CN107843627A - Electrochemical sensor for practolol detection and preparation method thereof - Google Patents
Electrochemical sensor for practolol detection and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of electrochemical sensor for practolol detection and preparation method thereof, sensor of the invention is to be based on CoFe2O4Magnetic nano-particle modifies the electrochemical sensor of nano-graphene.Compared with other electrochemical sensors for practolol detection, it has the advantages of high sensitivity, good selectivity and low test limit etc. are notable to the novel sensor of the present invention, and has highly stable electrocatalysis characteristic in oxidation of the electrode surface to practolol of modification.
Description
Technical field
The present invention relates to electrochemical sensor technology field, more particularly to a kind of electrochemical sensing for practolol detection
Device and preparation method thereof.
Background technology
Graphene is not only one kind most thin in known materials, also unusual rigid；As simple substance, it is passed at room temperature
The speed for passing electronics is all faster than known conductor.Graphene is two dimension (plane) crystal, and composition single layer of carbon atom is arranged in honeybee
Nest network and hexatomic ring, it is two-dimentional carbon structure.Conceptually graphene can be regarded as an indefinite extension two dimension aromatic series and divide greatly
Son.
Structure is very special on an atomic scale for graphene.Connection in graphene between each carbon atom is very flexible, when
When applying external mechanical force, carbon atom face, so that carbon atom need not be rearranged to adapt to external force, is also just protected with regard to flexural deformation
Stability Analysis of Structures is held.The lattice structure of this stabilization makes carbon atom have outstanding electric conductivity.And the electronics in graphene exists
When being moved in track, it will not be scattered because of lattice defect or introducing foreign atom.Because interatomic force is very strong,
Under normal temperature, even if surrounding carbon atom telescopes, the interference that the electronics in graphene is subject to is also very small.Spinel-type magnetic is received
Rice corpuscles (MFe2O4, M=Mn, Co, Ni, Zn) modification NGS can significantly improve its optics, magnetic and chemical property.Magnetic
NGS has very extensive application in fields such as magnetic data storage, microwave absorbing material and drug deliveries.
Electrochemical method detection has become a kind of non-in environmental monitoring, medicine and biotechnology and industrial stokehold
Often important method.Chemically modified electrode is absorbing instrument in the electrochemistry trace detection of many materials.Special work
The critically important aspect that chemically modified electrode is applied in work is exactly that the trim of most convenient is selected according to analyte, because
The sensitivity of electrochemical response and selectivity depend on the characteristic of trim.
Practolol (antazoline hydrochloride) is a kind of for treating available for room, VPB, paroxysmal tachycardia
Deng a kind of medicine.So far, a variety of methods, such as liquid extraction, fluorescence method, high performance liquid chromatography-electron ion mass spectrum connection
Usage, HPLC- UV detection method and voltammetry, it is already used to detect practolol.Nano-graphene it is unique
Electric property shows its electron transfer reaction that can be used to adjust electro-active species in solution as the decorative material of electrode.
The content of the invention
For overcome the deficiencies in the prior art, received it is an object of the invention to provide one kind based on magnetic nano-particle modification
Electrochemical sensor emergence for being used for practolol detection of rice graphene and preparation method thereof.Preparation method of the present invention is simple, obtains
To electrochemical sensor be used for detect gains in depth of comprehension timing, detection speed is fast, and testing result is accurate, high sensitivity.
Technical scheme is specifically described as follows.
The present invention provides a kind of preparation method of the electrochemical sensor for practolol detection, comprises the following steps that：
(1) preparation of nano-graphene modified electrode
By nano-graphene respectively and HNO3, HCl and H2SO415~18h of solution mixing backflow；Then, nano-graphene is washed
Centrifuged and in drying at room temperature after washing；Then by nano-graphene after acidifying, ultrasonic vibration obtains a nanometer stone in dimethylformamide
Black alkene modified electrode suspension；Again by nano-graphene modified electrode hanging drop to the table of the glassy carbon electrode by pretreatment
Dried behind face in 70~85 DEG C of thermal current, obtain active nano graphene modified electrode；
(2) preparation based on magnetic nano-particle modification nano-graphene electrode
Active nano graphene modified electrode is added in citric acid or oxalic acid solution and ultrasound, obtained suspension with
Co(NO3)2·6H2O and Fe (NO3)3·9H2O solution is mixed, and the pH of mixed solution is adjusted to 8.5~9.5 with azanol, then 40
15~30h is stirred at a temperature of~55 DEG C and completes reaction；Obtained product is forged in inert atmosphere at a temperature of 450~650 DEG C
4~6h is burnt, obtains powder；Suspension finally is made in powder, on hanging drop to glassy carbon electrode, will obtain being used for practolol
The electrochemical sensor of detection.
In the present invention, in step (1), HNO3, HCl and H2SO4Solution concentration is 5~6mol/L, return time is 15~
18h, nano-graphene and HNO3The mass volume ratio of solution is 1：4~1：5g/mL.
In the present invention, in step (1), the mass ratio of nano-graphene and dimethylformamide is 160:3~75:1.
In step (1), the mass ratio of nano-graphene and dimethylformamide is 500:9~70:1.
In the present invention, in step (1), the pre-treatment step of glassy carbon electrode is as follows：First with 0.035~0.15 μm of oxidation
Aluminium powder polishing, then in the in the mixed solvent supersound washing of ethanol/water, fully washed with redistilled water again afterwards.
In the present invention, in step (2), active nano graphene modified electrode and the quality volume of citric acid or oxalic acid solution
Than for 1：8~1: 18g/mL.
In the present invention, in step (2), the concentration of azanol is 0.1~0.2mol/L.
In the present invention, in step (2), the Co (NO3)2·6H2O and Fe (NO3)3·9H2In O, Co: Fe mol ratio=
2∶3；Active nano graphene modified electrode and Co (NO3)2·6H2O mass ratio is 1:4~1:6.
In the present invention, in step (2), calcining heat is 500~600 DEG C.
The present invention also provides the electrochemical sensor for being used for practolol detection that a kind of above-mentioned preparation method obtains.
Compared to the prior art, the beneficial effects of the present invention are：
In sensor of the present invention, magnetic nanoparticle-nano-graphene composite quilt in electrochemical method
As a kind of most suitable conditioning agent.Compared with other electrochemical sensors for practolol detection, prepared is new
Sensor has the advantages of high sensitivity, good selectivity and low test limit etc. are notable.
Embodiment
In order to deepen the understanding of the present invention, with reference to implementing, the invention will be further described.
Embodiment 1
One kind is based on CoFe2O4The model electrochemical for being used for practolol detection of magnetic nano-particle modification nano-graphene
The preparation method of sensor, its step are as follows：
(1) preparation of nano-graphene (NGS) modified electrode：In order to activate NGS and remove the kish on its surface,
1.00g NGS and 8mL6.0mol/L HNO3Solution is fitted into flask the 20h that flows back.Then, after NGS is washed with deionized
Centrifuge (2200rpm) and in drying at room temperature.Then stable NGS suspension in dimethylformamide (0.18mg), NGS by existing
The in the mixed solvent supersound washing of ethanol/water (1: 1.5, v/v), fully washes ultrasonic vibration in (10mL) with deionized water again afterwards
Obtain.Glassy carbon electrode (GCE) is first standby with 0.08 μm of alumina powder polishing, washing.The NGS of 18 μ L stabilization hangs
Supernatant liquid is dried after dripping to GCE surface in 60 DEG C of thermal current.
(2)CoFe2O4The preparation of-NGS modified electrodes：1.2g activity NGS is first added to 18mL1.6mol/L citric acid
In solution and ultrasonic 18min.Obtained suspension and 24mL0.70mol/L Co (NO3)2·6H2O and 1.6mol/L Fe
(NO3)3·9H2O solution is mixed, and the pH of mixed solution is adjusted to 9.0 with 0.12mol/L oxyammonia.Obtained mixed solution is 40
DEG C stirring 22h complete reaction.Obtained product 580 DEG C of calcining 4h, obtained powder in nitrogen atmosphere are labeled as CoFe2O4-
NGS.Finally take 18 μ L CoFe2O4- NGS hanging drop is to obtaining CoFe on GCE2O4- NGS modified electrodes.
(3) electrochemical property test：The test of prepared electrochemical sensor chemical property is in electrochemical workstation
Upper progress.CoFe2O4- NGS modified electrodes are used as working electrode, and platinum electrode is used as auxiliary electrode, saturation Ag/AgCl (KCl) electrode
As reference electrode.
Embodiment 2
One kind is based on CoFe2O4The model electrochemical for being used for practolol detection of magnetic nano-particle modification nano-graphene
The preparation method of sensor, its step are as follows：
(1) preparation of nano-graphene (NGS) modified electrode：In order to activate NGS and remove the kish on its surface,
0.800g NGS and 10mL5.40mol/L HCl solution are fitted into flask the 20h that flows back.Then, NGS is washed with deionized
(2200rpm) is centrifuged afterwards and in drying at room temperature.Stable NGS suspension is by the way that at dimethylformamide (0.15mg), NGS is then
In the in the mixed solvent supersound washing of ether/water (1: 1.3, v/v), ultrasound shake in (12mL) is fully washed with deionized water again afterwards
Swing to obtain.Glassy carbon electrode (GCE) is first standby with 0.06 μm of alumina powder polishing, washing.The NGS of 12 μ L stabilization
Hanging drop in 65 DEG C of thermal current to drying behind GCE surface.
(2)CoFe2O4The preparation of-NGS modified electrodes：The oxalic acid that 1.0g activity NGS is first added to 15mL1.2mol/L is molten
In liquid and ultrasonic 18min.Obtained suspension and 20mL0.60mol/L Co (NO3)2·6H2O and 1.2mol/L Fe
(NO3)3·9H2O solution is mixed, and the pH of mixed solution is adjusted to 8.5 with 0.12mol/L oxyammonia.Obtained mixed solution is 45
DEG C stirring 24h complete reaction.Obtained product 560 DEG C of calcining 5.5h, obtained powder in argon atmosphere are labeled as CoFe2O4-
NGS.Finally take 12 μ L CoFe2O4- NGS hanging drop is to obtaining CoFe on GCE2O4- NGS modified electrodes.
(3) electrochemical property test：The test of prepared electrochemical sensor chemical property is in electrochemical workstation
Upper progress.CoFe2O4- NGS modified electrodes are used as working electrode, and platinum electrode is used as auxiliary electrode, saturation Ag/AgCl
(KCl) electrode is used as reference electrode.
Embodiment 3
One kind is based on CoFe2O4The model electrochemical for being used for practolol detection of magnetic nano-particle modification nano-graphene
The preparation method of sensor, its step are as follows：
(1) preparation of nano-graphene (NGS) modified electrode：In order to activate NGS and remove the kish on its surface,
1.200g NGS and 8mL5.80mol/L H2SO4Solution is fitted into flask the 22h that flows back.Then, NGS is washed with deionized
(2200rpm) is centrifuged afterwards and in drying at room temperature.Stable NGS suspension is by the way that at dimethylformamide (0.16mg), NGS is then
In the in the mixed solvent supersound washing of ether/water (1: 1.1, v/v), ultrasound shake in (10mL) is fully washed with deionized water again afterwards
Swing to obtain.Glassy carbon electrode (GCE) is first standby with 0.04 μm of alumina powder polishing, washing.The NGS of 10 μ L stabilization
Hanging drop in 65 DEG C of thermal current to drying behind GCE surface.
(2)CoFe2O4The preparation of-NGS modified electrodes：1.4g activity NGS is first added to 18mL1.2mol/L citric acid
In solution and ultrasonic 20min.Obtained suspension and 15mL0.48mol/L Co (NO3)2·6H2O and 1.0mol/L Fe
(NO3)3·9H2O solution is mixed, and the pH of mixed solution is adjusted to 8.2 with 0.10mol/L oxyammonia.Obtained mixed solution is 48
DEG C stirring 23h complete reaction.Obtained product 570 DEG C of calcining 5.5h, obtained powder in argon atmosphere are labeled as CoFe2O4-
NGS.Finally take 10 μ L CoFe2O4- NGS hanging drop is to obtaining CoFe on GCE2O4- NGS modified electrodes.
(3) electrochemical property test：The test of prepared electrochemical sensor chemical property is in electrochemical workstation
Upper progress.CoFe2O4- NGS modified electrodes are used as working electrode, and platinum electrode is used as auxiliary electrode, saturation Ag/AgCl (KCl) electrode
As reference electrode.
Under 480mV potential, oxidation of the sensor to practolol prepared by embodiment 1~3 has highly stable
Electrocatalysis characteristic.Detection of the electrochemical sensor to practolol has detection range wide by (0.5~1000 × 10-6Mol/L), detect
Limit low (0.09 × 10-6Mol/L) the characteristics of.Meanwhile practolol is to the testing result of authentic sample (such as urine of medicine, patient)
Show that prepared sensor has extraordinary actual application value.
Claims (10)
1. the preparation method of a kind of electrochemical sensor for practolol detection, it is characterised in that comprise the following steps that：
(1) preparation of nano-graphene modified electrode
By nano-graphene and HNO315~18h of solution mixing backflow；Then, centrifuge and done in room temperature after nano-graphene washing
It is dry；Then by nano-graphene after acidifying, ultrasonic vibration obtains the suspension of nano-graphene modified electrode in dimethylformamide
Liquid；Again by nano-graphene modified electrode hanging drop to behind the surface of the glassy carbon electrode of pretreatment at 70~85 DEG C
Dried in thermal current, obtain active nano graphene modified electrode；
(2) preparation based on magnetic nano-particle modification nano-graphene electrode
Active nano graphene modified electrode is added in citric acid solution simultaneously ultrasound, obtained suspension and Co (NO3)2·
6H2O and Fe (NO3)3·9H2O solution is mixed, and the pH of mixed solution is adjusted to 8.5~9.5 with azanol, then in 40~55 DEG C of temperature
15~30h of the lower stirring of degree completes reaction；Obtained product is calcined 4~6h, obtained in inert atmosphere at a temperature of 450~650 DEG C
To powder；Suspension finally is made in powder, the electrification for practolol detection on hanging drop to glassy carbon electrode, will be obtained
Learn sensor.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), HNO3The concentration of solution is 5~6mol/
L, return time are 15~18h, nano-graphene and HNO3The mass volume ratio of solution is 1：4~1：5g/mL.
3. preparation method as claimed in claim 1, it is characterised in that：In step (1), nano-graphene and dimethylformamide
Mass ratio be 160:3~75:1.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), nano-graphene and dimethylformamide
Mass ratio be 500:9~70:1.
5. preparation method as claimed in claim 1, it is characterised in that in step (1), the pre-treatment step of glassy carbon electrode is such as
Under：First with 0.035~0.15 μm of alumina powder polishing, then in the in the mixed solvent supersound washing of ethanol/water, it
Fully washed with redistilled water again afterwards.
6. preparation method as claimed in claim 1, it is characterised in that：In step (2), active nano graphene modified electrode and
The mass volume ratio of citric acid solution is 1：8~1: 18g/mL.
7. preparation method as claimed in claim 1, it is characterised in that in step (2), the concentration of azanol is 0.1~0.2mol/
L。
8. preparation method as claimed in claim 1, it is characterised in that：In step (2), CoNO3)2·6H2O and Fe (NO3)3·
9H2In O, Co: Fe mol ratio is=2:3；Active nano graphene modified electrode and Co (NO3)2·6H2O mass ratio is 1:
4~1:6.
9. preparation method as claimed in claim 1, it is characterised in that in step (2), calcining heat is 500~600 DEG C.
A kind of 10. electrochemical sensing for being used for practolol detection that preparation method as described in one of claim 1~9 obtains
Device.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103399053A (en) * | 2013-08-15 | 2013-11-20 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensors for sotalol detection based on NiFe2O4 magnetic nanoparticle modified carbon nanotube |
| CN106248766A (en) * | 2016-07-11 | 2016-12-21 | 衡阳师范学院 | A kind of CoFe2o4nWs/RGO nano composite material and the acetaminophen electrochemical sensor prepared thereof |
| KR101774154B1 (en) * | 2016-04-26 | 2017-09-13 | 세종대학교산학협력단 | Composite comprising spinel type material and perovskite type material and Electrochemical Device having the same |
-
2017
- 2017-10-30 CN CN201711037610.9A patent/CN107843627A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103399053A (en) * | 2013-08-15 | 2013-11-20 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensors for sotalol detection based on NiFe2O4 magnetic nanoparticle modified carbon nanotube |
| KR101774154B1 (en) * | 2016-04-26 | 2017-09-13 | 세종대학교산학협력단 | Composite comprising spinel type material and perovskite type material and Electrochemical Device having the same |
| CN106248766A (en) * | 2016-07-11 | 2016-12-21 | 衡阳师范学院 | A kind of CoFe2o4nWs/RGO nano composite material and the acetaminophen electrochemical sensor prepared thereof |
Non-Patent Citations (3)
| Title |
|---|
| ABBAS AFKHAMI等: "Facile simultaneous electrochemical determination of codeine and acetaminophen in pharmaceutical samples and biological fluids by graphene CoFe2O4 nancomposite modified carbon paste electrode", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 孙心齐等: "定量测定盐酸安他唑啉中有机溶剂残留量", 《河南大学学报(自然科学版)》 * |
| 邱颖姮等: "反相高效液相色谱法测定盐酸安他唑啉片的含量", 《中国药业》 * |
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Application publication date: 20180327 |