CN108862245A - A kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation method and application - Google Patents
A kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation method and application.The Electrochemical Modification material is MCFs-rGO, and preparation method is：Under hydrazine hydrate effect, make it compound with the template polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) of synthesis large aperture foam silicon in graphene oxide reduction process, obtain compound P123-rGO, again using P123 and mesitylene TMB as template and expanding agent, using tetraethyl orthosilicate as silicon source, make MCFs growth in situ on P123-rGO by Silanization reaction, finally removes template, obtain MCFs-rGO compound.The Electrochemical Modification material of preparation has good electric conductivity and biocompatibility, which is applied in biosensor, the application in the fields such as electrochemical analysis, bio-sensing has been expanded.
Description
Technical field
The present invention relates to bioelectrochemistry fields, and in particular to a kind of large aperture foam silicon-redox graphene base electricity
Chemical modification material and its application in Electrochemical Detection.
Background technique
Biosensor is that a kind of pair of biological substance is sensitive and its concentration is converted to the instrument that electric signal detects.It is
It is made of the biological substance of immobilization, energy converter and signal amplifying apparatus, obtains many concerns in recent years.
In the past few years, people pay close attention to the research of enzyme electrode further, and Direct Electrochemistry is for biosensor reality
Existing enzyme has a very important role with interelectrode electronics transfer.Due to its big specific surface area, excellent leads graphene
The open structure of electrical and strong mechanical strength and two dimension, is utilized extensively in bioelectrochemistry field.And as a kind of new
Profile material, redox graphene have both electric conductivity and have chemically active defect sites, widely paid close attention to gradually.Example
Such as, in field of biosensors, in the recent period it is found that it as a kind of electrode material can help enzyme realize with it is interelectrode straight
Electron-transport is connect, to become the suitable material of building biosensor.However unmodified redox graphene table
The hydrophobicity in face may cause leakage or the conformational change of enzyme, reduce enzymatic activity, to make the reduced performance of sensor.Therefore
The method of the suitable surface modification of selection is beneficial to graphene-based biosensor further answering in bioelectrochemistry field
With.Large aperture foam silicon is solid in enzyme due to the water-wet behavior with biggish specific surface area and biggish duct and surface
Cause widely to pay attention in load.But as with silica material as main component, its electron-transporting is poor, makes
It obtains its sensor performance obtained and wants inferior many relative to other carbon-based materials.
Summary of the invention
The present invention devises a kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation side
Method and application.
The technical solution adopted by the present invention is that：A kind of large aperture foam silicon-redox graphene based electrochemical modification material
Material, the Electrochemical Modification material are MCFs-rGO.
A kind of above-mentioned large aperture foam silicon-redox graphene based electrochemical modification material preparation method, including such as
Lower step：Under hydrazine hydrate effect, graphene oxide (GO) and template triblock copolymer polyethylene oxide-polycyclic oxygen third
Alkane-polyethylene oxide (P123) is compound, obtains compound P123-rGO, then make MCFs on P123-rGO by Silanization reaction
Growth in situ finally removes template, obtains Electrochemical Modification material MCFs-rGO.Specially：
1) synthesis of compound P123-rGO：By graphene oxide GO ultrasonic disperse in deionized water, three block is added
After copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide P123 and ammonium hydroxide, continue stirring 20~30 minutes, water is added
After closing hydrazine, the pH value of mixed solution is adjusted between 9~10, mixed system is flowed back 24 hours at 110 DEG C, be centrifuged, washing,
Obtain compound P123-rGO.
Preferably, graphene oxide GO, triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide P123
Mass ratio be 1:(3.8-4.2).
Preferably, triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide P123, hydrazine hydrate and ammonium hydroxide
Mass ratio be 1:(4.3-4.5):(4.4-4.7).
2) synthesis of Electrochemical Modification material MCFs-rGO：Under stiring, by triblock copolymer polyethylene oxide-polycyclic
Ethylene Oxide-polyethylene oxide P123 is added to after being completely dissolved in hydrochloric acid solution, at 38 DEG C, be added compound P123-rGO and
The dispersion liquid of mesitylene TMB continues stirring 60~70 minutes, adds tetraethyl orthosilicate TEOS, by mixture at 38 DEG C
Lower stirring is transferred in hydrothermal reactor after 20 hours, is reacted 24 hours at 110 DEG C, after cooling, successively uses toluene and acetone
Washing, vacuum drying, is finally calcined 1-2 hours at 500 DEG C.
Preferably, triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide P123, hydrochloric acid, compound
The ratio between amount of substance of P123-rGO, mesitylene TMB and tetraethyl orthosilicate is 1:(552~553):(0.5-0.55):(33
~34):(39~40).
A kind of above-mentioned large aperture foam silicon-redox graphene based electrochemical decorative material is in electrochemical sensor
Application.The electrochemical sensor is Hb-MCFs-rGO/GC modified electrode, and preparation method includes the following steps：It will be upper
The large aperture foam silicon-redox graphene based electrochemical decorative material MCFs-rGO and Hb H b stated is in deionized water
Middle mixing, and by mixture whirlpool 20 minutes, continue whirlpool 10 minutes after 1.25%nafion solution is added, is uniformly mixed, and
Coated on glass-carbon electrode GC, it is prepared into Hb-MCFs-rGO/GC modified electrode.
Preferably, above-mentioned application, MCFs-rGO, Hb H b and nafion mass ratio be 1:(2.3~
2.7):(0.20~0.25).
A kind of method of Electrochemical Detection hydrogen peroxide, method are as follows：Using Hb-MCFs-rGO/GC modified electrode as work
Electrode, platinum filament are to electrode, and Ag/AgCl is reference electrode, are 7.0 by pH of the three-electrode system insertion containing hydrogen peroxide
In PBS buffer solution, within the scope of 0.2~0.8V of potential, fast 0.2Vs is swept-1Under detected.
The principle of the present invention is：The present invention, by closing it with large aperture foam silicon
At template P123 it is compound, obtain compound P123-rGO, then make MCFs in rGO growth in situ by in-situ synthesis, most
After remove template, obtain MCFs-rGO compound, then by the method for simple blend drop coating prepare modified hemoglobin electricity
Pole, and biosensor has further been probed into the electrochemical catalysis performance and Concentration Testing of hydrogen peroxide.
The present invention has the advantages that：A kind of large aperture foam silicon-redox graphene base that the present invention synthesizes
Electrochemical Modification material, it is multiple by the template P123 for synthesizing it with large aperture foam silicon
It closes, then makes MCFs in rGO growth in situ by in-situ synthesis, obtain compound, preparation method is easy, and material has both excellent lead
Electrical property and biocompatibility, be conducive to enzyme it is immobilized and keep bioactivity.Biosensor produced by the present invention is to hydrogen peroxide
Reduction show excellent electro-chemical activity, may be implemented to concentration of hydrogen peroxide highly sensitive, low detection limit, high selection
Property detection.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of GO (a) He P123-rGO (b).
Fig. 2 is MCFs-rGO (transmission electron microscope picture.
Fig. 3 is the Raman spectrogram of GO (a), rGO (b) and MCFs-rGO (c).
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure (UV-vis) of MCFs-rGO (a), P123-rGO (b) and GO (c).
Fig. 5 is the fourier conversion infrared spectrum (FT- of MCFs (a), MCFs-rGO (b), P123-rGO (c) and GO (d)
IR)。
Fig. 6 is the contact angle photo of rGO (A), MCFs-rGO (B) and MCFs (C)；
Wherein, illustration is from top to bottom the photo of rGO, MCFs-rGO and MCFs dispersion in aqueous solution.
Fig. 7 is fourier conversion infrared spectrum (FT-IR) of Hb (a) and Hb-MCFs-rGO (b).
Fig. 8 is the ultraviolet-visible absorption spectroscopy figure (UV-vis) of Hb (a) He Hb-MCFs-rGO (b).
Fig. 9 is the electrochemical impedance spectrogram (EIS) of rGO (a), MCFs-rGO (b), MCFs (c) and Hb-MCFs-rGO (d)；
Frequency range：0.1 to 105Hz；Sweep speed：200mVs-1；Illustration is that the electrochemical impedance spectrogram (EIS) of rGO is put
Greatly.
Figure 10 is MCFs-rGO/GC electrode (a), Hb-MCFs-rGO/GC electrode (b), Hb/GC electrode (c), Hb-MCFs/
GC electrode (d) and cyclic voltammogram of the Hb-P123-rGO/GC electrode (e) in 0.1M PBS (pH 7.0)；Sweep speed is
0.2Vs-1。
Figure 11 is cyclic voltammogram of the Hb-MCFs-rGO/GC electrode in 0.1M PBS (pH 7.0)；Sweep speed from
0.2 to 1.0Vs-1。
Figure 12 is cyclic voltammetric cathode and anode peak value of the Hb-MCFs-rGO/GC electrode in 0.1M PBS (pH 7.0)
The relational graph of electric current and sweep speed.
Figure 13 is Hb-MCFs-rGO/GC electrode containing 0 (a), 16 μM (b), 32 μM (c), 48 μM (d), 64 μM (e), 80
μM (f), 96 μM of (g) H2O2Cyclic voltammogram in solution, sweep speed 0.2Vs-1。
Figure 14 is that Hb-MCFs-rGO/GC electrode is continuously added in the 0.1M PBS (pH 7.0) of stirring at -0.48V
H2O2Exemplary currents-time response figure.Steady-state current and H2O2The relationship of concentration.
Figure 15 is that Hb-MCFs-rGO/GC electrode is continuously added to H at -0.48V2O2To the 0.1M PBS (pH7.0) of stirring
In exemplary currents-time response figure steady-state current and H2O2The relationship of concentration.
Figure 16 is that Hb-MCFs-rGO/GC electrode is added 1 μM at -0.48V in the 0.1M PBS (pH 7.0) of stirring
H2O2, 20 μM of UA, 20 μM of AA, exemplary currents-time response figure of 20 μM of LA.
Specific embodiment
Technical solution for a better understanding of the present invention, spy are described in further detail with specific embodiment, but side
Case is without being limited thereto.
A kind of large aperture foam silicon of embodiment 1-redox graphene based electrochemical decorative material
(1) preparation method is as follows：
1, the preparation of graphene oxide
Graphene oxide GO is synthesized according to improved Hummers method.10g natural graphite powder is added to containing 98%
In the aqueous solution of sulfuric acid, it is stirred at room temperature at least 24 hours.1g NaNO is then added3, continue stirring 30 minutes.Then exist
At a temperature of 5 DEG C, 30g KMnO is added4, 35~40 DEG C are heated the mixture to, continues stirring 30 minutes, obtains mixture
System.460mL water is added slowly in mixed system in 25 minutes.Later, 1400mL water and 100mL 30%H is added2O2Stop
GO is dispersed in distilled water, again centrifugally operated, 40 by only reaction process after products therefrom GO centrifugation by using ultrasonic wave
It is dry under DEG C vacuum, obtain graphene oxide GO.
2, the synthesis of P123-rGO
The preparation of P123-rGO is completed by the reduction process of GO.The GO of 0.0125g grind into powder is added to
In 10mL deionized water, after ultrasonic disperse 30 minutes, addition 0.5g P123 and 10mL ammonium hydroxide, ultrasonic disperse 20~30 minutes.So
Afterwards, 2.5mL hydrazine hydrate is added, adjusting PH is 9-10, and above-mentioned mixed solution is flowed back 24 hours at 110 DEG C, is centrifuged, with distillation
It is washed to neutrality, obtains compound P123-rGO.
3, the synthesis of MCFs-rGO
Using P123-rGO as template, rGO modified mesoporous foam silicate (MCFs-rGO) is synthesized using Microemulsion Template method.?
Under stirring, 1.0g P123 is added in the mixed liquor of 7.6mL HCl (11.9mol/L) and 50mL P123-rGO, stirring one
Hour, after P123 is completely dissolved, the dispersion liquid of 0.72g TMB is added at 38 DEG C, while stirring 65 minutes.Then, it is added
After 1.41g TEOS, mixture is stirred 20 hours at 38 DEG C.Gained grey liquid is transferred in hydrothermal reactor, in
It is reacted 24 hours at 110 DEG C, product object uses 30mL toluene and acetone washing respectively, is dried under vacuum 24 hours, finally 500
It is calcined 1 hour at DEG C.
4, the synthesis of MCFs
Using P123 as template, using Microemulsion Template method mesoporous foam silicate MCFs.Under stiring, 1.5g P123 is added
Enter in the solution being made into 7.6mL HCl and 48.8mL deionized water, stirs one hour, after P123 is completely dissolved, at 38 DEG C
The dispersion liquid of 0.72g TMB is added, while stirring 65 minutes.Then, after 1.41g TEOS being added, mixture is stirred at 38 DEG C
It mixes 20 hours.Gained milky white liquid is transferred in hydrothermal reactor, is reacted 24 hours at 110 DEG C, product object is used respectively
30mL toluene and acetone washing are dried under vacuum 24 hours, finally calcine 8 hours at 500 DEG C, obtain MCFs.
(2) it detects
1, the characterization of P123-rGO and MCFs-rGO
Fig. 1 is the typical TEM image of GO (a) He P123-rGO (b).Typical case can be seen in Fig. 1 (a) and Fig. 1 (b)
The wrinkle membrane structure of rGO, and Fig. 1 (b) show the configuration of surface of GO while reduction in conjunction with P123 after there is no bright
Aobvious variation.
Fig. 2 is the typical TEM image of MCFs and MCFs-rGO.As shown in Fig. 2 (a), MCFs is that have about 25-30nm diameter
The silica bracket without hole array meso-hole structure.Compared with Fig. 2 (a), after Fig. 2 (b) is shown in further reaction, graphite
Alkene surface forms meso-hole structure, this is similar to the form of MCFs in Fig. 2 (a).
Fig. 3 is the Raman spectrogram of GO (a), rGO (b) and MCFs-rGO (c).GO as can see from Figure 3, rGO and
The Raman spectrum curve of MCFs-rGO has in 1354cm-1The D bands of a spectrum at place and in 1600cm-1The G bands of a spectrum at place.In hydrothermal reduction
Later, due to sp2The quantity of the C atom of hydridization increases and the reconstruction of conjugation graphene network, and the D/G of rGO and MCFs-rGO are strong
Degree increases to 1.12 from the 0.92 of GO than, it was demonstrated that GO is successfully reduced to rGO in composite material synthesis process.In addition, D
The increase of band also reveals the increase of graphene defect, it means that more positions occur can be used for immobilized enzyme and substrate.
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of MCFs-rGO (a), P123-rGO (b) and GO (c).GO is shown in 230nm
The absorption band at place, π → π * transition corresponding to aromatics C=C band in GO.After reduction, MCFs-rGO and P123-rGO are at 270nm
Display absorbs, this is because the red shift of the absorption peak at 230nm.This is observation is that since the electronics conjugate in GO is in warm
It is restored after processing, to confirm that GO is successfully reduced.
Fig. 5 is the fourier transform infrared spectroscopy figure of MCF (a), MCFs-rGO (b), P123-rGO (c) and GO (d).It can by figure
See 466cm present on MCF-1, 801cm-1And 1087cm-1The characteristic peak at place, this is attributed to Si-O flexural vibrations peak and Si-O-
Si symmetric and anti-symmetric stretching vibration peak, same peak also appear on MCFs-rGO, it was demonstrated that the successful preparation of the material.By
GO curve can see is attributed to carbonyl, the 1375cm of carboxyl C=O stretching motion and OH wide absorption respectively-1, 1724cm-1With
3457cm-1Characteristic absorption peak, and these peaks on MCFs-rGO all weaken and even disappear, and clearly illustrate in P123-rGO
It is reduced with MCFs compound tense oxygen-containing group.
Fig. 6 is the contact angle photo of rGO (A), MCFs-rGO (B) and MCFs (C).Illustration be then rGO, MCFs-rGO and
The photo of MCFs dispersion in aqueous solution.Contact-angle measurement is used for the hydrophily of test material.As shown in fig. 6, unmodified rGO
Contact angle is 77.7 °, shows apparent hydrophobicity, and MCFs is due to hydroxy functional group, the contact angle of 9.5 ° of display, with good
Good hydrophily, and as can be seen that MCFs greatly improves the hydrophily of rGO, so that compound after the two combination
Contact angle become 49.3 °.This shows on the one hand the compound of rGO and MCFs increases the specific surface area of material, on the other hand
Material is carried out inorganic modified to increase SiO by establishing in hydrophobic rGO substrate hydrophilic radical2Specific surface area so that multiple
The surface nature of condensation material is changed.This hydrophily is promoting the Direct electron transfer side between immobilised enzymes and electrode
Face plays an important role, because it helps to maintain the bioactivity of immobilised enzymes and increases the load of enzyme.This surface modification
Enzyme is greatly promoted in the fixation of electrode surface.By illustration it is found that rGO forms irreversible aggregation in water, it is deposited in bottle
Bottom shows apparent hydrophobicity.And with P123 it is compound after show uniform black dispersion liquid, further prove and the network of P123
Close the hydrophily for improving rGO.MCFs shows the transparent dispersion of stable and uniform in water, shows good dispersibility.
2 electrochemical sensor Hb-MCFs-rGO/GC modified electrode of embodiment
(1) preparation method of Hb-MCFs-rGO/GC modified electrode
1, the pretreatment of electrode
This experiment uses diameter for the glass-carbon electrode of 3mm, respectively with 1.0,0.3,0.05 μm of Al2O3To glass-carbon electrode into
Row polishing is cleaned by ultrasonic 1min with ultrapure water.With glass-carbon electrode (GC) for working electrode, platinum filament is to electrode, Ag/AgCl electrode
For reference electrode, three-electrode system is constituted.In 1mM K3Fe(CN)61M KCl solution in carry out electrochemistry cyclic voltammetric (CV)
Test, scanning range -200-800mV (vs.Ag/AgCl), sweep speed 200mV/s.When the oxidation peak and reduction of electrode
When the peak position difference at peak is less than 70.0mV, illustrate that the electrode reaches the requirement of activation clean.Glass-carbon electrode is taken out, it is clear with ultrapure water
It washes, high pure nitrogen (N2) drying it is spare.
2, the synthesis of Hb-MCFs-rGO
MCFs-rGO (or MCFs) prepared by 1.0mg embodiment 1 is uniformly dispersed in 0.5mL deionized water, then plus
Enter the pH that 0.25mL contains 2.5mg Hb for 7.0 phosphate buffer solution, stirs 20 minutes.It is molten that 0.25mL5%nafion is added
Continue stirring 10 minutes after liquid, obtains Hb-MCFs-rGO composite material.
3, the preparation of Hb-MCFs-rGO/GC modified electrode
It takes on 6 microlitres of Hb-MCFs-rGO composite material sol drops to the glass-carbon electrode handled well, then mask on the electrode
The beaker of one dried and clean, it is 24 hours dry at 4 DEG C, make moisture slow evaporation, obtains Hb-MCFs-rGO/GC modified electrode.
(2) characterization of Hb-MCFs-rGO composite material
Fig. 7 is the fourier conversion infrared spectrum of Hb (a) and Hb-MCFs-rGO (b).Hb-MCFs-rGO is shown in figure
(there is 1689.0cm on curve b)-1And 1531.5cm-1Two peaks at place, this is attributed to amide I band (C=O) and amide II band
(NH).This with Hb (unanimously, this shows that Hb remains active structure when being fixed on MCFs-rGO compound to curve a), and
The active reservation of Hb is attributed to the good biocompatibility of biggish specific surface area and MCFs-rGO compound.
Fig. 8 is the ultraviolet-visible absorption spectroscopy figure of Hb (a) He Hb-MCFs-rGO (b).As shown in figure 8, being fixed on MCFs-
(the Soret absorption band of curve b) is located at about 405nm Hb on rGO, and (curve a) unanimously, shows that Hb remains its conformation with Hb
It the essential characteristic of integrality and also shows that MCFs-rGO has and good biocompatibility and will not cause to fix thereon
Protein denaturation.
(3) characterization of the chemical property of Hb-MCFs-rGO/GC modified electrode
In electrochemical Characterization test, this experiment is to sweep fast 200mV/s in the PBS buffer solution of 0.1M pH=7.0
Under conditions of carry out.Using three-electrode system, Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, Hb-MCFs-
RGO/GC modified electrode (or rGO/GC modified electrode or MCFs-rGO/GC modified electrode or MCFs/GC modified electrode or Hb/
GC electrode or Hb-MCFs/GC electrode or Hb-P123-rGO/GC electrode) it is working electrode.Under identical experiment condition, often
Hb-MCFs-rGO/GC modified electrode continuous scanning 50 is enclosed before secondary test, detects the stability and applicability of its electrode material.
Fig. 9 is the electrochemical impedance spectrogram of rGO (a), MCFs-rGO (b), MCFs (c) and Hb-MCFs-rGO (d).Illustration
For the enlarged drawing of the electrochemical impedance spectrogram of rGO.As shown, the electronics transfer resistance of bare electrode is almost a straight line, MCFs-
The electronics transfer resistance of rGO/GC electrode is less than the electronics transfer resistance of MCFs/GC electrode, this demonstrate that the successful load of rGO is aobvious
Enhance electronics transfer between material and electrode.In addition, the increase of the electron transmission resistance of Hb-MCFs-rGO/GC electrode
Show that Hb is successfully fixed on modified electrode.
Figure 10 is MCFs-rGO/GC electrode (a), Hb-MCFs-rGO/GC electrode (b), Hb/GC electrode (c), Hb-MCFs/
GC electrode (d) and cyclic voltammogram of the Hb-P123-rGO/GC electrode (e) in 0.1M PBS (pH 7.0), sweep speed are
0.2Vs-1.Redox peaks are not observed on MCFs-rGO/GC electrode, and (curve a) shows in selected scanning range
MCFs-rGO does not show electroactive.When Hb is fixed, Hb-MCFs-rGO/GC electrode (curve b), Hb/GC electrode is observed
(((curve e) display is a pair of reversible and stable for curve d) and Hb-P123-rGO/GC electrode for curve c), Hb-MCFs/GC electrode
Redox peaks, current potential is -0.31V, with FeIII/FeIIElectricity is consistent to characteristic potential, shows that the electronics in response composite is returned
Because in hemoglobin core.By comparing the peak current of several electrodes it is found that Hb-MCFs-rGO/GC electrode peak current is significantly greater than
Other electrodes, peak position difference are 31mV, hence it is evident that are less than other electrodes.Since MCFs-rGO has better conductivity and bio-compatible
Property, this species diversity confirms the invertibity of Hb and swift electron transmitting on Hb-MCFs-rGO/GC electrode.
Figure 11 is cyclic voltammogram of the Hb-MCFs-rGO/GC electrode in 0.1M PBS (pH 7.0), has sweep speed
From 0.2 to 1.0Vs-1.With the increase of frequency sweep rate, the peak position of peak cathode and anode peak value does not have significant change, anode
It is all linearly increasing with the peak point current of cathode.
Figure 12 is cyclic voltammetric cathode and anode peak value of the Hb-MCFs-rGO/GC electrode in 0.1M PBS (pH 7.0)
The relational graph of electric current and sweep speed.It is surface by the bright Hb of chart reacting between the peak value Hb and electrode surface of electrode surface
Control process.In addition, calculate the surface coverage of Hb according to Faraday's law, the result is that the surface concentration of Hb be 1.03 ×
10-10mol cm-2, theoretical monolayer surface concentration 1.89 × 10 higher than Hb-11mol cm-2, it was demonstrated that Hb is in electrode surface by multilayer
Covering.According to La Weini equation, the calculating Apparent electron transfer rate constant of reaction is 11.036s-1, it is raw to be higher than other graphenes
Object sensor.Illustrate that the Hb being fixed on MCFs-rGO/GC electrode has very fast electron transfer rate and high-affinity.
The characterization of the electrocatalysis characteristic of 3 Hb-MCFs-rGO/GC electrode of embodiment
Figure 13 is Hb-MCFs-rGO/GC electrode containing 0 μM (a), 16 μM (b), 32 μM (c), 48 μM (d), 64 μM (e),
80 μM (f), 96 μM of (g) H2O2Cyclic voltammogram in solution, sweep speed 0.2Vs-1.As shown in the figure.With H2O2Plus
Enter, the reduction peak of -0.31V gradually increases, along with fading away with oxidation peak.This shows Hb-MCFs-rGO/GC electrode
To H2O2Reduction have good bioelectrocatalytic activity.
Figure 14 is that Hb-MCFs-rGO/GC electrode is continuously added in the 0.1M PBS (pH 7.0) of stirring at -0.48V
H2O2Exemplary currents-time response figure.Steady-state current and H2O2The relationship of concentration.As shown in figure 14, Hb-MCFs-rGO/GC electricity
Extremely to addition H2O2It is sensitively responded with quick.This is because the opening laminated structure and excellent hydrophily of composite material.
In addition, electrode response electric current and H2O2Concentration is directly proportional
Figure 15 is that Hb-MCFs-rGO/GC electrode is continuously added to H at -0.48V2O2To the 0.1M PBS (pH7.0) of stirring
In exemplary currents-time response figure steady-state current and H2O2The relationship of concentration.It can be seen from the figure that Hb-MCFs-rGO/
The current-responsive of GC electrode is with H2O20.5~5.0 μM of concentration linearly increasing, and sensitivity is μ A/ μM/cm2.From La Weilong equation
It is calculatedIt is 0.748, shows that there is high-affinity between electrode and enzyme.The result shows that Hb-MCFs-rGO/GC is electric
Great to have good catalytic performance, high sensitivity, detection limit is low, and the range of linearity is wide.
The selection Journal of Sex Research of 4 Hb-MCFs-rGO/GC modified electrode of embodiment
Figure 16 is that Hb-MCFs-rGO/GC electrode is added 1 μM at -0.48V in the 0.1M PBS (pH 7.0) of stirring
H2O2With 20 μM of UA, 20 μM of AA, exemplary currents-time response figure of the interfering substances such as 20 μM of LA.In figure, it can be seen that Hb-
MCFs-rGO/GC electrode continuously adds 1 μM of H in 0.1M PBS (pH 7.0) is under the application potential of -0.45V2O2, 20 μM
UA, 20 μM of AA, 20 μM of LA finally add other 1 μM of H2O2In the case where, it can be seen that it is observed during chaff interferent is added
There is no interference electric currents, and when hydrogenperoxide steam generator is added still shows the response of rapid sensitive, and it is excellent to show that biosensor has
Different selectivity.
Claims (9)
1. a kind of large aperture foam silicon-redox graphene based electrochemical decorative material, which is characterized in that the electrochemistry
Decorative material is MCFs-rGO.
2. a kind of preparation side of large aperture foam silicon-redox graphene based electrochemical decorative material described in claim 1
Method, which is characterized in that include the following steps：Under hydrazine hydrate effect, graphene oxide GO and template triblock copolymer are poly-
Oxide-polypropylene oxide-polyethylene oxide P123 is compound, obtains compound P123-rGO, then make by Silanization reaction
MCFs growth in situ on P123-rGO, finally removes template, obtains Electrochemical Modification material MCFs-rGO.
3. preparation method according to claim 2, which is characterized in that be specially：
1) synthesis of compound P123-rGO：By graphene oxide GO ultrasonic disperse in deionized water, triblock copolymer is added
After object polyethylene oxide-polypropylene oxide-polyethylene oxide P123 and ammonium hydroxide, continue stirring 20~30 minutes, hydrazine hydrate is added
Afterwards, the pH value of mixed solution is adjusted between 9~10, mixed solution is flowed back 24 hours at 110 DEG C, is centrifuged, and washing must answer
Close object P123-rGO；
2) synthesis of Electrochemical Modification material MCFs-rGO：Under stiring, by triblock copolymer polyethylene oxide-polycyclic oxygen third
Alkane-polyethylene oxide P123 is added in the mixed liquor of hydrochloric acid and compound P123-rGO, after stirring is completely dissolved to P123,
Mesitylene TMB is added at 38 DEG C, continues stirring 60~70 minutes, then, tetraethyl orthosilicate TEOS is added, mixture is existed
Be transferred in hydrothermal reactor after being stirred 20 hours at 38 DEG C, reacted 24 hours at 110 DEG C, after cooling, successively with toluene and
Acetone washing, vacuum drying, finally calcines 1-2 hours at 500 DEG C, obtains Electrochemical Modification material MCFs-rGO.
4. preparation method according to claim 3, which is characterized in that in step 1), graphene oxide GO, triblock copolymer
The mass ratio of object polyethylene oxide-polypropylene oxide-polyethylene oxide P123 is 1:(3.8~4.2)；Triblock copolymer is poly-
Oxide-polypropylene oxide-polyethylene oxide P123, hydrazine hydrate and ammonium hydroxide mass ratio is 1:(4.3~4.5):(4.4
~4.7).
5. preparation method according to claim 3, which is characterized in that in step 2), triblock copolymer polyethylene oxide-
Polypropylene oxide-polyethylene oxide P123, hydrochloric acid, compound P123-rGO, mesitylene TMB and tetraethyl orthosilicate substance
The ratio between amount be 1:(552~553):(0.5-0.55):(33~34):(39~40).
6. a kind of large aperture foam silicon-redox graphene based electrochemical decorative material described in claim 1 is in electrochemistry
Application in sensor.
7. application according to claim 6, which is characterized in that the electrochemical sensor is that Hb-MCFs-rGO/GC is repaired
Electrode is adornd, preparation method includes the following steps：By large aperture foam silicon-redox graphene base described in claim 1
Electrochemical Modification material MCFs-rGO was mixed in deionized water with Hb H b, and by mixture whirlpool 20 minutes, was added
Continue whirlpool 10 minutes after 1.25%nafion solution, be uniformly mixed, and be coated on glass-carbon electrode GC, is prepared into Hb-MCFs-
RGO/GC modified electrode.
8. application according to claim 7, which is characterized in that MCFs-rGO, Hb H b and nafion quality it
Than being 1:(2.3~2.7):(0.20~0.25).
9. a kind of method of Electrochemical Detection hydrogen peroxide, which is characterized in that method is as follows：Electricity is modified with Hb-MCFs-rGO/GC
Extremely working electrode, platinum filament are to electrode, and Ag/AgCl is reference electrode, and three-electrode system is inserted into the pH containing hydrogen peroxide
Within the scope of 0.2~0.8V of potential, to sweep fast 0.2Vs in 7.0 PBS buffer solution-1Under detected.
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