CN104090006B - Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes - Google Patents
Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes Download PDFInfo
- Publication number
- CN104090006B CN104090006B CN201410360297.2A CN201410360297A CN104090006B CN 104090006 B CN104090006 B CN 104090006B CN 201410360297 A CN201410360297 A CN 201410360297A CN 104090006 B CN104090006 B CN 104090006B
- Authority
- CN
- China
- Prior art keywords
- electrode
- nitrogen
- polycarbazole
- doped graphene
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes, electrode is by glass-carbon electrode as substrate, and conducting polymer polycarbazole and nitrogen-doped graphene form.The present invention adopts to drip and is coated with and polymerization two-step approach acquisition PCZ/N-GE modified glassy carbon electrode, and make PCZ and N-GE two kinds of components produce more obviously synergy, make it have stronger catalytic action to the reduction of p-nitrophenol, reduction potential increases obvious.Raw material used is easy to get, and drug dosage is few.Preparation method is simple and quick, reproducible, the electrode environment good stability prepared.
Description
Technical field
The present invention relates to a kind of polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes.
Background technology
Graphene is that thickness is only 0.35nm by the crystal structure of carbon atom compact arranged hexagonal honeycomb shape, and its basic structural unit is benzene hexatomic ring the most stable in organic material.Desirable Graphene has good electric conductivity, has the characteristic of relatively large specific surface area, thus has a lot of unique physics, chemistry and mechanical property, is widely used in electrochemical sensor field.Some heteroatomss are doped in the mechanism of Graphene as N, B etc., destroy the SP2 hydridization that carbon atom is desirable, thus cause Graphene electronic property and chemical activity that great change occurs.And nitrogen-atoms is due to adjacent with carbon atom in the periodic table of elements, and there is a pair lone pair electrons, therefore after doping, there is good electric conductivity equally.And polycarbazole is as a kind of conducting polymer of superior performance, be widely used in multiple field.The multipolymer of polycarbazole and derivant thereof has been used as electrochemical sensor for detecting dopamine.The compound modified glassy carbon electrode of the employing polycarbazole such as Lei Wu and Graphene achieves the detection to pesticide imidacloprid.There is lower detectability and sensitivity.Therefore, polycarbazole has application prospect more widely in electrochemical sensing field.
P-nitrophenol, as one of the most serious environmental contaminants, is widely used in dyestuff, the fields such as pesticide explosive.Because it is to people, the special toxicity of animal and plant, and be difficult to be degraded by traditional treatment method, therefore p-nitrophenol and derivant thereof are classified as one of 114 kinds of organic contaminants by Environmental Protection Agency.Very necessary to its detection.There are many methods can be used for detecting paranitrophenol at present, as vapor-phase chromatography, high performance liquid chromatography, spectroscopic methodology etc.But these methods are all very complicated.Consuming time and costly, be unsuitable for applying.
Summary of the invention
The object of the present invention is to provide a kind of excellent performance, prepare simple and rapid polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes.
Technical solution of the present invention is:
A kind of polycarbazole/nitrogen-doped graphene modified electrode, it is characterized in that: by glass-carbon electrode as substrate, conducting polymer polycarbazole and nitrogen-doped graphene form.
A preparation method for polycarbazole/nitrogen-doped graphene modified electrode, is characterized in that: comprise the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, clean with water and acetone rinsing, for subsequent use;
(2) a certain amount of nitrogen-doped graphene is dissolved in NN-dimethyl formamide, the finely dispersed mixed solution of ultrasonic rear formation dark-brown; Get above-mentioned mixed solution, drop on the glass-carbon electrode handled well through step (1).Dry for standby under infrared lamp;
(3) electrochemical polymerization selects cyclic voltammetry, and use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, and containing in the boron trifluoride ether solution of carbazole, adjustment electronegative potential is-0.2 ~ 0.4V, noble potential is 1.4 ~ 1.8V, sweep velocity is 50 ~ 200mVs-1, scanning 4 ~ 12 circle, and the modified electrode obtained uses second alcohol and water repeatedly to rinse, and dry up with nitrogen, obtained PCZ/N-GE modified electrode.
A kind of polycarbazole/nitrogen-doped graphene modified electrode, for detecting p-nitrophenol, is characterized in that: detection method comprises the following steps:
Be positioned over by PCZ/N-GE modified glassy carbon electrode in the buffer solution of pH value 4.6, logical nitrogen 10 minutes, adds p-nitrophenol, uses cyclic voltammetry, the electrochemical response of detecting electrode p-nitrophenol to environmental pollutants.
Buffer solution selects acetic acid and sodium acetate.P-nitrophenol concentration range is 0.8 ~ 20 μM.
The present invention compared with prior art, its remarkable advantage is: (1) adopts to drip and is coated with and polymerization two-step approach acquisition PCZ/N-GE modified glassy carbon electrode, PCZ and N-GE two kinds of components are made to produce more obviously synergy, make it have stronger catalytic action to the reduction of p-nitrophenol, reduction potential increases obviously.Raw material used is easy to get, and drug dosage is few.Preparation method is simple and quick, reproducible, the electrode environment good stability prepared.(2) modified electrode prepared has strong current-responsive on CV curve, and the Electrochemical Detection being applied to p-nitrophenol has lower detection limit (~ 10-8M), and linearly dependent coefficient is 0.9971.Detection method fast and accurately.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the preparation (the polymerization curve of carbazole on nitrogen-doped graphene modified glassy carbon electrode) of embodiment of the present invention 1PCZ/N-GE.
Fig. 2, Fig. 3 are the scanning electron microscope (SEM) photographs of PCZ/N-GE modified electrode prepared by the embodiment of the present invention 1.
Fig. 4 be the embodiment of the present invention 1 prepare PCZ/N-GE modified electrode and other modified electrodes to the cyclic voltammetry curve of p-nitrophenol.
Fig. 5, Fig. 6 are that the PCZ/N-GE modified electrode of the embodiment of the present invention 1 preparation is to cyclic voltammetry curve (0.8 ~ 20 μM), the linear relationship chart of p-nitrophenol current-responsive respectively.
Embodiment
Embodiment 1:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, clean with water and acetone rinsing, for subsequent use.
(2) nitrogen-doped graphene (N-GE) is dissolved in DMF (DMF) middle rank forms 2mgml
-1solution.Pipetting 10 μ L with accurate pipettor drops on the glass-carbon electrode handled well, and infrared lamp is dried.
(3) electrochemical polymerization selects cyclic voltammetry, use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, the glass-carbon electrode that N-GE modifies is working electrode, and in the boron trifluoride ether solution containing 0.5mM carbazole, adjustment electronegative potential is 0V, noble potential is 1.4V, and sweep velocity is 100mVs
-1, scanning 8 circle, the modified electrode obtained uses second alcohol and water repeatedly to rinse, and dries up with nitrogen, obtained PCZ/N-GE modified electrode (see figure 1).The glass-carbon electrode that N-GE and PCZ/N-GE modifies is carried out sem test (see Fig. 2, Fig. 3) respectively.As can be seen from Figure 2, N-GE has the same structure of the typical thin paper of Graphene, has larger surface area.As can be seen from Figure 3, after be polymerized one deck polycarbazole on N-GE, surface has had loose structure, so that analysis thing and electronics mutually transmit between solution and electrode.
Embodiment 2:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, clean with water and acetone rinsing, for subsequent use.
(2) nitrogen-doped graphene (N-GE) is dissolved in DMF (DMF) middle rank forms 0.5mgml
-1solution.Pipetting 10 μ L with accurate pipettor drops on the glass-carbon electrode handled well, and infrared lamp is dried.
(3) electrochemical polymerization selects cyclic voltammetry, use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, the glass-carbon electrode that N-GE modifies is working electrode, in the boron trifluoride ether solution containing 0.5mM carbazole, regulates electronegative potential to be-0.2V, noble potential is 1.4V, and sweep velocity is 200mVs
-1, scanning 8 circle, the modified electrode obtained uses second alcohol and water repeatedly to rinse, and dries up with nitrogen, obtained PCZ/N-GE modified electrode.
Embodiment 3:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, clean with water and acetone rinsing, for subsequent use.
(2) nitrogen-doped graphene (N-GE) is dissolved in a certain amount of DMF (DMF) middle rank forms 1mgml
-1solution.Pipetting 10 μ L with accurate pipettor drops on the glass-carbon electrode handled well, and infrared lamp is dried.
(3) electrochemical polymerization selects cyclic voltammetry, use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, the glass-carbon electrode that N-GE modifies is working electrode, and in the boron trifluoride ether solution containing 0.5mM carbazole, adjustment electronegative potential is 0V, noble potential is 1.8V, and sweep velocity is 50mVs
-1, scanning 8 circle, the modified electrode obtained uses second alcohol and water repeatedly to rinse, and dries up with nitrogen, obtained PCZ/N-GE modified electrode.
Embodiment 4: by the electrode prepared by embodiment 1 and N-GE, Graphene (GE), polycarbazole (PCZ) and naked glass-carbon electrode, in the p-nitrophenyl phenol solution of 0.1mM, carry out cyclic voltammetry.See Fig. 4.As can be seen from the figure, the current-responsive of the electrode that N-GE and PCZ modifies is stronger than naked glass carbon doubly a lot of, and on the electrode of N-GE modification, the current potential of its reduction peak is larger than naked glass carbon potential, shows the also original very strong catalytic action of N-GE to p-nitrophenol.And the electrode that PCZ/N-GE modifies than both at the strong manyfold of electric current, reduction potential is corrected, and catalytic action is stronger, and this is mainly because the synergy of PCZ and N-GE causes.Make PCZ/N-GE modified glassy carbon electrode as a kind of electrochemical sensor, p-nitrophenol can be detected quickly and easily.
Embodiment 5:
PCZ/N-GE modified glassy carbon electrode embodiment 1 prepared is in the application of testing environment pollutant p-nitrophenol, and detection method is as follows:
The PCZ/N-GE modified glassy carbon electrode obtained is positioned in the acetate buffer solution of pH value 4.6, logical nitrogen 10 minutes, adds the p-nitrophenyl phenol solution of different amount, use cyclic voltammetry, the electrochemical response of detecting electrode p-nitrophenol to environmental pollutants.Experimental result is shown in Fig. 5, Fig. 6.Fig. 5 is cyclic voltammetry curve.Fig. 6 is the concentration of electric current and p-nitrophenol within the scope of 0.8 ~ 20 μM is good linear relationship.Linear relationship is Ipc (μ A)=0.6549+1.6531C (μM), and related coefficient is that 0.9971. detection is limited to 0.062 μM (S/N=3).Show that this modified electrode has good linear relationship and low detectability to p-nitrophenol.
Claims (1)
1. a preparation method for polycarbazole/nitrogen-doped graphene modified electrode, is characterized in that: described polycarbazole/nitrogen-doped graphene modified electrode is by glass-carbon electrode as substrate, and conducting polymer polycarbazole and nitrogen-doped graphene form; Comprise the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, clean with water and acetone rinsing, for subsequent use;
(2) a certain amount of nitrogen-doped graphene is dissolved in NN-dimethyl formamide, the finely dispersed mixed solution of ultrasonic rear formation dark-brown; Get above-mentioned mixed solution, drop on the glass-carbon electrode handled well through step (1); Dry for standby under infrared lamp;
(3) electrochemical polymerization selects cyclic voltammetry, and use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, and containing in the boron trifluoride ether solution of carbazole, adjustment electronegative potential is-0.2 ~ 0.4V, noble potential is 1.4 ~ 1.8V, sweep velocity is 50 ~ 200mv/s, scanning 4 ~ 12 circle, and the modified electrode obtained uses second alcohol and water repeatedly to rinse, and dry up with nitrogen, obtained PCZ/N-GE modified electrode.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510946735.8A CN105548309B (en) | 2014-07-25 | 2014-07-25 | The purposes of polycarbazole/nitrogen-doped graphene modified electrode |
| CN201410360297.2A CN104090006B (en) | 2014-07-25 | 2014-07-25 | Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410360297.2A CN104090006B (en) | 2014-07-25 | 2014-07-25 | Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510946735.8A Division CN105548309B (en) | 2014-07-25 | 2014-07-25 | The purposes of polycarbazole/nitrogen-doped graphene modified electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104090006A CN104090006A (en) | 2014-10-08 |
| CN104090006B true CN104090006B (en) | 2016-04-20 |
Family
ID=51637740
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410360297.2A Active CN104090006B (en) | 2014-07-25 | 2014-07-25 | Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes |
| CN201510946735.8A Active CN105548309B (en) | 2014-07-25 | 2014-07-25 | The purposes of polycarbazole/nitrogen-doped graphene modified electrode |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510946735.8A Active CN105548309B (en) | 2014-07-25 | 2014-07-25 | The purposes of polycarbazole/nitrogen-doped graphene modified electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104090006B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188505B (en) * | 2016-07-14 | 2018-04-17 | 广东工业大学 | A kind of modified polycarbazole and preparation method thereof |
| CN110386600B (en) * | 2019-07-23 | 2022-02-15 | 合肥工业大学 | Detection method for trace mercury ions in water environment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9847534B2 (en) * | 2012-04-26 | 2017-12-19 | Indian Institute Of Technology Madras | Metal-alloy graphene nanocomposites and methods for their preparation and use |
| CN103196985A (en) * | 2013-04-26 | 2013-07-10 | 黑龙江大学 | Method for measuring p-nitrophenol in water system |
| CN103808779B (en) * | 2014-01-22 | 2016-03-23 | 西北师范大学 | A kind of graphene modified glass-carbon electrode of PDDA functionalization detects the method for p-nitrophenol |
-
2014
- 2014-07-25 CN CN201410360297.2A patent/CN104090006B/en active Active
- 2014-07-25 CN CN201510946735.8A patent/CN105548309B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯及其衍生物纳米复合材料的电化学传感研究;吴秋菊;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140715(第7期);第10、38、38页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105548309A (en) | 2016-05-04 |
| CN104090006A (en) | 2014-10-08 |
| CN105548309B (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Voltammetric determination of phytoinhibitor maleic hydrazide using PEDOT: PSS composite electrode | |
| WO2009115840A1 (en) | Method of electrochemically detecting a capsaicinoid in a sample | |
| CN104090006B (en) | Polycarbazole/nitrogen-doped graphene modified electrode and preparation method and purposes | |
| CN108828033A (en) | A kind of solid ionic electrodes selective and preparation method based on single corner electrode | |
| Kruanetr et al. | Electrochemical Oxidation of Acetyl Salicylic Acid and its voltammetric sensing in real samples at a sensitive edge plane Pyrolytic Graphite Electrode modified with Graphene | |
| Yardım et al. | Voltammetric sensing of triclosan in the presence of cetyltrimethylammonium bromide using a cathodically pretreated boron-doped diamond electrode | |
| CN103293205B (en) | Based on the preparation method of all solid state ion-selective electrode of double membrane structure | |
| Mehmeti et al. | Highly selective electrochemical determination of phlorizin using square wave voltammetry at a boron-doped diamond electrode | |
| CN101915795A (en) | Preparation method of carbon nano tube modified electrode used for detecting melamine | |
| CN104730132A (en) | Graphene modified electrode as well as preparation and rapid detection on phoxim | |
| CN105466995A (en) | Nano-gold and carbon paper electrochemical sensor, preparation method thereof and synchronous detection method of catechol and hydroquinone | |
| Santos et al. | Evaluation of the potentialities of a carbon nanotubes/silicone rubber composite electrode in the determination of hydrochlorothiazide | |
| Ardelean et al. | Electrochemical detection of fluoxetine using a boron-doped diamond electrode | |
| Rivera-Hernández et al. | Voltammetric determination of ibuprofen using a carbon paste–multiwalled carbon nanotube composite electrode | |
| JP2006317360A5 (en) | ||
| Zhang et al. | A flexible calligraphy-integrated in situ humidity sensor | |
| CN103454331A (en) | Per-oxidized poly(3,4-ethylenedioxythiophene-graphite oxide (PEDOT/GO) modified electrode and electrochemical detection method thereof to pesticide imidacloprid | |
| Tang et al. | Determination of methyl parathion by solid-phase extraction on an ionic liquid–carbon nanotube composite electrode | |
| CN104977293A (en) | Method for detecting metal ions through electrochemiluminescence | |
| CN103472120A (en) | Electrochemical method for detecting pesticide phoxim | |
| Vu et al. | Electrochemical detection of TNT by differential pulse adsorptive stripping voltammetry at carbon paste electrode modified by 1‐butyl‐3‐methylimidazolium tetrafluoroborate | |
| CN104569119A (en) | Method for synergically enriching and detecting naphthol isomers | |
| CN103604850B (en) | A kind of polycarbazole modified electrode and the detection method to explosive hexogen thereof | |
| Hadi et al. | Electroanalytical sensing of piperazine at carbon nanotubes/nafion composite-modified glassy carbon and screen-printed carbon electrodes in human plasma | |
| CN102928487A (en) | Plate-type working electrode and method for manufacturing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211020 Address after: 322001 floor 2, No. 968, Xuefeng West Road, Beiyuan street, Yiwu City, Jinhua City, Zhejiang Province Patentee after: Yiwu ransheng Technology Co.,Ltd. Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230407 Address after: 322015 2a, science and technology building, No. 968, Xuefeng West Road, Beiyuan street, Yiwu City, Jinhua City, Zhejiang Province Patentee after: Zhejiang Jinguo Intellectual Property Co.,Ltd. Address before: 322001 floor 2, No. 968, Xuefeng West Road, Beiyuan street, Yiwu City, Jinhua City, Zhejiang Province Patentee before: Yiwu ransheng Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |