CN105181770A - Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method - Google Patents
Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method Download PDFInfo
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- CN105181770A CN105181770A CN201510568873.7A CN201510568873A CN105181770A CN 105181770 A CN105181770 A CN 105181770A CN 201510568873 A CN201510568873 A CN 201510568873A CN 105181770 A CN105181770 A CN 105181770A
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Abstract
The invention relates to a preparation method of a manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of the preparation method, which belong to the technical field of electrochemical analysis and detection. The preparation method and the application thereof are mainly characterized in that the photo-reduction capability of nano titanium dioxide is utilized to prepare a manganese dioxide/graphene/titanium dioxide sensing material. The preparation method of the modified glassy carbon electrode comprises the following steps of firstly, mixing a graphene oxide solution and the titanium dioxide, performing uniform ultrasonic dispersion on a mixture, and reducing with ultraviolet light; dropping a potassium permanganate solution into the reduced graphene solution, and performing photo-reduction to obtain a manganese dioxide/graphene/titanium dioxide-modified carbon material; then dispensing the manganese dioxide/graphene/titanium dioxide-modified carbon material in a glassy carbon electrode and drying to obtain the manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode. The invention relates to a novel photo-reduction preparation method which can be used for direct and rapid electrochemical determination of the hydrogen peroxide, and has the advantages of high catalytic activity, good stability, high sensitivity and the like.
Description
Technical field
The present invention relates to a kind of preparation method and the application thereof that are used as the manganese dioxide/Graphene/titania modified glassy carbon electrode of hydrogen peroxide Electrochemical Detection; Belong to electrochemical analysis detection technique field.
Background technology
Hydrogen peroxide, is hydrogen peroxide again, is colourless transparent liquid, is a kind of strong oxidizer, can with water arbitrarily than mixing.Its aqueous solution is applicable to medical wound sterilization and environment disinfected and food sterilization.Pure hydrogen peroxide is nattier blue thick liquid, explosive strong oxidizer.Hydrogen peroxide self does not fire, but can react with combustible and release amount of heat and atmosphere and cause Fire explosion.Hydrogen peroxide is the most stable when pH value is 3.5 ~ 4.5, very easily decomposes in alkaline solution, also can decompose when chance high light, particularly short-wave ray irradiate.When being heated to more than 100 DEG C, start sharply to decompose.It and many organism such as sugar, starch, alcohols, petroleum products etc. form explosive mixture, at shock, are heated or can blast under electric spark effect.Can decompose and cause exploding rapidly after hydrogen peroxide contacts with many mineral compounds or impurity, release a large amount of heats, oxygen and water vapor.Most of heavy metal (as copper, silver, lead, mercury, zinc, cobalt, nickel, chromium, manganese etc.) and oxide thereof and salt are all active catalysts, and dust, cigarette ash, carbon dust, iron rust etc. also can accelerated decomposition.The hydrogen peroxide of concentration more than 74%, in the closed container with suitable incendiary source or temperature, can produce gas phase blast.High-strength hydrogen peroxide has strong corrosivity.Suck this product steam or mist has intense stimulus to respiratory tract.It is even blind that the direct contact liq of eye can cause irreversible damage.Suffering from abdominal pain, have a chest pain, having difficulty in breathing, vomitting appears in oral ingestion, momentary motion and sensory disturbance, body temperature rising etc.There is vision disorder, epileptic spasm, paresis in single cases.Hydrogen peroxide is widely used in the fields such as food, medicine, health and war industry as one, and therefore its concentration of Accurate Determining is significant.At present, because electrochemical method determining hydrogen peroxide possesses economy, the feature such as simple, quick, and extensive concern is received.
Graphene (Graphene) be a kind of by carbon atom with
sp2hybrid orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness, its thickness only has 0.3354nm, this structure is the performance that Graphene has many excellences, as high Young modulus and carrier mobility, huge specific surface area, high light transmittance, excellent conductivity and thermal conductivity etc.The two-dimensional structure of Graphene can accelerated charge transfer velocity greatly, can provide more catalytic reaction activity site, improve analytical performance.
In general titania has three kinds of crystal structures, respectively: Detitanium-ore-type (Anatase), and rutile-type (Rutile), and brookite type (Brookite).Titania is a kind of excellent semiconductor, and the illumination being less than 387nm when wavelength is penetrated and the electronics in titania valence band can be excited at that time to make it transit to conduction band get on.At this moment in valence band, just creating photohole, conduction band is then light induced electron.Light induced electron and hole have very strong reduction-oxidation ability, to such an extent as to gunslinging free radical and negative oxygen ion can be produced with the water and oxygen reaction being adsorbed on titanium deoxid film surface, these materials be easy to titania around organism or reducing substances react, it decomposes the most at last.Utilize the mode of photo-reduction to prepare manganese dioxide/redox graphene/titania sensing material and have simple synthetic method, material activity is high, can not introduce the advantages such as impurity.
Summary of the invention
The present invention relates to a kind of preparation method and the application thereof that are used as the manganese dioxide/Graphene/titania modified glassy carbon electrode of hydrogen peroxide Electrochemical Detection
A kind of preparation method being used as the modified glassy carbon electrode of hydrogen peroxide Electrochemical Detection of the present invention, is characterized in that having following process and step:
A. the process of glass-carbon electrode: get a glass-carbon electrode, the polishing plate being 0.05 μm of alundum (Al2O3) powder is polished smooth to electrode surface containing diameter, and ultrasonic cleaning 3min successively in ultrapure water, absolute ethyl alcohol and ultrapure water, dries up for subsequent use respectively.
B. the preparation of manganese dioxide/Graphene/titania: getting 5mL concentration is 1mg/mL graphene oxide water solution and 1mg titania (P25), ultrasonicly mixes, and uses UV-irradiation 1h, adds 0.6mgKMnO
4mix UV-irradiation 30min, keep in Dark Place.
C. the preparation of glass carbon modified electrode: toast 5min under the glass-carbon electrode handled well is placed on infrared lamp, then get the manganese dioxide/Graphene/titania 5uL prepared and evenly drip and be coated on glass-carbon electrode, toast dry under being placed on infrared lamp.
Be used as purposes and the using method of the manganese dioxide/Graphene/titania modified glassy carbon electrode of hydrogen peroxide Electrochemical Detection, its purposes is: this modified glassy carbon electrode can be directly used in the electrochemical gaging of concentration of hydrogen peroxide as sensor; Using method and assay method as follows: the glass-carbon electrode that manganese dioxide/Graphene/titania is modified as working electrode, saturated calomel electrode as contrast electrode, platinum plate electrode as auxiliary electrode, composition three-electrode system; During electrochemical gaging, described modified electrode is placed in phosphate buffered solution that stir with constant rate of speed, pH=8.0; In 0 ~ 1.0V potential window cyclic voltammetry be scanned up to figure stable after, the electrochemical behavior of research hydrogen peroxide on manganese dioxide/Graphene/titania modified electrode surface.The modified electrode that experiment obtains has good electrocatalysis to hydrogen peroxide.In concentration 1.0 × 10
-6to 4.0 × 10
-3molL
-1in scope, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, minimum detectability is 0.3 × 10
-6molL
-1, its linearly dependent coefficient R=0.9995, utilizes this linear relationship and corresponding linear equation, the concentration of its mensuration hydrogen peroxide available.
Modified electrode in the present invention is a kind of electrochemical sensor of novelty, its preparation method is simple, quick, easy to operate, modifies mild condition, and the direct fast electrochemical that can be used for hydrogen peroxide measures, have that catalytic activity is high, good stability, sensitivity advantages of higher.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope phenogram of manganese dioxide/Graphene in the present invention/titania carbon modified electrode.
Fig. 2 is hydrogen peroxide time current figure and linear relationship chart on manganese dioxide/Graphene/titania modified glassy carbon electrode of variable concentrations in the present invention.
Embodiment
After now specific embodiments of the invention being described in.
Preparation process in embodiment and step as follows:
(1) process of glass-carbon electrode: get a glass-carbon electrode, the polishing plate being 0.05 μm of alundum (Al2O3) powder is polished smooth to electrode surface containing diameter, and ultrasonic cleaning 3min successively in ultrapure water, absolute ethyl alcohol and ultrapure water, dries up for subsequent use respectively.
(2) manganese dioxide/Graphene/titania preparation: getting 5mL concentration is 1mg/mL graphene oxide water solution and 1mg titania (P25), ultrasonicly mixes, and uses UV-irradiation 1h, adds 0.6mgKMnO
4mix, then UV-irradiation 30min, keep in Dark Place.
(3) preparation of glass carbon modified electrode: toast 5min under the glass-carbon electrode handled well is placed on infrared lamp, then get the manganese dioxide/Graphene/titania 5uL prepared and evenly drip and be coated on glass-carbon electrode, is baked to dry under being placed on infrared lamp.
Manganese dioxide/Graphene/titania modified glassy carbon electrode is as follows as the assay method of electrochemical sensor to concentration of hydrogen peroxide:
The glass-carbon electrode modified by manganese dioxide/Graphene/titania is as working electrode, and saturated calomel electrode as auxiliary electrode, forms three-electrode system as contrast electrode, platinum plate electrode; During electrochemical gaging, described modified electrode is placed in phosphate buffered solution that stir with constant rate of speed, pH=8.0; In 0 ~ 1.0V potential window cyclic voltammetry be scanned up to figure stable after, the electrochemical behavior of research hydrogen peroxide on manganese dioxide/Graphene/titania modified electrode surface.The modified electrode that experiment obtains has good electrocatalysis to hydrogen peroxide.In concentration 1.0 × 10
-6to 4.0 × 10
-3molL
-1in scope, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, minimum detectability is 0.3 × 10
-6molL
-1, its linearly dependent coefficient r=0.9995, utilizes this linear relationship curve and corresponding linear equation, the concentration of its mensuration hydrogen peroxide available.
electrochemical gaging
Under optimum controlling condition, the glass-carbon electrode that manganese dioxide/Graphene/titania is modified to the oxidation peak current value of variable concentrations hydrogen peroxide as shown in Figure 2.As seen from the figure, oxidation peak current (I
p) with its concentration C 1.0 × 10
-6~ 4.0 × 10
-3molL
-1good linear relationship is had in scope.Modified electrode prepared by the inventive method, stability is high, favorable reproducibility, and selectivity is good.For the inorganic metal ion that may exist and organic substance, as CO
3 2-, NO
3 -, CH
3cOO
-, Cl
-, K
+, Na
+, glucose, uric acid, ascorbic acid etc., can't produce obvious interference.
Claims (2)
1. a preparation method for the glass-carbon electrode that the manganese dioxide/Graphene/titania being used as hydrogen peroxide Electrochemical Detection is modified, is characterized in that having following process and step:
A. the process of glass-carbon electrode: get a glass-carbon electrode, the polishing plate being 0.05 μm of alundum (Al2O3) powder is polished smooth to electrode surface containing diameter, and ultrasonic cleaning 3min successively in ultrapure water, absolute ethyl alcohol and ultrapure water, dries up for subsequent use respectively;
B. the preparation of manganese dioxide/Graphene/titania: getting 5mL concentration is 1mg/mL graphene oxide water solution and 1mg titania (P25), ultrasonicly mixes, and uses UV-irradiation 1h, adds 0.6mgKMnO
4mix, then UV-irradiation 30min, keep in Dark Place;
C. the preparation of glass carbon modified electrode: toast 5min under the glass-carbon electrode handled well is placed on infrared lamp, then get the manganese dioxide/Graphene/titania 5uL prepared and evenly drip and be coated on glass-carbon electrode, is baked to dry under being placed on infrared lamp.
2. be used as purposes and the using method of the manganese dioxide/Graphene/titania modified glassy carbon electrode of hydrogen peroxide Electrochemical Detection, its purposes is: this modified glassy carbon electrode can be directly used in the electrochemical gaging of concentration of hydrogen peroxide as sensor; Using method and assay method as follows: the glass-carbon electrode that manganese dioxide/Graphene/titania is modified as working electrode, saturated calomel electrode as contrast electrode, platinum plate electrode as auxiliary electrode, composition three-electrode system; During electrochemical gaging, described modified electrode is placed in phosphate buffered solution that stir with constant rate of speed, pH=8.0; In 0 ~ 1.0V potential window cyclic voltammetry be scanned up to figure stable after, the electrochemical behavior of research hydrogen peroxide on manganese dioxide/Graphene/titania modified electrode surface, the modified electrode that experiment obtains has good electrocatalysis to hydrogen peroxide, in concentration 1.0 × 10
-6to 4.0 × 10
-3molL
-1in scope, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, minimum detectability is 0.3 × 10
-6molL
-1, its linearly dependent coefficient R=0.9995, utilizes this linear relationship curve and corresponding linear equation, the concentration of its mensuration hydrogen peroxide available.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107064252A (en) * | 2017-03-24 | 2017-08-18 | 广东工业大学 | A kind of hydrogen peroxide sensor and preparation method and application |
| CN112213289A (en) * | 2019-07-09 | 2021-01-12 | 苏州复氧环保科技有限公司 | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof |
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| CN112213289A (en) * | 2019-07-09 | 2021-01-12 | 苏州复氧环保科技有限公司 | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof |
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