CN106290506B - The graphene-supported golden core plation shell nanocomposite modified electrode of boron doping measures rutin method - Google Patents
The graphene-supported golden core plation shell nanocomposite modified electrode of boron doping measures rutin method Download PDFInfo
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Abstract
The graphene-supported golden core plation shell nanocomposite modified electrode of boron doping measures rutin method.Hummers methods prepare graphene oxide, and hydro-thermal method is boron source and reducing agent, synthesis boron doping graphene (BG) by raw material, diboron trioxide of graphene oxide.Frens ' methods prepare nano gold sol seed, and Seed inducement method prepares golden core plation core/shell nanoparticles (Au AuPt).Using the boron doping graphene of large specific surface area as carrier, Au AuPt nano-particles are embedded into graphene film interlayer, obtain the graphene-supported Au AuPt nanocomposites of boron doping.Using prepared novel nanocomposite materials modified glassy carbon electrode, successfully constructing can be to electrochemical sensor that rutin quickly detects.Obtain rutin concentration and oxidation peak current linear fit equation：IpThe detection of=6604.1c+8.2044, rutin are limited to 0.3 × 10‑12M。
Description
Technical field
The present invention relates to active component detection method field in tealeaves, more particularly to the graphene-supported golden core gold platinum of boron doping closes
The method that golden shell nanocomposite modified electrode measures rutin.
Background technology
In recent years, the relationship of free radical and a variety of diseases, is more and more taken seriously, and the development of free base biomedical makes
Seek the free radical scavenger of high-efficiency low-toxicity --- natural becomes the research hotspot of biochemistry and medicine and pharmacology.Oxidation
Effect is considered as the most important mechanism of tea health-care anticancer, and it is anti-that a large amount of research report confirms that Polyphenols of Tea has
The plurality of health care functions such as oxidation, anticancer, antimutation, reducing blood lipid, blood pressure lowering, sterilization, anti-inflammatory are that most important physiology is lived in tealeaves
Property ingredient.As a kind of antioxidant substance of flavonoids, have reduces capillary permeability, anti-inflammatory, antiallergy, resists rutin
Many-sided pharmacological activity such as tumour, antibacterial, antiviral and inhibition aldose reductase.Therefore establish it is a kind of detection rutin it is highly sensitive
The method of degree has food analysis, Pharmaceutical Analysis and medical research important meaning.Currently, the analysis method of rutin mainly has purple
Outer spectrophotometry, thin layer chromatography scanning, high performance liquid chromatography and capillary electrophoresis etc..First two method in these four methods
Sensitivity is poor, and the range of linearity is narrow；Latter two method then needs more complex and expensive instrument and equipment.Therefore it establishes a kind of quick
The analysis method of active ingredient Rutin has very important significance in easy detection tealeaves.
Contain 4 phenolic hydroxyl groups in rutin molecule, there is electro-chemical activity, therefore available electroanalysis chemical process carries out it
Detection.Easy to operation since electrochemical analysis method has detection speed fast, of low cost, detection limits the low and height that is quick on the draw
Etc. performances, electrochemically detection can obtain the wider range of linearity, and detection speed is very fast, therefore utilizes electrochemistry side
Method, which detects active constituent in tealeaves, has more wide application space.
Invention content
To solve the above-mentioned problems of the prior art, the purpose of the present invention is to provide the graphene-supported golden cores of boron doping
The method that plation shell nanocomposite modified electrode measures rutin, it is intended to real by simple electrochemical detection method
Quick, effective measurement of active constituent in existing tealeaves is enriched utilization of the tea product in high leading-edge field for Yunnan Province and is provided
Study foundation.
The sensitivity of electrochemical sensor and selectivity depend primarily on energy converter (signal conversion element) on electrode and
Identifier (sensing element), wherein the interface sensing material of energy converter need high electronic conductivity, high-specific surface area with it is good
Catalytic activity reduces redox reaction overpotential to improve absorption property and biocompatibility of the energy converter to sensitive material,
Improve selectivity and the sensitivity of biosensor.Therefore, dopant material of the present invention using boron oxide as graphene introduces electricity
In son or hole to grapheme material, the electronic structure of graphene is adjusted, its physicochemical properties is improved, to change graphene
Electronic transport property.What makes more sense is that boron doped point defect graphene can enhance tri- kinds of metals of Ag, Au, Pt and graphene
Between interaction, obtain the electrode interface decorative material of high electronics conduction.
In order to achieve the above objectives, the technical scheme is that：
The method that the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping measures rutin, step
It is as follows：
Step 1: the preparation of the graphene-supported golden core plation shell nanocomposite of boron doping
Boron doping graphene is synthesized by the hot method of hydro-thermal；Au@AuPt nuclear shell type nano meter particles are prepared using seed mediated growth method；
Finally, between thousands of up to a hundred nuclear shell type nano meter particles being embedded into boron doping graphene sheet layer structure by ultrasonic technique, into one
The stripping of boron doping graphene is single layer or several layers of lamellar structures by step, while boron doped point defect graphene enhances Au@
AuPt nuclear shell type nano meter particles eliminate the defect that nano-particle easily assembles inactivation in the adhewsive action power on its surface, to obtain
Obtain the electrode interface decorative material of BG/Au@AuPt high electronics conduction；
Step 2: the system based on the graphene-supported golden core plation shell nanocomposite electrochemical sensor of boron doping
It is standby
It is first the glass-carbon electrode (GCE) of 3mm by diameter, successively with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Solution exists
It is polished to minute surface on chamois leather, then uses 1.0MHNO respectively3It is cleaned by ultrasonic in solution, absolute ethyl alcohol and secondary water, finally with high-purity
Nitrogen dries up；The BG/Au@AuPt drop coatings that 10 μ L are prepared are taken to dry and save backup in glassy carbon electrode surface with liquid-transfering gun, electrode
Abbreviation BG/Au@AuPt/GCE；
Step 3: detecting rutin based on the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping
Quick detection by the BG/Au@AuPt/GCE built for rutin in tealeaves, wherein phosphate buffer solution
Optimal pH=4, enrichment time 400s, accumulating potential 0.4V；Under the best experimental conditions, sweep speed 1) has been investigated to rutin
The influence of electrochemical behavior illustrates modified electrode to reed according to sweep speed and oxidation, reduction peak current value linear fit equation
Fourth is mainly absorption and control；2) rutin is detected using differential pulse voltammetry, according to concentration and oxidation peak current value
Linear relationship show that the modified electrode limits the range of linearity that rutin detects with detection；It 3) will be graphene-supported based on boron doping
For golden core plation shell nanocomposite modified electrode in the presence of rutin after the circle of continuous scanning 25, redox is electric
Stream is not decreased obviously, and illustrates that doped graphene loads hud typed noble metal nano composite material and provided well for the sensor
Stability, while the stabilizing active and stability of sensor can be kept for a long time；4) modified electrode is shown when detecting rutin
Excellent anti-interference ability, the detection by standard samples recovery to the active constituent in tealeaves obtains the modified electrode to tea
Active ingredient Rutin in leaf has good response, can be used for the detection to actual sample.
Further, in the step 1, the specific preparation method of boron doping graphene is：Take 5mL graphene oxides and
30mL removes distilled water, is 1 according to the mass ratio of graphene oxide and diboron trioxide:10、1:20、1:25、1:30 weigh three oxygen
Change two boron, the diboron trioxide weighed is dissolved in 20mL distilled water.By graphene oxide solution, go distilled water, three oxidations
The mixing of two B solutions and ultrasound 1h are poured into after autoclave is warming up to 160 DEG C, react 3h, it is cooling after taking-up boron doping graphite
Alkene ultrasound 2h, you can obtain finely dispersed boron doping graphene.
Further, when preparing boron doping graphene in the step 1, B2O3It is 1 with graphene oxide mass ratio:20.
Further, in the step 1, the preparation method of Au@AuPt nuclear shell type nano meter particles is：Using Frens ' methods
Nano gold sol is prepared, by 50mL 0.01wt%HAuCl4Solution is put into three-neck flask, installs reflux, is being stirred
Under be heated to boiling after, be rapidly added 3mL 38.8mM sodium citrate solutions, solution gradually becomes blue by purple, finally at wine
Red illustrates that gold chloride has been reduced into nanogold, continues to keep boiling about 30min, be cooled to room temperature, you can gold kind is made
Son；A conical flask is taken, is separately added into 2mL's under condition of ice bath using Au nano-particles as seed using Seed inducement method
Then 680 μ L 1mM gold chlorides and 680 μ L 1mM chloroplatinic acids are added in aurosol, 640 μ L distilled water, mixed solution is in ice bath item
At least 2min is stirred under part, finally uniformly, is slowly instilled 660 μ L sodium borohydride solutions (10mM) with micro syringe above-mentioned
The reaction was continued in solution, and solution gradually becomes aubergine by the claret of Au colloidal sols, illustrates that Au AuPt nano-particles have been formed.
Further, in the step 3, electrochemistry of the rutin on modified electrode is investigated using differential pulse voltammetry
Behavior, the linear fit equation for obtaining rutin concentration and oxidation peak current are：Ip=6604.1c+8.2044, the detection limit of rutin
It is 0.3 × 10-12M。
Compared with the existing technology, beneficial effects of the present invention are：
It is of the invention a kind of based on the graphene-supported golden core plation shell nanocomposite modified electrode measurement of boron doping
The method of rutin, it is a kind of quick and simple method, detection method operation letter to prepare chemically modified electrode using this method
Just, quick and of low cost, effectively and quickly the active ingredient Rutin in tealeaves can be detected, have and promote and apply
Value.The method of the present invention can save the complicated processes of actual sample pre-treatment simultaneously, eliminate sample, the detection sample of preparation
Complicated, time-consuming defect, entire determination method is simple and convenient, favorable reproducibility, and analysis measurement sensitivity is high, by measuring tea
The content of active constituent in leaf enriches utilization of the tea product in high leading-edge field for Yunnan Province and provides research foundation, right
Studying physiologically active ingredient in tea product tealeaves has anti-oxidant, anticancer, antimutation, reducing blood lipid, blood pressure lowering, sterilization, anti-inflammatory etc.
The research of plurality of health care functions and pharmacy mechanism is of great significance.
Description of the drawings
Fig. 1 is the XRD diagram of graphene oxide and boron doping graphene；
Fig. 2 be different quality than boron doping graphene XRD diagram.
Fig. 3 is the XPS figures of boron doping graphene.
Fig. 4 is boron doping graphene scanning electron microscope (SEM) photograph.
Fig. 5 is the XRD diagram of Au and Au@AuPt nano-particles.
Fig. 6 is the scanning electron microscope (SEM) photograph of Au@AuPt nano-particles.
The XRD diagram of the graphene-supported Au@AuPt nanocomposites of Fig. 7 boron dopings.
The scanning electron microscope (SEM) photograph of the graphene-supported Au@AuPt nanocomposites of Fig. 8 boron dopings.
Fig. 9 is the cyclic voltammetry curve of blank PBS solution and the rutin PBS solution Han 0.5 μM/L.
The cyclic voltammetry curve of the rutin Han 0.5 μM/L, right figure are rutin peak in the PBS that Figure 10 left figures are different pH (1-7)
The Linear Fit Chart of electric current and pH.
Figure 11 left figures be accumulating potential 0.4V, enrichment different time (10s, 50s, 100s, 200s, 300s, 350s, 400s,
450s, 600s) after, the cyclic voltammetry curve of rutin, rutin oxidation peak (b), reduction peak (a) electric current after the enrichment of right figure different time
With the curve of time.
Figure 12 left figures are after different potentials (0.1-0.6V) are enriched with rutin 400s, and the cyclic voltammetry curve of rutin, right figure is not
With the curve of oxidation peak (b), reduction peak (a) electric current and accumulating potential after enrichment rutin under current potential.
Cyclic voltammetry curve of Figure 13 left figures rutin under different scanning speed (10-600mV/s), right figure is different scanning
The oxidation peak (b) of speed, the Linear Fit Chart of reduction peak (a) electric current and sweep speed.
The differential pulse voltammetry curve of Figure 14 left figure various concentration rutins, the oxidation peak current of right figure various concentration rutin with
The Linear Fit Chart of concentration.
Figure 15 contains the cyclic voltammetry curve that 0.5 μM/L rutin PBS solutions continuous scanning 25 is enclosed.
Specific implementation mode
Technical solution of the present invention is described in further detail with reference to the accompanying drawings and detailed description：
Test example：
1, the preparation of boron doping graphene
Laboratory apparatus and experiment reagent
Laboratory apparatus：Three-necked round bottom flask, blender, centrifuge, vacuum filtration pump, bottle,suction, electronic analytical balance, shifting
Liquid rifle, drying box, vacuum drying chamber, transmission electron microscope.Autoclave, beaker are cleaned by ultrasonic instrument.
Experiment reagent：Graphite powder, ice, dense H2SO4、KMnO4, 30%H2O2, distilled water, diboron trioxide, graphene oxide.
The preparation of graphene oxide
Graphene oxide is prepared according to Hummer classical ways：The dense H of 92mL are taken under condition of ice bath2SO4In three-neck flask,
It is stirred continuously lower addition 2g graphite powders and 2gNaNO into flask3Solid mixture, then gradation 12g KMnO4, being sufficiently stirred makes instead
Object is answered to be uniformly mixed.Then mixed liquor is transferred to 30 DEG C~40 DEG C of one hour of stirred in water bath, forms taupe paste
Object.It takes out mixed liquor and 160mL distilled water is added at room temperature, the violent bubbling of solution can be observed, be then warming up to 85 DEG C~95
DEG C continue stirring 30 minutes, adds water and be diluted to 560mL.It is last that 12mL 30%H are slowly added several times2O2, solution is by dark brown
Discoloration filters obtained product at glassy yellow while hot, and centrifugation is cleaned until neutrality with warm water.
Clean specific steps：
1. heating water fully dissolves it after the completion of filtering while hot；
2. discarding lower layer's impurity after the rotating speed centrifugation 1min of 3000r/d with centrifuge；
3. the rotating speed centrifugation 3min with centrifuge in 8000r/d discards upper layer substance；
4. the rotating speed centrifugation 5min with centrifuge in 10000r/d discards upper layer substance；
5. the rotating speed with centrifuge in 13000r/d centrifuges 5min；Graphite oxide is prepared to close to neutrality in cleaning
Alkene.
The preparation of boron doping graphene
It takes 5mL graphene oxides and 30mL to remove distilled water, is 1 according to the mass ratio of graphene oxide and diboron trioxide:
10、1:20、1:25、1:30 weigh diboron trioxide, and the diboron trioxide weighed is dissolved in 20mL distilled water.Stone will be aoxidized
Black alkene solution removes distilled water, the mixing of diboron trioxide solution and ultrasound 1h, pours into after autoclave is warming up to 160 DEG C, reacts
3h takes out boron doping graphene ultrasound 2h, you can obtain finely dispersed boron doping graphene after cooling.
Experimental result and discussion
Fig. 1 is the XRD diagram of graphene oxide and boron doping graphene, as can be seen from the figure carrys out graphene oxide in diffraction
Angle (2 θ) is 10.68 ° and a diffraction maximum occurs, and the incorporation of boron so that the diffraction maximum disappears, while being in the angle of diffraction (2 θ)
24.44 ° there is a diffraction maximum, illustrate that graphene oxide has been reduced.
Fig. 2 be different quality than boron doping graphene XRD diagram.By B2O3From graphene oxide with different mass ratioes
Hybrid reaction can obtain the different boron doping graphene of boron content.As can be seen from Figure 2 come, work as B2O3With graphene oxide
Mass ratio is 1:25、1:When 30, while there is the diffraction maximum of boron doping graphene, B2O3Two diffraction maximums also occur therewith,
Illustrate B2O3It does not react completely, there is residue, this is because diboron trioxide addition is excessively caused.And B2O3With graphite oxide
Alkene mass ratio is 1:10、1:20 diffraction maximums for boron doping graphene occur, do not occur B2O3Diffraction maximum, so B2O3
With graphene oxide mass ratio 1:20 be the optimum quality ratio for preparing boron doping graphene.
Fig. 3 is the XPS figures of boron doping graphene.The chemistry of boron doping graphene is detected with x-ray photoelectron spectroscopy (XPS)
Ingredient, it can be seen from the figure that in 298.48~279.68eV, 545.48~528.68eV, 196.48~180.68eV ranges
Inside there are 3 strong peaks, be respectively belonging to the characteristic peak of C1s, O1s, B1s, illustrates that boron doping graphene is successfully prepared.
Fig. 4 is the scanning electron microscope (SEM) photograph of boron doping graphene, and boron doping graphene is in unordered, translucent, accordion, middle part
Divide thin slice stacked together, forms multilayered structure, this edge curl fold pattern is since boron atom is doped into graphene
Defect caused by lattice so that graphene surface has many active sites, therefore part group has occurred in boron doping graphene
It is poly-.2, the preparation of Au@AuPt nano-particles
Laboratory apparatus and experiment reagent
Laboratory apparatus：Three-necked round bottom flask, condensing reflux pipe, magnetic stirring apparatus, magnetic stir bar, volumetric flask, electronics day
Flat, magnetic stir bar, liquid-transfering gun, conical flask, beaker, volumetric flask, culture dish, liquid-transfering gun, transmission electron microscope, UV, visible light
Light spectrophotometer.
Experiment reagent：Trisodium citrate, gold chloride, distilled water, chloroplatinic acid, sodium borohydride, distilled water.
The preparation of gold seeds
Nano gold sol is prepared using Frens ' methods, by 50mL 0.01wt%HAuCl4Solution is put into three-neck flask, peace
Install reflux, after being heated to boiling under stiring, be rapidly added 3mL 38.8mM sodium citrate solutions, solution by purple by
Blue is faded to, finally at claret, illustrates that gold chloride has been reduced into nanogold, continues to keep boiling about 30min, cooling
To room temperature, you can gold seeds are made.
The preparation of Au@AuPt nano-particles
A conical flask is taken, is separately added under condition of ice bath using Au nano-particles as seed using Seed inducement method
Then 680 μ L 1mM gold chlorides and 680 μ L 1mM chloroplatinic acids are added in the aurosol of 2mL, 640 μ L distilled water, mixed solution is in ice
At least 2min is stirred under the conditions of bath, finally uniformly, is slowly instilled 660 μ L sodium borohydride solutions (10mM) with micro syringe
The reaction was continued in above-mentioned solution, and solution gradually becomes aubergine by the claret of Au colloidal sols, illustrates Au AuPt nano-particles shape
At.
Results and discussion
Fig. 5 is the XRD diagram of Au and Au@AuPt nano-particles, the angle of diffraction (2 θ) of the nano-particle of Au 38.20 °,
44.38 °, 64.62 ° and 77.7 °, it is belonging respectively to the diffraction of nano-particle (111), (200), (220) and (311) crystal face of Au
Peak illustrates that prepared gold nanoparticle is face-centred cubic structure.Plation is wrapped up into golden core surface, Au@AuPt nanoparticles
At 38.36 °, 44.58 °, 64.74 ° and 77.86 °, the angle of diffraction (2 θ) of the nano-particle relative to Au goes out the angle of diffraction (2 θ) of son
Show and moved to right, has tentatively illustrated that Au AuPt nano-particles are successfully prepared.
Fig. 6 is the scanning electron microscope (SEM) photograph of Au@AuPt nano-particles, and the nano-particle of the nutty structure in figure is Au@
AuPt nano-particles, nano-particle is substantially spherical in shape, and average grain diameter is about 20nm.
3, it is based on the graphene-supported golden core plation shell nanocomposite electrochemical sensor of boron doping and detects rutin
Laboratory apparatus and experiment reagent
Laboratory apparatus：Beaker, glass bar, liquid-transfering gun, is cleaned by ultrasonic instrument, glass plate, electrochemical workstation, platinum at volumetric flask
Electrode, Ag/AgCl electrodes, wash bottle, glass-carbon electrode, chamois leather.
Experiment reagent：Distilled water, alundum (Al2O3) nano-polishing powder, potassium ferricyanide solution, sodium dihydrogen phosphate, phosphoric acid hydrogen two
Sodium, rutin standard items, tealeaves.
The preparation of the graphene-supported golden core plation shell nanocomposite of boron doping
With boron doping graphene solution：Au@AuPt nano-particle solutions volume ratio 1:The two mixed solution is placed in beaker by 2
Middle ultrasound 3h, it is desirable that temperature is no more than 35 DEG C, you can obtain the nano combined material of the graphene-supported golden core plation shell of boron doping
Material.
The XRD diagram of the graphene-supported golden core plation shell nanocomposite of Fig. 7 boron dopings, the angle of diffraction (2 θ) are
22.4 ° be boron doping graphene diffraction maximum, occur Au@AuPt nanoparticles at 38.36 °, 44.58 °, 64.74 ° and 77.86 °
The diffraction maximum of son illustrates successfully to prepare the graphene-supported golden core plation shell nanocomposite of boron doping.
The scanning electron microscope (SEM) photograph of the graphene-supported golden core plation shell nanocomposite of Fig. 8 boron dopings.Boron doping graphite
After alkene and Au@AuPt nanocomposites are by ultrasonic disperse, Au@AuPt nano-particles are more uniformly embedded into boron doping stone
In black alkene lamella, due to the insertion of Au@AuPt nano-particles, boron doping graphene has been stripped into individual layer laminated structure, centainly
The reunion of boron doping graphene is eliminated in degree.
3, graphene-supported golden core plation shell nanocomposite modified glassy carbon electrode (the BG/Au@AuPt/ of boron doping
GCE preparation)
First by glass-carbon electrode successively with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Solution is polished to minute surface on chamois leather, so
Use 1.0M HNO respectively afterwards3It is cleaned by ultrasonic in solution, absolute ethyl alcohol and secondary water, is finally dried up with high pure nitrogen, in 10mL 1M
It is detected with cyclic voltammetry in potassium ferricyanide solution, redox peaks potential difference is no more than 80mV.If more than repeating the above steps,
Until no more than until 80mV.The graphene-supported Au@AuPt of boron doping for finally taking 10 μ L to prepare with liquid-transfering gun are nano combined
Droplets of material is coated in glassy carbon electrode surface, dries and saves backup.
Electrochemical behavior of the modified electrode to rutin
0.01mM rutin standard samples are configured, pH ranges take 10mL PBS in inspection in 3~5 phosphate buffer solution (PBS)
It surveys in bottle, 500 μ L 0.01mM rutin standard samples, scanning range 0-0.8V, sweep speed 50mV/s is added.
Fig. 9 is the PBS solution of blank and the cyclic voltammetry curve of the rutin PBS solution Han 0.5 μM/L.For the PBS of blank
Solution does not have redox peaks appearance, and after 0.5 μM/L rutins are added, there are apparent redox peaks, illustrates BG/Au@
AuPt/GCE has good response to rutin.Rutin Electrooxidation Mechanism on modified electrode can be expressed as：Rutin first loses one
Proton forms univalent anion, and then univalent anion is oxidized to radical anion, and radical anion is further subjected to
One reversible oxidation process is oxidized to dehydrogenation rutin.
Cyclic voltammetric of Figure 10 rutins on different modifying electrode GCE (a), BG/GCE (b), BG/Au@AuPt/GCE (c)
Curve.As seen from the figure, when bare electrode surveys rutin, there are not redox peaks, illustrate that bare electrode does not respond to rutin；And
When BG/GCE detects rutin, then there are apparent redox peaks, when Au@AuPt nano-particles are embedded into boron doping graphene
Afterwards, redox peaks of the rutin on BG/Au@AuPt/GCE further increase, and illustrate that Au@AuPt nano-particles are embedded into boron and mix
It is further single layer or several layers of lamellar structures, while boron doping by the stripping of boron doping graphene between miscellaneous graphene sheet layer structure
Point defect graphene enhance Au@AuPt nuclear shell type nano meter particles in the adhewsive action power on its surface, eliminate nano-particle
The BG/Au@AuPt electrode interface decorative materials of the easily defect of aggregation inactivation, acquisition are the excellent materials for detecting rutin.
Influences of the different pH to detection rutin
The cyclic voltammetry curve of the rutin Han 0.5 μM/L in the PBS that Figure 11 left figures are pH=1-7.With the gradual increase of pH,
Redox peak current also gradually increases, and spike potential moves to left.When pH is 4, peak current is maximum, and peak current but gradually subtracts therewith
It is small.It can thus be concluded that the optimal pH for going out to detect rutin is 4.
Influence of the different enrichment times to detection rutin
Rutin is mainly by absorption and control, first, influence of the time to absorption to electrode；Second is that influence of the potential to absorption.
Therefore it to be enriched with before with cyclic voltammetry rutin, the rutin in PBS buffer solutions is enriched to electrode as possible
The error in continuous mode is reduced on surface.Figure 12 (left figure) is accumulating potential when being 0.4V, is enriched with different time (10-
600s) cyclic voltammetry curve of rutin, (right figure) are the oxidation peak (b) of rutin, reduction peak (a) electric current after different enrichment times afterwards
With the curve of time.As enrichment time is constantly elongated, redox peak current gradually increases, when enrichment time reaches 400s
When, peak current is maximum, just on a declining curve later, and therefore, the best enrichment time of rutin is 400s.
Influence of the difference enrichment potential to detection rutin
Figure 13 left figures are the cyclic voltammetry curve of rutin after enrichment 400s under different accumulating potentials (0.1-0.6V), and right figure is
Different potentials be enriched with the oxidation peak (b) of rutin after 400s, reduction peak (a) electric current and accumulating potential curve.With accumulating potential
Continuous increase, redox peak current becomes larger, and when accumulating potential is 0.4V, redox peak current is maximum, it
Just on a declining curve afterwards, therefore, the best enrichment potential of rutin is 0.4V.
Influence of the sweep speed to rutin electrochemical behavior
Cyclic voltammetry curve of Figure 14 left figures rutin under different scanning speed (10-600mV/s), the difference of right figure rutin
The oxidation peak (b) of rutin, reduction peak (a) electric current and the Linear Fit Chart for sweeping speed under sweep speed.In left figure, sweep speed from
10mV/s increases to 600mV/s, and oxidation peak current increases with the increase of sweep speed；In 10~600mV/s scanning ranges,
Oxidation peak, reduction peak electricity IpLinear with sweep speed υ, oxidation peak current equation of linear regression is Ip=0.0542 υ-
5.4432 R2=0.9904, reduction peak current electric current equation of linear regression is Ip=0.0382 υ+3.8547, R2=0.9905, it says
Bright rutin is absorption and control within the scope of the sweep speed.
Differential pulse voltammetry detects rutin
Figure 15 left figures are the differential pulse voltammetry curve of various concentration rutin, and right figure is the oxidation peak electricity of various concentration rutin
The Linear Fit Chart of stream and concentration.It keeps the bottoms PBS liquid constant, different amounts of rutin is added, various concentration rutin can be obtained
Peak current, show that its equation of linear regression is I according to the relationship of peak current and rutin concentrationp=6604.1c+8.2044, R2
=0.9955, detection is limited to：4×10-12M。
The stability of modified electrode
During being scanned to rutin with cyclic voltammetry, all parameter constants are molten to the PBS for containing 0.5 μM/L rutins
Liquid continuous scanning 25 is enclosed, and with the increase of the scanning number of turns, the redox peaks of rutin go out peak position, peak current size substantially not
Become, cyclic voltammetry curve is substantially overlapping, illustrates that the graphene-supported golden core plation shell nanocomposite of boron doping can be very well
Good catalytic activity is fixed on the electrode and is kept on ground, has higher stability.
Detection of the modified electrode to actual sample
Weigh 0.05g black tea be put into it is spare in beaker.Measurement 50mL distilled water is heated to 80 DEG C and pours into the burning equipped with black tea
10min is boiled in cup heating, places to room temperature, filtering.Certain tea is measured, is preserved after 100 times of dilution and is used as measuring practical sample
Product are used.Tea stoste is measured first, then carries out mark-on reclaims.With same method parallel determination 3 times, the recycling of rutin is obtained
Rate 89.26-99.17% meets the detection of actual sample.
It summarizes
It is embedded into boron doping graphene film interlayer by ultrasonic technique Au AuPt nano-particles, obtains boron doping graphene
Load Au@AuPt nanocomposites.Due to the insertion of Au AuPt nano-particles, by the stripping of boron doping graphene at the number of plies compared with
Few structure, from the influence that elimination boron doping graphene is reunited to a certain degree.It is steady that Au@AuPt nano-particles are also improved simultaneously
Qualitative and catalytic, and Au AuPt nano-particles are securely attached to graphene film interlayer.
The electrochemical sensor based on the graphene-supported Au@AuPt core-shell nano composite materials of boron doping is built, by right
When the optimization of the pH of PBS buffer solutions obtains pH=4, the redox peak current of rutin is maximum, therefore the pH is to measure rutin
Optimal pH.Different enrichment times has large effect from different accumulating potentials to detection rutin, when investigating different enrichments
Between and accumulating potential, it can be deduced that best enrichment time is 400s, and the best potential that is enriched with is 0.4V.By investigating sweep speed pair
The influence of rutin electrochemical behavior show that modified electrode is mainly absorption and control to rutin.In Optimal pH, enrichment time, enrichment
Differential pulse voltammetry detection is carried out to rutin under potential condition, obtains rutin concentration and oxidation peak current linear fit equation：
IpThe detection of=6604.1c+8.2044, rutin are limited to 0.3 × 10-12M.Under optimal testing conditions, rutin is carried out continuous
The cyclic voltammetry scans of 25 circles can show that the electrode is with good stability, reproducibility.Modified electrode is finally used for rutin
The detection of actual sample show that BG/Au@AuPt/GCE have good response to rutin in tealeaves, can be used for actual sample rutin
Detection.
The operation principle of the present invention is that：
The present invention prepares graphene oxide with Hummers methods；Boron doping graphene is prepared by hydro-thermal method again；Utilize seed
Growth method prepares gold seeds；It is reducing agent by HAuCl using sodium borohydride using Seed inducement method4And H2PtCl6Reduction is in gold kind
Au@AuPt nano-particles are prepared in sublist face；The boron doping graphite for introducing large specific surface area is dilute as carrier, load Au@
AuPt core-shell nanos obtain the graphene-supported Au@AuPt nanocomposites of boron doping；Finally with prepared Performances of Novel Nano-Porous
Nano composite material modified glassy carbon electrode detects rutin.
1, graphene oxide is prepared with Hummers methods；Boron doping graphene is prepared by hydro-thermal method again；From graphene oxide
XRD diagram with boron doping graphene is it is found that boron doping graphene occurs for 24.44 ° relative to graphene oxide in the angle of diffraction (2 θ)
Boron doping graphene diffraction maximum illustrates that it is feasible to select diboron trioxide as the reducing agent and boron source for preparing boron doping graphene
's.In addition, experiment obtains B2O3Mass ratio with graphene oxide is 1:20 be the optimum quality ratio for preparing boron doping graphene.
Occur C1s, O1s, B1s at 284.3eV, 533.11eV, 193.45eV it can be seen from the XPS figures of boron doping graphene
Characteristic peak, illustrate successfully to prepare boron doping graphene.
2, nanometer gold seeds are prepared using Frens ' methods, HAuCl is added in gold seeds solution4And H2PtCl6, with boron hydrogen
Change sodium makes its reduction on gold seeds surface for reducing agent, and Au@AuPt nano-particles are prepared.Pass through the XRD of Au@AuPt particles
Figure, it can be seen that the angle of diffraction (2 θ) of the nano-particle of Au is in 38.20 °, 44.38 °, 64.62 ° and 77.7 °, according to the literature, Pt
The angle of diffraction (2 θ) of nano-particle is at 39.76 °, 46.24 °, 67.46 ° and 81.29 °, after plation is wrapped up golden core surface,
The angle of diffraction (2 θ) of Au@AuPt nano-particles is at 38.36 °, 44.58 °, 64.74 ° and 77.86 °, the nano-particle relative to Au
The angle of diffraction (2 θ) move to right, illustrate that golden core plation core/shell nanoparticles have synthesized success.The Au@known to scanning electron microscope (SEM) photograph
The average grain diameter of AuPt particles is about 20nm.
3, by by boron doping graphene and Au@AuPt nano materials with 1:2 ratios mixing ultrasound obtains boron doping graphite
Alkene loads Au@AuPt nanocomposites.By XRD diagram obtain the nanocomposite the angle of diffraction (2 θ) be 39.76 °,
46.24 °, 67.46 ° and 81.29 °, 24.44 °, while there is the diffraction of Au@AuPt core-shell nanos, boron doping graphene
Levy peak；It can be seen that by scanning electron microscope (SEM) photograph, graphene is removed the laminated structure at single-layer or multi-layer by the insertion of nano material, and one
Determine to eliminate the reunion of boron doping graphene in degree, while core-shell nano material is also securely attached to graphene film interlayer.
4, detection of the graphene-supported Au@AuPt nanocomposites electrochemical sensor of boron doping to rutin, by excellent
The pH value for changing PBS solution show that the Optimal pH for measuring rutin is 4.Different enrichment times is from different accumulating potentials to detection
Rutin has large effect, according to the difference of enrichment time and accumulating potential, it can be deduced that best enrichment time is 400s, most preferably
Accumulating potential is 0.4V.Influence by investigation different scanning speed to rutin electrochemical behavior, obtain sweep speed and aoxidize,
The linear fit equation of reduction peak current illustrates that rutin on modified electrode surface is mainly absorption and control.In Optimal pH, enrichment
Between, using differential pulse voltammetry rutin is detected under the conditions of accumulating potential, obtain rutin concentration and oxidation peak current
Linear fit equation：IpThe detection of=6604.1c+8.2044, rutin are limited to 0.3 × 10-12M.It is right under optimal detection condition
Rutin carries out the cyclic voltammetry scans of continuous 25 circle, show that modified electrode is with good stability, reproducibility.Finally by adding
Mark absorption method is detected the rutin in tealeaves, can show that BG/Au@AuPt/GCE have good sound to the rutin in tealeaves
It answers, can be used for the detection of actual sample.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
The change or replacement expected without creative work, should be covered by the protection scope of the present invention.Therefore, of the invention
Protection domain should be determined by the scope of protection defined in the claims.
Claims (5)
1. the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping measures rutin method, feature exists
In steps are as follows：
Step 1: the preparation of the graphene-supported golden core plation shell nanocomposite of boron doping
Boron doping graphene is synthesized by hydro-thermal method；Au@AuPt nuclear shell type nano meter particles are prepared using seed mediated growth method；Finally,
Between nuclear shell type nano meter particle is embedded into boron doping graphene sheet layer structure by ultrasonic technique, further by boron doping graphene
Stripping is single layer or several layers of lamellar structures, while boron doped point defect graphene enhances Au@AuPt core-shell type nano grains
Son eliminates the defect that nano-particle easily assembles inactivation in the adhewsive action power on its surface, and boron doping graphite is based on to obtain
The high electronics conducting electrode modifying interface material of alkene/gold core plation shell nanocomposite；
Step 2: the preparation based on the graphene-supported golden core plation shell nanocomposite electrochemical sensor of boron doping
It is first the glass-carbon electrode GCE of 3mm by diameter, successively with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Solution is on chamois leather
It is polished to minute surface, 1.0MHNO3 solution is then used respectively, is cleaned by ultrasonic in absolute ethyl alcohol and secondary water, finally use High Purity Nitrogen air-blowing
It is dry；The graphene-supported golden core plation shell nanocomposite drop coating of boron doping for taking 10 μ L to prepare with liquid-transfering gun is in glass carbon
Electrode surface is dried and is saved backup, electrode abbreviation BG/Au@AuPt/GCE；
Step 3: detecting rutin based on the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping
Quick detection by the BG/Au@AuPt/GCE built for rutin, wherein Optimal pH=4 of phosphate buffer solution,
Enrichment time 400s, accumulating potential 0.4V；Under the best experimental conditions, sweep speed 1) has been investigated to rutin electrochemical behavior
Influence, illustrate modified electrode to rutin master according to the equation that sweep speed and oxidation, reduction peak current value linear fit obtain
If absorption and control；2) rutin is detected using differential pulse voltammetry, according to the linear of concentration and oxidation peak current value
Relationship show that the modified electrode limits the range of linearity of rutin and detection；3) the graphene-supported golden core plation shell of boron doping
Nanocomposite modified electrode is in the presence of rutin, after continuous scanning 25 is enclosed, under redox current is not apparent
Drop, illustrates that the nanocomposite provides good stability for the sensor, while can keep the stabilization of sensor for a long time
Activity and stabill；4) modified electrode shows excellent anti-interference ability when detecting rutin, passes through standard samples recovery pair
Active constituent in tealeaves is detected, and show that the modified electrode has good response to the rutin in tealeaves, for reality
The detection of border sample.
2. the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping according to claim 1 is surveyed
Determine rutin method, which is characterized in that in the step 1, the specific preparation method of boron doping graphene is：Take 5mL graphite oxides
Alkene and 30mL remove distilled water, are 1 according to the mass ratio of graphene oxide and diboron trioxide:10、1:20、1:25、1:30 weigh
The diboron trioxide weighed is dissolved in 20mL distilled water by diboron trioxide, by graphene oxide, goes distilled water, three oxidations
The mixing of two B solutions and ultrasound 1h, are transferred to autoclave, 3h are reacted after being warming up to 160 DEG C, finally by cooling boron doping
Graphene takes out and ultrasound 2h, you can obtains finely dispersed boron doping graphene.
3. the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping according to claim 2 is surveyed
Determine rutin method, which is characterized in that when preparing boron doping graphene in the step 1, B2O3It is with graphene oxide mass ratio
1:20。
4. the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping according to claim 1 is surveyed
Determine rutin method, which is characterized in that in the step 1, the preparation method of Au@AuPt nuclear shell type nano meter particles is：Using
Frens ' methods prepare nano gold sol, by 50mL 0.01wt%HAuCl4Solution is put into three-neck flask, installs reflux dress
It sets, after being heated to boiling under stirring condition, is rapidly added 3mL 38.8mM sodium citrate solutions, solution gradually becomes blue by purple
Color illustrates that gold chloride has been reduced into nanogold finally at claret, continues to keep boiling about 30min, be cooled to room temperature,
It can be prepared by gold seeds；Using Seed inducement method, using Au nano-particles as seed, the gold that 2mL is added under condition of ice bath is molten
Glue is then slowly added into the mixed liquor of 680 μ L 1mM gold chlorides and 680 μ L 1mM chloroplatinic acids, 640 μ L distilled water, mixed solution
At least 2min is stirred under condition of ice bath, finally uniformly, is slowly dripped 660 μ L sodium borohydride solutions 10mM with micro syringe
Enter in above-mentioned solution, the reaction was continued 40min, solution gradually becomes aubergine by the claret of Au colloidal sols, illustrates AuPt nanometers of Au@
Particle has been formed.
5. the graphene-supported golden core plation shell nanocomposite modified electrode of boron doping according to claim 1 is surveyed
Determine rutin method, which is characterized in that in the step 3, electricity of the rutin on modified electrode is investigated using differential pulse voltammetry
Chemical behavior, rutin concentration and oxidation peak current linear fit equation are：The detection of Ip=6604.1c+8.2044, rutin are limited to
0.3×10-12M。
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