CN102692440A - Production method and application of needle-point graphene electrochemical electrode - Google Patents
Production method and application of needle-point graphene electrochemical electrode Download PDFInfo
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- CN102692440A CN102692440A CN2012101479762A CN201210147976A CN102692440A CN 102692440 A CN102692440 A CN 102692440A CN 2012101479762 A CN2012101479762 A CN 2012101479762A CN 201210147976 A CN201210147976 A CN 201210147976A CN 102692440 A CN102692440 A CN 102692440A
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Abstract
The invention discloses a production method and application of a needle-point graphene electrochemical electrode. The production method includes the steps of transferring a graphene film synthesized by chemical vapor deposition to the surface of a micro-nano glass needle point, and using liquid conductive silver glue to connect the graphene and a lead to obtain a needle-point graphene electrode; using cobalt nitrate aqueous solution as electrolyte to deposit cobalt hydroxide on the surface of the needle-point graphene electrode by electrochemical deposition, and heating in a muffle furnace at 300-500 DEG C for 2-4 hours to obtain the needle-point graphene electrochemical electrode functionally modified by tricobalt tetroxide. The needle-point graphene electrochemical electrode can be used to detect micro-droplet samples. After surface modification by tricobalt tetroxide, a high-sensitivity electrochemical biosensor available for enzyme-free detection of glucose is obtained. In addition, the needle-point graphene electrochemical electrode can be used to puncture an active cell to detect intracellular metabolic process in real time.
Description
Technical field
The present invention relates to a kind of preparation method of the needle point formula Graphene electrochemical electrode that is used for the electrochemica biological sensing and in the application of electrochemica biological sensory field.
Background technology
Electrochemica biological sensor plays crucial effects in current highly sensitive biomolecule detection, clinical medicine and genetic engineering research field.Wherein, Electrochemical electrode is a focus in the biological sensing Study of An field to the analyzing and testing and being detected as in real time of endocellular metabolism process of micro-drop sample, and the improvement of electrochemical electrode performance and improving the expansion electrochemica biological sensor in the application in micro-example analyzing and testing field with guarantee that its stable operation plays a decisive role.
The bi-dimensional cellular shape crystal structure that Graphene is made up of the monolayer carbon atom; Have the electron mobility of superelevation, big specific surface area and excellent physics, chemistry, optics and mechanical property; In field effect transistor, nanoelectronic bio-sensing, transparent conductive film, prepare composite boundless application prospect is arranged; Wherein the Graphene modified glassy carbon electrode has obtained extensive studies in the bio-sensing field; But these are big based on the functionalization electrochemical electrode size that graphene oxide modification glass-carbon electrode obtains, functional modification is difficult; Particularly be difficult to realize real-time monitoring that pH value, glucose, protein, signal factor etc. in the detection of micro-drop biological sample and the competent cell are changed; This has limited its application in the bio-sensing field to a certain extent widely, optimizes on the basis at material property, and the electrochemical electrode for preparing micro-nano needle point structure can fundamentally address the above problem.
Graphene has Stability Analysis of Structures, good conductivity, specific surface area and realizes characteristics such as surface-functionalized modification and leakage current are little greatly, easily, is the decline ideal electrode material of nano electrochemical electrode of preparation high sensitive electrochemical biological sensor electrode, particularly needle point.Yet, utilize at present Graphene combine micro-nano needle point directly prepare research after electrochemical electrode and the functionalization its at application of electrochemica biological sensory field rare report also.
Summary of the invention
Technical matters:The purpose of this invention is to provide a kind of preparation method of the needle point formula Graphene electrochemical electrode that is used for the electrochemica biological sensing and in the application of electrochemica biological sensory field.
Technical scheme:A kind of method for preparing needle point formula Graphene electrochemical electrode provided by the present invention and needle point formula electrochemical electrode are in the application in bio-sensing field, and its preparation method may further comprise the steps:
1) chemical vapor deposition is synthetic graphene film is transferred to the glass needle surface;
2) with conductive silver glue graphene film one end is connected with plain conductor one end, forms the needle point formula Graphene electrochemical electrode of non-functionalized;
3) with the cobalt nitrate aqueous solution be electrolytic solution, at needle point formula Graphene surface electrochemistry deposition cobalt hydroxide, sedimentation time is 30 ~ 600s;
The needle point formula electrochemical electrode that 4) will deposit cobalt hydroxide is with distilled water washing and oven dry, in muffle furnace 300-500 ℃ following roasting 2-4 hour, form the needle point formula Graphene electrochemical electrode of cobalt oxide functionalization.
The glass needle point diameter of described needle point formula Graphene electrochemical electrode is 100 nm ~ 10 μ m.
Described plain conductor material is copper, titanium, gold or silver-colored.
Described non-functionalized needle point formula Graphene electrochemical electrode can be used as micro-nano to electrode, can constitute the loop with working electrode.
The no enzyme that described cobalt oxide functional needle point formula Graphene electrochemical electrode can carry out glucose detects.
Described cobalt oxide functional needle point formula Graphene electrochemical electrode can carry out the selectivity of glucose in micro-drop sample or the cell does not have the enzyme detection.
Beneficial effect:Compare with existing electrochemical electrode biosensor technique, the invention has the advantages that
1, the present invention discloses a kind of novel needle point formula Graphene electrochemical electrode preparation method first, and this technology for preparing electrode is simple, cheap;
2, the prepared needle point formula Graphene electrochemical electrode size of the present invention is little, can realize the real-time detection to the analyzing and testing and the competent cell intracellular metabolite process of micro-drop sample;
3, the prepared easy functional modification in needle point formula Graphene electrochemical electrode surface of the present invention, and realize the highly sensitive and high specific selectivity of different biological molecules in the micro-drop is detected.
Description of drawings
Fig. 1. be the structural representation of the needle point formula Graphene electrochemical electrode of preparation among the embodiment 1.
Fig. 2. be the needle point formula Graphene electrochemical electrode of preparation among the embodiment 1 and the comparison of gold electrode cyclic voltammetry curve.
Fig. 3. be the SEM photo of the needle point formula Graphene electrochemical electrode of the cobalt oxide functional modification of the present invention's preparation among the embodiment 2.
Fig. 4. be the VA characteristic curve of needle point formula Graphene electrochemical electrode before and after the cobalt oxide functional modification of preparation among the embodiment 2.
Fig. 5. be the cyclic voltammetry curve of cobalt oxide functional needle point formula Graphene electrochemical electrode in the variable concentrations glucose solution of the present invention's preparation among the embodiment 3.
Fig. 6. be the cobalt oxide functional needle point formula Graphene electrochemical electrode of the present invention preparation among the embodiment 3 no enzyme detection time-map of current to glucose.
Fig. 7. the needle point formula Graphene electrochemical electrode for preparing for the present invention among the embodiment 4 is the device synoptic diagram of working electrode to micro-drop sample detection.
Fig. 8. the needle point formula Graphene electrochemical electrode for preparing for the present invention among the embodiment 4 is that working electrode does not have the time current curve that enzyme detects to 10 micromole's glucose.
Embodiment
Below in conjunction with accompanying drawing and instantiation the present invention is elaborated.
Embodiment 1:
The graphene film that chemical vapor deposition is synthetic is directly transferred to the glass needle surface;
Be connected with plain conductor one end with the end of 0.5mg conductive silver glue glue with graphene film, the elargol glue curing promptly obtains the needle point formula Graphene electrochemical electrode of non-functionalized after 15 minutes;
The tip diameter of glass needle point is 5.0 microns.
The plain conductor material is a copper.
Fig. 1 is the structural representation of the needle point formula Graphene electrochemical electrode of method for preparing; Fig. 2 is the comparison of the needle point formula Graphene electrochemical electrode and the gold nano electrode cyclic voltammetry curve of method for preparing.
Embodiment 2:
The graphene film that chemical vapor deposition is synthetic is directly transferred to the glass needle surface;
With 0.5mg conductive silver glue glue graphene film one end is connected with plain conductor one end, the elargol glue curing obtains the needle point formula Graphene electrochemical electrode of non-functionalized after 15 minutes;
The tip diameter of glass needle point is 1.0 microns.
The plain conductor material is a titanium.
Cobalt nitrate aqueous solution with 10.0 mMs is an electrolytic solution, and 60 seconds of electrochemical deposition under-1.0 volts of permanent electromotive forces are at needle point Graphene surface deposition one deck cobalt hydroxide.
Surface deposition is put into 400 ℃ of following roastings of muffle furnace 2 hours after the Graphene needle point washing drying of cobalt hydroxide is arranged, and promptly obtains the functionalization needle point formula Graphene electrochemical electrode that cobaltosic oxide is modified.
Fig. 3 is the SEM figure of needle point formula Graphene electrochemical electrode under different amplification of cobalt oxide functionalization, and Fig. 4 is respectively the VA characteristic curve before and after needle point formula Graphene electrochemical electrode is modified with cobaltosic oxide.
Embodiment 3:
The graphene film that chemical vapor deposition is synthetic is directly transferred to the glass needle surface;
With 0.5mg conductive silver glue glue graphene film one end is connected with plain conductor one end, the elargol glue curing obtains the needle point formula Graphene electrochemical electrode of non-functionalized after 15 minutes;
The tip diameter of glass needle point is 1.0 microns.
The plain conductor material is a copper.
Cobalt nitrate aqueous solution with 10.0 mMs is an electrolytic solution, and 60 seconds of electrochemical deposition under-1.0 volts of permanent electromotive forces are at needle point Graphene surface deposition one deck cobalt hydroxide.
Surface deposition is put into 400 ℃ of following roastings of muffle furnace 2 hours after the Graphene needle point washing drying of cobalt hydroxide is arranged, and promptly obtains the functionalization needle point formula Graphene electrochemical electrode that cobaltosic oxide is modified.
Fig. 5 is the galvanochemistry cyclic voltammetry curve of the micro-nano electrode pair glucose of above-mentioned functions Graphene, and Fig. 6 is the electric current-time curve of the micro-nano electrode pair variable concentrations of functionalization graphene glucose detection.
Embodiment 4:
The Graphene that chemical vapor deposition is synthetic is directly transferred to the glass needle surface;
With 0.5mg conductive silver glue glue graphene film one end is connected with plain conductor one end, the elargol glue curing obtains the needle point formula Graphene electrochemical electrode of non-functionalized after 15 minutes;
The tip diameter of glass needle point is 1.0 microns.
The plain conductor material is a copper.
Cobalt nitrate aqueous solution with 10.0 mMs is an electrolytic solution, and 60 seconds of electrochemical deposition under-1.0 volts of permanent electromotive forces are at needle point Graphene surface deposition one deck cobalt hydroxide.
Surface deposition is put into 400 ℃ of following roastings of muffle furnace 2 hours after the Graphene needle point washing drying of cobalt hydroxide is arranged, and promptly obtains the functionalization needle point formula Graphene electrochemical electrode that cobaltosic oxide is modified.
With functionalization needle point formula Graphene electrochemical electrode is working electrode; The Graphene electrochemical electrode is that electrode is made up pick-up unit as shown in Figure 7; When the test sample volume was 4 microlitres, functionalization needle point formula Graphene electrochemical electrode was as shown in Figure 8 to the no enzyme detection curve of 10 micromole's glucose.
Claims (6)
1. the preparation method of a needle point formula Graphene electrochemical electrode is characterized in that this method may further comprise the steps:
1) chemical vapor deposition is synthetic graphene film is transferred to micro-nano glass needle surface;
2) with conductive silver glue graphene film one end is connected with plain conductor one end, forms the needle point formula Graphene electrochemical electrode of non-functionalized;
3) be electrolytic solution with the cobalt nitrate aqueous solution, the method for utilizing electrochemical deposition is at needle point Graphene surface deposition cobalt hydroxide, and sedimentation time is 30 ~ 600s;
The needle point that 4) will deposit cobalt hydroxide decline the nano electrochemical electrode with distilled water washing and oven dry after, put into muffle furnace, at 300-500 ℃ of following roasting 2-4 hour, form the needle point formula Graphene electrochemical electrode of cobalt oxide functional modification.
2. the preparation method of needle point formula Graphene electrochemical electrode according to claim 1, the diameter that it is characterized in that described micro-nano glass needle point is 100 nm ~ 10 μ m.
3. the preparation method of needle point formula Graphene electrochemical electrode according to claim 1 is characterized in that its material of described plain conductor is copper, titanium, gold or silver-colored.
4. application of adopting the described needle point formula of claim 1 Graphene electrochemical electrode is characterized in that described non-functionalized needle point formula Graphene electrochemical electrode can constitute the loop with working electrode as micro-nano to electrode.
5. application of adopting the described needle point formula of claim 1 Graphene electrochemical electrode is characterized in that the needle point formula Graphene electrochemical electrode of described cobalt oxide functionalization can carry out the highly sensitive no enzyme detection of glucose.
6. the application of needle point formula Graphene electrochemical electrode according to claim 5 is characterized in that selectivity that described functionalization needle point formula Graphene electrochemical electrode can carry out glucose in micro-drop sample or the cell do not have enzyme and detect.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924209A (en) * | 2014-04-30 | 2014-07-16 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene on surface of needle point |
| CN105353014A (en) * | 2015-11-06 | 2016-02-24 | 北京理工大学 | Preparation method for a porous graphene microelectrode and applications |
| CN108658037A (en) * | 2018-04-27 | 2018-10-16 | 国家纳米科学中心 | A kind of graphene functionalized nanometer pinpoint and preparation method thereof |
| CN109778172A (en) * | 2019-02-21 | 2019-05-21 | 东华大学 | One kind is for non-enzymatic glucose sensor composite nano materials and preparation method thereof |
| CN110137430A (en) * | 2019-05-13 | 2019-08-16 | 上海大学 | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof |
-
2012
- 2012-05-14 CN CN2012101479762A patent/CN102692440A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《Chem. Commun.》 20120504 Xuewan Wang等 A graphene-cobalt oxide based needle electrode for non-enzymatic glucose detection in micro-droplets 第6490-6492页 1-6 第48卷, 第52期 * |
| JUN YAN等: "Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors", 《ELECTROCHIMICA ACTA》 * |
| XUEWAN WANG等: "A graphene–cobalt oxide based needle electrode for non-enzymatic glucose detection in micro-droplets", 《CHEM. COMMUN.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924209A (en) * | 2014-04-30 | 2014-07-16 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene on surface of needle point |
| CN105353014A (en) * | 2015-11-06 | 2016-02-24 | 北京理工大学 | Preparation method for a porous graphene microelectrode and applications |
| CN108658037A (en) * | 2018-04-27 | 2018-10-16 | 国家纳米科学中心 | A kind of graphene functionalized nanometer pinpoint and preparation method thereof |
| CN108658037B (en) * | 2018-04-27 | 2019-11-22 | 国家纳米科学中心 | A kind of graphene functionalized nanometer pinpoint and preparation method thereof |
| CN109778172A (en) * | 2019-02-21 | 2019-05-21 | 东华大学 | One kind is for non-enzymatic glucose sensor composite nano materials and preparation method thereof |
| CN110137430A (en) * | 2019-05-13 | 2019-08-16 | 上海大学 | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof |
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Application publication date: 20120926 |