CN108398474A - It is a kind of to can be used for the electric potential type microelectrode sensors and its application that deposit intermediate ion detects - Google Patents
It is a kind of to can be used for the electric potential type microelectrode sensors and its application that deposit intermediate ion detects Download PDFInfo
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Abstract
The present invention relates to electric potential type microelectrode sensors, specifically a kind of electric potential type microelectrode sensors can be used for Heavy Metal In Sediments ion detection and its application.Electric potential type microelectrode sensors are polymer film ion-selective microelectrode, are made of gold microelectrode, PEDOT (PSS) conducting shells and ion selectivity polymer film；The ion selectivity polymer film is ion selectivity carrier containing measured ion to be checked and lipophilicity ion-exchanger (four (3,5 two (trichloromethyl) phenyl) Boratexes in molar ratio 1:2 to 1:4 ratios mix, and add polyvinyl chloride and ortho-nitrophenyl octyl ether is formulated.Solid contact microelectrode of the present invention have many advantages, such as simple for production, high sensitivity, it is at low cost, be easy to miniaturization, while having many advantages, such as that microelectrode mass transfer rate is high, current density is big, fast response time, and can realize the live in-situ study of deposit intermediate ion.Type by changing ion selective membrane intermediate ion carrier can realize the detection to different kinds of ions in deposit.
Description
Technical field
The present invention relates to electric potential type microelectrode sensors, specifically one kind can be used for the inspection of Heavy Metal In Sediments ion
The electric potential type microelectrode sensors of survey and its application.
Background technology
Deposit is source and the remittance of heavy metal pollution, and heavy metal enters after water body through absorption, flocculation and precipitation
Into deposit.Pore water in marine sediment refers to occupy hole between sea-bottom deposit composition granule and rock particles water-soluble
Liquid, and can re-dissolve into pore water by diffusion layer if heavy metal when the change of physical chemistry (such as pH, Eh) condition and enter
To overlying water, lead to secondary pollution.
The monitoring of country's Heavy Metal In Sediments, especially in-situ monitoring method are very limited at present.Film balancing technique
Heavy metal scene high-resolution can be achieved to measure, but equilibration time is longer (generally for 24 hours).Diffusive gradients in thin-films technology is mesh
The preferable metal assay technology of front simulation bio-absorbable.Its advantage is：(1) analyte can be absorbed and is concentrated in stationary phase；
(2) matrix influence can preferably be eliminated.Disadvantage：(1) disturbance effect can not avoid；(2) operating process is cumbersome；(3) journey is parsed
It spends limited.
Pore water brings no small challenge as a microcosmic ecological environment, to in-site detecting.As Electroanalytical Chemistry
Disciplinary Frontiers, sensing technology of the development based on electrochemistry microelectrode is that heavy metal analysis in pore water provides a new think of
Road.
Electrochemistry microelectrode includes current mode microelectrode and electric potential type microelectrode.Current mode microelectrode：It is dissolved in pore water
Oxygen, Mn2+、Fe2+With the current mode Hg-Au microelectrode situ detection systems of S (- II).However it and is not used for other heavy in deposit
The in-site detecting of metal ion, main cause are that dissolved oxygen interferes and electrode sensitivity is not high.Electric potential type microelectrode：Based on metal
The microelectrode of platinum is chiefly used in pH detections；Liquid film microelectrode can be used for Cl in pore water-, Na+, K+And Ca2+Equal high concentration ions inspection
It surveys, is currently only used for laboratory scientific research and test analysis.
Polymer film ion selective electrode is an important branch of electrochemical sensor, and testing principle is based on sensitivity
The response pctential of film and analyte ions activity relationship meet can this special (Nernst) equation, and this kind of electrode is widely used to
The direct measurement of various ions in whole blood, serum, urine, tissue, intracellular fluid and its dilution.
In recent years, can detect micro updating sample, high sensitivity up to picomole quantities low detection limits micro-polymer film from
Sub- electrodes selective has been born, and in conjunction with solid contact electrode technology, this kind of electrode has been successfully applied to environmental monitoring etc.
Field；But measure deposit when it is higher to the requirement of mechanical strength of electrode so that there is an urgent need for it is a kind of be suitable for measure the general of deposit
Suitable microelectrode.
Invention content
The purpose of the present invention is to provide a kind of with the electric potential type microelectrode sensors of universality and its preparation and hole
The application of the detection of heavy metal ion in water.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of electric potential type microelectrode sensors can be used for the detection of deposit intermediate ion, electric potential type microelectrode sensors are poly-
Compound film ion-selective microelectrode is made of gold microelectrode, PEDOT (PSS) conducting shells and ion selectivity polymer film；Institute
It is ion selectivity carrier and lipophilicity ion-exchanger (four (3,5- containing measured ion to be checked to state ion selectivity polymer film
Two (trichloromethyl) phenyl) Boratex in molar ratio 1:2 to 1:4 ratios mix, and add polyvinyl chloride and ortho-nitrophenyl octyl ether
It is formulated.
Ionophore wherein used has high specific to measured ion, and has good choosing to other interfering ions
Selecting property, and by change carrier and with the ratio of lipophilicity ion-exchanger can realize under varying environment to be measured
The detection of ion.Copper ion carrier used in inventive sensor can realize the detection to the copper ion of low concentration, and be carried on the back to seawater
Sodium at high concentration ion, potassium ion, calcium ion, magnesium ion etc. all have good anti-interference ability under scape.
Further, PODOT (PSS) is modified by electro-deposition mode and is used as solid conductive in microelectrode surface,
Ion selectivity polymer film will then be added dropwise again, and then ion selectivity polymer film gold microelectrode is made.
The microelectrode is gold microelectrode, filamentary silver microelectrode, carbon fiber microelectrodes with micro pipette tips or platinum filament microelectrode.
In the ion selectivity polymer film containing wait for measured ion ion selectivity carrier be lead ion selectivity carrier,
Copper ion selectivity carrier, iron ion selectivity carrier, chromium ion selectivity carrier, sodium ion selective carrier, potassium ion choosing
Selecting property carrier, ammonium ion selectivity carrier, calcium ion selective carrier or magnesium ion selectivity carrier；
Meanwhile the property of further change film is required according to inventive sensor, while can realize nonmetallic ion
Detection, so in film carrier can be chlorion selectivity carrier, bromide ion selectivity carrier, carbanion selectivity carrier or
Phosphoric acid radical ion-selective carrier.
A kind of application for the electric potential type microelectrode sensors can be used for the detection of deposit intermediate ion, the electric potential type microelectrode
Application of the sensor in realizing to ambient deposition object in the in situ detection of different kinds of ions.
The environment is lake doposit, river water deposit or Marine Sediment.
Using the microelectrode by measuring the potential response of microelectrode, and then obtain ion concentration to be detected.
Further, using the sensor first by measuring the electrode under blank background and Copenhagen water background
Under to the potential response of metal ion (by taking copper ion as an example) observe its measure solution linear concentration range and detection limit, then
It takes sediment sample, isolated deposit pore water to carry out copper ion detection, and compared with ICP-MS, observes
Its detection accuracy.
Wherein gold microelectrode can prepare in the following manner：
Spun gold is connected with copper wire using graphite-filled type conductive silver glue, is inserted into glass capillary, spun gold and capillary
One end flushes, and then fixes copper wire in the other end of glass tube filling epoxy resin.Glass tube one end of spun gold one end is put
It in alcolhol burner flame envelope, slowly rotates so that glass tube is fused with spun gold, and fusion one end is polished on sand paper, is cleaned up standby
With.It is whether good by cyclic voltammetry detecting electrode performance.
It can be seen that electric potential type microelectrode sensors detection limit of the present invention it is low, it can be achieved that the heavy metal ion to low concentration inspection
It surveys, such as the detection of copper ion.The electric potential type microelectrode sensors can realize the detection of micro volume sample, detect sample volume
Can be ten microlitres of supreme hectolambdas.
Testing principle：It is currently preferred by using spun gold as material preparation gold microelectrode, cover PEDOT on its surface
(PSS) conducting shell, containing deposit ion (by taking copper ion as an example) selective polymerisation object film to be detected so that be made microelectrode, utilize
Microelectrode its in Cu2+Standard solution inner potential responds, and to Cu in Sediment Pore Water2+It is measured, and then can make
Gained microelectrode can be used for scene and carry out in situ detection to copper ion；In microelectrode of the present invention containing deposit ion to be detected (with
For copper ion) selective polymerisation object film can select corresponding ionophore according to the difference of measured ion is waited for, and be gathered by adjusting
Compound film constituent species and ratio can realize the specific detection for object ion.Microelectrode has because geometric dimension is small
The advantages that mass transfer rate is high, and the response time is short, and iR drops are small further improves micro- after the modification for carrying out solid conductive
The stability and reactivity worth of electrode.Electrode detection principle be electrochemical principle Nernst equation, i.e., the variation of electrode potential with
The logarithm of the chemical concentration is directly proportional, and electric potential type microelectrode when measuring is realized by ion selective membrane, when micro- electricity
When pole is with solution equilibria, the detection to the ion is realized in film both sides since the ionic effect forms potential difference, and in hole
Heavy metal ion is measured in gap water detects low-concentration heavy metal ions without interruption and with lower detection limit.
The advantage of the invention is that：
1. the present invention can be used polymer film ion-selective microelectrode and detect ion as Copper diethlydithiocarbamate, there is inspection
Rising limit it is low, it can be achieved that in Sediment Pore Water low concentration copper ion detection.
2. the present invention can be used polymer film ion-selective microelectrode and detect ion as Copper diethlydithiocarbamate, do not examined
Volumetric constraint is surveyed, and geometric dimension is small, can be used for the detection of micro volume sample (ten microlitres of supreme hectolambdas).
3. the present invention detects ion using polymer film ion-selective microelectrode as Copper diethlydithiocarbamate, seawater is carried on the back
Scape has the advantages that compared with strong anti-interference the detection, it can be achieved that this complicated microenvironment of pore water.
4. the present invention, as Copper diethlydithiocarbamate, has high mechanical strength using polymer film ion-selective microelectrode,
It is small, it can be achieved that under this microenvironment form of deposit ion live in situ detection.
5. the present invention has preferably machinery using the solid contact ion selectivity polymer membrane electrode of no internal-filling liquid
Flexibility and be easy to miniaturization the features such as.
6. electrode spun gold surface modification PEDOT (PSS) conducting shells of the present invention further increase electricity as solid conductive
Stabilizer pole improves electrode reaction performance.
Description of the drawings
Fig. 1 is gold microelectrode structural schematic diagram provided in an embodiment of the present invention.
Fig. 2 is gold microelectrode pictorial diagram provided in an embodiment of the present invention.
Fig. 3 is gold microelectrode cyclic voltammogram provided in an embodiment of the present invention, and wherein gold microelectrode is in 4mM K4[Fe
(CN)6] cyclic voltammogram, background solution be 1M KCl, sweep speed be 50mV s-1。
Fig. 4 is that electrode cycle voltammetry is examined before and after microelectrode provided in an embodiment of the present invention deposits PEDOT (PSS) conducting shell
Survey result figure；Wherein, the electrodeposited front and back cyclic voltammogram in 0.1M KCl solution of gold microelectrode, sweep speed 50mV
s-1；Solid line is before depositing, and dotted line is after depositing 5 μ C charges.
Fig. 5 is that gold microelectrode provided in an embodiment of the present invention deposits electrode impedance measurement knot before and after PEDOT (PSS) conducting shell
Fruit is schemed；Wherein, impedance in 0.1M KCl solution (is enclosed) in fact after (void circle) and 5 μ C charges of deposition before gold microelectrode is electrodeposited
Figure, sweep speed 0.01-100KHz, excitation amplitudes 100mV, illustration are impedance spectrum magnified partial view.
Fig. 6 is that (wherein A is golden fiber before deposition to gold microelectrode surface scan Electronic Speculum shape appearance figure provided in an embodiment of the present invention
Microelectrode microscope photo, B are gold microelectrode surface PEDOT (PSS) conducting shells scanning electron microscope (SEM) photograph after deposition).
Fig. 7 is that ion selectivity gold microelectrode provided in an embodiment of the present invention selectively measures result to other interfering ions
Figure.
Fig. 8 provides copper ion selectivity gold microelectrode CuCl under blank background for the embodiment of the present invention2Solution inner potential
Response diagram.Illustration is the potential correction curve of gold microelectrode.
Fig. 9 provides copper ion selectivity gold microelectrode CuCl under 0.5M NaCl solution backgrounds for the embodiment of the present invention2It is molten
Liquid inner potential response diagram；Illustration is the potential correction curve of gold microelectrode.
Figure 10 provides conventional copper ion electrodes selective CuCl under 0.5M NaCl solution backgrounds for the embodiment of the present invention2
Solution inner potential response diagram；Illustration is the potential correction curve of the electrode.
Figure 11 for Sediment Pore Water sample provided in an embodiment of the present invention point diagrams.
Figure 12 for the embodiment of the present invention provide copper ion selectivity gold microelectrode detect pore water in copper ion result and
Comparison diagram is carried out with ICP-MS methods；Wherein, potentiometry (round) measures copper ion concentration in pore water with ICP-MS (triangular form)
With change in depth result.
Specific implementation mode
In conjunction with attached drawing and by following embodiment, the present invention is further described in detail, but and is not so limited this
The content of invention.
Microelectrode of the present invention has the generality for being applicable in different kinds of ions detection, and has and can be used for deposit under a variety of environment
The direct in-situ of intermediate ion detects foreground.Specifically a kind of solid based on potentiometry testing principle with universality connects
Touch microelectrode development and its in deposit pore water heavy metal detection.Gold microelectrode is specially prepared first, and
It is modified and is characterized, ion selective membrane is then added dropwise to gold microelectrode surface, and then ion selectivity polymerization is made
Object film gold microelectrode detects deposit intermediate ion as Copper diethlydithiocarbamate.The solid contact microelectrode, which has, to be made
Simplicity, high sensitivity, it is at low cost, be easy to the advantages that miniaturization, while having that microelectrode mass transfer rate is high, current density is big, rings
The advantages that answering speed fast, and can realize the live in-situ study of deposit intermediate ion.By changing ion selective membrane intermediate ion
The type of carrier can realize the detection to different kinds of ions in deposit.
Embodiment 1
For detecting copper ion.Specific detecting step is as follows：
1. carbon fiber is connected with copper wire first with graphite-filled type conductive silver glue, the spun gold of copper wire end will be connected to
It is inserted into glass tube from the other end of glass tube and is flushed to spun gold end with glass tube, then in the other end ring type filling of glass tube
Oxygen resin fixes copper wire.The glass tube one end flushed with spun gold is placed on alcolhol burner flame envelope, is slowly rotated, glass tube will be with
Spun gold fuses, it is polished (Fig. 1, Fig. 2) on sand paper.
2. whether good by cyclic voltammetry detecting electrode, detection solution is 4mM K4[Fe2(CN)6], 1M KCl (figures
3).Show that electrode performance is good if electrode detection obtains in figure " S " type curve, can be used for next step experimental study.
3. good electrode will be detected through 1M HNO315min is cleaned, it is each then in turn through deionized water, absolute ethyl alcohol
Ultrasonic cleaning 5min, room temperature are dried.By setting the galvanostatic deposition time PEDOT (PSS) deposition point is controlled as 0s, 100s
Not Wei 0,5 μ C, and pass through the front and back electrode capacitance variation (Fig. 4) of cyclic voltammetry detection deposition, it is seen that gold microelectrode is after deposit
Electrode capacitance significantly increases, and electrode impedance is obviously reduced (Fig. 5)
4. passing through the above-mentioned electrode surface pattern before and after electrode surface deposits PEDOT (PSS) conducting shell of scanning electron microscopic observation
Variation (Fig. 6, A are before depositing, and B is after depositing).As seen from the figure, it after electro-deposition, is formed on gold microelectrode surface uniform and continuous
Fine and close PEDOT (PSS) film (figure B).PEDOT (PSS) film surfaces are less than 1 μm of the good microspheres group of separation by diameter
At.
5. the preparation of polymer film copper ion gold microelectrode：Above-mentioned surface is deposited to micro- electricity of PEDOT (PSS) conducting shell
Pole is cleaned up through distilled water, and room temperature is dried, and is dripped 0.8 μ L copper ion selective membrane solution to electrode surface after drying, is put into perseverance
In warm drying box, dry spare to get to copper ion selectivity gold microelectrode；Wherein, copper ion selective membrane solution is by weight
Percentages, copper ion carrier ETH1062:1.00%, four (3,5- bis- (trichloromethyl) phenyl) Boratex:1.02%, adjacent nitre
Base benzene octyl ether:65.32% and polyvinyl chloride:After 32.66% mixing, 0.8mL tetrahydrofurans are dissolved in, for use.
6. selectivity (Fig. 7) of its copper ion electrodes selective to a variety of interfering ions is detected by separate solution method, it can
See that the electrode all has good selectivity to a variety of interfering ions, wherein being -11.2 to sodium ion selective, according to formulaIt can be calculated under the conditions of with seawater background similar 0.5M NaCl substantially, the electrode is to copper ion
Detection limit can reach 1.6 × 10-12M, it is seen then that the electrode is expectable under seawater background to realize very low concentration of copper ion
Detection, sodium at high concentration ion does not interfere the detection to copper ion substantially under seawater background.
7. polymer film copper ion gold microelectrode is in CuCl2Solution inner potential responds：By above-mentioned acquisition copper ion selectivity
Gold microelectrode is 10-3M CuCl21h is activated in solution, then detects it successively a concentration of 10-9-10-3M CuCl2It is electric in solution
Position variation, finds the electrode 10-7-10-3M CuCl2Linear response (S=30.7 ± 1.3mV/dec, R are presented in solution2=
0.997), detection limit reaches 6.3 × 10-9M (Fig. 8).
8. polymer film copper ion gold microelectrode CuCl under 0.5M NaCl backgrounds2Solution inner potential responds：It is obtained above-mentioned
Copper ion selectivity gold microelectrode is obtained 10-3M CuCl21h is activated in solution, then detects it successively in 0.5M NaCl backgrounds
Under a concentration of 10-8-10-3M CuCl2Solution inner potential changes, and finds the electrode 10-6-10-3M CuCl2Line is presented in solution
Property response (S=28.1 ± 1.8mV/dec, R2=0.999), detection limit reaches 4.0 × 10-8M (Fig. 9).It is normal by detecting simultaneously
Advise ion-selective microelectrode CuCl under 0.5M NaCl backgrounds2Solution detection is limited to 4.0 × 10-7M (Figure 10), it is seen that ion
The detection limit of selectivity micro-electrode has obtained effective reduction.
F. it chooses and carries out sediment sample acquisition (Figure 11) at some littoral zone mouth of the river, to sample after vacuum filtration
It carries out centrifugal treating and obtains pore water, enriching HNO3Acidification, dense HNO are carried out to pore water3Additional proportion is 1mL pore waters
1 μ L are added, the content of copper ion in above-mentioned acquisition pore water are detected using standard addition method, and carry out with ICP-MS testing results
It compares (Figure 12), it can be seen that the two measurement result is almost the same, which is expected to be applied to heavy metal in Coast Deposits Carbonatite On Their
The in situ detection of ion.
By above-mentioned detection it is found that the present embodiment obtain microelectrode to sodium ion, potassium ion, magnesium ion, hydrogen ion, copper from
Son, cadmium ion all have good selectivity, these ions present in briny environment will not interfere the electrode to copper ion
It measures.
Wait for that carrier in polymer film is replaced by the different of measured ion according to detect according to above-mentioned record simultaneously, and
And according to the present invention provide polymer film composition proportion setting configuration film component, then according to above-described embodiment record step into
Row operation can get to the greatest extent the microelectrode of corresponding ion, and gained micro machine equally has the characteristics such as anti-interference.
Claims (7)
1. a kind of electric potential type microelectrode sensors can be used for the detection of deposit intermediate ion, it is characterised in that：Electric potential type microelectrode
Sensor is polymer film ion-selective microelectrode, is polymerize by gold microelectrode, PEDOT (PSS) conducting shells and ion selectivity
Object film forms；The ion selectivity polymer film is ion selectivity carrier and lipophilicity ion exchange containing measured ion to be checked
Agent (four (3,5- bis- (trichloromethyl) phenyl) Boratexes in molar ratio 1:2 to 1:4 ratios mix, and add polyvinyl chloride and neighbour
Nitrobenzene octyl ether is formulated.
2. the electric potential type microelectrode sensors as described in claim 1 that can be used for the detection of deposit intermediate ion, it is characterised in that：
PODOT (PSS) is modified by electro-deposition mode and is used as solid conductive in microelectrode surface, ion selectivity is then added dropwise again
Polymer film, and then obtain polymer film ion selectivity gold microelectrode.
3. the electric potential type microelectrode sensors as described in claim 1 or 2 that can be used for the detection of deposit intermediate ion, feature exist
In：The microelectrode is gold microelectrode, filamentary silver microelectrode, carbon fiber microelectrodes with micro pipette tips or platinum filament microelectrode.
4. the electric potential type microelectrode sensors as described in claim 1 or 2 that can be used for the detection of deposit intermediate ion, feature exist
In：The ion selectivity carrier containing measured ion to be checked is lead ion selectivity carrier, copper in the ion selectivity polymer film
Ion selectivity carrier, iron ion selectivity carrier, chromium ion selectivity carrier, sodium ion selective carrier, potassium ion selection
Property carrier, ammonium ion selectivity carrier, calcium ion selective carrier or magnesium ion selectivity carrier.
5. a kind of application of the electric potential type microelectrode sensors described in claim 1 can be used for the detection of deposit intermediate ion,
It is characterized in that：The electric potential type microelectrode sensors answering in the in situ detection of different kinds of ions in realizing to ambient deposition object
With.
6. the application of the electric potential type microelectrode sensors as described in claim 5 that can be used for the detection of deposit intermediate ion, special
Sign is：The environment is lake doposit, river water deposit or Marine Sediment.
7. the application of the electric potential type microelectrode sensors as described in claim 5 that can be used for the detection of deposit intermediate ion, special
Sign is：Using the microelectrode by measuring the potential response of microelectrode, and then obtain ion concentration to be detected.
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