrode gap 8 and graphene microchip aggregation 81 are exposed in bottom, upper cover plate 2 and the
One microelectrode array 51 accompanies the first extraction winding displacement 61, and the upper cover plate 2 and the second microelectrode array 52 accompany the second extraction row
Line 62, graphene microchip aggregation 81 at microelectrode gap 8 respectively with the first microelectrode array 51, the second microelectrode array 52
It combines closely.
Substrate of glass 7 is accompanied between first microelectrode array 51, the second microelectrode array 52 and lower cover slip 1.
It is fixedly clamped as shown in Figure 2 by trip bolt 3 between upper cover plate 2 and lower cover slip 1, the quantity of trip bolt 3 is 4
It is a.
As shown in figure 4, the first microelectrode array 51 is by the first microelectrode 1, the first microelectrode 2 516, first micro- electricity
Pole 3 517 forms, and the first microelectrode 1, the first microelectrode 2 516 and the alignment of 3 517 both ends of the first microelectrode are mutually parallel,
Homonymy one end has arc sections, the second microelectrode array 52 micro- by the second microelectrode 1, the second microelectrode 2 525 and second
Electrode 3 526 forms, and the second microelectrode 1, the second microelectrode 2 525 and the alignment of 3 526 both ends of the second microelectrode are mutually flat
Row, homonymy one end have round plate, the circle for being enclosed with the first microelectrode 1 are corresponded to outside the round plate of the second microelectrode 1
Arc portion and the second microelectrode 1 and the first microelectrode 1 are on same straight line, the round plate of the second microelectrode 2 525
Outer correspondence is enclosed with the arc sections of the first microelectrode 2 516, and corresponding outside the round plate of the second microelectrode 3 526 to be enclosed with first micro-
The arc sections of electrode 3 517, every group of first microelectrode and the second microelectrode are placed on same straight line.
As shown in Figure 1 and Figure 2, multi-stage micro-fluidic chamber 4 it is coaxial by several, etc. the hollow cylinders of outer diameters be stacked, from
The internal diameter of the top of multi-stage micro-fluidic chamber 4 to bottom, hollow cylinder becomes smaller successively, bottom centre's face of multistage miniflow chamber 4
8 center of microelectrode gap, and 1.5 times of bottom inner diameter=microelectrode clearance distance of multistage miniflow chamber 4.
The material of multi-stage micro-fluidic chamber 4 uses organic glass.
The inner surface of multi-stage micro-fluidic chamber 4 is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400.
Operating method
With embodiment 1.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of heavy metal ion sensor based on grapheme material, which is characterized in that including the first microelectrode array, second
Microelectrode array, upper cover plate, lower cover slip and multi-stage micro-fluidic chamber, first microelectrode array and the second microelectrode array are all provided with
Be placed between upper cover plate and lower cover slip, and in the same plane, first microelectrode array and the second microelectrode array it
Between there are microelectrode gap, the bottom transverse of the multi-stage micro-fluidic chamber across and be installed on the first microelectrode array and the second microelectrode
The upper surface of array, and expose microelectrode gap and graphene microchip aggregation, the upper cover plate and the first microelectrode array
The first extraction winding displacement is accompanied, the upper cover plate and the second microelectrode array accompany the second extraction winding displacement, and the graphene microchip is poly-
Collective combines closely with the first microelectrode array, the second microelectrode array respectively in microelectrode gap location.
2. the heavy metal ion sensor based on grapheme material as described in claim 1, which is characterized in that described first is micro-
Substrate of glass is accompanied between electrod-array, the second microelectrode array and lower cover slip.
3. the heavy metal ion sensor based on grapheme material as claimed in claim 1 or 2, which is characterized in that on described
It is fixedly clamped by trip bolt between cover plate and lower cover slip, the quantity of the trip bolt is 4.
4. the heavy metal ion sensor based on grapheme material as claimed in claim 1 or 2, which is characterized in that described
One microelectrode array and the second microelectrode array are all made of identical strip microelectrode, and the strip of first microelectrode array is micro-
Electrode and the dislocation of the strip microelectrode of the second microelectrode array and parallel arranged opposite.
5. the heavy metal ion sensor based on grapheme material as claimed in claim 1 or 2, which is characterized in that described
One microelectrode array by single or multiple there are arc sections, the first microelectrode parallel to each other to form, the second microelectrode battle array
Row by single or multiple there is round plate, the second microelectrode parallel to each other to form, right outside the round plate of second microelectrode
The arc sections of the first microelectrode should be enclosed with, the first microelectrode and the second microelectrode are placed on same straight line described in every group.
6. the heavy metal ion sensor based on grapheme material as claimed in claim 1 or 2, which is characterized in that described more
Grade miniflow body cavity is coaxial by several, etc. the hollow cylinders of outer diameters be stacked, extremely from the top of the multi-stage micro-fluidic chamber
The internal diameter of bottom, the hollow cylinder becomes smaller successively, bottom centre's face microelectrode gap center of the multistage miniflow chamber,
And 1.5 times of bottom inner diameter≤microelectrode clearance distance of microelectrode clearance distance≤multistage miniflow chamber.
7. the heavy metal ion sensor based on grapheme material as claimed in claim 6, which is characterized in that the multistage is micro-
The material of fluid cavity uses dimethyl silicone polymer, organic glass or off-stoichiometry thiol-ene polymer.
8. the heavy metal ion sensor based on grapheme material as claimed in claim 6, which is characterized in that the multistage is micro-
The inner surface of fluid cavity is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400.
9. the operating method of the heavy metal ion sensor based on grapheme material as described in claim 1, which is characterized in that
Including step in detail below：
Step 1:The multi-stage micro-fluidic chamber after inner wall is coated with the polyethylene glycol liquid that molecular weight ranges are 200-400
It is placed in baking oven and carries out heating, drying；
Step 2:The multi-stage micro-fluidic chamber that completion is dried in the step 1 is mounted on the huge sum of money based on grapheme material
Belong on ion transducer, and the heavy metal ion sensor based on grapheme material and Conventional electrochemical work station are connected
It connects；
Step 3:On the basis of the step 2, apply 1-3V between the first extraction winding displacement and the second extraction winding displacement
Sine voltage signal, and signal frequency is adjusted to 1M-3MHz, using positive dielectrophoresis technology by the graphite oxide of partial reduction
Alkene microplate manipulates the microelectrode gap location for being moved to the first microelectrode array and the first microelectrode array, and it is poly- to form graphene microchip
Collective, meanwhile, by microscopic observation so that the graphene microchip aggregation reaches setting density；
Step 4：On the basis of the step 3, the metal ion solution to be measured of 5 μ L-100 μ L will be taken to instill the multistage micro-
Fluid cavity；
Step 5：On the basis of the step 4, the conductivity of the graphene microchip aggregation after adsorbing metal ions is tested,
And current break and VA characteristic curve under constant voltage are generated by the computer that the electrochemical workstation connects；
Step 6：The current break and VA characteristic curve that are obtained in the step 5 are recorded into knowledge base, and according to
The opposite variation of the conductivity of graphene microchip aggregation after adsorbing metal ions compares and analyzes, and then differentiates current sample
The concentration or type of product；
Step 7:When continuing the sample of a kind of concentration or next metal ion species under measuring, step 4 is repeated to step 6.
10. the operating method of the heavy metal ion sensor based on grapheme material, feature exist as claimed in claim 9
In the temperature of, the baking oven heating, drying process in the step 1 be 60-70 °, when a length of 1h.
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