CN103334122A - Preparation method and applications of reduced graphene and palladium composite modified electrode - Google Patents
Preparation method and applications of reduced graphene and palladium composite modified electrode Download PDFInfo
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- CN103334122A CN103334122A CN2013102074823A CN201310207482A CN103334122A CN 103334122 A CN103334122 A CN 103334122A CN 2013102074823 A CN2013102074823 A CN 2013102074823A CN 201310207482 A CN201310207482 A CN 201310207482A CN 103334122 A CN103334122 A CN 103334122A
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Abstract
The invention discloses a preparation method of reduce graphene and palladium composite glass carbon electrode and a detection method of nitrite in the water. The preparation method comprises following steps: a three-electrode system consisting of a graphite oxide modified glass carbon work electrode, a platinum counter electrode and a calomel reference electrode is emerged in a phosphatic solution and reduced by the cyclic voltammetry method. After a certain period of time, graphite oxide on the surface of the glass carbon electrode is reduced to form graphene. Then the modified electrode is washed by deionized water, and then forms a tree-electrode system with a platinum counter electrode and a calomel reference electrode. The three-electrode system is put into a potassium chloride solution, and nano particles are deposited on the surface of the graphene by adopting the potentiostatic method. Then a graphene-palladium composite modified glass carbon work electrode, a platinum counter electrode, and a calomel reference electrode forms a three-electrode system, which is used for detecting the density of nitrite in a phosphatic solution. From a mechanism sketch map, it can be obviously observed that nitrite ions are oxidized to nitrates on the surface of graphene palladium composite.
Description
Technical field
The present invention relates to a kind of glass-carbon electrode, particularly a kind of preparation of reducing Graphene-palladium mixture modified glassy carbon electrode the invention still further relates to this modified electrode in catalysis and detects application in the water nitrite acid group.
Background technology
Nitrite anions has been widely applied to industrial production as a kind of foodstuff additive commonly used, sanitas.In excessive nitrite environment, oxyphorase can be oxidized as if long-term exposure for the people.In addition, nitrite anions can the amine in human body be combined the production nitrosamine, and this material can cause cancer and hypertension.Therefore, to the real-time detection of nitrite anions be one very must and significant thing.Electrochemical process is one of common method that detects nitrite anions, and reason is that electrochemical techniques do not need to continue to add chemical reagent, and is simple to operate.But nitrite anions usually shows inertia in traditional electrode material surface.One of way that addresses this problem is exactly the electrode of selecting nano composite material to modify.From the Geim of Univ Manchester UK in 2004 professor and co-worker thereof separate first make since, single-layer graphene (Graphene) causes the extensive concern in fields such as physics, chemistry and materialogy because of its electroconductibility free from worldly cares, thermal conductivity and stability.2010, Nobel Prize in physics was authorized the Geim of Univ Manchester UK and Novoselov professor, achieves in the revolutionary character aspect the grapheme material research to commend them.Since then, Graphene becomes after conductive polymers, the another new lover of material educational circles.Graphene has been widely used in various fields such as sensor, nuclear magnetic resonance, energy storage device, catalytic carrier.It is reported that the specific surface area of single-layer graphene is up to 2630 m
2/ g, and be easy to realize mixing and modified with functional group.Up-to-date domestic and international result of study show that the graphene nano material can be degraded efficiently or planar water in pollutent.
Summary of the invention
Technical problem to be solved by this invention provides the reduction Graphene-palladium mixture modified glassy carbon electrode of the scalable water body pH of a kind of energy environment, utilize the efficiently catalyzing and oxidizing performance of reduction Graphene and Pd nano particle, the poisonous nitrite anions of catalysis water body is also realized its Electrochemical Detection.Utilize reduction Graphene and electrochemical method, easy to operate, non-secondary pollution.
Reduction Graphene of the present invention-palladium mixture modified glassy carbon electrode is to be prepared from by following method:
1) employed three electrodes of electrolyzer are set, this three electrode is modified glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode by graphite oxide and is formed;
2) configuration phosphate solution, its concentration is 0.01 ~ 2.0 mol dm
-3, feeding 0.5 ~ 2 h nitrogen is driven the oxygen in the solution away;
3) three electrodes of step 1) are put into the phosphate solution that configures and formed the three-electrode system electrolyzer, reduce graphene oxide with cyclic voltammetry, voltage range is controlled at-2.0 ~ 1.0 V;
4) after reduction finishes, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing the Graphene modified glassy carbon;
5) employed three electrodes of electrolyzer are set, this three electrode is modified glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode by the reduction Graphene and is formed;
6) configuration Palladous chloride, Repone K mixed solution, wherein Palladous chloride concentration is 0.001 ~ 1.0 mol dm
-3, potassium chloride concentration is 0.5 ~ 3.0 mol dm
-3
7) three electrodes of step 5) are put into the mixed solution that configures and formed the three-electrode system electrolyzer, carry out electrolysis with potentiostatic method, form reduction Graphene-palladium mixture on the glass-carbon electrode surface in the electrolytic process, the potentiostatic deposition voltage range is-2.0 ~ 0.5 V;
8) after electrolysis is finished, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing Graphene-palladium mixture modified glassy carbon electrode.
The present invention also provides the catalysis of above-mentioned conductive copolymer modified glassy carbon and detects the method for water nitrite acid group, may further comprise the steps:
A) will reduce three electrodes that Graphene-palladium mixture modified glassy carbon electrode and platinum electrode and saturated calomel electrode form puts into 0.1 ~ 0.2 mol dm
-3, in the nitrite anions of pH=4.0 and the phosphoric acid salt mixed solution, with cyclic voltammetry oxidation nitrite anions, the scanning control of Electric potentials is at-0.5 ~ 1.5V, and scanning speed is 5 ~ 200 mVs
-1
B) will reduce three electrodes that Graphene-palladium mixture modified glassy carbon electrode and platinum electrode and saturated calomel electrode form puts into 0.1 ~ 0.2 mol dm
-3, in the pH=4.0 phosphate solution, dropwise add the sodium nitrite solution of different concns, detect nitrite anions with potentiostatic method, control of Electric potentials is at-1.0 ~ 2.0 V.
This application is to utilize reduction Graphene and Pd nano particle efficient catalytic characteristic, catalysis water nitrite acid group.
The present invention utilizes reduction Graphene-palladium mixture modified glassy carbon electrode, utilizes the efficiently catalyzing and oxidizing performance of reduction Graphene and Pd nano particle, and the poisonous nitrite anions of catalysis water body is also realized its Electrochemical Detection.Utilize reduction Graphene and electrochemical method, easy to operate, non-secondary pollution.
Description of drawings
Fig. 1 is the schematic flow sheet that the present invention prepares;
Fig. 2 is that the present invention reduces the Graphene-cyclic voltammogram of palladium mixture modified electrode in containing different concns nitrite anions solution;
Fig. 3 be the present invention reduce Graphene-palladium mixture modified electrode the ampere response curve;
Fig. 4 is nitrite anions concentration and the response current figure that the present invention relates to.
Embodiment
Further specify the preparation of reduction Graphene-palladium mixture modified glassy carbon electrode: embodiment 1 in conjunction with the embodiments as shown in Figure 1:
1) employed three electrodes of electrolyzer are set, this three electrode is modified glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode by graphite oxide and is formed;
2) configuration phosphate solution, its concentration is 0.5 mol dm
-3, feed 1 h nitrogen and drive oxygen in the solution away;
3) three electrodes of step 1) are put into the phosphate solution that configures and formed the three-electrode system electrolyzer, reduce graphene oxide with cyclic voltammetry, voltage range is controlled at-2.0 ~ 1.0 V;
4) after reduction finishes, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing the Graphene modified glassy carbon;
5) employed three electrodes of electrolyzer are set, glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode that this three electrode is modified by the reduction Graphene are formed;
6) configuration Palladous chloride, Repone K mixed solution, wherein Palladous chloride concentration is 0.002 mol dm
-3, potassium chloride concentration is 1.0 mol dm
-3
7) three electrodes of step 5) are put into the mixed solution that configures and formed the three-electrode system electrolyzer, carry out electrolysis with potentiostatic method, form reduction Graphene-palladium mixture on the glass-carbon electrode surface in the electrolytic process, the potentiostatic deposition voltage range is-2.0 ~ 0.5 V;
8) after electrolysis is finished, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing Graphene-palladium mixture modified glassy carbon electrode.
1) employed three electrodes of electrolyzer are set, this three electrode is modified glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode by graphite oxide and is formed;
2) configuration phosphate solution, its concentration is 1.5 mol dm
-3, feed 1.5 h nitrogen and drive oxygen in the solution away;
3) three electrodes of step 1) are put into the phosphate solution that configures and formed the three-electrode system electrolyzer, reduce graphene oxide with cyclic voltammetry, voltage range is controlled at-2.0 ~ 1.0 V;
4) after reduction finishes, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing the Graphene modified glassy carbon;
5) employed three electrodes of electrolyzer are set, glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode that this three electrode is modified by the reduction Graphene are formed;
6) configuration Palladous chloride, Repone K mixed solution, wherein Palladous chloride concentration is 0.002 mol dm
-3, potassium chloride concentration is 1.0 mol dm
-3
7) three electrodes of step 5) are put into the mixed solution that configures and formed the three-electrode system electrolyzer, carry out electrolysis with potentiostatic method, form reduction Graphene-palladium mixture on the glass-carbon electrode surface in the electrolytic process, the potentiostatic deposition voltage range is-2.0 ~ 0.5 V;
8) after electrolysis is finished, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing Graphene-palladium mixture modified glassy carbon electrode.
Further specify reduction Graphene-palladium mixture modified glassy carbon electrode catalysis water nitrite acid group in conjunction with the embodiments:
Embodiment:
Reduction Graphene-palladium mixture modified glassy carbon electrode and three electrodes that platinum electrode and saturated calomel electrode are formed are put into 0.1 mol dm
-3, in the nitrite anions of pH=4.0 and the phosphoric acid salt mixed solution, with cyclic voltammetry oxidation nitrite anions.Its cyclic voltammogram as shown in Figure 2.
Fig. 2 is the reduction Graphene-cyclic voltammogram of palladium mixture modified glassy carbon electrode in the phosphate solution of pH=4.0.Curve a-d represents the nitrite anions that contains 0,1,2,8 μ mol respectively.As can be seen from the figure: after stable reduction Graphene-palladium mixture modified glassy carbon electrode is moved into and contains the nitrite anions water body, the redox electric current increases along with the increase of nitrite anions concentration, redox has taken place at reduction Graphene-palladium mixture in this explanation nitrite anions, and namely nitrite anions changes nitrate radical into.
Further specify reduction Graphene-palladium mixture modified glassy carbon electrode in conjunction with the embodiments and detect the water nitrite acid group:
Embodiment:
Reduction Graphene-palladium mixture modified glassy carbon electrode and three electrodes that platinum electrode and saturated calomel electrode are formed are put into 0.15 mol dm
-3, in the pH=4.0 phosphate solution, dropwise add the sodium nitrite solution of different concns, detect nitrite anions with potentiostatic method.Its ampere response curve as shown in Figure 3.
As can be seen from Figure 2: reduction Graphene-palladium mixture modified glassy carbon electrode is to 10
-5Mol dm
-3Nitrite anions can both produce response.Fig. 4 is the figure that nitrite anions concentration and the response current of Fig. 3 are done.As can be seen from the figure: at 0.04 to 108 μ mol dm
-3Scope in all keep good linear relationship.
More than be thinking of the present invention and implementation method, concrete application approach is a lot, should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (6)
1. one kind is reduced the preparation of Graphene-palladium mixture modified glassy carbon electrode, it is characterized in that may further comprise the steps successively:
1) employed three electrodes of electrolyzer are set, this three electrode is modified glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode by graphite oxide and is formed;
2) configuration phosphate solution, its concentration is 0.01 ~ 2.0 mol dm
-3, feeding 0.5 ~ 2 h nitrogen is driven the oxygen in the solution away;
3) three electrodes of step 1) are put into the phosphate solution that configures and formed the three-electrode system electrolyzer, reduce graphene oxide with cyclic voltammetry;
4) after reduction finishes, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing the Graphene modified glassy carbon;
5) employed three electrodes of electrolyzer are set, glass carbon working electrode, platinum counter electrode and saturated calomel reference electrode that this three electrode is modified by the reduction Graphene are formed;
6) configuration Palladous chloride, Repone K mixed solution, wherein Palladous chloride concentration is 0.001 ~ 1.0 mol dm
-3, potassium chloride concentration is 0.5 ~ 3.0 mol dm
-3
7) three electrodes of step 5) are put into the mixed solution that configures and formed the three-electrode system electrolyzer, use the potentiostatic method electrolysis, form reduction Graphene-palladium mixture on the glass-carbon electrode surface in the electrolytic process;
8) after electrolysis is finished, take off glass-carbon electrode, with deionized water wash for several times, obtain reducing Graphene-palladium mixture modified glassy carbon electrode.
2. reduction Graphene according to claim 1-palladium mixture modified glassy carbon electrode, it is characterized in that: step 3) cyclic voltammetry voltage range is controlled between-2.0 ~ 1.0 V.
3. reduction Graphene according to claim 1-palladium mixture modified glassy carbon electrode is characterized in that: step 7) potentiostatic method electrolysis voltage scope is-2.0 ~ 0.5 V.
4. the application of the described reduction Graphene of claim 1-palladium mixture modified glassy carbon electrode is characterized in that catalysis and detects the water nitrite acid group may further comprise the steps:
A) will reduce three electrodes that Graphene-palladium mixture modified glassy carbon electrode and platinum electrode and saturated calomel electrode form puts into 0.1 ~ 0.2 mol dm
-3, in the nitrite anions of pH=4.0 and the phosphoric acid salt mixed solution, with cyclic voltammetry oxidation nitrite anions;
B) will reduce three electrodes that Graphene-palladium mixture modified glassy carbon electrode and platinum electrode and saturated calomel electrode form puts into 0.1 ~ 0.2 mol dm
-3, in the pH=4.0 phosphate solution, dropwise add the sodium nitrite solution of different concns, detect nitrite anions with potentiostatic method.
5. the application of reduction Graphene according to claim 4-palladium mixture modified glassy carbon electrode is characterized in that the scanning control of Electric potentials of step a) at-0.5 ~ 1.5V, and scanning speed is 5 ~ 200 mVs
-1
6. the application of reduction Graphene according to claim 4-palladium mixture modified glassy carbon electrode is characterized in that the control of Electric potentials of step b) is at-1.0 ~ 2.0 V.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558274A (en) * | 2013-11-07 | 2014-02-05 | 扬州大学 | Preparation method of reduced graphene-polyaniline-o-aminophenol-palladium compound modified glassy carbon electrode and application thereof in detection of bromate in water body |
| CN105675688A (en) * | 2015-11-04 | 2016-06-15 | 东莞理工学院 | Preparation method and application of nano-wire/nano-particle modified electrode |
| CN109574153A (en) * | 2018-12-18 | 2019-04-05 | 北京工业大学 | A kind of synchronous high-efficiency coupling technique of cathodic reduction chlorophenol and anodic oxidation phenol |
| CN114166904A (en) * | 2020-10-30 | 2022-03-11 | 中国科学院烟台海岸带研究所 | Method for detecting nitrate ions |
| CN116254525A (en) * | 2023-02-20 | 2023-06-13 | 合肥国轩高科动力能源有限公司 | Inner electrode alloy layer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103033544A (en) * | 2012-12-11 | 2013-04-10 | 常州大学 | Electrochemical DNA sensor based on graphene-precious metal composite and preparation method thereof |
-
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- 2013-05-30 CN CN2013102074823A patent/CN103334122A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103033544A (en) * | 2012-12-11 | 2013-04-10 | 常州大学 | Electrochemical DNA sensor based on graphene-precious metal composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YA ZHANG ETC.: ""Electrocatalysis and detection of nitrite on a reduced graphene/Pd nanocomposite modified glassy carbon electrode"", 《 SENSORS AND ACTUATORS B》, vol. 185, 27 May 2013 (2013-05-27) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558274A (en) * | 2013-11-07 | 2014-02-05 | 扬州大学 | Preparation method of reduced graphene-polyaniline-o-aminophenol-palladium compound modified glassy carbon electrode and application thereof in detection of bromate in water body |
| CN103558274B (en) * | 2013-11-07 | 2015-12-09 | 扬州大学 | The preparation method of reduced graphene-polyaniline o-aminophenol-palladium compound modified glassy carbon electrode and the application in detection water body bromate thereof |
| CN105675688A (en) * | 2015-11-04 | 2016-06-15 | 东莞理工学院 | Preparation method and application of nano-wire/nano-particle modified electrode |
| CN105675688B (en) * | 2015-11-04 | 2018-02-23 | 东莞理工学院 | A kind of preparation method and applications of nano wire-nano-particle modified electrode |
| CN109574153A (en) * | 2018-12-18 | 2019-04-05 | 北京工业大学 | A kind of synchronous high-efficiency coupling technique of cathodic reduction chlorophenol and anodic oxidation phenol |
| CN109574153B (en) * | 2018-12-18 | 2021-05-28 | 北京工业大学 | Synchronous efficient coupling process for reducing chlorophenol by cathode and oxidizing phenol by anode |
| CN114166904A (en) * | 2020-10-30 | 2022-03-11 | 中国科学院烟台海岸带研究所 | Method for detecting nitrate ions |
| CN114166904B (en) * | 2020-10-30 | 2023-11-28 | 中国科学院烟台海岸带研究所 | Method for detecting nitrate ions |
| CN116254525A (en) * | 2023-02-20 | 2023-06-13 | 合肥国轩高科动力能源有限公司 | Inner electrode alloy layer and preparation method thereof |
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Application publication date: 20131002 |