CN104897755B - One kind is based on the pH detecting electrodes of graphene/PEDOT composite membranes - Google Patents
One kind is based on the pH detecting electrodes of graphene/PEDOT composite membranes Download PDFInfo
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- CN104897755B CN104897755B CN201510330752.9A CN201510330752A CN104897755B CN 104897755 B CN104897755 B CN 104897755B CN 201510330752 A CN201510330752 A CN 201510330752A CN 104897755 B CN104897755 B CN 104897755B
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Abstract
The invention discloses a kind of pH detecting electrodes for being based on graphene/PEDOT composite membranes, including electrode and the graphene/PEDOT composite membranes for being coated on electrode outer surface, electrode to be selected from one kind of ito glass electrode, stainless steel gold-plated electrode or gold disc electrode.The preparation method of above-mentioned pH detecting electrodes, comprises the following steps：(1) pretreatment of electrode；(2) electrolyte quota；(3) electrochemical polymerization.The pH that above-mentioned pH detecting electrodes are used for phosphate buffer is detected, and using oxidation peak current as detection signal, realizes detection of the pH value in the range of 1 11.Compared with common pH detecting electrodes, the pH detecting electrode volumes based on graphene/PEDOT composite membranes are smaller, price is lower, detection is more convenient, front and rear without specially treated using.During using oxidation peak current as detection signal, detection range is bigger, and detection sensitivity improves about 228%.
Description
Technical field
The present invention relates to a kind of pH detecting electrodes, and in particular to pH detection electricity of the one kind based on graphene/PEDOT composite membranes
Pole.
Background technology
PH measures closely bound up with the field such as medical science, bioengineering, modern industry, agricultural, environment and scientific research.Mesh
Before, if most popular two kinds of pH sensor mains glass electrodes and metal oxide electrode, wherein glass electrode is to pH's
Measurement is relatively more accurate (except measurement error be present in the case of highly acidity and high alkalinity), but glass electrode is because volume is compared with disaster
To realize the analysis of live body microcell or microenvironment, and electrode internal resistance is high, cracky.And the pH sensings based on metal oxide
Device, such as IrO2, WO3Or Ni (OH)2Although being easy to be miniaturized, these metal oxides are poisonous, therefore they are not
Biology or medical science detection can be used for.
The change of hydrogen ion concentration can cause the change of electric electrode current or electrical conductivity in solution, be repaiied with conducting polymer
Decorations sensor electrode can strengthen weak signal, make electrode electric conductivity change under different pH environment more notable.PEDOT is EDOT
The polymer of (3,4-ethylene dioxythiophene), currently without the Patents for being used for pH detections on PEDOT, the report of pertinent literature
Road is also seldom, and the research and development of the research of this respect to pH sensors have great importance.
The content of the invention
In view of the shortcomings of the prior art, technical problem to be solved is the present invention：Graphene/PEDOT composite membranes are in pH
Application in detection.
To achieve these goals, the present invention is prepared for stone using electrochemical cyclic voltammetry in ito glass electrode surface
Black alkene/PEDOT composite membranes, and the pH detections of phosphate buffer (PBS) are used it for, using oxidation peak current as detection signal,
The high-sensitivity detection in the range of pH 1-11 is realized, is had in terms of the miniaturization pH detecting electrodes of biology, medical field are developed
There is very high application value.
The first aspect of the present invention, disclose a kind of pH detecting electrodes for being based on graphene/PEDOT composite membranes, including electricity
Pole and the graphene/PEDOT composite membranes for being coated on electrode outer surface, the electrode are selected from ito glass electrode, the gold-plated electricity of stainless steel
One kind among pole or gold disc electrode.Taking full advantage of PEDOT high conductivity realizes high-sensitivity detection to pH, and leads to
Crossing amino graphene and the compound of PEDOT further improves detection sensitivity.
Preferably, electrode is ito glass electrode, and composite membrane is coated on the outer surface of glass electrode ITO layer.
The second aspect of the present invention, the preparation method of above-mentioned pH detecting electrodes is disclosed, is comprised the following steps：
(1) pretreatment of electrode：Ito glass electrode is successively in 5% concentration NaOH solution, deionized water, acetone, ethanol
It is ultrasonically treated, then sticking adhesive tape without the part of coated graphite alkene/PEDOT composite membranes in ito glass electrode surface stops, needs
The area for wanting coated graphite alkene/PEDOT composite membranes is 1 × 1cm2；
(2) electrolyte quota：Amino graphene is in LiClO4First time ultrasonic disperse in acetonitrile solution, obtains stable homogeneous
Graphene dispersing solution, into graphene dispersing solution be added dropwise EDOT be configured to EDOT monomer electrolyte；Second of ultrasound is carried out again
Lead to nitrogen after scattered, as the standby monomer electrolyte for preparing graphene/PEDOT composite membranes；
(3) electrochemical polymerization：Monomer electrolyte is made through step using cyclic voltammetry (CV) in electrochemical workstation
(1) pretreated ito glass electrode surface electropolymerization.
Preferably, in step (1) in 5% concentration NaOH solution, deionized water, acetone, ethanol each ultrasonic 5-15 minutes.
Preferably, the concentration of amino graphene is 0.1-0.5mg/ml in step (2).LiClO4The concentration of acetonitrile solution is
0.1M.The concentration of EDOT monomer electrolyte is 1-10mM.Ultrasonic disperse 1-4 hours first time, second of ultrasonic disperse half an hour,
Logical nitrogen 15min.
Preferably, polymerization potential range be-0.9-1.0V in step (3), sweep speed 50mV/s, the circle of polyase 13-10.
The third aspect of the present invention discloses the application process of above-mentioned pH detecting electrodes, and pH detecting electrodes delay for phosphate
The pH detections of fliud flushing, using oxidation peak current as detection signal, realize detection of the pH value in the range of 1-11.
The beneficial effects of the invention are as follows：Compared with common pH detecting electrodes, the pH inspections based on graphene/PEDOT composite membranes
Survey electrode volume is smaller, price is lower, detection is more convenient, front and rear without specially treated using.Using oxidation peak as detection signal
When, deposited graphite alkene/PEDOT electrode (pH 1-11) is bigger than the detection range of pure PEDOT modified electrodes (pH 3-11), inspection
Survey sensitivity and improve about 228%, graphene and the PEDOT compound electrode pair solution ph that significantly improves obtain Detection results.
Design, concrete structure and the caused technique effect of the present invention are described further below with reference to accompanying drawing, with
It is fully understood from the purpose of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is the TEM figures after the amino graphene dispersion that a preferred embodiment of the present invention uses；
Fig. 2 is polymerization CV figure of a preferred embodiment of the present invention in graphene/EDOT monomer solutions；
Fig. 3 is the graphene/PEDOT composite membranes of a preferred embodiment of the present invention in 0.1M LiClO4In acetonitrile solution
CV figure；
Fig. 4 is the graphene/PEDOT composite membranes of a preferred embodiment of the present invention in different pH value phosphate buffers
CV figure；
Fig. 5 is the graphene/PEDOT composite membranes and PEDOT films oxidation peak current and PBS of a preferred embodiment of the present invention
The graph of a relation of solution ph.
Embodiment
Embodiments of the invention are elaborated below in conjunction with the accompanying drawings：The present embodiment using technical solution of the present invention before
Put and implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
The embodiment stated.
With the development of life science, require to carry out the measure of live body pH value more and more, therefore continue to use traditional glass
Electrode just has certain difficulty, and the conducting polymer sensitive to pH has good biocompatibility, easy processing, cheap etc. excellent
Gesture, beneficial approach is provided for being miniaturized of pH sensors, low cost.The present invention exists first by electrochemical cyclic voltammetry
Simple glass electrode ITO surfaces are prepared for graphene/PEDOT composite membranes, and use it for the pH inspections of phosphate buffer (PBS)
Survey, using oxidation peak current as detection signal, realize the high-sensitivity detection in the range of pH 1-11, in exploitation biology, medical treatment neck
There is very high application value in terms of the miniaturization pH detecting electrodes in domain.
In the present embodiment, the operating procedure for preparing pH detecting electrodes is as follows：
(1) pretreatment of electrode：Glass electrode is respectively in 5%NaOH solution, deionization made of ITO electro-conductive glass
Each ultrasonic 10 minutes in water, acetone, ethanol.Being taped on ito glass makes effective area be 1 × 1cm2.Effective area herein
Refer to the area for needing polymer and graphite alkene/PEDOT composite membranes.
(2) electrolyte quota：Respectively by 0.1-0.5mg/ml amino graphene in 0.1M LiClO4It is ultrasonic in acetonitrile solution
Scattered 1-4 hours, obtain the graphene dispersing solution of stable homogeneous.EDOT is added dropwise into graphene dispersing solution again, is configured to 0.1M
EDOT monomer electrolyte, then ultrasonic half an hour, lead to nitrogen 15min, as the monomer electrolyte for preparing composite membrane.
(3) electrochemical polymerization：Electropolymerization, polymerization are carried out using cyclic voltammetry (CV) in electrochemical workstation CHI660E
Potential range is-0.9-1.5V, sweep speed 50mV/s, and polyase 13-10 encloses.
The detecting electrode of the present invention can be in the carry out Electrochemical Detection in different pH value PBS solutions.Optimize by contrast, choose
In 0.1mg/ml graphene+1mM EDOT+0.1M LiClO4In acetonitrile solution, pass through stone made from the circle of cyclic voltammetry deposition 5
Black alkene/PEDOT films, carry out pH sensitivity techniques.Deposition is had to the ITO electrode of graphene/PEDOT films, immerses different pH
In the PBS solution of value, using platinized platinum as to electrode, Ag/AgCl is reference electrode, using cyclic voltammetry, investigate graphene/
Electrical behavior of the PEDOT composite membranes in different pH environment.
Specifically detection method is：5ml solution to be measured is taken to add electrolytic cell, deposition has the pH of graphene/PEDOT composite membranes
Detecting electrode is working electrode, platinum electrode be reference electrode to electrode, Ag/AgCl, three electrodes of connection to electrochemical workstation,
Setting potential range is -0.9-1V, sweep speed 100mV/s, the circle of scanning 2, can be with according to the oxidation peak current value of CV curves
Draw the pH value of corresponding solution.
Compared with common pH detecting electrodes, the pH detecting electrode volumes based on graphene/PEDOT composite membranes are smaller, price
Lower, detection is more convenient, front and rear without specially treated using.During using oxidation peak as detection signal, deposited graphite alkene/PEDOT
Electrode (pH 1-11) it is bigger than the detection range of pure PEDOT modified electrodes (pH 3-11), detection sensitivity improves about
228%, graphene and the PEDOT compound electrode pair solution ph that significantly improves obtain Detection results.
Application field：The fields such as medical science, bioengineering, modern industry, agricultural, environment and scientific research；Application mode：
It is used to pH in a manner of small-sized pH sensors detect.
Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without
Creative work can is needed to make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (9)
1. the preparation method of pH detecting electrode of the one kind based on graphene/PEDOT composite membranes, it is characterised in that including following step
Suddenly：
(1) pretreatment of electrode：Ito glass electrode is ultrasonic in 5% concentration NaOH solution, deionized water, acetone, ethanol successively
Adhesive tape is sticked in processing, the part that the graphene/PEDOT composite membranes then need not be coated in the ito glass electrode surface, needs
The area for coating the graphene/PEDOT composite membranes is 1 × 1cm2；
(2) electrolyte quota：Amino graphene is in LiClO4First time ultrasonic disperse in acetonitrile solution, obtain the stone of stable homogeneous
Black alkene dispersion liquid；EDOT is added dropwise into the graphene dispersing solution and is configured to EDOT monomer electrolyte, the EDOT monomers electrolysis
Liquid leads to nitrogen after carrying out second of ultrasonic disperse, as the standby monomer electrolyte for preparing the graphene/PEDOT composite membranes；
(3) electrochemical polymerization：The standby monomer electrolyte is made in step (1) using cyclic voltammetry in electrochemical workstation
Pretreated ito glass electrode surface electropolymerization, after the completion of obtain the pH detecting electrodes.
2. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, ito glass electrode described in step (1) is each ultrasonic 5-15 points in NaOH solution, deionized water, acetone, ethanol
Clock.
3. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, the concentration of amino graphene described in step (2) is 0.1-0.5mg/ml.
4. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, LiClO described in step (2)4The concentration of acetonitrile solution is 0.1M.
5. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, the concentration of EDOT monomer electrolyte described in step (2) is 1-10mM.
6. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, ultrasonic disperse 1-4 hours first time in step (2), second of ultrasonic disperse half an hour, leads to nitrogen 15min.
7. a kind of preparation method of pH detecting electrodes based on graphene/PEDOT composite membranes according to claim 1, its
It is characterised by, the polymerization potential range that electropolymerization uses in step (3) is-0.9-1.5V, sweep speed 50mV/s, polyase 13-
10 circles.
8. the preparation method of the pH detecting electrodes according to claim 1 based on graphene/PEDOT composite membranes is prepared
One kind be based on graphene/PEDOT composite membranes pH detecting electrodes, it is characterised in that the pH detecting electrodes include electrode and
It is coated on graphene/PEDOT composite membranes of the electrode outer surface, the electrode is ito glass electrode, the graphene/
PEDOT composite membranes are coated on the outer surface of the electrode ITO layer.
A kind of 9. detections of the pH based on graphene/PEDOT composite membranes that preparation method according to claim 1 is prepared
The application process of electrode, it is characterised in that the pH that the pH detecting electrodes are used for phosphate buffer is detected, with oxidation peak current
For detection signal, detection of the pH value in the range of 1-11 is realized.
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| WO2017160721A1 (en) * | 2016-03-14 | 2017-09-21 | The Trustees Of The University Of Pennsylvania | Ph sensing technique based on graphene electrodes |
| CN105842313B (en) * | 2016-05-09 | 2018-06-26 | 江苏大学 | A kind of graphene-based bionical pH sensors of micro-nano texturing and preparation method thereof |
| CN109786124B (en) * | 2018-12-05 | 2024-04-05 | 南通南京大学材料工程技术研究院 | Flexible asymmetric supercapacitor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103454331A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Per-oxidized poly(3,4-ethylenedioxythiophene-graphite oxide (PEDOT/GO) modified electrode and electrochemical detection method thereof to pesticide imidacloprid |
| CN103604858A (en) * | 2013-11-20 | 2014-02-26 | 南京理工大学 | Electrochemical detection method of acetaminophen medicine by PEDOT (Polymer Ethylenedioxy Thiophene)/GO (Graphene Oxide)/GCE (Glassy Carbon Electrode) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103454331A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Per-oxidized poly(3,4-ethylenedioxythiophene-graphite oxide (PEDOT/GO) modified electrode and electrochemical detection method thereof to pesticide imidacloprid |
| CN103604858A (en) * | 2013-11-20 | 2014-02-26 | 南京理工大学 | Electrochemical detection method of acetaminophen medicine by PEDOT (Polymer Ethylenedioxy Thiophene)/GO (Graphene Oxide)/GCE (Glassy Carbon Electrode) |
Non-Patent Citations (1)
| Title |
|---|
| "A facile one-step redox route for the synthesis of graphene/poly (3,4-ethylenedioxythiophene) nanocomposite and their applications in biosensing";Limin Lu等;《Sensors and Actuators B: Chemical》;20130216;第2.2.1节 * |
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