CN104049015B - Polypyrrole-Hemin-reduced graphene trielement composite material the application of microwave solvent method thermal synthesis - Google Patents
Polypyrrole-Hemin-reduced graphene trielement composite material the application of microwave solvent method thermal synthesis Download PDFInfo
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Abstract
The invention discloses the application of the polypyrrole Hemin reduced graphene ternary complex of a kind of microwave solvent thermal synthesis.Using polypyrrole Hemin reduced graphene ternary complex as biosensor modified electrode materials application in measure content of hydrogen peroxide, wherein, described complex is made up of polypyrrole, protohemin and reduced graphene: the mass fraction of hemin is 10.8% ~ 19.6%, graphite oxide mass fraction is 33.3% ~ 60.2%, and the mass fraction of polypyrrole is 20.2% ~ 55.9%.The present invention proposes a kind of simple to operate, fast and easy, highly sensitive Electrochemical Detection instrument and method, the modified electrode of preparation strong CV current-responsive the most original to hydrogen peroxide, and detection is limited to 1.3 ~ 7 × 10‑7M and linearly dependent coefficient are 0.998.
Description
Technical field
The present invention relates to the modified electrode materials application of a kind of sensor, prepared by a kind of microwave solvent heating
Polypyrrole-Hemin-reduced graphene tri compound applications to nanostructures, belongs to Material Field and enzyme biologic sensor
Technical field.
Background technology
Hydrogen peroxide (H2O2) it is the metabolite of many biomolecule, sensitive quick detection H2O2Content at ring
The aspects such as guarantor, medical science, environment have very important effect.Under normal circumstances, detection method have chemoluminescence method,
Fluorescence method, spectrophotography and electrochemical methods etc..Wherein electrochemical techniques due to required instrument simple, can sensitive,
Quickly directly detect H2O2Rather well received.Be combined with enzyme sensor be more expected to show simple and fast, highly sensitive,
The advantages such as selectivity is good.
Protohemin (hemin), as catalatic active center, can effectively be catalyzed H2O2Molecule
Reduction, and low cost compared with natural biology enzyme, become current H2O2One of focus of biosensor research.So
And, enzyme electrode preparation process is complicated, and its stability and activity are easily disturbed by external condition, thus it is independent to limit it
Application in terms of biosensor.How to fix enzyme and at electrode surface and keep Activity and stabill, how to carry
The supported quantity of high enzyme, is devoted to find one for these Study on Problems persons and can have bigger specific area and have again preferably
The matrix material of biocompatibility adsorbs fixing hemin molecule.
Functionalized nano composite, due to the physics of its uniqueness, chemical property, is applied and in field of biosensors is
Trend of the times.Wherein the Graphene (GE) of π-pi-conjugated structure has bigger serface, good stability and good electric conductivity etc.
Feature, can interact to be combined with hemin molecule by π-π builds Graphene/hemin nano composite material.Teng
Xue et al. uses that GE with hemin obtained by hydrazine hydrate reduction graphite oxide is ultrasonic to be mixed, and prepares
GE/hemin nano composite material (Angew Chem Int Ed Engl2012,51,3822).Yujing Guo etc.
People based on Graphene/hemin binary composite to H2O2Molecule carry out detecting (Sensors and Actuators B:
Chemical2011,160,295), but the hemin steric hindrance of macromolecule makes the most again direct electron transfer process be subject to
Hinder.Select suitable electron transfer mediator can promote the electronic transmission process of enzyme active center and electrode surface, add
Speed electron transfer rate, improves the sensitivity of sensor.Haiyan Song et al. is first electrode surface electro-deposition Jenner
Rice grain, then combines with both Graphene-hemin and obtains tri compound hybrid material (Analytica Chimica
Acta, 2013,788,24).High in view of cost of material cost, surface of metal particles activation energy great Yi reunion etc. is asked
Topic, the macromolecule of the best electric conductivity, because having the advantages such as synthetic method is simple, raw material is easy to get, passes as electronics
Passing medium is good selection.Polypyrrole (PPY)/hemin binary composite is obtained by one-step synthesis method
(Applied Material Interfaces2014,6,500), is also applicable in hydrogen peroxide detection field, so closing
The conducting polymer-polypyrrole that one-tenth method is simple, raw material is easy to get is expected to the biosensor constructing low cost, performance is high
Part.
Microwave solvent full-boiled process is different from conventional heating and solvent-thermal method, and it has uniformly heating, rapidly and efficiently, applicable
In large-scale production.The strong oxidizer such as hydrazine hydrate etc. that additionally generally reduction-oxidation graphite is added, has toxicity,
Environment is had harm, but uses microwave method reduction-oxidation graphite then to need not extra strong oxidizer, be a kind of green ring
The route of synthesis protected.
Polypyrrole-Hemin-reduced graphene tri compound nano material have not been reported at present.
Summary of the invention
For problem of the prior art, it is an object of the invention to provide a kind of simple efficient microwave solvent full-boiled process synthesis
Polypyrrole-Hemin-reduced graphene (PPY-He-RGO) trielement composite material, the detection peroxidating of Direct Electrochemistry method
Application on hydrogen.
The technical solution realizing the object of the invention is: the polypyrrole-Hemin-of a kind of microwave solvent heating synthesis
Reduced graphene trielement composite material, described composite is by polypyrrole, protohemin and reduction graphite
Alkene forms；Wherein, the mass fraction of hemin is 10.8%～19.6%, and graphite oxide mass fraction is 33.3%～60.2%,
The mass fraction of polypyrrole is 20.2%～55.9%.
A kind of preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvent full-boiled process synthesis,
With GO/Hemin dispersion liquid in a solvent as presoma, add pyrrole monomer and carry out microwave solvent and add thermal polymerization,
Comprise the steps:
The first step: carry out graphite oxide colloid in alcohol-water mixed solvent ultrasonic obtaining finely dispersed graphite oxide
Alkene (GO) suspension；
Second step: the GO suspension obtained with the first step after hemin is dissolved completely in ammonia mixes, and for a long time
Stirring makes it fully adsorb；
3rd step: pyrrole monomer is joined obtained by second step in mixed system, magnetic agitation again so that it is dispersion
Uniformly；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carry out microwave heating reaction；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that PPY-He-RGO ternary
Composite.
The ultrasonic disperse time described in step one is 1～3h, in alcohol-water mixed solvent alcohol used be respectively isopropanol,
In ethylene glycol or ethanol any one, alcohol and water volume ratio are 1:1.
Ammonia pH described in step 2 is 10～13, and graphite oxide is 3.08 with the mass ratio of hemin, and stirring is inhaled
The attached time is 4～8h.
Pyrrole monomer molar concentration described in step 3 is 10～50mmolL-1, pyrrole monomer and hemin mass ratio
1.03～5.15, mixing time is 0.5h～2h.
Microwave heating temperature described in step 4 is 100 DEG C～180 DEG C；Heat time heating time is 10～30min.
Centrifugation described in step 5 uses centrifuge, and its rotating speed is 1600r/min, is separated into time 10min.
The application of the polypyrrole-Hemin-reduced graphene ternary complex of a kind of microwave solvent thermal synthesis, by above-mentioned knot
Polypyrrole-Hemin-reduced graphene the ternary complex of structure as the modified electrode materials application of biosensor in survey
Determine content of hydrogen peroxide.
Described assay method includes cyclic voltammetry or current versus time curve method.
In said determination step, using three-electrode system, with modified electrode as working electrode, saturated calomel electrode is ginseng
Ratio electrode, platinum filament is to electrode, and described modified electrode is by polypyrrole-Hemin-reduced graphene ternary complex
Drop coating is prepared from glass-carbon electrode；Wherein, the concentration of polypyrrole-Hemin-reduced graphene dispersion liquid is
1mgmL-1, dripping quantity is 5～20 μ L.
The step using current versus time curve method to measure content of hydrogen peroxide is: modified electrode is positioned over pH7.0 and contains
In the electrolyzer of the disodium hydrogen phosphate of 0.1M/sodium dihydrogen phosphate cocktail buffer, logical nitrogen 5～15min, it is continuously added to
Hydrogen peroxide, makes hydrogen peroxide concentration in electrolyzer control at 0.13～70 μM, uses current versus time curve method,
Set initial potential as-0.1V～-0.35V, detect the modified electrode response to hydrogen peroxide.
The step of employing cyclic voltammetry content of hydrogen peroxide is: modified electrode is positioned over pH7.0 containing 0.1M
In the electrolyzer of disodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer, logical nitrogen 5～15min, in the peroxidating of 1mM
In hydrogen solution, setting scanning current potential is 100mVs as-0.8V～0.2V, scanning speed-1, detection modified electrode is to peroxide
Change the response of hydrogen.
Compared with prior art, present invention have the advantage that the microwave solvent full-boiled process that (1) uses, replace with microwave
Traditional agitating heating mode, prepares polypyrrole-Hemin-also by changing the parameters such as the temperature and time of microwave
Former Graphene trielement composite material.Comparing hydro-thermal method, the method has uniformly heating, required time is short, utilization rate is high
Etc. advantage, it is a kind of simple, efficient and environmental protection, has the preparation method utilizing large-scale production；(2) work of enzyme needed for
Property center hemin, overcomes the traditional biological enzyme such as temperature of environmental condition to external world, the rigors of pH value etc..?
PPY-He-RGO composite introduces PPY and RGO, on the one hand can fix hemin and make it still retain enzymatic activity,
On the other hand substantially increase the effective area of electrode and promote the electron transmission between decorative material and electrode surface；(3)
Propose a kind of simple to operate, quick and portable, highly sensitive Electrochemical Detection instrument and method, the modification electricity of preparation
Extremely there are strong CV current-responsive, detection to be limited to 1.3～7.0 × 10 to hydrogen peroxide-7M and linearly dependent coefficient are 0.998.
Accompanying drawing explanation
Accompanying drawing 1 is the TEM photo of the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 1.
Accompanying drawing 2 is the x-ray photoelectron power spectrum of the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 1
Figure.
Accompanying drawing 3 is the ultraviolet-visible spectrogram (A) of the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 2
With FTIR spectrum figure (B)；
Accompanying drawing 4 is the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 2, and it is carried out electro-chemical test,
Naked glass carbon GEC (a) and modified electrode PPY-He-RGO/GCE (b) are adding H2O2After cyclic voltammetry curve；
Accompanying drawing 5 is the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 3, the AC impedance of modified electrode
Collection of illustrative plates (A) and the cyclic voltammogram (B) in hydrogenperoxide steam generator, difference swept under speed；
Accompanying drawing 6 is the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 3, is dripping quantitative peroxide continuously
Current versus time curve (A) when changing hydrogen and corresponding peak current and sweep the linear relationship curve (B) of square root of speed；
PPY-He-RGO trielement composite material prepared by accompanying drawing 7 embodiment of the present invention 4, to dropping disturbance thing continuously
The current versus time curve figure of matter.
Detailed description of the invention
The following examples can make those skilled in the art that the present invention is more fully understood.
Embodiment 1: the present invention, the preparation method of microwave synthesis PPY-He-RGO under isopropanol/water mixed solvent system,
Comprise the following steps:
The first step: take graphite oxide colloid 0.91g the mixing in 20mL isopropanol/water (1:1v/v) that mass fraction is 4.4%
Bonding solvent carries out ultrasonic disperse 1h, obtains finely dispersed graphene oxide solution；
Second step: 1.3mg hemin is dissolved completely in ammonia (pH13) and mixes with the GO suspension of the first step, and
Long agitation 4h makes it fully adsorb；
3rd step: 10mM pyrrole monomer (13.4mg) is joined obtained by second step in mixed system, be again stirring for 0.5h,
Make it be uniformly dispersed；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carry out microwave heating, reaction temperature is
120 DEG C, the response time is 30min；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that PPY-He-RGO tri compound
Material；
As shown in Figure 1, PPY is nano bar-shape to the TEM image of trielement composite material, and the average length of rod is
1.1 μm and central diameter are about 200nm, bar-shaped PPY ending are distributed in the surface of reduced graphene, structure with connecting formula
Become conductive network structure.
As shown in Figure 2, containing carbon in x-ray photoelectron power spectrum (XPS), oxygen, nitrogen and four kinds of elements of ferrum, say
Clear hemin is still entrained in hybrid material, and trielement composite material is by polypyrrole, hemin and reduced graphene
Constitute.
Embodiment 2: the present invention, the preparation method of microwave synthesis PPY-He-RGO under glycol/water mixed solvent system,
Comprise the following steps:
The first step: take graphite oxide colloid 0.91g the mixing in 20mL glycol/water (1:1v/v) that mass fraction is 4.4%
Bonding solvent carries out ultrasonic disperse 2h, obtains finely dispersed graphene oxide solution；
Second step: 1.3mg hemin is dissolved completely in ammonia (pH11) and mixes with the GO suspension of the first step, and
Long agitation 6h makes it fully adsorb；
3rd step: 25mM pyrrole monomer (33.5mg) is joined obtained by second step in mixed system, be again stirring for 1h,
Make it be uniformly dispersed；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carry out microwave heating, reaction temperature is
150 DEG C, the response time is 15min；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that PPY-He-RGO tri compound
Material；
As shown in fig. 3 a, the ultraviolet absorption peak of hemin there occurs displacement, shows from 389nm red shift to 413nm
Existence conjugation between trielement composite material PPY-He-RGO redox graphene and hemin and PPY.
Infrared spectrum (FTIR) such as Fig. 3 B of contrast different component, it is known that existing in PPY-He-RGO composite
The characteristic absorption peak of hemin has again 1521 and 1442cm-1Pyrrole ring characteristic absorption peak, it was demonstrated that at different solvents
Under the conditions of, the most successfully prepare PPY-He-RGO trielement composite material.
Embodiment 3: the present invention, the preparation method of microwave synthesis PPY-He-RGO, bag under ethanol/water mixed solvent system
Include following steps:
The first step: take graphite oxide colloid 0.91g that mass fraction is 4.4% in the mixing of 20mL ethanol/water (1:1v/v)
Solvent carries out ultrasonic disperse 3h, obtains finely dispersed graphene oxide solution；
Second step: 1.3mg hemin is dissolved completely in ammonia (pH10) and mixes with the GO suspension of the first step, and
Long agitation 8h makes it fully adsorb；
3rd step: 50mM pyrrole monomer (67.0mg) is joined obtained by second step in mixed system, be again stirring for 2h,
Make it be uniformly dispersed；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carry out microwave heating, reaction temperature is
180 DEG C, the response time is 10min；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that polypyrrole-Hemin-reduces stone
Ink alkene trielement composite material；
Accompanying drawing 4 is that it is to H2O2Electrochemical response, in PBS buffer solution, sweep speed for 100mV/s time, by
PPY-He-RGO modified electrode cyclic voltammetry (CV) curve, it can be deduced that after adding 1mM hydrogen peroxide,
There is obvious H in-0.15V place2O2Reduction peak, illustrates that ternary hybrid material is to H2O2Have and be preferably catalyzed reduction.
Embodiment 4: the present invention, the preparation method of microwave synthesis PPY-He-RGO under isopropanol/water mixed solvent system,
Comprise the following steps:
The first step: take graphite oxide colloid 0.91g the mixing in 20mL isopropanol/water (1:1v/v) that mass fraction is 4.4%
Bonding solvent carries out ultrasonic disperse 1h, obtains finely dispersed graphene oxide solution；
Second step: 1.3mg hemin is dissolved completely in ammonia (pH10) and mixes with the GO suspension of the first step, and
Long agitation 4h makes it fully adsorb；
3rd step: 50m pyrrole monomer (67.0mg) is joined obtained by second step in mixed system, be again stirring for 0.5h,
Make it be uniformly dispersed；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carry out microwave heating, reaction temperature is
120 DEG C, the response time is 30min；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that PPY-He-RGO tri compound
Material.
Application example 1:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, rushes with water and ethanol
Wash clean, dries under room temperature, standby；
(2) by composite PPY-He-RGO through supersound process 1h, heavily after dispersion dilution, 1.0mgmL is joined to obtain-1
Uniform dispersion；
(3) take 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode being made ready beforehand for, natural drying, obtain
PPY-He-RGO modified electrode；
2. the modified electrode detection method to hydrogen peroxide, comprises the following steps:
Using three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and glass-carbon electrode is work
Electrode, is positioned over step (3) gained modified electrode in the PBS of 10mL pH=7 immersion, is passed through nitrogen
After 15min, add 1mM hydrogen peroxide magnetic agitation, use cyclic voltammetry, potential window is set to
-0.8～0.2V, sweep speed for 100mVs-1, detection modified electrode is to H2O2Electrochemical response.
Application example 2:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, rushes with water and ethanol
Wash clean, dries under room temperature, standby；
(2) by composite PPY-He-RGO through ultrasonic 1h, heavily after dispersion dilution, 1.0mgmL is joined to obtain-1All
Even dispersion liquid；
(3) take 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode being made ready beforehand for, natural drying, obtain
PPY-He-RGO modified electrode；
2. the modified electrode detection method to hydrogen peroxide, comprises the following steps:
Using three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and glass-carbon electrode is work
Electrode, is positioned over step (3) gained modified electrode in the PBS of 10mL pH=7 immersion, is passed through nitrogen
After 15min, using AC impedence method, arranging frequency range is 1.0～106Hz, as Fig. 5 A can be clearly observed,
The electrode that hemin modifies has the impedance of maximum, and after being combined with Graphene, impedance is significant lower.But compare unitary,
Two yuan of composites, the impedance of trielement composite material PPY-He-RGO is less, illustrates that trielement composite material can be significantly
Promote the electron transmission between electrode surface and decorative material, improve current responsing signal.
Application example 3:
1. the preparation of modified electrode, comprises the following steps:
(4) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, rushes with water and ethanol
Wash clean, dries under room temperature, standby；
(5) by composite PPY-He-RGO through ultrasonic 1h, heavily after dispersion dilution, 1.0mgmL is joined to obtain-1All
Even dispersion liquid；
(6) take 10 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode being made ready beforehand for, natural drying, obtain
PPY-He-RGO modified electrode；
2. the modified electrode detection method to hydrogen peroxide, comprises the following steps:
Using three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and glass-carbon electrode is work
Electrode, is positioned over step (3) gained modified electrode in the PBS of 10mL pH=7 immersion, is passed through nitrogen
After 10min, add 2mM hydrogen peroxide magnetic agitation, use cyclic voltammetry, potential window is set to
-0.8～0.2V, as shown in Figure 5 B, 30～200mVs-1In the range of, along with sweeping fast increase, a pair oxygen of hemin
The response changing reduction peak current increases the most therewith, illustrates that the stability of electrode is preferable.Hydrogen peroxide peak point current with sweep speed
Square root linear, illustrate that hydrogen peroxide belongs to diffusion into the surface process on modified electrode surface.
Application example 4:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, rushes with water and ethanol
Wash clean, dries under room temperature, standby；
(2) by composite PPY-He-RGO through ultrasonic 1h, heavily after dispersion dilution, 1.0mgmL is joined to obtain-1All
Even dispersion liquid；
(3) take 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode being made ready beforehand for, natural drying, obtain
PPY-He-RGO modified electrode；
2. the modified electrode detection method to hydrogen peroxide, comprises the following steps:
Using three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and glass-carbon electrode is work
Electrode, is positioned over step (3) gained modified electrode in the PBS of 10mL pH=7 immersion, is passed through nitrogen
After 15min, after dripping quantitative hydrogen peroxide magnetic agitation 5min continuously, as shown in Figure 6, current-vs-time is used
Curve method, arranging initial potential is-0.15V, detects the modified electrode response to hydrogen peroxide.Such as Fig. 6 (A) institute
Show that response step occurs after once adding hydrogen peroxide immediately, show that modified electrode is rapid to the response of hydrogen peroxide,
Catalysis reduction occurs the most therewith, and in the range of 1.3～70 μMs, response current and H2O2Concentration has the most linear closing
System (Fig. 6 (B)).
The modified electrode response to common interference material:
1. the preparation of modified electrode, comprises the following steps:
(4) glass-carbon electrode is ground to respectively on the aluminium oxide of 0.1 and 0.03 μm smooth, rushes with water and ethanol
Wash clean, dries under room temperature, standby；
(5) by composite PPY-He-RGO through ultrasonic 1h, heavily after dispersion dilution, 1.0mgmL is joined to obtain-1All
Even dispersion liquid；
(6) use liquid-transfering gun to take 5 μ L dispersant liquid drops and apply on the glass-carbon electrode being made ready beforehand for, natural drying, obtain
PPY-He-RGO modified electrode；
2. the modified electrode detection method to hydrogen peroxide, comprises the following steps:
Using three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and glass-carbon electrode is work
Electrode, is positioned over step (3) gained modified electrode in the PBS of 10mL pH=7 immersion, is passed through nitrogen
After 15min, add 10 μMs of hydrogen peroxide magnetic agitation 5min, use current versus time curve method, arrange initial
Current potential is-0.15V, detects the modified electrode response to common interference material；As it is shown in fig. 7, modified electrode is to 10
Common interference material dopamine, uric acid, ascorbic acid and the glucose of times concentration, all without obvious responsing to, show to modify electricity
Pole detection hydrogen peroxide has good selectivity.
Claims (7)
1. an application for the polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis, it is special
Levy and be, using polypyrrole-Hemin-reduced graphene ternary complex as the modified electrode material of biosensor
Material is applied to measure content of hydrogen peroxide, and wherein, described complex is by polypyrrole, protohemin
Form with reduced graphene: the mass fraction of hemin is 10.8%～19.6%, and graphite oxide mass fraction is
33.3%～60.2%, the mass fraction of polypyrrole is 20.2%～55.9%；Described complex passes through following steps
Preparation:
The first step: carry out graphite oxide colloid in alcohol-water mixed solvent ultrasonic obtaining finely dispersed oxidation
Graphene suspension；
Second step: the graphene oxide suspension obtained with the first step after hemin is dissolved completely in ammonia is mixed
Closing, and long agitation makes it fully adsorb, wherein, graphite oxide is 3.08 with the mass ratio of hemin；
3rd step: pyrrole monomer is joined obtained by second step in mixed system, magnetic agitation again so that it is
It is uniformly dispersed, wherein, pyrrole monomer and hemin mass ratio 1.03～5.15；
4th step: the mixed solution of above-mentioned mix homogeneously is transferred in microwave reaction tank carries out microwave heating anti-
Should；
5th step: be centrifuged the 4th step product separating, and repeatedly wash with alcohol, it is thus achieved that described ternary is multiple
Condensation material.
Polypyrrole-Hemin-reduced graphene the ternary of microwave solvent thermal synthesis the most according to claim 1
The application of complex, it is characterised in that assay method is cyclic voltammetry.
Polypyrrole-Hemin-reduced graphene the ternary of microwave solvent thermal synthesis the most according to claim 1
The application of complex, it is characterised in that assay method is current versus time curve method.
4. according to the polypyrrole-Hemin-reduction graphite of the arbitrary described microwave solvent thermal synthesis of claim 1-3
The application of alkene ternary complex, it is characterised in that assay method uses three-electrode system, with modified electrode as work
Making electrode, saturated calomel electrode is reference electrode, and platinum filament is to electrode.
Polypyrrole-Hemin-reduced graphene the ternary of microwave solvent thermal synthesis the most according to claim 4
The application of complex, it is characterised in that described modified electrode is by polypyrrole-Hemin-reduced graphene three
Unit's complex drop coating is prepared from glass-carbon electrode；Wherein, polypyrrole-Hemin-reduced graphene dispersion liquid
Concentration be 1mgmL-1, dripping quantity is 5～20 μ L.
Polypyrrole-Hemin-reduced graphene the ternary of microwave solvent thermal synthesis the most according to claim 2
The application of complex, it is characterised in that the response of step of hydrogen peroxide is by employing cyclic voltammetry detection: will
Modified electrode is positioned over the electrolyzer of pH7.0 disodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer containing 0.1M
In, logical nitrogen 5～15min, in the hydrogenperoxide steam generator of 1mM, sets and scan current potential as-0.8V～0.2V,
Scanning speed is 100mVs-1, detect the modified electrode response to hydrogen peroxide.
Polypyrrole-Hemin-reduced graphene the ternary of microwave solvent thermal synthesis the most according to claim 3
The application of complex, it is characterised in that the step using current versus time curve method to measure content of hydrogen peroxide is:
Modified electrode is positioned over the electrolyzer of pH7.0 disodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer containing 0.1M
In, logical nitrogen 5～15min, it is continuously added to hydrogen peroxide, makes hydrogen peroxide concentration in electrolyzer control
0.13～70 μM, using current versus time curve method, sets initial potential as-0.1V～-0.35V, detection modification is electric
The extremely response to hydrogen peroxide.
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| CN102147389A (en) * | 2011-03-17 | 2011-08-10 | 南京师范大学 | Method for testing hydrogen peroxide in cell based on horseradish peroxidase-attapulgite nanometer composite material |
| CN102585174A (en) * | 2012-01-09 | 2012-07-18 | 南京大学 | Method for preparing graphene/ poly (3,4-ethylenedioxythiophene) complex nano material |
| CN103454333A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Electrochemical detection method for pesticide imidacloprid based on polypyrrole/reduced graphene oxide (PPy/RGO) modified glassy carbon electrode |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102147389A (en) * | 2011-03-17 | 2011-08-10 | 南京师范大学 | Method for testing hydrogen peroxide in cell based on horseradish peroxidase-attapulgite nanometer composite material |
| CN102585174A (en) * | 2012-01-09 | 2012-07-18 | 南京大学 | Method for preparing graphene/ poly (3,4-ethylenedioxythiophene) complex nano material |
| CN103454333A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Electrochemical detection method for pesticide imidacloprid based on polypyrrole/reduced graphene oxide (PPy/RGO) modified glassy carbon electrode |
Non-Patent Citations (2)
| Title |
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| A facile one-pot method to synthesize a polypyrrole/hemin nanocomposite and its application in biosensor,dye removal,and photothermal therapy;Peng Hu,et al.;《Applied materials and interfaces》;20131205(第6期);摘要 * |
| Hemin functionalized graphene nanosheets-based dual biosensor platforms for hydrogen peroxide and glucose;Guo Y et al.;《Sensors and Actuators B:Chemical》;20111231(第160期);第2.3节，第2.4节，第3.3节，第3.4节及图3、4 * |
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