CN103076375A - Preparation method and application of coaxial entity/nano porous gold/Co3O4 compound electrode material - Google Patents
Preparation method and application of coaxial entity/nano porous gold/Co3O4 compound electrode material Download PDFInfo
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- CN103076375A CN103076375A CN2012105630164A CN201210563016A CN103076375A CN 103076375 A CN103076375 A CN 103076375A CN 2012105630164 A CN2012105630164 A CN 2012105630164A CN 201210563016 A CN201210563016 A CN 201210563016A CN 103076375 A CN103076375 A CN 103076375A
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Abstract
The invention relates to a preparation method and application of a coaxial entity/nano porous gold/Co3O4 compound electrode material, particularly relates to a preparation method and application of a metal/oxidate compound electrode of a novel biosensor, and aims to prepare a self-support coaxial entity/nano porous gold electrode material by utilizing an electrochemical alloying/dealloying in-situ etching technology and modifying Co3O4 nano particles on the outer layer porous gold of the material through a hydro-thermal synthesis manner. The invention is based on a three-electrode electrochemical system; the self-support coaxial entity/nano porous gold electrode material is prepared on a gold thread through electrochemical alloying/dealloying; the material is characterized in that after hydro-thermal synthesis is performed to cobalt nitrate and hexadecyl trimethyl ammonium bromide solution, a compound nano-structure of the self-support coaxial entity/nano porous gold/Co3O4 is prepared, and the material is used for electrochemical detection of glucose. Results show that due to the crosscorrelation of Au and Co3O4 and common effects of a specific microstructure, the material has very high sensitivity to glucose.
Description
Technical field:
The present invention relates to nano metal/oxide structure preparation and chemical analysis detection technique field.
Background technology:
That the biology sensor that is used for glucose detection need to have is highly sensitive, good reliability, be swift in response, selectivity is good and cost is low characteristics.At present mainly for detection of method have: optical means, colourimetry, electrochemical process and Electrochemiluminescince.Wherein, simple, highly sensitive, the cost of electrochemical method is also very low and be subject to extensive concern.
Usually the electrochemical glucose sensor based on biology enzyme utilizes biocatalyst glucose dehydrogenase (GDH) and glucose oxidase (GOx).The glucose biological sensor of GDH base is to produce nicotinamide adenine dinucleotide (NADH) by GDH enzymatic electrochemical oxidation reactions, but because electron transfer dynamics is slow among the NADH, determined that its electrochemical oxidation needs higher current potential 0.7～1.0V (vs.SCE).And the glucose biological sensor of GOx base is to generate H by the catalysis glucose oxidase
2O
2, this process also needs to surpass the noble potential of 0.6V (vs.SCE).Under so high current potential, multiple electrochemical activity kind coexists in biological fluid, such as ascorbic acid, Microbial biomass C, uric acid, etc., also with oxidized, thereby produce undesired signal.And exist following shortcoming based on the sensor of biology enzyme: (1) lacks long-time stability, and this is the inherent characteristic of enzyme; (2) enzyme comprises GOx, and price is all very expensive, and cost is higher; (3) activity of enzyme extremely easily is subject to temperature, solution pH value, the impact of humidity and other impurity such as noble metal.And glucose oxidase is soluble in water, and character is unstable, and the activated centre of enzyme is buried at protein interior, these factor affecting the sensitivity of glucose biological sensor, stability and reappearance, also limited its industrialized development.
For the problem that above-mentioned biological enzyme agent faces, the non-enzymatic catalysis agent is used in glucose detection huge development space.Recently, the metal oxide of nanostructured is because it is cheap, high bio-compatibility and electro catalytic activity, and the electronics transfer that strengthens and adsorptive power and paid close attention to widely, the nanostructured metal oxides that will have a high catalytic activity has been introduced into as a kind of new electrode material in the middle of the application of sensor, for improvement non-enzyme glucose biological sensor provides new chance.Yet, the electric conductivity that metal oxide nanostructure is ultralow, for example Co of room temperature
3O
4Conductivity only be 10
-5S m
-1, their widespread use in high responsive and reliability, rapid-action electrochemica biological sensor of serious limitation.Enhancing the electrochemica biological sensing wherein one of the method for electron transport ability be the composite materials that design has high catalytic activity material and high conductivity.Although study mainly based on zero dimension, one dimension or two-dimensional nanostructure material with carbon element or metal nanoparticle at present, and obtained preliminary progress.But the electric transmission distance is limited in these low-dimensional nano structures, all can produce high contact resistance between each structure and with the integrated of current collector.The electric conductivity modification of the overall electrode that therefore is assembled into by these low-dimensional nano structures is still very limited, limits its widespread use in high sensitivity, the low detectable concentration limit and rapid-action electrochemical sensor.
Summary of the invention:
The purpose of this invention is to provide a kind of coaxial entity/nano-porous gold with high mechanical stability, self-supporting/Co
3O
4The preparation method of combination electrode material and application, the particularly application in the trace glucose detection.The mode that this invention combines with Hydrothermal Synthesis by electrochemical in-situ alloying/removal alloying is compound in metal oxide in the metal duct of three-D nano-porous structure, and this nano-porous structure is integrated in current collector, realizes improving simultaneous minimization active substance and the current collector contact resistance of electro catalytic activity.This composite nanostructure has distinctive dual link nano pore and metal ligament, can strengthen simultaneously the transmission of analyte and electronics, and the superhigh specific surface area that provides of the nano-porous structure electro catalytic activity that can utilize effectively, fully the metal/oxide compound substance to strengthen.
The present invention passes through western volume technical scheme and realizes:
A kind of coaxial entity/nano-porous gold/Co
3O
4The preparation method of combination electrode material may further comprise the steps:
A, in 60 ℃ of water-baths, the anhydrous ZnCl2 of purity 99.9% stirred fully to be dissolved in the phenmethylol (BA99%) through magneton obtain ZnCl
2/ BA electrolytic solution, concentration of electrolyte are 1～2M;
B, with diameter be the gold thread of 0.01～0.2mm as working electrode, the Zn plate is as to electrode, the Zn line is assembled into the three-electrode electro Chemical system as contrast electrode, above mixed organic solvents is that electrolyte heats in oil bath and maintains 100～120 ℃;
C, in the scope of-0.8～1.9V take Electrochemical Scanning speed as 5～50mV/s scan cycle, through behind 20～50 alloys/go the alloy cyclic process, obtain the gold electrode material of the coaxial entity/nano-porous structure of self-supporting.
Described a kind of coaxial entity/nano-porous gold/Co
3O
4The preparation method of combination electrode material, the gold thread among the described step b utilizes acetone, ethanol and high purity water to clean after polishing successively, and at last oven dry is as working electrode.
Described a kind of coaxial entity/nano-porous gold/Co
3O
4The preparation method of combination electrode material prepares the coaxial entity/nano-porous structure of self-supporting, produces the coaxial entity/nano-porous gold of self-supporting/Co
3O
4Combination electrode material may further comprise the steps:
A, be the Co (NO of 3:1 with concentration ratio
3)
2And CTAB (cetyl trimethyl ammonium bromide) ratio of being placed on is to stir in the second alcohol and water of 6:1;
B, be that the gold electrode material of coaxial entity/nano-porous structure picks up with propclip and stands upright on configuration solution central authorities with the sample of claim 1, can both fully contact solution around making it;
C, ready sample and solution are placed in the reactor, temperature setting is set to 180 ℃, obtains the coaxial entity/nano-porous gold of self-supporting/Co behind 60～120min
3O
4Combination electrode material.
Coaxial entity/the nano-porous gold of described a kind of self-supporting/Co
3O
4Combination electrode material is directly used in the electro-chemical test to concentration of glucose, may further comprise the steps:
A, with described sample as working electrode, Pt is as to electrode, Ag/AgCl forms three-electrode system as contrast electrode;
B,, the characteristic scope of cyclic voltammetric is decided to be during as the working electrode electrochemical gaging with described sample-0.8～0.6V carries out cyclic voltammetry scanning; The voltage of electric current-time curve is set as 0.26V, after background current reaches stable state (1～2min), writing time, the current curve section (1～2min), and add the glucose solution sample with microsyringe and stir simultaneously (1～2min), the sensor that will measure under different glucose solution concentration is to the current-responsive value of glucose, in 5nM～70mM scope, obtain the linear relationship of electric current and concentration of glucose;
C, described sample change as the linear relationship of the electric current of working electrode and the concentration of glucose slope with the not collinearity of concentration.
Structure of the present invention is used as a kind of novel electrochemical glucose sensor as electrode, is directly used in the quick super low concentration electrochemical gaging of glucose, the coaxial entity/nano-porous gold of self-supporting/Co
3O
4The nano particle combination electrode material has the advantages such as catalytic performance is high, good stability, strong interference immunity as electrode, and high to the detection efficiency of glucose, and accuracy is high.
Description of drawings:
Coaxial entity/the nano-porous gold of Fig. 1, self-supporting/Co
3O
4The manufacturing process schematic diagram of nano particle combination electrode material, wherein:
(a) entity gold thread;
(b) coaxial entity/nanoporous gold thread;
(c) coaxial entity/nanoporous/cobalt oxide composite structure.
Scanning electron microscope (SEM) phenogram of the coaxial entity of Fig. 2, self-supporting/nanoporous gold thread, wherein:
(a) coaxial entity/nanoporous gold thread low power SEM phenogram;
(b) the coaxial entity/transversal section SEM of nanoporous gold thread phenogram;
(c) coaxial entity/nanoporous gold thread top view SEM phenogram.
Coaxial entity/the nano-porous gold of Fig. 3, self-supporting/Co
3O
4The scanning electron microscope of nano particle combination electrode material (SEM) phenogram.
Coaxial entity/the nano-porous gold of Fig. 4, self-supporting/Co
3O
4The transmission electron microscope of nano particle combination electrode material (TEM) phenogram.
Coaxial entity/the nano-porous gold of Fig. 5, self-supporting/Co
3O
4The Raman spectrogram of nano particle combination electrode material.
Coaxial entity/the nano-porous gold of Fig. 6, self-supporting/Co
3O
4The XRD spectrum figure of nano particle combination electrode material.
Coaxial entity/the nano-porous gold of Fig. 7, self-supporting/Co
3O
4The porous gold toughness test contrast picture that nano particle combination electrode material and 20 μ m are thick, wherein:
(a) pure nano-porous gold;
(b) coaxial entity/nano-porous gold.
Coaxial entity/the nano-porous gold of Fig. 8, self-supporting/Co
3O
4To be electrode contain (b) at the KOH of 0.5M solution (a) to the nano particle combination electrode material does not contain cyclic voltammetric family curve in the 10mM glucose, wherein:
(a) contain (b) and do not contain cyclic voltammetric family curve in the 10mM glucose;
(b) do not contain cyclic voltammetric family curve in the 10mM glucose.
Coaxial entity/the nano-porous gold of Fig. 9, self-supporting/Co
3O
4The quick response curve that the nano particle combination electrode material is surveyed as electrode pair glucose, wherein:
(a) quick response curve,
(b) typical curve.
Coaxial entity/the nano-porous gold of Figure 10, self-supporting/Co
3O
4The nano particle combination electrode material is as detection limit and the anti-interference of electrode, wherein:
(a) detection limit of electrode,
(b) anti-interference of electrode.
Embodiment:
Further specify particular content of the present invention and embodiment below in conjunction with embodiment.
Embodiment
Preparation process and step in the present embodiment are as follows:
(1) in 60 ℃ of water-baths, be 99.9%ZnCl with purity
2Stirring fully is dissolved in the phenmethylol (BA99%) and obtains ZnCl through magneton
2/ BA electrolytic solution, concentration of electrolyte are 1.5M, are 0.2mm with diameter, and the gold thread of long 1.5cm polishes, and then utilize successively acetone, ethanol and high purity water to clean, and oven dry is stand-by as working electrode at last.With the zinc wire of the long 4cm of wide 1mm as contrast electrode, with wide zine plate for the long 4cm of 5mm as to electrode.Three electrodes are placed in the above-mentioned preparation solution, need not to arrange salt bridge and connect, and utilize three-electrode system scan cycle on gold electrode to carry out electrochemical alloy/removal alloying process under 120 ℃.The voltage range that scans is-0.72～1.88V (vs.Zn), and repeatedly the sweep speed of circulation is chosen to be 10mV/S, behind circulation 50 circles, with successively successively order cleaning in phenmethylol, ethanol and deionized water of gold electrode.
(2) with the Co (NO of 6mM
3)
2Be placed in 30mL ethanol and the 5mL water with the CTAB (cetyl trimethyl ammonium bromide) of 2mM and stir; The gold thread of porous gold parcel picked up with propclip stand upright on configuration solution central authorities, can both fully contact solution around making self-supporting porous gold parcel gold thread structure, to be ready to sample and solution is placed in the reactor, temperature setting is set to 180 ℃, and reaction 90min obtains the coaxial entity/nano-porous gold of self-supporting/Co
3O
4The nano particle combination electrode material.
(3) during electrochemical gaging, the characteristic scope of cyclic voltammetric is decided to be-0.8～0.6V carries out cyclic voltammetry scanning, the voltage of electric current-time curve is set as 0.26V, after background current reaches stable state (2min), current curve section writing time (2min), and add the glucose solution sample with microsyringe and stir simultaneously (2min), the sensor that will measure under different glucose solution concentration is to the current-responsive value of glucose, in 5nM～70mM scope, obtain the linear relationship of electric current and concentration of glucose; The linear relationship of electric current and concentration of glucose changes with the slope of the not collinearity of concentration; With interfering material UA (uric acid), AP (acetaminophen), AA (ascorbic acid) join in the three electrode test systems and carry out interference detection, and be identical with the glucose detection steps, splashes at last glucose and carry out the anti-interference contrast.
A kind of coaxial entity/nano-porous gold of the self-supporting as glucose sensor/Co
3O
4The nano particle combination electrode material is as purposes and the method for electrode, and its purposes is the electrochemical gaging that is directly used in concentration of glucose; Using method is as follows: during electrochemical gaging, the characteristic scope of cyclic voltammetric is decided to be-0.8～0.6V carries out cyclic voltammetry scanning, the voltage of electric current-time curve is set as 0.26V, after background current reaches stable state (1～2min), writing time, the current curve section (1～2min), and add the glucose solution sample with microsyringe and stir simultaneously (1～2min), the sensor that will measure under different glucose solution concentration is to the current-responsive value of glucose, in 5nM～70mM scope, obtain the linear relationship of electric current and concentration of glucose; The linear relationship of electric current and concentration of glucose changes with the slope of the not collinearity of concentration
As the coaxial entity/nano-porous gold of the self-supporting of glucose sensor/Co
3O
4The sign of nano particle combination electrode material:
Observe the coaxial entity/nano-porous gold of self-supporting/Co by scanning electron microscope (SEM)
3O
4The configuration of surface of nano particle combination electrode material is consulted Fig. 2 and Fig. 3.As can be seen from the figure, the porous structure of the three-dimensional co-continuous on coaxial entity/nanoporous gold thread surface is even, effectively raises the specific surface area of material, the coaxial entity/nano-porous gold of self-supporting/Co
3O
4Nano particle combination electrode material surface is by Co
3O
4Nano particle uniform fold parcel in the situation that electric conductivity is very large, has increased the specific surface area of this composite structure more, can effectively bring into play Co simultaneously
3O
4The characteristic of particle, thus cause sensor to produce high responsive current-responsive.Consult Fig. 5 and Fig. 6, self-supporting porous gold parcel gold thread and self-supporting porous gold parcel gold thread are by Co
3O
4A kind of nucleocapsid structure that particle wraps up has again carried out the sign of XRD and DES, and the product that proves this structure preparation process really is Co
3O
4Particle.
Toughness is measured:
Electrode material of the present invention and the thick porous gold of 20um are done respectively toughness test, and its maximum bending degree of real-time follow-up, find the coaxial entity/nano-porous gold of self-supporting of the present invention/Co
3O
4The nano particle combination electrode material is bent into arbitrarily any shape and does not fracture.
Electrochemical gaging:
Under best test condition, the coaxial entity/nano-porous gold of self-supporting/Co
3O
4The nano particle combination electrode material is consulted shown in Figure 8 to the cyclic voltammetric of glucose and the response of timing electric current.This electrode material is having larger current density than the coaxial entity of self-supporting/nanoporous gold thread, and when consulting its detecting glucose of Figure 10 the current-responsive time very short, this mainly is because the coaxial entity/nano-porous gold of the self-supporting by this method preparation/Co
3O
4The nano particle combination electrode material has the electric conductivity of good biocompatibility, poriness and superelevation.Fig. 9 shows is increase along with concentration of glucose, and sensor increases gradually to the response of glucose, and electric current and concentration of glucose are linear.
The electrode of the present invention preparation, when consulting its detecting glucose of Figure 10 the current-responsive time very short, less than 1s.The susceptibility that glucose is surveyed is high, and surveying minimum concentration of glucose is 5nM, to interfering material UA (uric acid), and AP (acetaminophen), AA (ascorbic acid) repellence is high.
Claims (4)
1. coaxial entity/nano-porous gold/Co
3O
4The preparation method of combination electrode material may further comprise the steps:
A, in 60 ℃ of water-baths, with the anhydrous ZnCl of purity 99.9%
2Stirring fully is dissolved in the phenmethylol (BA99%) and obtains ZnCl through magneton
2/ BA electrolytic solution, concentration of electrolyte are 1～2M;
B, with diameter be the gold thread of 0.01～0.2mm as working electrode, the Zn plate is as to electrode, the Zn line is assembled into the three-electrode electro Chemical system as contrast electrode, above mixed organic solvents is that electrolyte heats in oil bath and maintains 100～120 ℃;
C, in the scope of-0.8～1.9V take Electrochemical Scanning speed as 5～50mV/s scan cycle, through behind 20～50 alloys/go the alloy cyclic process, obtain the gold electrode material of the coaxial entity/nano-porous structure of self-supporting.
2. according to a kind of coaxial entity/nano-porous gold claimed in claim 1/Co
3O
4The preparation method of combination electrode material, the gold thread among the described step b utilizes acetone, ethanol and high purity water to clean after polishing successively, and at last oven dry is as working electrode.
3. according to a kind of coaxial entity/nano-porous gold claimed in claim 1/Co
3O
4The preparation method of combination electrode material prepares the coaxial entity/nano-porous structure of self-supporting, produces the coaxial entity/nano-porous gold of self-supporting/Co
3O
4Combination electrode material may further comprise the steps:
A, be the Co (NO of 3:1 with concentration ratio
3)
2And CTAB (cetyl trimethyl ammonium bromide) ratio of being placed on is to stir in the second alcohol and water of 6:1;
B, be that the gold electrode material of coaxial entity/nano-porous structure picks up with propclip and stands upright on configuration solution central authorities with the sample of claim 1, can both fully contact solution around making it;
C, ready sample and solution are placed in the reactor, temperature setting is set to 180 ℃, obtains the coaxial entity/nano-porous gold of self-supporting/Co behind 60～120min
3O
4Combination electrode material.
4. according to the coaxial entity/nano-porous gold of a kind of self-supporting claimed in claim 3/Co
3O
4Combination electrode material is directly used in the electro-chemical test to concentration of glucose, may further comprise the steps:
A, with described sample as working electrode, Pt is as to electrode, Ag/AgCl forms three-electrode system as contrast electrode;
B,, the characteristic scope of cyclic voltammetric is decided to be during as the working electrode electrochemical gaging with described sample-0.8～0.6V carries out cyclic voltammetry scanning; The voltage of electric current-time curve is set as 0.26V, after background current reaches stable state (1～2min), writing time, the current curve section (1～2min), and add the glucose solution sample with microsyringe and stir simultaneously (1～2min), the sensor that will measure under different glucose solution concentration is to the current-responsive value of glucose, in 5nM～70mM scope, obtain the linear relationship of electric current and concentration of glucose;
C, described sample change as the linear relationship of the electric current of working electrode and the concentration of glucose slope with the not collinearity of concentration.
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Cited By (9)
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|---|---|---|---|---|
| CN103359796A (en) * | 2013-07-12 | 2013-10-23 | 上海大学 | Preparation method of supercapacitor cobaltous oxide electrode material |
| CN104383938A (en) * | 2014-09-25 | 2015-03-04 | 北京科技大学 | Glucose oxidation electrocatalyst and preparation method thereof |
| CN105506726A (en) * | 2016-03-02 | 2016-04-20 | 沈阳建筑大学 | In-situ electrochemical preparation method for silver nanometer thin films |
| CN105680010A (en) * | 2016-01-18 | 2016-06-15 | 吉林大学 | Method and application for improving discharge capacity and high rate discharge performance of hydrogen storage alloy through Co3O4 in-site compounding |
| CN105734643A (en) * | 2016-03-02 | 2016-07-06 | 沈阳建筑大学 | In-situ electrochemical preparation method of nanometer silver oxide film |
| CN106770567A (en) * | 2016-11-25 | 2017-05-31 | 江苏丰格测控技术有限公司 | A kind of Platinum Nanoparticles cobalt/porous gold/graphene composite material and preparation method thereof |
| CN108593729A (en) * | 2018-06-27 | 2018-09-28 | 中山大学 | A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme |
| CN109239151A (en) * | 2018-08-10 | 2019-01-18 | 广州钰芯传感科技有限公司 | A kind of pair of modification microneedle electrodes and preparation method thereof and blood glucose micropin electrochemical sensor electrodes |
| CN111239217A (en) * | 2020-02-07 | 2020-06-05 | 中国人民解放军军事科学院军事医学研究院 | N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359796A (en) * | 2013-07-12 | 2013-10-23 | 上海大学 | Preparation method of supercapacitor cobaltous oxide electrode material |
| CN104383938A (en) * | 2014-09-25 | 2015-03-04 | 北京科技大学 | Glucose oxidation electrocatalyst and preparation method thereof |
| CN105680010A (en) * | 2016-01-18 | 2016-06-15 | 吉林大学 | Method and application for improving discharge capacity and high rate discharge performance of hydrogen storage alloy through Co3O4 in-site compounding |
| CN105506726A (en) * | 2016-03-02 | 2016-04-20 | 沈阳建筑大学 | In-situ electrochemical preparation method for silver nanometer thin films |
| CN105734643A (en) * | 2016-03-02 | 2016-07-06 | 沈阳建筑大学 | In-situ electrochemical preparation method of nanometer silver oxide film |
| CN105506726B (en) * | 2016-03-02 | 2017-12-19 | 沈阳建筑大学 | A kind of in-situ electrochemistry preparation of silver-colored nano thin-film |
| CN106770567A (en) * | 2016-11-25 | 2017-05-31 | 江苏丰格测控技术有限公司 | A kind of Platinum Nanoparticles cobalt/porous gold/graphene composite material and preparation method thereof |
| CN108593729A (en) * | 2018-06-27 | 2018-09-28 | 中山大学 | A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme |
| CN109239151A (en) * | 2018-08-10 | 2019-01-18 | 广州钰芯传感科技有限公司 | A kind of pair of modification microneedle electrodes and preparation method thereof and blood glucose micropin electrochemical sensor electrodes |
| CN111239217A (en) * | 2020-02-07 | 2020-06-05 | 中国人民解放军军事科学院军事医学研究院 | N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof |
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