CN104090009B - The preparation method of a kind of electrochemical sensor based on graphene nanometer sheet modified electrode - Google Patents
The preparation method of a kind of electrochemical sensor based on graphene nanometer sheet modified electrode Download PDFInfo
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Abstract
The present invention has prepared a kind of based on the nano-particle modified redox graphene nanometer sheet (Fe of ferric oxide2O3/ rGO) electrochemical sensor, and the detection for nitrite. First the present invention has prepared Fe by eco-friendly method2O3/ rGO mixture, then uses Fe2O3Glassy carbon electrode is carried out modification by/rGO mixture, has prepared a kind of novel electrochemical sensor for nitrite detection. The detection of nitrite is presented high sensitivity, stability, repeatability and selectivity by electrochemical sensor involved in the present invention, is with a wide range of applications in the field such as environment, food.
Description
Technical field
The present invention relates to the preparation method of a kind of electrochemical sensor, particularly relate to the preparation method of a kind of electrochemical sensor based on the nano-particle modified redox graphene nanometer sheet modified electrode of ferric oxide.
Background technology
The use of nitrogenous fertilizer and the discharge of trade effluent cause the mankind can with the pollution of surface water, wherein nitrite is all toxic to environment and human health, nitrite contacts with amine class and forms nitrosamine, can cause such as multiple diseases such as methemoglobinemia, congenital heart defects and cancer of the stomach. In World Health Organization's regulation mankind's drinkable water, the most high-content of nitrite is 3mg/L, therefore, is extremely important for the high-sensitivity detection of nitrite publilc health, environment and foodstuffs industry.
Up to the present the method detecting nitrite mainly contains spectrophotometric spectra method, chemiluminescence, electrocapillary phoresis method and chromatography, and these methods need expensive equipment usually, complicated trace routine and normally very consuming time.
Compare with these methods, the method of electrochemistry provides a kind of simple, instant analysis method that relative price is cheap, reliable, sensitive, it may be achieved a kind of fast, do not need sample is carried out pre-treatment and by the nitrite detection method of other material interference.
Carbon nanomaterial (soccerballene, carbon nanotube and Graphene) has been widely used in electrochemistry, these materials have a lot of significant advantage, such as the easy reproducibility of excellent chemical stability and surface in little residual current, wide electromotive force mouth, different ionogen. Graphene (a kind of desirable two-dimensional layer material) has been widely used for fixing metal oxide nano particle due to the process based prediction model of its uniqueness, showing electro catalytic activity based on the sensor of copper ingotism and redox graphene (rGO) in the detection of nitrite, graphene nanometer sheet and Nano carbon balls also show the electro catalytic activity to nitrite at electrode surface.
Metal oxide ferric oxide (Fe2O3) it is a kind of narrow important n shaped metal oxide compound that can be with (Eg=2.2eV), the very big concern of people is caused in recent years, since its low price, preparation nontoxic, easy and the easy feature stored, Fe2O3A lot of application is had in catalysis, food, magneticsubstance, gas sensor, biosensor and field of lithium ion battery.
In sum, metal oxide/graphene film mixture is applied to electrochemical method, is for detecting nitrite the most reliable the sensitiveest method in prior art. The preparation method of metal oxide/graphene film mixture mainly contains pyrolytic decomposition, forged burning, chemical reduction, Microwave synthesize harmony chemical synthesis process, and these methods generally comprise two steps, and forged is burnt and added the reduction of the graphene film of toxicity hydrazine induction. The very obvious energy consumption of these methods is usually all very high, and needs to use complicated laboratory apparatus and technology, and environment can cause certain pollution.
Summary of the invention
For the shortcoming of prior art, the present invention prepared a kind of simple, for nitrite detection, based on the nano-particle modified redox graphene nanometer sheet (Fe of ferric oxide2O3/ rGO) the highly sensitive electrochemical sensor of modified electrode. Fe2O3/ rGO mixture is synthesized by one step hydro thermal method in ethanol, and electrochemical sensor involved in the present invention shows good sensitivity, selectivity and repeatability.
Step of the present invention is as follows:
(1) preparation of graphene oxide: powdered graphite joins in the vitriol oil under 0 DEG C of condition, potassium permanganate composition mixture is added under ice-water bath agitation condition, 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 vitriol oil, g/mL) it is 1:40��1:50, it is preferable that 1:45. Said mixture dilutes with water after stirring 2��3h at 60��80 DEG C at 50 DEG C. Finally dropwise add the hydrogen peroxide of 30%, wash after its filtration with the hydrochloric acid soln of more than 100mL 1:10, then wash with water until the pH of solution reaches 6.3, grind into powder after the yellow solid obtained 55��80 DEG C of vacuum-drying 12��20h.
(2)Fe2O3The preparation of/rGO mixture: 20��40mg graphene oxide is distributed in 80��120mL ethanol ultrasonic concussion 50��120min and is formed the solution of equal one, adds FeCl2With 25% ammoniacal liquor in above-mentioned solution, FeCl2Being (g/mL/mL): 1:1:1000 with the ammoniacal liquor of 25% and the ratio of above-mentioned solution, the mixture obtained is 90��110 DEG C of reacting by heating 5��8h then cool to room temperature gradually in retort furnace; After throw out is filtered out, by deionized water and washing with alcohol 7��10 times, then vacuum-drying 7��12h under 50��70 DEG C of conditions.
(3)Fe2O3The preparation of/rGO mixture modified electrode: the surface aluminum oxide suspension (0.6��0.9 ��m of ol/L) of glassy carbon electrode carries out physics polishing, then by electrode successively with second alcohol and water supersound washing 3��8min, get 10 �� LFe2O3/ rGO mixture, is distributed in water, and concentration is 0.5mg/mL, and the surperficial final vacuum dripping to glassy carbon electrode is dry, can obtain Fe2O3/ rGO mixture modified electrode.
First the present invention has prepared Fe by eco-friendly method2O3/ rGO mixture, then uses Fe2O3Glassy carbon electrode is carried out modification and has prepared a kind of novel electrochemical sensor for nitrite detection by/rGO mixture. Fe2O3/ rGO modified electrode can provide high specific surface area, thus the medium as transfer transport improves the charge transfer between electrode surface and nitrite. The detection of nitrite is presented high sensitivity, stability, repeatability and selectivity by electrochemical sensor involved in the present invention, it is possible to be widely used in the field such as environment, food.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with enforcement, the invention will be further described.
Based on the preparation method of the highly sensitive electrochemical sensor for nitrite detection of the nano-particle modified redox graphene nanometer sheet of ferric oxide, its step is as follows:
(1) preparation of graphene oxide: 4g powdered graphite joins in the 180mL vitriol oil under 0 DEG C of condition, 32g potassium permanganate composition mixture is added under ice-water bath agitation condition, mixture dilutes with 800mL water at 50 DEG C after stirring 3h at 75 DEG C, the last hydrogen peroxide dropwise adding 50mL30%, wash after its filtration with the hydrochloric acid soln of 100mL1:10, wash with water again until the pH of solution reaches 6.3, grind into powder after the yellow solid obtained 60 DEG C of vacuum-drying 15h.
(2)Fe2O3The preparation of/rGO mixture: 40mg graphene oxide to be distributed in 200mL ethanol ultrasonic concussion 50min formed equal one solution, 0.2gFeCl2Join in above-mentioned solution with the ammoniacal liquor of 200 �� L20%, the mixture obtained in retort furnace after 90 DEG C of reacting by heating 5h, cool to room temperature gradually, after throw out is filtered out, by deionized water and washing with alcohol 7 times, then vacuum-drying 8h under 70 DEG C of conditions.
(3)Fe2O3The preparation of/rGO mixture modified electrode: first the surface of the glassy carbon electrode aluminum oxide suspension of 0.8 ��m of ol/L carries out physics polishing, then by electrode successively with second alcohol and water supersound washing 3min; 10 �� LFe2O3The surperficial final vacuum that/rGO mixture (is distributed in water, 0.5mg/mL) to drip to glassy carbon electrode is dry, can obtain Fe2O3/ rGO mixture modified electrode.
Claims (6)
1., based on the preparation method of electrochemical sensor for graphene nanometer sheet modified electrode, its step is as follows:
(1) preparation of graphene oxide: powdered graphite joins in the vitriol oil under 0 DEG C of condition, under ice-water bath agitation condition, add potassium permanganate form mixture, the mass ratio of powdered graphite and potassium permanganate is 1:6��1:10, the mass volume ratio of powdered graphite and the vitriol oil is 1:40��1:50, said mixture stirs 2��3h at 60��80 DEG C and then dilutes with water at 50 DEG C, dropwise add the hydrogen peroxide of 30%, wash after its filtration with the hydrochloric acid soln of more than 100mL 1:10, wash with water until the pH of solution reaches 6.3 again, grind into powder after the yellow solid obtained 55��80 DEG C of vacuum-drying 12��20h,
The unit of described powdered graphite and the vitriol oil is respectively g, mL;
(2)Fe2O3The preparation of/rGO mixture: 20��40mg graphene oxide is distributed in 80��120mL ethanol ultrasonic concussion 50��120min and is formed the solution of stable homogeneous, adds FeCl2With 25% ammoniacal liquor in above-mentioned solution, FeCl2With the ammoniacal liquor of 25% and the ratio of above-mentioned solution it is: 1:1:1000, the mixture obtained is 90��110 DEG C of reacting by heating 5��8h cool to room temperature gradually in retort furnace, throw out filter out after by deionized water and washing with alcohol 7��10 times, then vacuum-drying 7��12h under 50��70 DEG C of conditions;
Described FeCl2, 25% ammoniacal liquor, graphene oxide be distributed in ethanol formed Solution Unit be respectively g, mL, mL;
(3)Fe2O3The preparation of/rGO mixture modified electrode: the surface aluminum oxide suspension of glassy carbon electrode carries out physics polishing, then by electrode successively with second alcohol and water supersound washing 3��8min, get 10 �� LFe2O3/ rGO mixture, is distributed in water, is mixed with the solution that concentration is 0.5mg/mL, and the surperficial final vacuum dripping to glassy carbon electrode is dry, can obtain Fe2O3/ rGO mixture modified electrode;
The concentration of described aluminum oxide suspension is 0.6��0.9 ��m of ol/L.
2. the preparation method of electrochemical sensor according to claim 1, it is characterised 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, it is characterised in that: described in step (1), the mass volume ratio of powdered graphite and the vitriol oil is 1:45.
4. the preparation method of electrochemical sensor according to claim 1, it is characterised in that: grind into powder after the 60 DEG C of vacuum-drying 15h of yellow solid described in step (1).
5. the preparation method of electrochemical sensor according to claim 1, it is characterised in that: the time of the described ultrasonic concussion of step (2) is 50min.
6. the preparation method of electrochemical sensor according to claim 1, it is characterised in that: the concentration of step (3) described aluminum oxide suspension is: 0.8 ��m of ol/L.
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| CN104634848A (en) * | 2015-01-25 | 2015-05-20 | 浙江大学 | Nitrite electrochemical sensor and manufacturing method thereof |
| 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 |
| 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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|---|---|---|---|---|
| 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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|---|---|---|---|---|
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Non-Patent Citations (4)
| Title |
|---|
| Electro-reduced graphene oxide film modified glassy carbon electrode as an electrochemical sensor for sibutramine;Nagappa L.Teradal等;《Analytical Methods》;20131231;第5卷(第24期);第7090-7095页 * |
| Nanocomposites of hematite (a-Fe2O3) nanospindles with crumpled reduced graphene oxide nanosheets as high-performance anode material for lithiumion batteries;Song Bai等;《RSC Adv.》;20121231;第2卷;第10977–10984页 * |
| Nanostructured Reduced Graphene Oxide/Fe2O3 Composite As a High-Performance Anode Material for Lithium Ion Batteries;Xianjun Zhu等;《acsnano》;20110328;第5卷(第4期);第3333–3338页 * |
| 纳米Fe3O4/石墨烯电极材料制备及电化学性能研究;胡爱平;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20131215(第12期);第1-119页 * |
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