CN106000381B - A kind of graphene package zinc oxide three-dimensional composite material catalyst and its preparation method and application - Google Patents
A kind of graphene package zinc oxide three-dimensional composite material catalyst and its preparation method and application Download PDFInfo
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- CN106000381B CN106000381B CN201610435909.9A CN201610435909A CN106000381B CN 106000381 B CN106000381 B CN 106000381B CN 201610435909 A CN201610435909 A CN 201610435909A CN 106000381 B CN106000381 B CN 106000381B
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Abstract
The present invention relates to a kind of graphenes to wrap up zinc oxide three-dimensional composite material catalyst and its preparation method and application, and the mass percent of zinc oxide is 66-70% in the three-dimensional composite material catalyst；The zinc oxide of graphene coated is three-dimensional fusiform in the composite catalyst.Preparation method includes：Zinc foil is immersed in graphene oxide water solution, hydro-thermal reaction 0.5-1 hours at 80-100 DEG C, ultrasonic vibration, washing, it is dry to get.The modification of gained composite material builds electrochemical sensor in glassy carbon electrode surface, directly applies to the Sensitive Detection of chloramphenicol, Monitoring lower-cut is up to 0.5 μM.The present invention is easy to operate, and quickly prepared three-dimensional composite material can be applied to the electrochemical sensing of chloramphenicol, have the characteristics that high sensitivity, stability are good, reusable, have potential application foreground in electrochemica biological sensor.
Description
Technical field
The invention belongs to the preparation of catalyst material and electrochemical sensor field, more particularly to a kind of graphene wraps up oxygen
Change zinc three-dimensional composite material catalyst and preparation method and application.
Background technology
Electrochemical sensor is a kind of variation based on electrochemical signals such as current potential, electric current, resistance etc. in chemical sensor
To detect the sensitive and simple method of material concentration.Have the advantages that be easy to automation, miniaturization and intelligentized.And electro-catalysis
Agent is then the critical material in electrochemical sensor, therefore develops the preparation method for the composite material elctro-catalyst efficiently and stablized
With important scientific meaning and application value.Inertia is modified using semiconductor nano material (such as graphene, metal oxide)
The electrochemical sensor that electrode surface is constructed can further improve sensitivity, selectivity and stability of analysis method etc..
Chloramphenicol has high antibacterial activity and low cost, since generation nineteen fifty, has been widely used in treating animal biography
The antibiotic medicine caught an illness.But research finds that the abuse of chloramphenicol can lead to alpastic anemia, cardiovascular collapse, leukaemia
With the diseases such as grey baby's syndrome, therefore the detection method of exploitation chloramphenicol receives to monitor the service condition of antibiotic in recent years
People pay close attention to.
Invention content
Technical problem to be solved by the invention is to provide a kind of graphenes to wrap up zinc oxide three-dimensional composite material catalyst
And its preparation method and application, it is prepared for graphene coated fusiform zinc oxide using zinc foil hydrothermal reduction graphene oxide one-step method
Three-dimensional composite material catalyst, both had the characteristics that it is simple and quick, environmentally protective, can also can be improved and to construct outside prepared by magnanimity
Electrochemical sensor sensitivity, stability and durability, and may be directly applied to measure chloramphenicol concentration.
A kind of graphene of the present invention wraps up zinc oxide three-dimensional composite material catalyst, the three-dimensional composite material catalyst
The mass percent of middle zinc oxide is 66-70%；The zinc oxide of graphene coated is three-dimensional shuttle in the composite catalyst
Shape, a length of 300-1000nm, width 50-300nm.
A kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst of the present invention, including：
Zinc foil is immersed in graphene oxide water solution, hydro-thermal reaction 0.5-1 hours at 80-100 DEG C, surface is had
The zinc foil ultrasonic vibration of black precipitate washs, dry, obtains graphene coated zinc oxide three-dimensional composite material catalyst (powdery
Object)；Wherein, the mass percent of zinc oxide is 66-70% in three-dimensional composite material catalyst；In the composite catalyst
The zinc oxide of graphene coated is three-dimensional fusiform.
A concentration of 0.5~1mg/mL of the graphene oxide water solution；Zinc foil thickness is 0.5~1mm.
The area of the zinc foil and the volume ratio of graphene oxide solution are 3cm2：20mL.
The graphene oxide preparation method includes：By 0.5-1g graphite powders and commercially available concentrated nitric acid (1.5-3mL) and dense sulphur
Sour (15-30mL) is mixed in ice-water bath, is added with stirring 2-5g potassium permanganate, is gradually warming up to 45 DEG C and 90 DEG C each reactions 1
Hour, it is cooling, it stands overnight；By gained washing of precipitate, it is drying to obtain graphene oxide solid.
The graphite, potassium permanganate, the concentrated sulfuric acid and concentrated nitric acid ratio be 1g:5g:30mL:3mL.
The washing is that ethyl alcohol washs 3 times.
The graphene oxide 10-30mg ultrasounds are dispersed in 20-60mL distilled water for 30 minutes, are transferred them to
In 50-100mL reaction kettles, and zinc foil is immersed in above-mentioned graphene oxide water solution, is placed in baking oven (specific at 80-100C °
Value) under keep the temperature 0.5-1h redox graphenes；It is multiple to obtain graphene coated zinc oxide three-dimensional for centrifuge washing after cooling, drying
Condensation material catalyst 3DRGO-ZnO.
The application of the graphene package zinc oxide three-dimensional composite material catalyst of the present invention, applied to preparing electrochemical sensing
Device detects chloramphenicol and optimizing detection condition.
Ranging from 1-113 μM of the working concentration of the electrochemical sensor, Monitoring lower-cut are 0.5 μM, can be directly exposed to
It is preserved in air.
It is described prepare electrochemical sensor detection chloramphenicol include：
(1) in ethanol by graphene coated zinc oxide three-dimensional composite material catalyst ultrasonic disperse, dispersion liquid is obtained；So
After be transferred to glass-carbon electrode active surface, it is dry, obtain the glass of graphene coated zinc oxide three-dimensional composite material catalyst modification
Carbon electrode；
(2) using the glass-carbon electrode modified in step (1) as working electrode, saturated calomel electrode is reference electrode, and platinum filament is
Auxiliary electrode, test bottom liquid are phosphate buffer；Using method differential pulse voltammetry volt-ampere analysis；By molten to chloramphenicol standard
Liquid is tested, and using chloramphenicol concentration as abscissa, current strength is ordinate, establishes standard working curve, strong by electric current
The numerical value of degree can calculate the concentration of chloramphenicol in sample.
The graphene coated zinc oxide three-dimensional composite material catalyst be ultrasonic disperse in ethanol, a concentration of 1-2mg/
ML pipettes 10-20 μ L by liquid-transfering gun and is transferred to glass-carbon electrode active surface, is passed through infrared lamp rapid draing to prepare electrochemistry
Sensor.
Phosphate buffer pH=7.4, a concentration of 5-10mM in the step (2).
Test voltage ranging from -0.4V to -0.7V in the step (2).
The present invention is quickly prepared for graphene coated zinc oxide three-dimensional composite material catalyst by hydro-thermal method, and is applied to
Construct chloramphenicol electrochemical sensor；The three-dimensional composite material method for preparing catalyst time is short, it is efficient, can mass production and
Any organic reducing agent need not be used to reduce pollution；The chloramphenicol electrochemical sensor of exploitation has high sensitivity, detection
The range of linearity is wide, stability is good and the features such as can reusing for a long time, has potential answer in non-enzymatic electrochemica biological sensor
Use foreground.
Advantageous effect
(1) reducing agent of the present invention using easy to operate and control, environment friendly and pollution-free zinc foil as graphene oxide, quickly
It restores while coating fusiform zinc oxide and form composite material, it can magnanimity preparation；
(2) present invention using can magnanimity prepare graphene coated zinc oxide three-dimensional composite material modified electrode, improve
The active area and detection sensitivity of electrode；
(3) it is mould that the electrochemical sensor constructed the present invention is based on graphene coated zinc oxide three-dimensional composite material measures chlorine
Element has the characteristics that high sensitivity, the range of linearity are wide, stability is good and reusable.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of graphene coated zinc oxide three-dimensional composite material catalyst in embodiment 2；
Fig. 2 is the differential pulse voltammetry volt-ampere curve that Different electrodes respond chloramphenicol in embodiment 3；
Fig. 3 is the electrochemical sensing based on graphene coated zinc oxide three-dimensional composite material catalyst preparation in embodiment 3
The differential pulse voltammetry volt-ampere curve (a) that device responds various concentration chloramphenicol, and accordingly between current strength and chloramphenicol concentration
Linear relationship (b)；
Fig. 4 is the electrochemical sensing based on graphene coated zinc oxide three-dimensional composite material catalyst preparation in embodiment 4
Device, which is exposed to, preserves one month stability in air.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The preparation of graphene oxide.
1g graphite powders are mixed with commercially available concentrated nitric acid (3mL) and the concentrated sulfuric acid (30mL) in ice-water bath, 2- is added with stirring
5g potassium permanganate is warming up to 45 DEG C and reacts 1 hour, then is warming up to 90 DEG C and reacts 1 hour, is cooled to room temperature, stands overnight；By institute
Must precipitate make to be washed with distilled water 3 times, ethyl alcohol wash 1 time after in 40C ° dry 24 hours to get graphene oxide solid.
Embodiment 2
The preparation of graphene coated zinc oxide three-dimensional composite material catalyst (3DRGO-ZnO).
It weighs graphene oxide 30mg prepared in embodiment 1 and ultrasound is dispersed in 60mL distilled water in 30 minutes
In, it transfers them in 100mL reaction kettles, and zinc foil is immersed in above-mentioned graphene oxide water solution, is placed in baking oven
1h redox graphenes are kept the temperature under 100C °；Zinc metal sheet is transferred in clean beaker with tweezers after being cooled to room temperature, is added
20mL distilled water sonic oscillations, acquired solution centrifugation, solid are washed with distilled water 3 times, and ethyl alcohol washs 1 time and is placed on 40C ° of baking oven
Middle drying 24 hours, as shown in TEM figures (Fig. 1), obtained solid are graphene coated zinc oxide three-dimensional composite material catalyst
3DRGO-ZnO。
As a comparison, not zincification foil is prepared for graphene under similarity condition using hydrazine hydrate hydrothermal reduction graphene oxide
Catalyst material (RGO).
Embodiment 3
Electrochemical sensor prepares and the quantitative determination to chloramphenicol.
Weigh graphene coated zinc oxide three-dimensional composite material catalyst 3DRGO-ZnO 2mg prepared in embodiment 2
And ultrasound is dispersed in 1mL absolute ethyl alcohols for 5 minutes, compound concentration is the catalyst dispersion of 2.0mg/mL, uses liquid-transfering gun
10 μ L dispersion liquids are shifted to the active face of clean glass-carbon electrode and are dried to get electrochemical sensor using infrared lamp.Respectively
Using saturated calomel electrode as reference electrode, platinum filament is auxiliary electrode, and phosphate buffer solution (pH=7.4) is to measure medium ,-
0.4V to -0.7V is measured under voltage range, and Electrochemical Scanning is carried out to chloramphenicol standard solution using Differential Pulse Voltammetry method,
It can be seen that graphene coated zinc oxide three-dimensional composite material catalyst 3DRGO-ZnO is compared with grapheme material (RGO) and naked glass carbon electricity
Pole (GCE) has strongest current-responsive intensity (Fig. 2), shows that 3DRGO-ZnO prepared by the present invention is greatly improved detection
Sensitivity.
Further pass through gradient sample introduction, recording voltage-current curve, it is seen that with the increase of chloramphenicol concentration, response current
Intensity also increases (Fig. 3 a).Chloramphenicol concentration is located measurement current value with -0.56V to be fitted using software Origin8, in chlorine
A linear work curve is obtained within the scope of a concentration of 1-113 μM of mycin, linear regression constant is 0.9978, equation of linear regression y
=-0.11x-8.53, y represent current strength, and x represents chloramphenicol concentration, and Monitoring lower-cut is 0.5 μM.Measurement can be passed through accordingly
The concentration (Fig. 3 b) of chloramphenicol is calculated in current strength.
Embodiment 4
The electrochemical gaging of chloramphenicol concentration in the stability and actual sample of electrochemical sensor.
The electrochemical sensor prepared in embodiment 3 is directly exposed to preserve one month in air, 50 were tested every 5 days
The response current intensity of the chloramphenicol standard solution of μm ol/L.As shown in figure 4, being used continuously one month, current strength only decays
About 0.6%, it is seen that the electrochemical sensor is with good stability and reusability.
The electrochemical gaging of chloramphenicol concentration, specific practice are as follows in actual sample：By commercially available chloramphenicol ophthalmic solution PBS
(pH=7.4) current value y is directly measured according to step in embodiment 3 after buffer solution dilutes 300 times, substitutes into equation of linear regression
It is 26 μM that Chloramphenicol In Chloramphenicol Eye Drops content x can be calculated in y=-0.11x-8.53, and measurement standard deviation is three times
2%, it is equivalent to a concentration of 7.8mM of chloramphenicol in eye drops, it is consistent with the concentration 7.7mM results that producer provides, it is seen that the electricity
Chemical sensor, which has, is applied to foreground in actual sample analysis.
Claims (8)
1. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst, including：
Zinc foil is immersed in graphene oxide water solution, hydro-thermal reaction 0.5-1 hours at 80-100 DEG C, ultrasonic vibration, washing,
It is dry, obtain graphene coated zinc oxide three-dimensional composite material catalyst；Wherein, zinc oxide in three-dimensional composite material catalyst
Mass percent is 66-70%；The zinc oxide of graphene coated is three-dimensional fusiform in composite catalyst.
2. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 1,
It is characterized in that, a concentration of 0.5~1mg/mL of the graphene oxide water solution；Zinc foil thickness is 0.5~1mm.
3. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 1,
It is characterized in that, the area of the zinc foil and the volume ratio of graphene oxide solution are 3cm2：20mL.
4. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 1,
It is characterized in that, the washing is that ethyl alcohol washs 3 times.
5. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 1,
It is characterized in that, the graphene coated zinc oxide three-dimensional composite material catalyst is mould applied to electrochemical sensor detection chlorine is prepared
Element and optimizing detection condition.
6. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 5,
It is characterized in that, ranging from 1-113 μM of the working concentration of the electrochemical sensor, Monitoring lower-cut is 0.5 μM.
7. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 5,
It is characterized in that, the electrochemical sensor detection chloramphenicol for preparing includes：
(1) in ethanol by graphene coated zinc oxide three-dimensional composite material catalyst ultrasonic disperse, dispersion liquid is obtained；Then turn
Glass-carbon electrode active surface is moved to, it is dry, obtain the glass carbon electricity of graphene coated zinc oxide three-dimensional composite material catalyst modification
Pole；
(2) using the glass-carbon electrode modified in step (1) as working electrode, saturated calomel electrode is reference electrode, and platinum filament is auxiliary
Electrode, test bottom liquid are phosphate buffer；Using differential pulse voltammetry volt-ampere analysis, standard working curve is established, is calculated
The concentration of chloramphenicol in sample.
8. a kind of preparation method of graphene package zinc oxide three-dimensional composite material catalyst according to claim 7,
It is characterized in that, phosphate buffer pH=7.4, a concentration of 5-10mM in the step (2).
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| CN106596674B (en) * | 2016-12-19 | 2019-02-12 | 哈尔滨理工大学 | A kind of preparation of zinc oxide nano rod-graphene nanometer sheet composite material |
| CN110627108A (en) * | 2019-09-27 | 2019-12-31 | 东华大学 | Zinc oxide/reduced graphene oxide composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430401A (en) * | 2011-09-20 | 2012-05-02 | 上海大学 | Nanometer ZnO/graphene photo-catalyst and preparation method thereof |
| CN102658108A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing photocatalytic filtering membrane based on graphene/semiconductor by an electrospinning method |
| JP2015142882A (en) * | 2014-01-31 | 2015-08-06 | 博 久保田 | Hydrogen formation catalyst |
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| US20140183415A1 (en) * | 2012-12-31 | 2014-07-03 | Cheil Industries Inc. | Graphene-Based Composite and Method of Preparing the Same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430401A (en) * | 2011-09-20 | 2012-05-02 | 上海大学 | Nanometer ZnO/graphene photo-catalyst and preparation method thereof |
| CN102658108A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing photocatalytic filtering membrane based on graphene/semiconductor by an electrospinning method |
| JP2015142882A (en) * | 2014-01-31 | 2015-08-06 | 博 久保田 | Hydrogen formation catalyst |
Non-Patent Citations (3)
| Title |
|---|
| One-pot facile fabrication of graphene-zinc oxide composite and its enhanced sensitivity for simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid;Xuan Zhang等;《Sensors and Actuators B:Chemical》;20151228;第227卷;第488-496页 * |
| ZnO/氧化石墨烯的制备及其对亚硝酸盐的光催化降解;张永勇等;《化工环保》;20141231;第34卷(第5期);全文 * |
| 石墨烯_氧化锌纳米棒复合材料的超声法制备及其光催化性能;陈洪亮等;《功能材料》;20141231;第45卷(第6期);全文 * |
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