CN104049015A - Application of polypyrrole-Hemin-reduced graphene ternary composite material thermosynthesized by microwave solvent method - Google Patents
Application of polypyrrole-Hemin-reduced graphene ternary composite material thermosynthesized by microwave solvent method Download PDFInfo
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Abstract
The invention discloses an application of a polypyrrole-Hemin-reduced graphene ternary compound thermosynthesized by a microwave solvent method. The polypyrrole-Hemin-reduced graphene ternary compound is used as a modified electrode material of a biosensor to be used for determining the content of hydrogen peroxide. The compound contains polypyrrole, perchloride iron heme and reduced graphene; the mass fraction of the Hemin is 10.8 to 19.6 percent, the mass fraction of the graphite oxide is 33.3 to 60.2 percent, and the mass fraction of the polypyrrole is 20.2 to 55.9 percent. The invention provides an electrochemical detector and an electrochemical method, which are simple in operation, convenient, rapid and high in sensitivity. A prepared modified electrode has a strong CV (coefficient of variation) current response to the reduction of hydrogen peroxide, the detection limit is (1.3-7)*10<-7>M, and the linear correlation coefficient is 0.998.
Description
Technical field
The present invention relates to a kind of modified electrode material application of sensor, the application of polypyrrole-Hemin-reduced graphene tri compound nano material that particularly prepared by a kind of microwave solvent heating, belongs to Material Field and enzyme biologic sensor technical field.
Background technology
Hydrogen peroxide (H
2o
2) be the metabolic product of many biomolecule, sensitive fast detecting H
2o
2content have very important effect at aspects such as environmental protection, medical science, environment.Under normal circumstances, detection method has chemoluminescence method, fluorescence method, spectrophotometric method and electrochemical methods etc.Wherein electrochemical techniques, because required instrument is simple, can directly detect H sensitive, fast
2o
2rather well received.Be combined with enzyme sensor and be more expected to show the advantages such as simple and fast, highly sensitive, selectivity is good.
X-factor (hemin) is as catalatic activated centre, effectively catalysis H
2o
2the reduction of molecule, and cost is low compared with natural biology enzyme, becomes current H
2o
2one of focus of biology sensor research.But, enzyme electrode preparation process complexity, its stability and activity are disturbed by external condition very easily, thereby have limited its application aspect biology sensor separately.How fixed biologically enzyme is at electrode surface and maintenance Activity and stabill, how to improve the supported quantity of enzyme, be devoted to find for these Study on Problems persons and a kind ofly can have larger specific area and have again the matrix material of better biocompatibility to adsorb fixing hemin molecule.
Functionalized nano compound substance is due to its unique physics, chemical property, and being applied in field of biosensors has been trend of the times.The Graphene (GE) of wherein π-pi-conjugated structure has the features such as bigger serface, good stability and good electric conductivity, can be interacted and is combined to build Graphene/hemin nano composite material with hemin molecule by π-π.The people such as TengXue use the GE obtaining by hydrazine hydrate reduction graphite oxide to mix with hemin is ultrasonic, prepare GE/hemin nano composite material (Angew Chem Int Ed Engl2012,51,3822).The people such as Yujing Guo based on Graphene/hemin binary compound substance to H
2o
2molecule detects (Sensors and Actuators B:Chemical2011,160,295), but the hemin steric hindrance of macromolecule makes greatly again direct electron transfer process be hindered.Select suitable electron transfer mediator can promote the electronic transmission process of enzyme active center and electrode surface, accelerate electric transmission speed, improve the sensitivity of sensor.The people such as Haiyan Song are first at electrode surface deposited Au nano particle, then with Graphene-hemin in conjunction with obtaining tri compound hybrid material (Analytica Chimica Acta, 2013,788,24).Consider that raw materials cost cost is high, the problems such as surface of metal particles energy of activation great Yi reunion, Comparatively speaking the macromolecule of good electric conductivity is because having the advantages such as synthetic method is simple, raw material is easy to get, and transmitting medium as electronics is good selection.Synthesize and obtain polypyrrole (PPY)/hemin binary compound substance (Applied Material Interfaces2014 by single stage method, 6,500), also be used in hydrogen peroxide detection field, so synthetic method conducting polymer-polypyrrole simple, that raw material is easy to get is expected to construct the bio-sensing device that cost is low, performance is high.
The hot method of microwave solvent is different from conventional heating and solvent-thermal method, and it has homogeneous heating, rapidly and efficiently, and applicable to large-scale production.Conventionally the strong oxidizer that reduction-oxidation graphite adds in addition as hydrazine hydrate etc., has toxicity, and environment is had to harm, but use microwave method reduction-oxidation graphite not need extra strong oxidizer, be a kind of route of synthesis of environmental protection.
Polypyrrole-Hemin-reduced graphene tri compound nano material have not been reported at present.
Summary of the invention
For the problem of prior art, the object of this invention is to provide a kind of simple synthetic polypyrrole-Hemin-reduced graphene (PPY-He-RGO) trielement composite material of the hot method of microwave solvent efficiently, Direct Electrochemistry method detects the application on hydrogen peroxide.
The technical solution that realizes the object of the invention is: polypyrrole-Hemin-reduced graphene trielement composite material that a kind of microwave solvent heating is synthetic, and described compound substance is made up of polypyrrole, X-factor and reduced graphene; Wherein, the massfraction of hemin is 10.8%～19.6%, and graphite oxide massfraction is 33.3%～60.2%, and the massfraction of polypyrrole is 20.2%～55.9%.
A preparation method for the synthetic polypyrrole-Hemin-reduced graphene trielement composite material of the hot method of microwave solvent, the dispersion liquid taking GO/Hemin in solvent is presoma, then adds pyrrole monomer to carry out microwave solvent heated polymerizable, comprises the steps:
The first step: graphite oxide colloid is carried out in alcohol-water mixed solvent to ultrasonic finely dispersed graphene oxide (GO) suspending liquid that obtains;
Second step: hemin is dissolved in to the GO suspending liquid obtaining with the first step after ammoniacal liquor completely and mixes, and long-time stirring fully adsorbed it;
The 3rd step: pyrrole monomer is joined to second step and obtain in mixed system, magnetic agitation again, is uniformly dispersed it;
The 4th step: the above-mentioned mixed solution mixing is transferred to and carries out microwave heating reaction in microwave reaction tank;
The 5th step: the 4th step product is carried out to centrifuging, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material.
Ultrasonic jitter time described in step 1 is 1～3h, in alcohol-water mixed solvent alcohol used be respectively in isopropyl alcohol, ethylene glycol or ethanol any one, alcohol and water volume ratio are 1:1.
Ammoniacal liquor pH described in step 2 is 10～13, and the mass ratio of graphite oxide and hemin is 3.08, and the stirring and adsorbing time is 4～8h.
Pyrrole monomer volumetric 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 is 10～30min.
Centrifuging described in step 5 adopts hydro-extractor, and its rotating speed is 1600r/min, is separated into time 10min.
An application for polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis, is applied to mensuration content of hydrogen peroxide using polypyrrole-Hemin-reduced graphene ternary complex of said structure as the modified electrode material of biology sensor.
Described assay method comprises cyclic voltammetry or electric current-time curve method.
In said determination step, adopt three-electrode system, taking modified electrode as working electrode, saturated calomel electrode is contrast electrode, platinum filament is to electrode, and described modified electrode is polypyrrole-Hemin-reduced graphene ternary complex to be dripped to be coated on glass-carbon electrode be prepared from; Wherein, the concentration of polypyrrole-Hemin-reduced graphene dispersion liquid is 1mgmL
-1, dripping quantity is 5～20 μ L.
The step that adopts electric current-time curve method to measure content of hydrogen peroxide is: modified electrode is positioned in the electrolytic cell of pH7.0 containing sodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer of 0.1M, logical nitrogen 5～15min, add continuously hydrogen peroxide, make the concentration of hydrogen peroxide in electrolytic cell be controlled at 0.13～70 μ M, use electric current-time curve method, setting initial potential is-0.1V～-0.35V, detects the response of modified electrode to hydrogen peroxide.
Adopt the step of cyclic voltammetry content of hydrogen peroxide to be: modified electrode is positioned in the electrolytic cell of pH7.0 containing sodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer of 0.1M, logical nitrogen 5～15min, in the superoxol of 1mM, setting scanning current potential is-0.8V～0.2V that sweep velocity is 100mVs
-1, detect the response of modified electrode to hydrogen peroxide.
Compared with prior art, tool of the present invention has the following advantages: the hot method of microwave solvent that (1) adopts, replace traditional agitating heating mode with microwave, prepare polypyrrole-Hemin-reduced graphene trielement composite material by the parameter such as temperature and time that changes microwave.Compare hydro-thermal method, the method has that homogeneous heating, required time are short, utilization factor advantages of higher, is a kind of simple, efficient and environmental protection, has the preparation method of the large-scale production of utilizing; (2) the activated centre hemin of required enzyme, overcome traditional biological enzyme to external world environmental baseline as temperature, the harsh requirement of pH value etc.In PPY-He-RGO compound substance, introduce PPY and RGO, can fix hemin on the one hand and make it still retain enzymatic activity, greatly improved on the other hand the useful area of electrode and promoted the electronics transmission between decorative material and electrode surface; (3) proposition is a kind of simple to operate, quick and portable, highly sensitive Electrochemical Detection instrument and method, and the modified electrode of preparation has strong CV current-responsive to hydrogen peroxide, detects and is limited to 1.3～7.0 × 10
-7m and linearly dependent coefficient are 0.998.
Brief description of the drawings
Accompanying drawing 1 is the TEM photo of the prepared PPY-He-RGO trielement composite material of the embodiment of the present invention 1.
Accompanying drawing 2 is x-ray photoelectron energy spectrograms of the prepared PPY-He-RGO trielement composite material of the embodiment of the present invention 1.
Accompanying drawing 3 is ultraviolet-visible spectrogram (A) and Fourier's infrared spectrograms (B) of the prepared PPY-He-RGO trielement composite material of the embodiment of the present invention 2;
Accompanying drawing 4 is the prepared PPY-He-RGO trielement composite materials of the embodiment of the present invention 2, and it is carried out to electro-chemical test, and naked glass carbon GEC (a) and modified electrode PPY-He-RGO/GCE (b) are adding H
2o
2after cyclic voltammetry curve;
Accompanying drawing 5 is the prepared PPY-He-RGO trielement composite materials of the embodiment of the present invention 3, the ac impedance spectroscopy (A) of modified electrode and in superoxol, difference is swept to the cyclic voltammogram (B) under speed;
Accompanying drawing 6 is the prepared PPY-He-RGO trielement composite materials of the embodiment of the present invention 3, the electric current-time curve (A) in the time dripping quantitative hydrogen peroxide continuously and corresponding peak current and the linear relationship curve (B) of sweeping fast square root; The PPY-He-RGO trielement composite material that accompanying drawing 7 embodiment of the present invention 4 are prepared, to the electric current-time plot of continuous dropping disturbance material.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend.
Embodiment 1: the present invention, the preparation method of the synthetic PPY-He-RGO of microwave under isopropanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction and be 4.4% graphite oxide colloid 0.91g and carry out ultrasonic dispersion 1h in the mixed solvent of 20mL isopropanol/water (1:1v/v), obtain finely dispersed graphene oxide solution;
Second step: 1.3mg hemin is dissolved in to (pH13) in ammoniacal liquor completely and mixes with the GO suspending liquid of the first step, and stir for a long time 4h it is fully adsorbed;
The 3rd step: 10mM pyrrole monomer (13.4mg) is joined to second step and obtain in mixed system, again stir 0.5h, it is uniformly dispersed;
The 4th step: the above-mentioned mixed solution mixing is transferred in microwave reaction tank and carries out microwave heating, and temperature of reaction is 120 DEG C, and the reaction time is 30min;
The 5th step: the 4th step product is carried out to centrifuging, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite 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 that 1.1 μ m and central diameter are about 200nm, and bar-shaped PPY ending join formula and the be distributed in surface of reduced graphene, forms conductive network structure.
As shown in Figure 2, in x-ray photoelectron power spectrum (XPS), contain carbon, oxygen, four kinds of elements of nitrogen and iron, have illustrated that hemin is still entrained in hybrid material, and trielement composite material is by polypyrrole, and hemin and reduced graphene form.
Embodiment 2: the present invention, the preparation method of the synthetic PPY-He-RGO of microwave under glycol/water mixed solvent system, comprises the following steps:
The first step: get massfraction and be 4.4% graphite oxide colloid 0.91g and carry out ultrasonic dispersion 2h in the mixed solvent of 20mL glycol/water (1:1v/v), obtain finely dispersed graphene oxide solution;
Second step: 1.3mg hemin is dissolved in to (pH11) in ammoniacal liquor completely and mixes with the GO suspending liquid of the first step, and stir for a long time 6h it is fully adsorbed;
The 3rd step: 25mM pyrrole monomer (33.5mg) is joined to second step and obtain in mixed system, again stir 1h, it is uniformly dispersed;
The 4th step: the above-mentioned mixed solution mixing is transferred in microwave reaction tank and carries out microwave heating, and temperature of reaction is 150 DEG C, and the reaction time is 15min;
The 5th step: the 4th step product is carried out to centrifuging, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material;
As shown in accompanying drawing 3A, there is displacement in the ultraviolet absorption peak of hemin, shown the conjugative effect that exists trielement composite material PPY-He-RGO redox graphene and hemin and PPY from 389nm red shift to 413nm.
The infrared spectrum (FTIR) of contrast different component is as Fig. 3 B, and in known PPY-He-RGO compound substance, the characteristic absorption peak of existing hemin has again 1521 and 1442cm
-1pyrrole ring characteristic absorption peak, confirm under different solvents condition, equally also successfully prepared PPY-He-RGO trielement composite material.
Embodiment 3: the present invention, the preparation method of the synthetic PPY-He-RGO of microwave under ethanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction and be 4.4% graphite oxide colloid 0.91g and carry out ultrasonic dispersion 3h in the mixed solvent of 20mL ethanol/water (1:1v/v), obtain finely dispersed graphene oxide solution;
Second step: 1.3mg hemin is dissolved in to (pH10) in ammoniacal liquor completely and mixes with the GO suspending liquid of the first step, and stir for a long time 8h it is fully adsorbed;
The 3rd step: 50mM pyrrole monomer (67.0mg) is joined to second step and obtain in mixed system, again stir 2h, it is uniformly dispersed;
The 4th step: the above-mentioned mixed solution mixing is transferred in microwave reaction tank and carries out microwave heating, and temperature of reaction is 180 DEG C, and the reaction time is 10min;
The 5th step: the 4th step product is carried out to centrifuging, and repeatedly with alcohol washing, obtain polypyrrole-Hemin-reduced graphene trielement composite material;
Accompanying drawing 4 is that it is to H
2o
2electrochemical response, in PBS buffer solution, sweep speed when the 100mV/s, by PPY-He-RGO modified electrode cyclic voltammetry (CV) curve, can draw to add after 1mM hydrogen peroxide, at-obvious the H of 0.15V place appearance
2o
2reduction peak, illustrates that ternary hybrid material is to H
2o
2there is good catalytic reduction effect.
Embodiment 4: the present invention, the preparation method of the synthetic PPY-He-RGO of microwave under isopropanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction and be 4.4% graphite oxide colloid 0.91g and carry out ultrasonic dispersion 1h in the mixed solvent of 20mL isopropanol/water (1:1v/v), obtain finely dispersed graphene oxide solution;
Second step: 1.3mg hemin is dissolved in to (pH10) in ammoniacal liquor completely and mixes with the GO suspending liquid of the first step, and stir for a long time 4h it is fully adsorbed;
The 3rd step: 50m pyrrole monomer (67.0mg) is joined to second step and obtain in mixed system, again stir 0.5h, it is uniformly dispersed;
The 4th step: the above-mentioned mixed solution mixing is transferred in microwave reaction tank and carries out microwave heating, and temperature of reaction is 120 DEG C, and the reaction time is 30min;
The 5th step: the 4th step product is carried out to centrifuging, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite 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 μ m smooth, water and alcohol flushing are clean, under room temperature, dry, for subsequent use;
(2), by the ultrasonic processing 1h of compound substance PPY-He-RGO process, heavily disperse, after dilution, to join to obtain 1.0mgmL
-1uniform dispersion;
(3) get 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode of getting ready in advance, natural drying, obtain PPY-He-RGO modified electrode;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mL pH=7 and soaks, and passes into after nitrogen 15min, add 1mM hydrogen peroxide magnetic agitation, use cyclic voltammetry, be set to-0.8～0.2V of potential window, sweeps speed for 100mVs
-1, detect modified electrode to H
2o
2electrochemical 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 μ m smooth, water and alcohol flushing are clean, under room temperature, dry, for subsequent use;
(2), by the ultrasonic 1h of compound substance PPY-He-RGO process, heavily disperse, after dilution, to join to obtain 1.0mgmL
-1uniform dispersion;
(3) get 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode of getting ready in advance, natural drying, obtain PPY-He-RGO modified electrode;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mL pH=7 and soaks, pass into after nitrogen 15min, use AC impedence method, it is 1.0～10 that frequency range is set
6hz, as Fig. 5 A can observe significantly, hemin modify electrode there is maximum impedance, compound with Graphene after, impedance is obviously lower.But compare monobasic, two yuan of compound substances, the impedance of trielement composite material PPY-He-RGO is less, illustrate that trielement composite material can promote the electronics transmission between electrode surface and decorative material significantly, 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 μ m smooth, water and alcohol flushing are clean, under room temperature, dry, for subsequent use;
(5), by the ultrasonic 1h of compound substance PPY-He-RGO process, heavily disperse, after dilution, to join to obtain 1.0mgmL
-1uniform dispersion;
(6) get 10 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode of getting ready in advance, natural drying, obtain PPY-He-RGO modified electrode;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, and glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mL pH=7 and soaks, pass into after nitrogen 10min, add 2mM hydrogen peroxide magnetic agitation, use cyclic voltammetry, be set to-0.8～0.2V of potential window, as shown in Figure 5 B, at 30～200mVs
-1in scope, along with sweeping fast increase, the response of a pair of redox peak current of hemin all increases thereupon, illustrates that the stability of electrode is better.Hydrogen peroxide peak point current, with to sweep fast square root linear, illustrates that hydrogen peroxide belongs to surface diffusion 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 μ m smooth, water and alcohol flushing are clean, under room temperature, dry, for subsequent use;
(2), by the ultrasonic 1h of compound substance PPY-He-RGO process, heavily disperse, after dilution, to join to obtain 1.0mgmL
-1uniform dispersion;
(3) get 5 μ L dispersant liquid drops with liquid-transfering gun and apply on the glass-carbon electrode of getting ready in advance, natural drying, obtain PPY-He-RGO modified electrode;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, and glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mL pH=7 and soaks, pass into after nitrogen 15min, drip continuously after quantitative hydrogen peroxide magnetic agitation 5min, as shown in Figure 6, use electric current-time curve method, initial potential is set is-0.15V, detects the response of modified electrode to hydrogen peroxide.As shown in Fig. 6 (A), once there is immediately response step after adding hydrogen peroxide, show that modified electrode is rapid to the response of hydrogen peroxide, catalytic reduction also occurs thereupon, and within the scope of 1.3～70 μ M, response current and H
2o
2concentration has good linear relationship (Fig. 6 (B)).
The response of modified electrode 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 μ m smooth, water and alcohol flushing are clean, under room temperature, dry, for subsequent use;
(5), by the ultrasonic 1h of compound substance PPY-He-RGO process, heavily disperse, after dilution, to join to obtain 1.0mgmL
-1uniform dispersion;
(6) use liquid-transfering gun to get 5 μ L dispersant liquid drops and apply on the glass-carbon electrode of getting ready in advance, natural drying, obtain PPY-He-RGO modified electrode;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mL pH=7 and soaks, and passes into after nitrogen 15min, add 10 μ M hydrogen peroxide magnetic agitation 5min, use electric current-time curve method, it is-0.15V to detect the response of modified electrode to common interference material that initial potential is set; As shown in Figure 7, modified electrode all without obviously response, shows that modified electrode detects hydrogen peroxide and has good selectivity to common interference material dopamine, uric acid, ascorbic acid and the glucose of 10 times of concentration.
Claims (7)
1. the application of polypyrrole-Hemin-reduced graphene ternary complex of a microwave solvent thermal synthesis, it is characterized in that, polypyrrole-Hemin-reduced graphene ternary complex is applied to mensuration content of hydrogen peroxide as the modified electrode material of biology sensor, wherein, described compound is made up of polypyrrole, X-factor and reduced graphene: the massfraction of hemin is 10.8%～19.6%, graphite oxide massfraction is 33.3%～60.2%, and the massfraction of polypyrrole is 20.2%～55.9%.
2. the application of polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis according to claim 1, is characterized in that, assay method is cyclic voltammetry.
3. the application of polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis according to claim 1, is characterized in that, assay method is electric current-time curve method.
4. according to the application of polypyrrole-Hemin-reduced graphene ternary complex of the arbitrary described microwave solvent thermal synthesis of claim 1-3, it is characterized in that, assay method adopts three-electrode system, taking modified electrode as working electrode, saturated calomel electrode is contrast electrode, and platinum filament is to electrode.
5. the application of polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis according to claim 4, it is characterized in that, described modified electrode is polypyrrole-Hemin-reduced graphene ternary complex to be dripped to be coated on glass-carbon electrode be prepared from; Wherein, the concentration of polypyrrole-Hemin-reduced graphene dispersion liquid is 1mgmL
-1, dripping quantity is 5～20 μ L.
6. the application of polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis according to claim 2, it is characterized in that, adopt cyclic voltammetry detection to the response of step of hydrogen peroxide to be: modified electrode is positioned in the electrolytic cell of pH7.0 containing sodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer of 0.1M, logical nitrogen 5～15min, in the superoxol of 1mM, setting scanning current potential is-0.8V～0.2V that sweep velocity is 100mVs
-1, detect the response of modified electrode to hydrogen peroxide.
7. the application of polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis according to claim 3, it is characterized in that, the step that adopts electric current-time curve method to measure content of hydrogen peroxide is: modified electrode is positioned in the electrolytic cell of pH7.0 containing sodium hydrogen phosphate/sodium dihydrogen phosphate cocktail buffer of 0.1M, logical nitrogen 5～15min, add continuously hydrogen peroxide, make the concentration of hydrogen peroxide in electrolytic cell be controlled at 0.13～70 μ M, use electric current-time curve method, setting initial potential is-0.1V～-0.35V, detect the response of modified electrode to hydrogen peroxide.
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| CN105572188A (en) * | 2014-10-17 | 2016-05-11 | 南京理工大学 | (PANI/RGO)n/Hemin modified electrode and electrochemical detection method of (PANI/RGO)n/Hemin modified electrode to hydrogen peroxide |
| CN105572188B (en) * | 2014-10-17 | 2018-12-14 | 南京理工大学 | (PANI/RGO)n/ Hemin modified electrode and its electrochemical detection method to hydrogen peroxide |
| CN113433189A (en) * | 2021-05-14 | 2021-09-24 | 苏州科技大学 | Graphite alkyne/heme composite material and preparation method and application thereof |
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