CN104090009A - Preparation method of electrochemical sensor based on graphene nano sheet modified electrode - Google Patents
Preparation method of electrochemical sensor based on graphene nano sheet modified electrode Download PDFInfo
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- CN104090009A CN104090009A CN201410368085.9A CN201410368085A CN104090009A CN 104090009 A CN104090009 A CN 104090009A CN 201410368085 A CN201410368085 A CN 201410368085A CN 104090009 A CN104090009 A CN 104090009A
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Abstract
The invention relates to an electrochemical sensor based on a ferric oxide nanoparticle-modified reduced graphene oxide nano sheet (Fe2O3/ rGO), which is used for detecting nitrite. A preparation method of the electrochemical sensor comprises the following steps of firstly, preparing a Fe2O3/ rGO compound by an environment-friendly method, and then modifying a glassy carbon electrode by the Fe2O3/ rGO compound, thus preparing the electrochemical sensor for detecting nitrite. When being used for detecting nitrite, the electrochemical sensor is high in sensitivity, stability, repeatability and selectivity, thus having wide application prospect in the fields such as environment and food.
Description
Technical field
The present invention relates to a kind of preparation method of electrochemical sensor, relate in particular to a kind of preparation method of the electrochemical sensor based on the nano-particle modified redox graphene nanometer sheet of di-iron trioxide modified electrode.
Background technology
The use of formulation fertilizer containing nitrogen and the discharge of industrial waste water have caused the mankind can use the pollution of surface water, its nitrite is all toxic to environment and human health, nitrite contacts with amine and forms nitrosamine, can cause as various diseases such as methemoglobinemia, congenital heart defects and cancer of the stomach.The World Health Organization (WHO) stipulates that the high-load of mankind's drinkable water nitrite is 3mg/L, and therefore, for publilc health, environment and food industry, the high-sensitivity detection of nitrite is very important.
Up to the present the method that detects nitrite mainly contains spectrophotometric spectra method, chemiluminescence, electrocapillary phoresis method and chromatography, and these methods need expensive equipment conventionally, complicated trace routine and normally very consuming time.
With these methods, compare, electrochemical method provides a kind of simple, instant analysis method that relative price is cheap, reliable, sensitive, can realize a kind of nitrite detection method that sample is carried out pre-treatment and not disturbed by other material of fast, not needing.
Carbon nanomaterial (fullerene, carbon nano-tube and Graphene) has been widely used in galvanochemistry, these materials have a lot of significant advantages, as little residual current, wide electromotive force mouth, the easy reproducibility of good chemical stability and surface in different electrolyte.Graphene (a kind of desirable two-dimensional layer material) is because its unique physics and chemistry performance has been widely used for fixing metal oxide nano particle, sensor based on copper ingotism and redox graphene (rGO) has shown electro catalytic activity in the detection of nitrite, and graphene nanometer sheet and Nano carbon balls have also shown the electro catalytic activity to nitrite at electrode surface.
Metal oxide di-iron trioxide (Fe
2o
3) be a kind of narrow important N-shaped metal oxide that can band (Eg=2.2eV), in recent years, caused the very large concern of people because its at a low price, nontoxic, easily preparation and the feature that easily stores, Fe
2o
3in catalysis, food, magnetic material, gas sensor, biology sensor and lithium ion battery field, there are a lot of application.
In sum, metal oxide/graphene film compound is applied to electrochemical method, is for detection of nitrite the most reliable the sensitiveest method in prior art.The preparation method of metal oxide/graphene film compound mainly contains pyrolytic, forged burning, electronation, the synthetic harmony chemical synthesis process of microwave, and these methods generally comprise two steps, and the reduction of the graphene film of toxicity hydrazine induction is burnt and added to forged.These methods clearly energy consumption are conventionally all very high, and need to use complex experiment instrument and technology, and can cause certain pollution to environment.
Summary of the invention
For the shortcoming of prior art, the present invention prepared a kind of simple, for nitrite, detect, based on the nano-particle modified redox graphene nanometer sheet of di-iron trioxide (Fe
2o
3/ rGO) the high sensitivity electrochemical sensor of modified electrode.Fe
2o
3/ rGO compound synthesizes by one step hydro thermal method in ethanol, and electrochemical sensor involved in the present invention has demonstrated good sensitivity, selectivity and repeatability.
Step of the present invention is as follows:
(1) preparation of graphene oxide: powdered graphite joins in the concentrated sulphuric acid under 0 ℃ of condition, under ice-water bath stirring condition, add potassium permanganate composition mixture, the mass ratio of powdered graphite and potassium permanganate is 1:6～1:10, preferred 1:8, mass volume ratio (the w/v of powdered graphite and the concentrated sulphuric acid, g/mL) be 1:40～1:50, preferably 1:45.Said mixture stirs after 2～3h at 60～80 ℃, dilute with water at 50 ℃.Last 30% the hydrogen peroxide of dropwise adding, the hydrochloric acid solution with the above 1:10 of 100mL after being filtered washs, then washes until the pH of solution reaches 6.3 grind into powder after 55～80 ℃ of vacuum drying 12～20h of yellow solid that obtain with water.
(2) Fe
2o
3the preparation of/rGO compound: 20～40mg graphene oxide is distributed to the solution of ultrasonic concussion 50～120min formation homogeneous in 80～120mL ethanol, adds FeCl
2with 25% ammoniacal liquor in above-mentioned solution, FeCl
2with 25% ammoniacal liquor be (g/mL/mL): 1:1:1000 with the ratio of above-mentioned solution, the potpourri obtaining in muffle furnace 90～110 ℃ add then cool to room temperature gradually of thermal response 5～8h; After sediment leaches, with deionized water and ethanol, wash 7～10 times, then vacuum drying 7～12h under 50～70 ℃ of conditions.
(3) Fe
2o
3the preparation of/rGO compound modified electrode: the aluminum oxide suspension for surface of glassy carbon electrode (0.6～0.9 μ mol/L) carries out physics polishing, then electrode is successively used to second alcohol and water supersound washing 3～8min, gets 10 μ L Fe
2o
3/ rGO compound, is distributed in water, and concentration is 0.5mg/mL, and the surperficial final vacuum that drips to glassy carbon electrode is dry, can obtain Fe
2o
3/ rGO compound modified electrode.
First the present invention has prepared Fe by eco-friendly method
2o
3/ rGO compound, then uses Fe
2o
3/ rGO compound carries out modification to glassy carbon electrode and has prepared a kind of novel electrochemical sensor detecting for nitrite.Fe
2o
3/ rGO modified electrode can provide high specific surface area, thereby the medium shifting as electronics improves the charge transfer between electrode surface and nitrite.Electrochemical sensor involved in the present invention has presented high sensitivity, stability, repeatability and selectivity to the detection of nitrite, can be widely used in the fields such as environment, food.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with implementing, the invention will be further described.
The preparation method of the high sensitivity electrochemical sensor detecting for nitrite based on the nano-particle modified redox graphene nanometer sheet of di-iron trioxide, its step is as follows:
(1) preparation of graphene oxide: 4g powdered graphite joins in the 180mL concentrated sulphuric acid under 0 ℃ of condition, under ice-water bath stirring condition, add 32g potassium permanganate composition mixture, after stirring 3h at 75 ℃, dilutes with 800mL water at 50 ℃ in potpourri, the last hydrogen peroxide that dropwise adds 50mL30%, hydrochloric acid solution with 100mL1:10 after being filtered washs, wash again until the pH of solution reaches 6.3 grind into powder after the 60 ℃ of vacuum drying 15h of yellow solid that obtain with water.
(2) Fe
2o
3the preparation of/rGO compound: 40mg graphene oxide is distributed to the solution of ultrasonic concussion 50min formation homogeneous in 200mL ethanol, 0.2gFeCl
2join in above-mentioned solution with the ammoniacal liquor of 200 μ L20%, the potpourri obtaining in muffle furnace 90 ℃ add after thermal response 5h, cool to room temperature gradually, after sediment leaches, with deionized water and ethanol washing 7 times, then vacuum drying 8h under 70 ℃ of conditions.
(3) Fe
2o
3the preparation of/rGO compound modified electrode: first physics polishing is carried out with the aluminum oxide suspension of 0.8 μ mol/L in the surface of glassy carbon electrode, then electrode is successively used to second alcohol and water supersound washing 3min; 10 μ LFe
2o
3(be distributed in water, the surperficial final vacuum that 0.5mg/mL) drips to glassy carbon electrode is dry, can obtain Fe for/rGO compound
2o
3/ rGO compound modified electrode.
Claims (6)
1. a preparation method for the electrochemical sensor based on graphene nanometer sheet modified electrode, its step is as follows:
(1) preparation of graphene oxide: powdered graphite joins in the concentrated sulphuric acid under 0 ℃ of condition, under ice-water bath stirring condition, add potassium permanganate to form potpourri, the mass ratio of powdered graphite and potassium permanganate is 1:6～1:10, mass volume ratio (the w/v of powdered graphite and the concentrated sulphuric acid, g/mL) be 1:40～1:50, said mixture stirs then dilute with water at 50 ℃ of 2～3h at 60～80 ℃, dropwise add 30% hydrogen peroxide, hydrochloric acid solution with the above 1:10 of 100mL after being filtered washs, wash with water again until the pH of solution reaches 6.3, grind into powder after 55～80 ℃ of vacuum drying 12～20h of yellow solid that obtain,
(2) Fe
2o
3the preparation of/rGO compound: 20～40mg graphene oxide is distributed to the solution of ultrasonic concussion 50～120min formation stable homogeneous in 80～120mL ethanol, adds FeCl
2with 25% ammoniacal liquor in above-mentioned solution, FeCl
2with 25% ammoniacal liquor be (g/mL/mL): 1:1:1000 with the ratio of above-mentioned solution, the potpourri obtaining in muffle furnace 90～110 ℃ add thermal response 5～8h cool to room temperature gradually, sediment leaches rear deionized water and the ethanol used and washs 7～10 times, then vacuum drying 7～12h under 50～70 ℃ of conditions;
(3) Fe
2o
3the preparation of/rGO compound modified electrode: the aluminum oxide suspension for surface of glassy carbon electrode (0.6～0.9 μ mol/L) carries out physics polishing, then electrode is successively used to second alcohol and water supersound washing 3～8min, gets 10 μ L Fe
2o
3/ rGO compound, is distributed in water, is mixed with the solution that concentration is 0.5mg/mL, and the surperficial final vacuum that drips to glassy carbon electrode is dry, can obtain Fe
2o
3/ rGO compound modified electrode.
2. the preparation method of electrochemical sensor according to claim 1, is characterized in that: described in step (1), the mass ratio of powdered graphite and potassium permanganate is 1:8.
3. the preparation method of electrochemical sensor according to claim 1, is characterized in that: described in step (1), the mass volume ratio (w/v, g/mL) of powdered graphite and the concentrated sulphuric acid is 1:45.
4. the preparation method of electrochemical sensor according to claim 1, is characterized in that: grind into powder after 60 ℃ of vacuum drying 15h of yellow solid described in step (1).
5. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the amount of the described graphene oxide of step (2) and ethanol is respectively 40mg and 200mL, and the time of described ultrasonic concussion is 50min.
6. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the concentration of the described aluminum oxide suspension of step (3) is: 0.8 μ mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634848A (en) * | 2015-01-25 | 2015-05-20 | 浙江大学 | Nitrite electrochemical sensor and manufacturing method thereof |
| CN105136886A (en) * | 2015-10-14 | 2015-12-09 | 无锡百灵传感技术有限公司 | Electrode for detecting Sudan red rapidly and quantitatively |
| CN105911120A (en) * | 2016-04-13 | 2016-08-31 | 中国科学院过程工程研究所 | Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water |
| CN106910902A (en) * | 2017-01-22 | 2017-06-30 | 济南大学 | A kind of fuel cell oxygen reduction catalyst and preparation method thereof |
| CN110609069A (en) * | 2019-10-16 | 2019-12-24 | 常州大学 | Preparation of CuNi/reduced graphene non-enzymatic sulfite electrochemical sensor |
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| CN102507693A (en) * | 2011-11-03 | 2012-06-20 | 桂林医学院 | Functional-material-based glucose biosensor and manufacturing method thereof |
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| CN102507693A (en) * | 2011-11-03 | 2012-06-20 | 桂林医学院 | Functional-material-based glucose biosensor and manufacturing method thereof |
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| NAGAPPA L.TERADAL等: "Electro-reduced graphene oxide film modified glassy carbon electrode as an electrochemical sensor for sibutramine", 《ANALYTICAL METHODS》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634848A (en) * | 2015-01-25 | 2015-05-20 | 浙江大学 | Nitrite electrochemical sensor and manufacturing method thereof |
| CN105136886A (en) * | 2015-10-14 | 2015-12-09 | 无锡百灵传感技术有限公司 | Electrode for detecting Sudan red rapidly and quantitatively |
| CN105136886B (en) * | 2015-10-14 | 2018-05-01 | 广州智谱慧科技有限公司 | A kind of electrode of Quantitative detection tonyred |
| CN105911120A (en) * | 2016-04-13 | 2016-08-31 | 中国科学院过程工程研究所 | Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water |
| CN105911120B (en) * | 2016-04-13 | 2018-07-06 | 中国科学院过程工程研究所 | Glass-carbon electrode, preparation method and the method for carrying out heavy metal analysis in water of sulfur doping graphene oxide modification |
| CN106910902A (en) * | 2017-01-22 | 2017-06-30 | 济南大学 | A kind of fuel cell oxygen reduction catalyst and preparation method thereof |
| CN110609069A (en) * | 2019-10-16 | 2019-12-24 | 常州大学 | Preparation of CuNi/reduced graphene non-enzymatic sulfite electrochemical sensor |
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| CN104090009B (en) | 2016-06-01 |
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Effective date of registration: 20191028 Address after: Room 818-091, 8th floor, New Material Venture Building, No. 7 Fenghuizhong Road, Haidian District, Beijing Patentee after: Maya Forest (Beijing) International Technology Co., Ltd. Address before: Xishan Economic Development Zone, Jiangsu province 214192 Technology Park in Wuxi city (three Furong Road No. 99) cloud six Patentee before: Wuxi Bailing Sensing Technology Co., Ltd. |