CN107422015A - Gold film electrode, electrochemica biological sensor electrode, sensor and preparation method thereof - Google Patents
Gold film electrode, electrochemica biological sensor electrode, sensor and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of gold film electrode, electrochemica biological sensor electrode, sensor and preparation method thereof.The gold film electrode includes：Substrate；Gold thin film on substrate, the thickness of the gold thin film are 200~400nm, the gold thin film be 5~10nm with the surface roughness Ra on substrate opposite side surface and the hole depth on surface is 20~40nm.To be obtained by roughening processing, the roughening processing preferably includes chemical etching processing for the surface roughness Ra and surface pore depth.The electrochemica biological sensor electrode includes：Above-mentioned gold film electrode and the decorative layer being formed on the gold thin film of the gold film electrode, the decorative layer include Prussian blue, and its thickness is 20~130nm, and described Prussian blue at least a portion exists with spherical and/or cubic particle form.
Description
Technical field
The invention belongs to nano meter biomaterial and electrochemica biological sensor field, it is related to a kind of surface roughening treatment
Gold film electrode and hydrogen peroxide sensor and their preparation and detection method based on it.
Background technology
Many biologies and chemical reaction process have hydrogen peroxide (H2O2) participation or generation.Especially in vivo, very
The byproduct of reaction of polyoxide enzyme all includes H2O2.For many hormones and metabolite in organism, as blood glucose, lactic acid,
The quantitative detection pattern of cholesterol, alcohol etc. is normally based on substrate for enzymatic activity and H2O2Redox reaction produce light, telecommunications
Number, then these signals are detected and completed.Therefore, it is clinical in Food processing, industrial textile, paper bleaching, pharmacy
The field such as medical science and disinfectant manufacture, accurate, the quantitative detection for hydrogen peroxide have highly important application value.
At this stage for H2O2Analysis method mainly have fluorescent spectrometry, chemoluminescence method, AAS and electrification
Learn detection method etc..Wherein electrochemical method is because easy to operate, and equipment cost is low, and measurement result is accurate, can especially obtain
Low recognizate concentration, it is considered as optimum detection method in biology sensor preparation.Direct H2O2Electrochemical detection method
Typically in electrode tables such as the platinum containing the material that can be reacted with hydrogen peroxide by chemical/electrochemical modification, gold, glass carbon
Face applies constant potential, while detects redox reaction electric current and realize.Horseradish peroxidase (HRP) with it is Prussian blue
(Prussian blue, PB) is wide variety of catalase in recent years.Because PB is to H2O2Electro-catalysis reduction be low
Carried out under current potential, can exclude many electroactive materials, such as uric acid, the interference of Paracetamol and ascorbic acid etc., therefore PB is repaiied
Adorn electrode pair H2O2Detection there is extremely strong selectivity.
For the substrate of modified electrode, the chemical property of magnetron sputtering golden film is stable, can carry out the more of PB functional layers
Kind of form is fixed, such as electrochemical deposition, the methods of silk-screen printing and chemical synthesis coat.Simultaneously as the thickness of golden film is small, tool
The standby ability for carrying out flexibility preparation, the usage comfort of organism sensor electrode can be improved.However, common magnetron sputters
The surface roughness of golden film is extremely low, and the fixation for electro-chemical activity functional layer is unfavorable.By being surface-treated, such as de- alloy
Surface porosity etc. is obtained, sensor function layer stability can be improved and and then improve its service behaviour.But pass through de-
Nanoporous golden film face crack is extremely more made from alloy, is easy to rupture, and easily departs from preparation process with substrate, is not suitable for
Carry out following process.Therefore, the process of surface treatment of magnetron sputtering golden film is improved, sensor function layer can be improved
Service behaviour, the fragility of electrode surface is avoided, it is carried out subsequent treatment, more stablized, sensitive and detection range is more
Wide electrochemical sensor.
Citation 1, a kind of preparation method of hydrogen peroxide electrochemical sensor is disclosed, it uses glass-carbon electrode piece table
Face plating multiple modification film, its first layer are naphthol green.The detectable limit of the sensor is 0.9 μM, corresponding linear model
Enclose for 8 × 10-6~1.8 × 10-4M。
Citation 2, it discloses electrochemical sensor, and it is in glassy carbon electrode surface deposited Au nano particle and magnetic
Property ferroso-ferric oxide, and it is 50nM to disclose its detectable limit.
Citation 3, it discloses a kind of hydrogen peroxide non-enzymatic electrochemical sensor and preparation method thereof, it is used such as
The noble metal nano particles such as gold are modified electrode.It uses ion beam current deposition to carry out the deposition of noble metal, controls deposition
For amount within 5 layers, the range of linearity of its detection to hydrogen peroxide is 4~44M.
Citation 4, it discloses a kind of gold microsphere-titanium nitride nano pipe array composite material and preparation method thereof, goes back
The composite is provided to prepare without the application in enzyme hydrogen peroxide electrochemical sensor.Its nitrogen of being removed mines on titanium nitride substrate
Change titanium nano-array pipe, and gold microsphere is formed on the array tube top.
Citation 5, it carries out Prussia on platinum electrode using cyclic voltammetry in the electrolyte of two kinds of different compositions
The electrochemical deposition of blue film, the cycle voltammetry behavior of modified membrane is measured in Klorvess Liquid, compare the electrification of two kinds of films
Learn impedance spectrum.Modification prussian blue film platinum electrode electrochemical impedance spectroscopy measurement result show, sedimentary condition and its deposition thickness
Degree has an impact to electron transfer process.
Thus, it will be seen that in the prior art for obtaining high detection sensitivity, the wide detection range of linearity, low inspection
Survey the limit, preferable useful life longevity and advantageously preparation method research still exist improve space.
Citation 1：CN102043002A
Citation 2：CN101986147A
Citation 3：CN103792271A
Citation 4：CN103952763A
Citation 5：" electro-deposition of prussian blue film and its electrochemical impedance spectroscopy ", Zhang Fenfen etc.,《Chemical research is with answering
With》, the 2nd phase of volume 15, in April, 2003.
The content of the invention
Problems to be solved by the invention
For as above problem, this invention address that providing a kind of gold film electrode of surface roughening treatment, based on the golden film
The electrochemica biological sensor electrode of electrode, and the electrochemica biological sensor based on these electrodes, are particularly used it for
When detecting concentration of hydrogen peroxide, detection detection sensitivity, the detection range of linearity and detectable limit can be obtained and using durable
The excellent characteristic of property.
In addition, present invention also offers one kind to prepare above gold film electrode, electrochemica biological sensor electrode, and it is based on
Simple, the effective preparation method of the electrochemica biological sensor of these electrodes.
The solution used to solve the problem
Present invention firstly provides a kind of gold film electrode, and it includes：
Substrate；
Gold thin film on substrate,
The thickness of the gold thin film is 200~400nm,
The gold thin film is 5~10nm and the hole depth on surface with the surface roughness Ra on substrate opposite side surface
For 20~40nm.
Gold film electrode in accordance with the above, the surface roughness Ra and surface pore depth be by roughening at
Manage and obtain, the roughening processing preferably includes chemical etching processing.
Gold film electrode in accordance with the above, the gold thin film are to be formed using sputtering method.
Gold film electrode in accordance with the above, intermediate metal, the metal transfer between substrate and gold thin film be present
Layer comprising in Cr, Ti and their alloy at least any one.
Gold film electrode in accordance with the above, the intermediate metal are formed using sputtering method, its thickness be 10~
40nm。
On the other hand, present invention also offers a kind of electrochemica biological sensor electrode, the electrode to include：It is described above
Gold film electrode and the decorative layer that is formed on the gold thin film of the gold film electrode,
The decorative layer includes Prussian blue, and its thickness is 20~130nm,
Described Prussian blue at least a portion exists with spherical and/or cubic particle form.
Sensor electrode in accordance with the above, the decorative layer are formed by electrochemical deposition method.
On the other hand, present invention also offers a kind of electrochemica biological sensor, it is based on the gold described in any of the above
Any described sensor electrode of membrane electrode or more forms.
On the other hand, present invention also offers a kind of hydrogen peroxide detection electrochemica biological sensor, the sensor
To detect the sensitivity of hydrogen peroxide with electrochemica biological sensor based on above-described sensor, the hydrogen peroxide detection
For 270~430mA/Mcm2, detectable limit is more than 0.27 μM, and the range of linearity is 1~X μM, and wherein X is more than 1000 and 4500
Below.
In addition, the invention provides a kind of preparation method of gold film electrode, methods described includes：
By sputtering method deposit thickness in substrate be 200~400nm gold thin film the step of and
By the gold thin film surface roughening make its surface roughness Ra be 5~10nm and the hole depth on surface be 20~
The step of 40nm.
Method in accordance with the above, the roughening include carrying out chemical etching processing.
Method in accordance with the above, wherein, it is included in before depositing gold thin film in substrate, is previously deposited intermediate metal
The step of, the intermediate metal include in Cr, Ti and their alloy at least any one.
In addition, the invention provides a kind of preparation method of electrochemica biological sensor electrode, methods described includes：
By the preparation method of above-described gold film electrode formed the step of being used as the gold film electrode of basal electrode and
On the basal electrode formed decorative layer the step of,
It is described on basal electrode formed decorative layer the step of be by electrochemical deposition method formed decorative layer, it is described to repair
Decorations layer include it is Prussian blue,
The gold thin film thickness is 200~400nm, and the decorative layer thickness is 20~130nm,
Described Prussian blue at least a portion exists with spherical and/or cubic particle form.
Further, present invention also offers a kind of preparation method of hydrogen peroxide detection electrochemica biological sensor, its
Including the method described in any of the above item, the detection sensitivity of the hydrogen peroxide detection electrochemica biological sensor is 270
~430mA/Mcm2, detectable limit is more than 0.27 μM, and the range of linearity is 1~X μM, and wherein X is more than 1000 and less than 4500.
The effect of invention
The present invention is used using the magnetron sputtering gold thin film that surface roughening has been carried out by chemical etching processing thereon
Electrochemical deposition method deposition includes Prussian blue film, has obtained a kind of the wide line inspection based on Prussian Blue Film Modified
Scope, high sensitivity, low detectable limit, and excellent in te pins of durability, and the electrochemica biological sensor of strong selectivity are surveyed, it is especially suitable
For the detection to hydrogen peroxide.
In addition, gold film electrode provided by the present invention, electrochemica biological sensor electrode and hydrogen peroxide detection electricity consumption
The preparation method of chemical biosensor, process is easy and effective, is more suitable for industrial mass production, and reduce and be manufactured into
This.
Brief description of the drawings
Fig. 1：The surface texture figure of magnetron sputtering gold thin film prepared by embodiment 1 and roughening gold thin film.Wherein figure (a) is
The magnetron sputtering gold thin film surface texture that AFM (AFM) measures, figure (b) are the height letter of line segment shown in figure (a)
Cease curve；Figure (c) is the gold thin film surface texture for the roughened processing that AFM (AFM) measures, and figure (d) is figure (c)
Shown in line segment elevation information curve.
Fig. 2：Thickness prepared by embodiment 2 is the surface texture figure of 25nm hydrogen peroxide sensor.(a) is wherein schemed to sweep
Electron microscope (SEM) picture is retouched, figure (b) is the PB films and golden film surface chart that AFM (AFM) measures, and figure (c) is
Scheme the elevation information of line segment shown in (b).
Fig. 3：Thickness prepared by embodiment 3 is the surface texture figure of 70nm hydrogen peroxide sensor.(a) is wherein schemed to sweep
Electron microscope (SEM) picture is retouched, figure (b) is the PB films and golden film surface chart that AFM measures, and figure (c) is figure (b)
Shown in line segment elevation information.
Fig. 4：Thickness prepared by embodiment 4 is the surface texture figure of 100nm hydrogen peroxide sensors.(a) is wherein schemed to sweep
Electron microscope (SEM) picture is retouched, figure (b) is the PB films and golden film surface chart that AFM measures, and figure (c) is figure (b)
Shown in line segment elevation information.
Fig. 5：Thickness prepared by embodiment 5 is the surface texture figure of 120nm hydrogen peroxide sensors.(a) is wherein schemed to sweep
Electron microscope (SEM) picture is retouched, figure (b) is the PB films and golden film surface chart that AFM measures, and figure (c) is figure (b)
Shown in line segment elevation information.
Fig. 6：Hydrogen peroxide sensor detection hydrogen peroxide performance map prepared by embodiment 2~5.Wherein a, b, c, d distinguish
It is hydrogen peroxide meter of the hydrogen peroxide sensor under -0.1V (with respect to Ag/AgCl) constant-pressure conditions described in embodiment 2,3,4,5
When current curve.
Fig. 7：Relation between the current density and concentration of hydrogen peroxide of hydrogen peroxide sensor prepared by embodiment 2~5
Figure.Wherein a~d is respectively the current density and concentration of hydrogen peroxide relation of hydrogen peroxide sensor prepared by embodiment 2~5,
Drawn by Fig. 6 digital simulations.
Fig. 8：Hydrogen peroxide sensor prepared by embodiment 2~5 utilizes cyclic voltammetry test durability comparison diagram.Wherein
Figure a~d is respectively after hydrogen peroxide sensor prepared by embodiment 2~5 carries out 1000 cyclic voltammetries, to be followed with 100 times
Ring is the CV curve images that interval obtains.
Fig. 9：The durability line of hydrogen peroxide sensor prepared by the embodiment 2~5 calculated by Fig. 8, in curve
Each point with percentage obtained by the cyclic voltammetry curve area of every 100 minor tick divided by first time cyclic voltammetry curve area,
It is calculated by Fig. 8.
Embodiment
Each embodiment of the present invention will be explained in detail below, wherein, unless specifically indicated, institute of the present invention
The term for occurring or using is respectively provided with the common physics in this area, chemical sense.Such as, in the present invention for the sake of brevity, use
" M " represents 1 mol/L or 1mol/L.
<First embodiment>
The first embodiment of the present invention, there is provided a kind of gold film electrode, it includes：Gold thin film on substrate, substrate,
The gold thin film is forms using sputtering method, and its thickness is 200~400nm, also, the gold thin film is opposite with substrate
The surface of side is handled by roughening.
Substrate
There is no particular limitation for the substrate of the present invention, as long as it can realize the effect above of the present invention.Such as can be with
Using the conventional substrate in this area, as long as it possesses required electric conductivity and supportive.
The substrate of the present invention can be selected from carbons, glass carbons substrate and semiconductor type substrate or conductive polymer subclass base
Body.
For carbons matrix, for example, can enumerate for graphite, CNT, graphene, diamond-like-carbon, boron doping gold
Carbon substrate of hard rock etc etc..For semiconductor type for example, can enumerate for silicon or ITO (tin indium oxide), IZO (indium oxides
Tin), AZO (Al-Doped ZnO), FTO (fluorine doped tin oxide) etc transparent conductive semiconductor film.In addition, for conducting polymer
Film, it is obtained for the membrane material or sheet fabrication formed using conducting polymer.So-called conducting polymer be by with grip altogether π-
The macromolecule of key makes it be changed into by insulator a kind of high polymer material of conductor through chemistry or electrochemistry " doping ".Macromolecule is led
Electric material is generally divided into the compound and major class of structural type two：1. composite polymer conductive material, by general high polymer material
It is made with various conductive materials by filled composite, surface recombination or the modes such as lamination is compound；2. structural type macromolecule is led
Electric material.Refer to macromolecular structure in itself or through having the high polymer material of conducting function after overdoping.According to electrical conductivity
Size can be divided into semiconducting polymer, high-molecule metal etc. again.
Also, from obtaining high detection scope, high sensitivity, from the point of view of the electrode of low detectable limit, base of the invention
Bottom is preferably silicon chip.
In addition, before using the optional substrate of present invention institute, necessary cleaning and/or activation can be carried out to substrate.Specifically
Cleaning, activation method be not particularly limited, can be carried out using mode generally in the art, as long as do not damage the present invention
Final effect.
Gold thin film and intermediate metal
The method using sputtering sedimentation in the present invention deposits in above-mentioned substrate forms one layer of gold thin film, and thin to the gold
Film carries out surface roughening treatment.
Specifically, the method that magnetron sputtering deposition is used in the present invention.Sputtering sedimentation is under vacuum conditions, to utilize lotus
Can Ions Bombardment material surface, make the particle deposition that is pounded in the technology of matrix surface.Magnetron sputtering deposition method is general
It is divided into unbalanced magnetron sputtering method and non-balance magnetically controlled sputter method.For the present invention, from size of foundation base and simple process
From the point of view of, preferably using unbalanced magnetron sputtering method.
Unbalanced magnetron sputtering is commonly referred to as conventional magnetron sputtering.Implement effectively control to secondary electron using magnetic field, from
And the shortcomings that becoming diode sputtering into itself the advantages of.The operation principle of unbalanced magnetron sputtering is orthogonal by secondary electron
In electromagnetic field, it is bound in target near surface and does circle rolling property motion around the magnetic line of force along " runway ", improve the ionization of gas
Rate, even if operating air pressure is reduced to 10-1~10-2The Pa orders of magnitude, remain to increase plasma density, so as to improve it is incident from
Sub- density, sputtering voltage is advantageously reduced, while improve sedimentation rate；And secondary electron could take off only after depleted of energy
Off-target surface falls on anode, so matrix avoids the bombardment of secondary electron, matrix temperature rise is low, not damaged.Unbalanced magnetron splashes
The surface modification of the matrix material strict to temperature requirement can be efficiently applied to by penetrating.
In the present invention, the deposit thickness of gold thin film is controlled in 200~400nm, preferably 200~350nm, is more preferably
250~330nm.Gold thin film thickness deposition it is too small, then have the worry that can not eliminate surface defect so that sensor electrode it is each
There is noise in item detection performance or repeatability is poor.But thickness is excessive, then on the one hand sensor electrode can not be significantly improved
Properties, another invention then increases manufacturing cost.
The surface roughening treatment of above-mentioned gold thin film can use chemical etching to handle.Specifically, as an example,
Gold thin film can be soaked in KI (KI) solution (also referred to as I2- KI solution) in carry out chemical etching, so as to carry out surface
Roughening.Soak time can be set as needed.
Gold thin film through surface roughening treatment has the surface texture more more coarse than magnetron sputtering gold thin film, its particle
Between hole depth it is deeper, there is bigger specific surface area and reactivity, the fixed efficiencies of PB functional layers is improved, using this
Not only test limit is lower for hydrogen peroxide electrochemica biological sensor prepared by gold film electrode, and sensitivity is higher.Through surface roughening
The gold thin film of processing, for example, surface roughness Ra is 5~10nm, and the hole depth on surface is 20~40nm, it is preferred that
Surface roughness Ra is 6~7.5nm, and the hole depth on surface is 28~35nm.
Further, in the preferred embodiment of the present invention, before above-mentioned sputtering sedimentation gold thin film is carried out, in advance in base
Layer of metal transition zone is deposited on bottom.
Depending on the factor such as condition of sputtering sedimentation control, when gold thin film is deposited directly on substrate, due to gold/
Substrate interface in some cases becomes the incubation time for causing gold thin film to be initially formed there is the unmatched phenomenon of lattice
It is long, while also cause easily to form surface defect and inequality when depositing gold thin film.In other situations, it is also possible to cause to sink
The associativity of gold thin film and substrate of the product on substrate is affected, undesirable so as to cause in follow-up electrochemistry circulation
Sensor timeliness.
Therefore, intermediate metal is pre-formed between gold thin film and substrate to be advantageous to avoid problem above.That is, it is of the invention
In preferred embodiment, between solution substrate and gold thin film that intermediate metal can be good existing lattice mismatch and
Increase the effect of the combination of gold thin film and substrate.
Intermediate metal can be deposited using magnetron sputtering deposition method as described above, the thickness of deposition for 10~
40nm, preferably 20~30nm.It is too small for the thickness of intermediate metal, Lattice Matching can not be played a part of, then passed through greatly very much
Ji property is deteriorated.
For the material of intermediate metal, as long as disclosure satisfy that the interfacial bonding property of improvement substrate/gold thin film, just without spy
Other restriction.For example, can be in Cr, Ti and their alloy at least any one.Preferably, in the present invention, metal
The material of transition zone is different from gold, particularly preferred, and in the present invention, intermediate metal is formed using Cr.
<Second embodiment>
Second embodiment of the present invention, there is provided a kind of electrochemica biological sensor electrode, gold film electrode and formation
Decorative layer on the gold thin film of the gold film electrode, the decorative layer include it is Prussian blue, and its thickness be 20~
130nm, described Prussian blue at least a portion exist with spherical and/or cubic particle form.
Decorative layer
The decorative layer of the present invention is electroactive substance layer, has specific selectivity.In the decorative layer of the present invention, bag
Include Prussian blue (PB).
In some embodiments of the present invention, on gold thin film, adopt be electrochemically deposited one layer it is Prussian blue
Layer.Typically, can be using gold thin film as working electrode, using Ag/AgCl as reference electrode, using Pt silks as to electricity when being deposited
Pole, to contain Fe3+And Fe (CN)6 4+, K+And HCl mixed solution is that electrolyte carries out electrochemical deposition, in constant deposition
Electrochemical deposition is carried out under voltage 0.4V (with respect to Ag/AgCl electrodes), obtains PB modified electrodes.
The time of deposition is controlled, the deposit thickness of PB layers can be controlled.The thickness of PB layers is 20~130nm in the present invention.
Sedimentation time can be 10~240s, and in some cases, sedimentation time can be 5~260s, as long as above-mentioned institute can be obtained
The deposit thickness needed, sedimentation time can carry out appropriate adjustment.
In the present embodiment, by the control and adjustment to PB deposit thickness, the high detection range of linearity can be obtained, it is high
The electrochemistry Hydrogen Peroxide Biosensor electrode of sensitivity, low detectable limit, preferable durability and strong selectivity.
The deposit thickness of reduction PB layers is proposed in some existing researchs can improve the sensitivity of detection.But
It is a discovery of the invention that if PB deposit thickness is too low, PB sedimentaries may be caused can not to realize uniform covering, it is also possible to cause
Some defect points that sedimentary occurs in PB deposition process can not be obtained with effectively repairing.Therefore, from this viewpoint,
The thickness of PB layers should be more than 20nm and then be more than 25nm in the application.On the other hand, it is a discovery of the invention that in the heavy of PB layers
Product thickness reaches certain level, when being, for example, more than 70nm, sensitivity present on the contrary with the increase of deposit thickness and it is increased become
Gesture.Its reason is presumed as follows：With the increase of PB layer deposit thickness, PB microscopic appearance is by predominantly (unformed) spherical mistake
Cross to predominantly cube (crystal formation) graininess, cube (crystal formation) graininess and be more beneficial for the charge-conduction in PB layers, make response electric
Rheology is big, improves sensitivity.
In addition, with the increase of PB deposit thickness, the range of linearity of detection substantially broadens.The reason for supposition may is that,
With the increase of PB deposit thickness so that improved the defects of PB surfaces, therefore, under constant voltage, can showed
The wider range of linearity, and linearly dependent coefficient is more than 0.99.
In addition, with the increase of PB layer deposit thickness, PB microscopic appearance is transitioned into by predominantly (unformed) is spherical
Predominantly cube (crystal formation) graininess, and the change of the pattern with PB layers, have influence on the useful life longevity of electrode.In some feelings
Under condition, due in the PB layers originally formed, based on unformed spheric granules, with the increase of PB thickness, durability
Increase.But pass through the deposition of further PB layers, in PB layers, the PB particles of cubic have been gradually formed, (unformed)
Spherical predominantly cube (crystal formation) granular period, the durability of being transitioned into hardly changes.Forming cubic
When continuing PB depositions after PB particles, cube (crystal formation) graininess is grown into, and result in the further increase of durability.But
Be, when cubic in PB layers PB Grain growths to a certain extent when, due to the effect of crystal boundary, it is also possible to cause PB layer surfaces
It is cracked.
Thus, it will be seen that for the deposit thickness of the PB layers in gold thin film, not only to consider to take into account excellent sensitive
Degree, will also take into account the wider detection range of linearity and the durability used etc..Therefore, it is of the invention for this angle
PB deposit thickness is 20~130nm, preferably 25~130nm, more preferably 70~120nm.
Other active materials
In the present embodiment, except in gold thin film electrochemical deposition PB can be used as active material layer in addition to, not by
Limitation, can be according to being actually needed, deposition uses other active matters in the independent layer beyond same layer, or PB layers
Matter.
Described active material can be various enzymes.What can be enumerated is：Glucose oxidase, LO, horseradish
One kind or several in catalase, cholesterol oxidase, xanthine oxidase, acetylcholine esterase, organic phosphine hydrolase etc.
Kind.
It can be deposited for above active material by the common deposition process in this area.And it is possible to according to need
Will, one or more layers deposition is carried out, on condition that not damaging the technique effect of the present invention.
<3rd embodiment>
In third embodiment of the present invention, there is provided a kind of electrochemica biological sensor.The sensor is based on<First is real
Apply mode>Described in or definition gold film electrode, or be based on<Second embodiment>Described in or definition sensor
Electrode.
The sensor can directly use separately as photostat, can detect the small molecule sensitive to PB,
Such as hydrogen peroxide.
In addition, as also described above, the sensor including other active material layers can be used as indirect sensors.
Enzyme referred to above can be used in combination, such as glucose, protein equimolecular or composition are detected.
Further, it is possible to the sensor is subjected to necessary encapsulation or other any modifications, as long as not damaging this
The effect of invention.By necessary encapsulation, go for various occasions, and be advantageous to improve the security that uses and
Ensure the validity of detection.
In addition, in embodiments of the present invention, while an electrochemica biological sensor is provided, it includes<First
Embodiment>In gold film electrode or<Second embodiment>In sensor electrode, and be based on this, be prepared as work electricity
Pole.In addition, the sensor also includes reference electrode and to electrode.The reference electrode can be the conventional reference electricity in this area
Pole, such as calomel electrode, silver/silver chloride electrode etc..For to electrode, Pt silks or plate etc. can be used.
Typically, the product of present embodiment is a kind of electrochemical student that can be directly detected to concentration of hydrogen peroxide
Thing sensor.Specifically, in same electrolytic cell, present embodiment uses three-electrode system, a working electrode, a ginseng
Than electrode, one uses the magnetron sputtering golden film through surface roughening to electrode, wherein working electrode.Hereafter, in electrolytic cell
A certain amount of deposition liquid is added, by applying constant voltage on the working electrode (s, golden film surface deposits one layer after certain time
Prussian blue film.After obtained Prussian blue modified electrode is carried out into certain chemistry, physical process processing, identical electrolysis is inserted
Chi Zhong, concentration of hydrogen peroxide measure is carried out by working electrode of Prussian blue modified electrode.Still in work electricity in continuous mode
Pole applies constant voltage, and a certain amount of phosphate buffer (PBS) is added in electrolytic cell, applies and instills various concentrations under stirring condition
Hydrogenperoxide steam generator, by current strength response detected.
<4th embodiment>
In the present embodiment, prepare gold film electrode the invention provides one kind, prepare electrochemica biological sensor electrode
And prepare a kind of method for detecting hydrogen peroxide electrochemica biological sensor.
Wherein, preparing the method for gold film electrode includes：
By sputtering method deposit thickness in substrate be 200~400nm gold thin film the step of and
By the gold thin film surface roughening make its surface roughness Ra be 5~10nm and the hole depth on surface be 20~
The step of 40nm.
Method in accordance with the above, wherein, the roughening is handled by chemical etching to carry out.
Method in accordance with the above, in the step of formation basal electrode, in addition to gold thin film is deposited in substrate
Before, the step of being previously deposited intermediate metal, the intermediate metal are included in Cr, Ti and their alloy extremely
Lack any one.
In addition, the step of preparation method of the electrochemica biological sensor electrode of present embodiment includes the above, and
Decorative layer is deposited on basal electrode the step of, it is described decorative layer is formed on basal electrode the step of to pass through electrochemical deposition
Method forms decorative layer, and the decorative layer includes Prussian blue, and the gold thin film thickness is 200~400nm, the decorative layer
Thickness is 20~130nm, and described Prussian blue at least a portion exists with spherical and/or cubic particle form.
In addition, the preparation method of the hydrogen peroxide detection electrochemica biological sensor of present embodiment includes the above
Step, it is optional, the step of can also including being formed or preparing other active material layers, prepare reference electrode, to electrode and
The step of any necessary encapsulation.
In those steps, used instrument or equipment, without special restriction, as long as being enough to realize the present invention
Effect.
More specifically, the technical scheme that the gold film electrode through surface roughening is prepared in present embodiment is as follows：
(1) silicon chip of 300 μ m thicks is placed in magnetron sputtering apparatus, is with ultrapure chromium (chromium content >=99.99wt.%)
Target, the chromium metal level of one layer of 20nm thickness is deposited first；Afterwards with golden (gold content >=99.99wt.%) for target, sputtering is heavy
The golden film of one layer of 200~400nm thickness of product.
(2) the square gold film electrode that size is 10mm × 10mm is made by cutting technique in gained golden film, and successively
In watery hydrochloric acid, diluted sodium hydroxide solution, deionized water, it is cleaned by ultrasonic and is dried up in acetone and alcohol.
(3) pretreated golden film will be carried out and be soaked in the solution left standstill one containing KI (KI) regularly, such as 5~
20s, preferably 10s.Pass through diluted sodium hydroxide solution, deionized water successively again afterwards, acetone and alcohol are cleaned by ultrasonic and dried up.
And then the technical scheme that electrochemica biological sensor electrode is prepared in present embodiment is as follows：
(4) using the gold film electrode through surface roughening obtained in above-mentioned (3) as working electrode, using Ag/AgCl as ginseng
Than electrode, using Pt silks as to electrode, to contain Fe3+And Fe (CN)6 4+, K+And HCl mixed solution is that electrolyte carries out electrification
Deposition is learned, sedimentation time is 10~240s, and deposition voltage is that 0.4V (with respect to Ag/AgCl electrodes) obtains PB modified electrodes.
(5) by resulting PB modified electrodes containing K+And HCl electrode activation is with carrying out cyclic voltammetric activation in solution,
Voltage range -0.05V~0.35V, voltage scan rate 50mV/s, cycle-index be 25~40, preferably 35 times.Afterwards in phosphoric acid
The stable polarization of constant potential is carried out in buffer solution, constant potential -0.1~0.1V (with respect to Ag/Cl electrodes), preferably -0.05V is (relatively
Ag/Cl electrodes), the stable polarization time is 120~600s, preferably 600s.PB modified electrodes are carried out clearly with deionized water afterwards
Wash and 1h is dried at 100 DEG C, obtain the electrochemica biological sensor electrode.
Further, deposition solution described in step (4) is 2.5mM FeCl3+2.5mM K3Fe(CN)6+0.1M KCl+
0.12M HCl solutions, it is made by above-mentioned inorganic salts and acid solution with 100mL deionized waters.
Further, step (4) described sedimentation time is 10s, and deposition voltage is 0.4V (with respect to Ag/AgCl electrodes), is obtained
PB film thicknesses are 25nm.
Further, step (4) described sedimentation time is 40s, and deposition voltage is 0.4V (with respect to Ag/AgCl electrodes), is obtained
PB film thicknesses are 70nm.
Further, step (4) described sedimentation time is 120s, and deposition voltage is 0.4V (with respect to Ag/AgCl electrodes), is obtained
PB film thicknesses are 100nm.
Further, step (4) described sedimentation time is 240s, and deposition voltage is 0.4V (with respect to Ag/AgCl electrodes), is obtained
PB film thicknesses are 120nm.
Further, step (5) electrode activation is 0.12M HCl+0.1M KCl solution with solution, by above-mentioned inorganic salts
It is made with concentrated hydrochloric acid solution and 100mL deionized waters.
Further, step (5) described phosphate buffer is 0.05M KH2PO4/K2HPO4+ 0.1M KCl solution, by above-mentioned
Inorganic salt powder is made with 100mL deionized waters.
Present embodiment can be used for the detection of hydrogen peroxide using Top electrode as photostat, in other embodiment party
In formula, coordinate other active material enzymes, as described above, it is possible to achieve the detection for materials such as glucose, protein
(that is, indirect sensors).
Function film (PB films) thickness of hydrogen peroxide sensor electrode of the present invention is 20~130nm, is preferably
25~130nm, more preferably 70~120nm, the detection to hydrogen peroxide are limited to more than 0.27 μM；Detection sensitivity be 270~
430mA/Mcm2, preferably 330~430mA/Mcm2, more preferably 380~430mA/Mcm2；The range of linearity is 1~X μM, wherein
X is more than 1000 and less than 4500, and preferably X is more than 2000 and less than 4500, and preferably X is more than 3500 and less than 4500.
Compared with prior art, the beneficial effects are mainly as follows：The present invention is using with through surface roughening
Gold film electrode modifies the hydrogen peroxide sensing that PB functional layers form as basal electrode and using electrochemical deposition method thereon
Device, its high sensitivity, the range of linearity is wide, and detectable limit is low and excellent in te pins of durability.The preparation of functional layer and fixed disposable completion.
Compared with other sensors, the present invention uses magnetron sputtering gold thin film, low with cost, simple to operate, and can realize flexibility
The advantages that experience of application and preparation living body detection is comfortable.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
The sensitivity of hydrogen peroxide sensor detection hydrogen peroxide of the present invention and durability test method are：
(1) sensitivity and detection range test：
With hydrogen peroxide sensor of the present invention (Au/PB electrodes) for working electrode, Ag/Cl is reference electrode, and Pt pieces are pair
Electrode.In with the 100mL phosphate buffers (PH=6.2) described in step (5), (rotor speed is under the conditions of gentle agitation
200~250RMP) chronoamperometry is used, the hydrogenperoxide steam generator that quantitative concentrations are constantly added dropwise enters line sensitivity and the range of linearity
Test, apply constant potential in working electrode in experimentation, voltage range -0.15~0.15V (with respect to Ag/Cl electrodes), preferably -
0.1V。
(2) durability test：
With hydrogen peroxide sensor of the present invention (Au/PB electrodes) for working electrode, Ag/Cl is reference electrode, Pt pieces
For to electrode.In with the 100mL phosphate buffers (PH=6.2) described in step (5), sensor is tested using cyclic voltammetry
Endurance quality.The voltage range of cyclic voltammetric is -0.05~0.35V (with respect to Ag/AgCl electrodes), sweep speed 50mV/s,
Cycle-index is 600~1200 times, and preferably 1000 times, durability is carried out by the cyclic voltammetry curve area for calculating each 100 times
Test.
Embodiment 1
(1) magnetron sputtering golden film is handled
The silicon chip of 200~400 μ m thicks is placed in magnetron sputtering apparatus, with ultrapure chromium (chromium content >=99.99wt.%)
For the chromium metal level of target, first one layer of 20nm thickness of deposition；Afterwards with golden (gold content >=99.99wt.%) for target, sputtering
Deposit the golden film of one layer of 200~400nm thickness.Afterwards, gained magnetron sputtering golden film is cut to 10mm × 10mm square
Gold film electrode, and successively in watery hydrochloric acid, diluted sodium hydroxide solution, deionized water, it is cleaned by ultrasonic in acetone and alcohol
30min, dried up afterwards using nitrogen gun, obtain pretreated golden film, it is standby.The surface texture of golden film such as Fig. 1 (a), (b)
It is shown.
(2) surface roughening treatment of magnetron sputtering golden film
Golden film made from step (1) is soaked in 30vol.% KI (KI) solution and stands 10s.Afterwards again successively
By diluted sodium hydroxide solution, deionized water, acetone and alcohol are cleaned by ultrasonic and dried up.The surface texture of golden film is roughened as schemed
1 (c), shown in (d).
Embodiment 2
(1) preparation of Prussian blue modification film
Using three-electrode system, the roughening gold film electrode after being handled using the step of embodiment 1 (2) is working electrode, with Ag/
AgCl is reference electrode, using Pt silks as to electrode, with final concentration of 2.5mM FeCl3, final concentration of 2.5mM K3Fe(CN)6,
Final concentration of 0.1M KCl and final concentration of 0.12M HCl solution be electrolyte carry out electrochemical deposition, sedimentation time 10s,
Deposition voltage is the PB modified electrodes that 0.4V (relative to Ag/AgCl electrodes) obtains that thickness is 25nm.
(2) resulting PB modified electrodes are mixed in final concentration of 0.12M HCl and final concentration of 0.1M KCl molten
Cyclic voltammetric activation, voltage range -0.05V~0.35V, voltage scan rate 50mV/s are carried out in liquid, the circulation number of turns is 25.It
Contain 0.05M KH in 100mL afterwards2PO4/K2HPO4It is stable that constant potential is carried out in+0.1M KCl phosphate buffer (PH=6.2)
Polarization, constant potential -0.05V (with respect to Ag/Cl electrodes), the stable polarization time is 120s.Afterwards by PB modified electrodes spend from
Sub- water is cleaned, and is dried 1h after being dried up using nitrogen gun at 100 DEG C, is obtained Hydrogen Peroxide Biosensor.The peroxidating
The surface texture and functional layer thickness of hydrogen biology sensor are as shown in Figure 2.
(4) hydrogen peroxide current-responsive is tested：
The Hydrogen Peroxide Biosensor that PB functional layers thickness is 30nm is placed in (PH=in 0.05M phosphate buffers
6.2) in, (rotor speed 200RMP) uses chronoamperometry under the conditions of gentle agitation, and the mistake of quantitative concentrations is constantly added dropwise
Hydrogen peroxide solution enters line sensitivity and the range of linearity is tested, and applies 0.1V (with respect to Ag/Cl electricity in working electrode in experimentation
Pole) constant potential.As a result as shown in a curves in a curves in Fig. 6 and Fig. 7, the detection of its hydrogen peroxide is limited to 0.85 μM of (signal to noise ratio
For 3), the range of linearity is 1 μM~1000 μM, detection sensitivity 338mA/Mcm2。
(5) durability test of Hydrogen Peroxide Biosensor
With hydrogen peroxide sensor of the present invention (Au/PB electrodes) for working electrode, Ag/Cl is reference electrode, Pt pieces
For to electrode.In phosphate buffer (PH=6.2), the endurance quality of sensor is tested using cyclic voltammetry.Cyclic voltammetric
Voltage range be -0.05~0.35V (with respect to Ag/AgCl electrodes), sweep speed 0.05V/s, cycle-index is 1000 times, often
Ratio calculating is carried out every the cyclic voltammetry curves of 100 times and cyclic voltammetry curve area first, obtains the circulation shown in a in Fig. 8
A curves in volt-ampere curve and Fig. 9.Experimental data shows that the electrode is after 1000 cyclic voltammetry scans are carried out, capacitance fade
Rate is about 35%.
Embodiment 3
Using three-electrode system, the roughening gold film electrode after being handled using the step of embodiment 1 (2) is working electrode, with Ag/
AgCl is reference electrode, and using Pt silks as to electrode, the electrolyte being carried out in example 2 carries out electrochemical deposition, and sedimentation time is
40s, deposition voltage are the PB modified electrodes that 0.4V (relative to Ag/AgCl electrodes) obtains that thickness is 70nm.By resulting PB
The activation of modified electrode in embodiment 1 is with carrying out cyclic voltammetric activation, voltage range -0.05V~0.35V, voltage in solution
Sweep speed 50mV/s, the circulation number of turns are 35.Constant potential is carried out in phosphate buffer (PH=6.2) afterwards in example 2
Stable polarization, constant potential -0.05V (with respect to Ag/Cl electrodes), the stable polarization time is 240s.PB modified electrodes are used afterwards
Deionized water is cleaned, and is dried 1h after being dried up using nitrogen gun at 100 DEG C, is obtained Hydrogen Peroxide Biosensor.The mistake
The surface texture and functional layer thickness of hydrogen oxide biology sensor are as shown in Figure 3.Detection of the sensor to hydrogen peroxide is sensitive
Degree and the range of linearity (detection method is with embodiment 2) are as shown in b curves in b curves in Fig. 6 and Fig. 7, the detection of its hydrogen peroxide
It is limited to 0.27 μM (signal to noise ratio 3), the range of linearity is 1 μM~2000 μM, detection sensitivity 272mA/Mcm2.The electrode it is resistance to
Long property test (method of testing is with embodiment 2) result is shown in Fig. 8 b curves in b and Fig. 9, after its 1000 cyclic voltammetry scans
Capacitance fade rate is about 22.5%.
Embodiment 4
Using three-electrode system, the roughening gold film electrode after being handled using the step of embodiment 1 (2) is working electrode, with Ag/
AgCl is reference electrode, and using Pt silks as to electrode, the electrolyte being carried out in example 2 carries out electrochemical deposition, and sedimentation time is
120s, deposition voltage are the PB modified electrodes that 0.4V (relative to Ag/AgCl electrodes) obtains that thickness is 100nm.Will be resulting
With cyclic voltammetric activation is carried out in solution, voltage range -0.05V~0.35V is electric for the activation of PB modified electrodes in example 2
Sweep speed 50mV/s is pressed, the circulation number of turns is 30.Permanent electricity is carried out in phosphate buffer (PH=6.2) afterwards in example 2
The stable polarization in position, constant potential -0.05V (with respect to Ag/Cl electrodes), the stable polarization time is 600s.Afterwards by PB modified electrodes
Cleaned with deionized water, dry 1h after being dried up using nitrogen gun at 100 DEG C, obtain Hydrogen Peroxide Biosensor.Should
The surface texture and functional layer thickness of Hydrogen Peroxide Biosensor are as shown in Figure 4.Detection spirit of the sensor to hydrogen peroxide
Sensitivity and the range of linearity (detection method such as embodiment 2) be shown in Fig. 6 in c curves and Fig. 7 shown in c curves, the inspection of its hydrogen peroxide
Survey is limited to 0.35 μM (signal to noise ratio 3), and the range of linearity is 5 μM~3500 μM, detection sensitivity 383mA/Mcm2.The electrode
Durability test (method of testing is with embodiment 2) result is shown in Fig. 8 c curves in c and Fig. 9, after its 1000 cyclic voltammetry scans
Capacitance fade rate be 25%.
Embodiment 5
Using three-electrode system, the roughening gold film electrode after being handled using the step of embodiment 1 (2) is working electrode, with Ag/
AgCl is reference electrode, and using Pt silks as to electrode, the electrolyte being carried out in example 2 carries out electrochemical deposition, and sedimentation time is
240s, deposition voltage are the PB modified electrodes that 0.4V (relative to Ag/AgCl electrodes) obtains that thickness is 120nm.Will be resulting
With cyclic voltammetric activation is carried out in solution, voltage range -0.05V~0.35V is electric for the activation of PB modified electrodes in example 2
Sweep speed 50mV/s is pressed, the circulation number of turns is 35.Permanent electricity is carried out in phosphate buffer (PH=6.2) afterwards in example 2
The stable polarization in position, constant potential -0.05V (with respect to Ag/Cl electrodes), the stable polarization time is 600s.Afterwards by PB modified electrodes
Cleaned with deionized water, dry 1h after being dried up using nitrogen gun at 100 DEG C, obtain Hydrogen Peroxide Biosensor.Should
The surface texture and functional layer thickness of Hydrogen Peroxide Biosensor are as shown in Figure 5.Detection spirit of the sensor to hydrogen peroxide
Sensitivity and the range of linearity (detection method such as embodiment 2) be shown in Fig. 6 in d curves and Fig. 7 shown in d curves, the inspection of its hydrogen peroxide
Survey is limited to 0.28 μM (signal to noise ratio 3), and the range of linearity is 1 μM~4500 μM, detection sensitivity 424mA/Mcm2.The electrode
Durability test (method of testing is with embodiment 2) result is shown in Fig. 8 d curves in d and Fig. 9, after its 1000 cyclic voltammetry scans
Capacitance fade rate be about 15%.
Embodiment 6 (reference example)
The experiment condition of embodiment 4 is repeated, it is thicker to obtain thickness except the time for depositing PB films is adjusted into 280s
PB deposition films.
Embodiment 7 (reference example)
In embodiment 5, except without above-mentioned steps (2) i.e. without the surface roughening treatment of magnetron sputtering golden film
Outside, operate similarly to Example 5, obtain the Hydrogen Peroxide Biosensor compared.Pass through inspection same as Example 2
Survey method determines detection sensitivity and the range of linearity of the sensor to hydrogen peroxide, and the detection of its hydrogen peroxide is limited to 2.38 μM
(signal to noise ratio 3), the range of linearity are 5~4500 μM, detection sensitivity 281mA/Mcm2。
From above example 2~5 as can be seen that as the increase of sedimentation time, the deposit thickness of PB films gradually increase.
Embodiment 2 shows that deposit thickness 30nm, its high sensitivity is in implementation in the case where sedimentation time is 10s
Example 3 (sedimentation time 40s, thickness 70nm), show that the thickness that the active material layer pointed by previous literature is formed is smaller then clever
The higher rule of sensitivity.But embodiment 3~5 is shown with the increase of PB thickness degree and sensitivity rise, with previous literature institute
The foregoing rule pointed out is different, thus it is speculated that it may be attributed to the change of PB grain shapes and its crystal formation.
For embodiment 2~5, the increase of the thickness with PB films is shown, the detection range of linearity gradually broadens, because
This, by the thickness control of PB films in appropriate scope, both can preferably be detected according to the data of embodiment 2~5
Sensitivity, wider detection range can also be taken into account.
For embodiment 6, when actually being operated, identical embodiment 6 is repeated, finds occur on some PB films surfaces
Crackle, test data is caused to occur scattered and unstable, this is probably due to increase (the especially PB films of deposit thickness
After thickness is more than 130nm), cubic crystal constantly grows in PB film layers, and it is relevant to occur segregation phenomenon between crystal boundary and crystal boundary.
It is visible with the contrast of embodiment 5 according to embodiment 7, by being carried out to the magnetron sputtering golden film for being used as sensor base
Surface roughening treatment, sensitivity can be greatly improved, and obtain broader detection range simultaneously, lower test limit.
Industrial applicability
The gold film electrode and electrochemica biological sensor of the present invention can be by industrial production, and can apply to organism mistake
The detection of hydrogen oxide.
Claims (14)
1. a kind of gold film electrode, it includes：
Substrate；
Gold thin film on substrate,
The thickness of the gold thin film is 200~400nm,
The gold thin film be 5~10nm with the surface roughness Ra on substrate opposite side surface and the hole depth on surface is 20
~40nm.
2. gold film electrode according to claim 1, the surface roughness Ra and surface pore depth are by coarse
Change processing and obtain, the roughening processing preferably includes chemical etching processing.
3. gold film electrode according to claim 1 or 2, the gold thin film is to be formed using sputtering method.
4. according to gold film electrode according to any one of claims 1 to 3, metal transfer between substrate and gold thin film be present
Layer, the intermediate metal include in Cr, Ti and their alloy at least any one.
5. gold film electrode according to claim 4, the intermediate metal is formed using sputtering method, and its thickness is 10
~40nm.
6. a kind of electrochemica biological sensor electrode, the electrode includes：Golden film electricity according to any one of claims 1 to 5
Pole and the decorative layer being formed on the gold thin film of the gold film electrode,
The decorative layer includes Prussian blue, and its thickness is 20~130nm,
Described Prussian blue at least a portion exists with spherical and/or cubic particle form.
7. sensor electrode according to claim 6, the decorative layer is formed by electrochemical deposition method.
8. a kind of electrochemica biological sensor, it is to be based on gold film electrode according to any one of claims 1 to 5 or right
It is required that what the sensor electrode described in 6 or 7 formed.
9. a kind of hydrogen peroxide detection electrochemica biological sensor, the sensor is based on the sensing described in claim 8
Device, the sensitivity of the hydrogen peroxide detection electrochemica biological sensor detection hydrogen peroxide is 270~430mA/Mcm2, inspection
It is more than 0.27 μM to survey the limit, and the range of linearity is 1~X μM, and wherein X is more than 1000 and less than 4500.
10. a kind of preparation method of gold film electrode, methods described include：
By sputtering method deposit thickness in substrate be 200~400nm gold thin film the step of and
The gold thin film surface roughening makes to its surface roughness Ra is 5~10nm and the hole depth on surface is 20~40nm
The step of.
11. according to the method for claim 10, wherein, the roughening includes carrying out chemical etching processing.
12. the method according to claim 10 or 11, wherein, it is included in before depositing gold thin film in substrate, is previously deposited
The step of intermediate metal, the intermediate metal include in Cr, Ti and their alloy at least any one.
13. a kind of preparation method of electrochemica biological sensor electrode, methods described include：
The golden film for being used as basal electrode is formed by the preparation method of the gold film electrode any one of claim 10~12
The step of electrode and on the basal electrode formed decorative layer the step of,
It is described on basal electrode formed decorative layer the step of for pass through electrochemical deposition method formed decorative layer, the decorative layer
Include it is Prussian blue,
The gold thin film thickness is 200~400nm, and the decorative layer thickness is 20~130nm,
Described Prussian blue at least a portion exists with spherical and/or cubic particle form.
14. a kind of preparation method of hydrogen peroxide detection electrochemica biological sensor, it includes appointing in claim 10~12
The preparation side of electrochemica biological sensor electrode described in the preparation method or claim 13 of gold film electrode described in one
Method, the detection sensitivity of the hydrogen peroxide detection electrochemica biological sensor is 270~430mA/Mcm2, detectable limit is
More than 0.27 μM, the range of linearity is 1~X μM, and wherein X is more than 1000 and less than 4500.
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| CN113702477A (en) * | 2021-04-30 | 2021-11-26 | 广州钰芯智能科技研究院有限公司 | Gold film modified electrode for heavy metal detection and preparation method thereof |
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| CN107422015B (en) | 2020-03-27 |
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