CN108652618A - A kind of microelectrode array and preparation method thereof of dendrite platinum modification - Google Patents
A kind of microelectrode array and preparation method thereof of dendrite platinum modification Download PDFInfo
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- CN108652618A CN108652618A CN201710203187.9A CN201710203187A CN108652618A CN 108652618 A CN108652618 A CN 108652618A CN 201710203187 A CN201710203187 A CN 201710203187A CN 108652618 A CN108652618 A CN 108652618A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/28—Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
- A61B5/283—Invasive
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
- A61N1/0526—Head electrodes
- A61N1/0529—Electrodes for brain stimulation
- A61N1/0531—Brain cortex electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/02—Details of sensors specially adapted for in-vivo measurements
- A61B2562/0209—Special features of electrodes classified in A61B5/24, A61B5/25, A61B5/283, A61B5/291, A61B5/296, A61B5/053
Abstract
The present invention provides a kind of microelectrode array of dendrite platinum modification, the electrode surface of the microelectrode array is provided with dendrite platinum decorative layer.The microelectrode array is using dendrite platinum as finishing coat, the good bonding strength of decorative layer and microelectrode substrates, it is not easy to fall off to lead to electrode failure, and the microelectrode surface area after modifying greatly increases, its electrochemical impedance is substantially reduced, electrode charge injection capacity and charge storage greatly increase, this advantageously reduces the system power dissipation of implantation, improve electrical stimulating effect, decorative layer has good biocompatibility and mechanical stability simultaneously, it is made to be greatly increased in the application of biomedical sector.The present invention also provides a kind of preparation methods of the microelectrode array of dendrite platinum modification.In a manner of electrochemical deposition, by one layer of dendrite platinum decorative layer of the surface modification of microelectrode array, this method solution prepare it is simple, it is mild condition, simple and practicable and without additives such as other noxious materials such as lead.
Description
Technical field
The present invention relates to microelectrode surface modification technology fields, more particularly to a kind of microelectrode array of dendrite platinum modification
And preparation method thereof.
Background technology
Nerve stimulation/recording electrode is as one of most important implanted micro element, to stimulate nerve fiber or note
Electroneurographic signal (electrocardio, brain electricity, cortex electric signal etc.) is recorded, brain-computer interface, nervous physiology, brain science research etc. are widely used in
Life science is very important research and clinic tool.
In order to reduce implantation wound, while to clinical point for providing more stimulus modalities and improve electro photoluminescence or record
Resolution, Neural stimulation electrodes/record develop-microelectrode array towards micromation and array direction.However, electrode
Size reduces the problem of with then electrode impedance being brought to increase, and finally influences the stimulation efficiency of electrode.Currently, not increasing electricity
In the case of the geometric dimension of pole, mainly increase the actual surface area of electrode by way of surface modification, and improves electrode
Chemical property.
Specifically, at present the method for microelectrode array surface modification substantially have it is following several：1, in electrode face finish one
Layer platinum black (Anal.Chem.1987,59,217-218), this mode can make the electrochemical impedance of electrode be reduced at least a number
Magnitude, but its mechanical stability is excessively poor, while so that it is not suitable for biomedicine containing noxious materials such as lead in its decorative layer
The application in field；2, in one layer of platinum ash of electrode face finish (USPatent 6974533,2005), this coating has good
Mechanical stability and nontoxic, but its surface roughness is not big enough, makes it in the surface modification of ultrahigh resolution electrode by certain
Limitation；3, oxidized iridium (Eng.Med.Biol.Soc.2004,4153-4156) or conducting polymer
(J.Biomed.Mater.Res.2001,56,261-272) microelectrode modified has fabulous chemical property (such as high electricity
Lotus injectability), but the adhesion strength of these materials is poor, in stimulating course, it is easy to be split away off from electrode surface.
Invention content
In consideration of it, the present invention is intended to provide a kind of using dendrite platinum decorative layer as the microelectrode array of finishing coat, this is repaiied
The binding force for adoring layer and microelectrode substrates is good, and microelectrode surface area is big, and surface roughness is big, and stability is good, and green nothing
Poison.
Specifically, first aspect present invention provides a kind of microelectrode array of dendrite platinum modification, the microelectrode array
Electrode surface be provided with dendrite platinum decorative layer.
In the present invention, the thickness of the dendrite platinum decorative layer is 500nm~10 μm.Different thickness can be such that microelectrode has
Different size of surface area.
In the present invention, the length of the dendrite platinum in the dendrite platinum decorative layer is 200nm~10 μm, and width is the μ of 50nm~2
M, thickness are 5nm~500nm.
In the present invention, the dendrite platinum decorative layer is arranged by way of electro-deposition.It is arranged in electricity by electro-deposition mode
The decorative layer of pole surface and the binding force of electrode surface are strong, and not easily to fall off, performance is highly stable.
The microelectrode array for the dendrite platinum modification that first aspect present invention provides, using dendrite platinum as finishing coat, this is repaiied
Adorn the good bonding strength of layer and microelectrode substrates, it is not easy to which falling off leads to electrode failure, and the microelectrode surface area after modification
It greatly increases, electrochemical impedance is substantially reduced, and electrode charge injection capacity and charge storage greatly increase, this is advantageous
In the system power dissipation for reducing implantation, improve electrical stimulating effect, while the decorative layer has good biocompatibility and machinery
Stability makes it be greatly increased in the application of biomedical sector.
Second aspect, the present invention provides a kind of preparation methods of the microelectrode array of dendrite platinum modification, including following step
Suddenly：
(1) platinum salt solution is provided, suitable weak reductant is added in the platinum salt solution, after mixing mixing, obtains electricity
Deposition solution；
(2) it is to electrode with platinized platinum, Ag/AgCl is reference electrode, and microelectrode to be finished is working electrode, with above-mentioned electricity
Deposition solution forms three-electrode system, and is connected with electrochemical workstation；
(3) under the conditions of 35 DEG C~60 DEG C, electro-deposition 3000s~6000s, the microelectrode surface forms the modification of dendrite platinum
Layer is to get the microelectrode array modified to dendrite platinum.
In the present invention, the mode of the electro-deposition is potentiostatic electrodeposition, galvanostatic deposition or pulse electrodeposition.
In the present invention, the voltage of the potentiostatic electrodeposition is -0.3V~-0.8V, and the electric current of galvanostatic deposition is -0.5 μ A
The peak current density of~-1.5 μ A, pulse electrodeposition are 0.8A/cm2~2.5A/cm2。
In the present invention, the voltage of the potentiostatic electrodeposition is -0.7V~-0.8V, and the electric current of galvanostatic deposition is -0.8 μ A
The peak current density of~-1.5 μ A, pulse electrodeposition are 1.5A/cm2~2.5A/cm2。
In the present invention, the platinum salt solution includes platinum nitrate, platinum chloride, chloroplatinic acid, ammonium chloroplatinate, platinic sodium chloride, six
It is one or more in potassium chloroplatinate and potassium chloroplatinite；In the electric depositing solution, a concentration of 1mmol/L of the platinum salt~
20mmol/L。
In the present invention, the weak reductant includes formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, anti-bad
It is one or more in hematic acid salt, hydroquinone, pyrogallol and 1,2,4 benzenetriols；In the electric depositing solution, it is described it is weak also
A concentration of 1mmol/L~20mmol/L of former agent.
The preparation method that second aspect of the present invention provides, this method is in the electric depositing solution containing platinum salt and weak reductant
In, in a manner of electrochemical deposition, by one layer of dendrite platinum decorative layer of the surface modification of microelectrode array, this method solution is prepared
Simply, and without other noxious materials (such as lead additive), mild condition, simple and practicable, can be quickly in microelectrode array table
Dendrite platinum, and the good bonding strength of decorative layer and microelectrode substrates are modified in face, can quickly increase the surface roughness of microelectrode,
Microelectrode surface area is greatly increased, very superior chemical property is made it have, thus has greatly expanded microelectrode battle array
It is listed in the application in nerve stimulation field.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1-Fig. 4 is scanning electron microscope (SEM) figure of the different size dendrite platinum decorative layers of the present invention；
Fig. 5 is the cycle of the microelectrode array and unmodified microelectrode of dendrite platinum modification prepared by the embodiment of the present invention 1
Volt-ampere (CV) comparison diagram；
Fig. 6 is the electrification of the microelectrode array and unmodified microelectrode of dendrite platinum modification prepared by the embodiment of the present invention 1
Learn impedance (EIS) comparison diagram；
Fig. 7 is the electrochemically stable test result of microelectrode array of dendrite platinum modification prepared by the embodiment of the present invention 1.
Specific implementation mode
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of not departing from principle of the embodiment of the present invention, several improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
Specifically, first aspect present invention provides a kind of microelectrode array of dendrite platinum modification, the microelectrode array
Electrode surface be provided with dendrite platinum decorative layer.
Contain dendrite platinum in the dendrite platinum decorative layer that embodiment of the present invention provides, dendrite platinum includes trunk and along trunk
The side shoot grown in an orderly manner, dendrite platinum can be that three-dimensional dendritic morphology can also be two-dimensional dendritic structure, when dendrite platinum is three-dimensional
When dendritic morphology, side shoot surrounds the side shoot that trunk is not waited in three-dimensional growth length.When dendrite platinum is two-dimensional dendritic knot
When structure, dendrite platinum is laminated structure.The present invention can obtain different size and Bu Tong specific shape by adjusting preparation process
The dendrite platinum of shape.Specifically, the length of the dendrite platinum in the dendrite platinum decorative layer is 200nm~10 μm, and width is 50nm~2
μm, thickness is 5nm~500nm.
Contain a large amount of apparatus derivatorius in dendrite platinum of the present invention, the specific surface area of dendrite platinum decorative layer greatly increases, and institute
The performance for stating dendrite platinum decorative layer is relatively stablized.
In the present invention, the thickness of the dendrite platinum decorative layer is 500nm-10 μm.Different dendrite platinum modifies layer thickness meeting
Make microelectrode that there is different size of surface area.
In the present invention, the dendrite platinum decorative layer has three-D nano-porous structure.Three-D nano-porous structure can be very big
Ground increases the surface area of microelectrode.
In the present invention, the dendrite platinum decorative layer is arranged by way of electro-deposition.It is arranged in electricity by electro-deposition mode
The decorative layer of pole surface and the binding force of electrode surface are strong, and not easily to fall off, performance is highly stable.
The microelectrode array for the dendrite platinum modification that first aspect present invention provides, using dendrite platinum as finishing coat, this is repaiied
Adorn the good bonding strength of layer and microelectrode substrates, it is not easy to which falling off leads to electrode failure, and the microelectrode surface area after modification
It greatly increases, electrochemical impedance is substantially reduced, and electrode charge injection capacity and charge storage greatly increase, this is advantageous
In the system power dissipation for reducing implantation, improve electrical stimulating effect, while the decorative layer has good biocompatibility and machinery
Stability makes it be greatly increased in the application of biomedical sector.
Second aspect, the present invention provides a kind of preparation methods of the microelectrode array of dendrite platinum modification, including following step
Suddenly：
(1) platinum salt solution is provided, weak reductant is added in the platinum salt solution, after mixing mixing, it is molten to obtain electro-deposition
Liquid；
(2) it is to electrode with platinized platinum, Ag/AgCl is reference electrode, and microelectrode to be finished is working electrode, with above-mentioned electricity
Deposition solution forms three-electrode system, and is connected with electrochemical workstation；
(3) under the conditions of 35 DEG C~60 DEG C, electro-deposition 3000s~6000s, the microelectrode surface forms the modification of dendrite platinum
Layer is to get the microelectrode array modified to dendrite platinum.
In the present invention, in step (1), argon gas 30min-1h is passed through to remove the air in solution to electric depositing solution, is prevented
Only coating aoxidizes, and helps to create the structure of dendrite.
In the present invention, before step (2), surface active is carried out to electrode, the operation of the surface active is as follows：
It is to electrode with platinized platinum, Ag/AgCl is reference electrode, and microelectrode to be finished is working electrode, forms three electrodes
System, and be connected with electrochemical workstation, in dilution heat of sulfuric acid, in such a way that CV recycles (cyclic voltammetry), in -0.2V
Within the scope of~1.2V, scan round 30~100 is enclosed.Surface active is carried out to remove the impurity of electrode surface to electrode, is contributed to
Subsequent electrodeposition operates, and improves the stability of coating.
In the present invention, the platinum salt solution is platinum nitrate, platinum chloride, chloroplatinic acid, ammonium chloroplatinate, platinic sodium chloride, chlordene
It is one or more in potassium platinate and potassium chloroplatinite；In the electric depositing solution, a concentration of 1mmol/L of platinum salt~
20mmol/L。
In the present invention, the weak reductant includes formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, anti-bad
It is one or more in hematic acid salt, hydroquinone, pyrogallol and 1,2,4 benzenetriols；In the electric depositing solution, it is described it is weak also
A concentration of 1mmol/L~20mmol/L of former agent.
The weak reductant being added in the present invention such as formic acid (HCOOH) can react with platinum salt, and HCOOH can be by oxygen in the process
Change and generates carbon dioxide (CO2), and porous platinum structure is formed, and high temperature of the present invention and high potential (or high current) are then
It can promote reaction, platinum ion reduction rate is made to accelerate, and more porous platinum structure is formed on microelectrode surface.
In the present invention, depositing temperature is 50 DEG C~60 DEG C in step (3).
In the present invention, the mode of the electro-deposition is potentiostatic electrodeposition, galvanostatic deposition or pulse electrodeposition.Optionally,
The voltage of the potentiostatic electrodeposition is -0.3V~-0.8V, and the electric current of galvanostatic deposition is -0.5 μ μ A of A~-1.5, and pulse electricity is heavy
Long-pending peak current density is 0.8A/cm2~2.5A/cm2.Optionally, the voltage of the potentiostatic electrodeposition be -0.7V~-
The electric current of 0.8V, galvanostatic deposition are -0.8 μ μ A of A~-1.5, and the peak current density of pulse electrodeposition is 1.5A/cm2~
2.5A/cm2。
In the present invention, the thickness of the dendrite platinum decorative layer is 500nm~10 μm.
In the present invention, the dendrite platinum decorative layer has three-D nano-porous structure.
In the present invention, microelectrode to be finished can be planar microelectrode, pin type microelectrode etc..
The microelectrode array preparation method for the dendrite platinum modification that second aspect of the present invention provides, this method containing platinum salt and
In the electric depositing solution of weak reductant, in a manner of electrochemical deposition, by one layer of dendrite platinum of the surface modification of microelectrode array
Decorative layer, this method solution are prepared simply, and without other noxious materials (such as lead additive), mild condition, simple and practicable, energy
It is enough quickly in the dendrite platinum decorative layer of microelectrode array surface modification three-dimensional, and the binding force of decorative layer and microelectrode substrates compared with
It is good, it can quickly increase the surface roughness of microelectrode, greatly increase microelectrode surface area, make it have very superior electricity
Chemical property, thus greatly expanded application of the microelectrode array in nerve stimulation field.
Embodiment 1
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the platinum chloride (PtCl of 1L water, 1mmol are added in a reservoir4) and 5mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 35 DEG C, with the depositional mode of constant potential, under the conditions of -0.3V (vsAg/AgCl), electro-deposition
3000s forms dendrite platinum decorative layer to get the microelectrode array modified to various sizes of dendrite platinum on microelectrode surface.
Fig. 1 is scanning electron microscope (SEM) figure of dendrite platinum decorative layer in the present embodiment, it can be seen from the figure that through
After modification, microelectrode surface forms the dendrite platinum with pine-tree structure.Fig. 2-Fig. 4 is sweeping for different size dendrite platinum decorative layers
Electron microscope (SEM) figure is retouched, various sizes of dendrite platinum can be obtained by adjusting parameters such as sedimentation time and depositing temperatures.
The electrodeposition time of dendrite platinum in Fig. 2-Fig. 4 is 4000s, 5000s and 6000s respectively, and electrodeposition temperature is 40 DEG C respectively,
50 DEG C and 60 DEG C.Fig. 5 is the cyclic voltammetric of the microelectrode array and unmodified microelectrode of the present embodiment dendrite platinum modification
(CV) comparison diagram, in figure, curve 1 is the cyclic voltammetry curve of unmodified microelectrode, and curve 2 is the modification of the present embodiment dendrite platinum
Microelectrode array cyclic voltammetry curve, figure 4, it is seen that compare unmodified microelectrode, dendrite platinum decorative layer
CV increases about 44 times (from 3.7mC/cm2Rise in value 162.4mC/cm2), show that it has more superior charge storage.Fig. 6
For electrochemical impedance (EIS) comparison diagram of the microelectrode array and unmodified microelectrode of the modification of the present embodiment dendrite platinum, in figure,
Curve 1 is the electrochemical impedance curve of unmodified microelectrode, and curve 2 is the microelectrode array of the present embodiment dendrite platinum modification
Electrochemical impedance curve, from fig. 6 it can be seen that comparing unmodified microelectrode, dendrite platinum decorative layer has lower electrification
Impedance is learned, the electrochemical impedance in 1KHz can be down to 1.3k Ω.Fig. 7 is the microelectrode array of the present embodiment dendrite platinum modification
Electrochemically stable test result, the microelectrode to being modified with dendrite platinum carries out long-term high-frequency pulse experiment, and test pulse
The variation of front and back charge storage (calculating in CV closed curves, obtained by the integral area of cathode portion), curve 1 is in figure
The CV curve graphs of the dendrite platinum decorative layer of pulse test are not carried out, curve 2 is to the uninterrupted high-frequency impulse of dendrite platinum decorative layer
CV curve graphs after 48h, curve 3 are the CV curve graphs after high-frequency impulse 96h uninterrupted to dendrite platinum decorative layer, can be with from Fig. 7
Find out, through a long time high-frequency impulse is (more than 2 × 106It is secondary), the charge storage of dendrite platinum decorative layer only has the loss of very little
(being less than 2%) shows that the dendrite platinum decorative layer prepared by the embodiment of the present invention has fabulous long-time stability.
Microelectrode used in the present embodiment is to prepare to complete by a series of micro fabrications, such as photoetching (EVG610
Ultraviolet exposure machine, Austria), sputtering, etching etc..
Embodiment 2
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the platinum nitrate (Pt (NO of 1L water, 1mmol are added in a reservoir3)4) and 10mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 50 DEG C, with the depositional mode of constant potential, under the conditions of -0.5V (vsAg/AgCl), electro-deposition
5000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 3
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the chloroplatinic acid (H of 1L water, 1mmol are added in a reservoir2PtCl6) and 8mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 60 DEG C, with the depositional mode of constant current, with the electric current of -1.0 μ A (vsAg/AgCl), electro-deposition
3000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 4
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the chloroplatinic acid (H of 1L water, 5mmol are added in a reservoir2PtCl6) and 1mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, in 55 DEG C of environment, in a manner of pulse electrodeposition, with duty ratio for 5 μ s：500 μ s, peak current density are
2.5A/cm2Pulse current, electro-deposition 3000s, microelectrode surface formed dendrite platinum decorative layer to get to dendrite platinum modify
Microelectrode array.
Embodiment 5
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the ammonium chloroplatinate ((NH of 1L water, 5mmol are added in a reservoir4)2PtCl6) and 5mmol
Formic acid (HCOOH), jiggles mixing, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 60 DEG C, in a manner of pulse electrodeposition, with duty ratio for 5 μ s：500 μ s, peak current density are
1.5A/cm2Pulse current, electro-deposition 5000s, microelectrode surface formed dendrite platinum decorative layer to get to dendrite platinum modify
Microelectrode array.
Embodiment 6
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the platinic sodium chloride (Na of 1L water, 5mmol are added in a reservoir2PtCl6) and 10mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 45 DEG C, with the depositional mode of constant potential, with the current potential of -0.8V (vsAg/AgCl), electro-deposition
3000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 7
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the potassium chloroplatinate (K of 1L water, 5mmol are added in a reservoir2PtCl6) and 20mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 45 DEG C, with the depositional mode of constant potential, with the current potential of -0.6V (vsAg/AgCl), electro-deposition
4000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 8
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the potassium chloroplatinate (K of 1L water, 10mmol are added in a reservoir2PtCl6) and 5mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 50 DEG C, with the depositional mode of constant current, with the electric current of -0.5 μ A (vsAg/AgCl), electro-deposition
6000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 9
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the sub- sour potassium (K of chlorine of 1L water, 10mmol are added in a reservoir2PtCl4) and 20mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 40 DEG C, with the depositional mode of constant current, with the electric current of -1.5 μ A (vsAg/AgCl), electro-deposition
5000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 10
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the sub- sour potassium (K of chlorine of 1L water, 20mmol are added in a reservoir2PtCl4) and 5mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 60 DEG C, in a manner of pulse electrodeposition, with duty ratio for 5 μ s：500 μ s, peak current density are
0.8A/cm2Pulse current, electro-deposition 6000s, microelectrode surface formed dendrite platinum decorative layer to get to dendrite platinum modify
Microelectrode array.
Embodiment 11
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the sub- sour potassium (K of chlorine of 1L water, 20mmol are added in a reservoir2PtCl4) and 10mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 40 DEG C, in a manner of pulse electrodeposition, with duty ratio for 5 μ s：500 μ s, peak current density are
2.5A/cm2Pulse current, electro-deposition 5000s, microelectrode surface formed dendrite platinum decorative layer to get to dendrite platinum modify
Microelectrode array.
Embodiment 12
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the chloroplatinic acid (H of 1L water, 20mmol are added in a reservoir2PtCl6) and 20mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 50 DEG C, with the depositional mode of constant potential, under the conditions of -0.3V (vsAg/AgCl), electro-deposition
6000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Embodiment 13
A kind of preparation method of the microelectrode array of dendrite platinum modification, includes the following steps：
(1) under room temperature environment, the chloroplatinic acid (H of 1L water, 20mmol are added in a reservoir2PtCl6) and 1mmol formic acid
(HCOOH), mixing is jiggled, and after being passed through argon gas 30min, forms electric depositing solution；
(2) in above-mentioned electric depositing solution, merging platinized platinum, Ag/AgCl reference electrodes and microelectrode, and with electrochemistry work
Make station to be connected, under the conditions of 40 DEG C, with the depositional mode of constant potential, under the conditions of -0.8V (vsAg/AgCl), electro-deposition
3000s forms dendrite platinum decorative layer to get the microelectrode array modified to dendrite platinum on microelectrode surface.
Using test method in the same manner as in Example 1 to the micro- of above-described embodiment 2-13 dendrite platinum modifications prepared
Electrod-array is tested, and test result shows the good bonding strength of obtained decorative layer and microelectrode substrates, electrochemistry resistance
Anti- low, charge injection and storage capacity is big, good biocompatibility has good development potentiality in nerve stimulation field.
Certainly, the present invention can also have other embodiment, without deviating from the spirit and substance of the present invention, affiliated skill
The technical staff in art field makes various corresponding change and deformations, but these corresponding change and deformations in accordance with the present invention
The scope of the claims of the present invention should all be belonged to.
Claims (10)
1. a kind of microelectrode array of dendrite platinum modification, which is characterized in that the electrode surface of the microelectrode array is provided with branch
Brilliant platinum decorative layer.
2. the microelectrode array of dendrite platinum modification as described in claim 1, which is characterized in that the thickness of the dendrite platinum decorative layer
Degree is 500nm~10 μm.
3. the microelectrode array of dendrite platinum modification as described in claim 1, which is characterized in that in the dendrite platinum decorative layer
The length of dendrite platinum is 200nm~10 μm, and width is 50nm~2 μm, and thickness is 5nm~500nm.
4. the microelectrode array of dendrite platinum modification as described in claim 1, which is characterized in that the dendrite platinum decorative layer passes through
The mode of electro-deposition is arranged.
5. a kind of preparation method of the microelectrode array of dendrite platinum modification, which is characterized in that include the following steps：
(1) platinum salt solution is provided, weak reductant is added in the platinum salt solution, mixing is mixed, obtains electric depositing solution；
(2) it is to electrode with platinized platinum, Ag/AgCl is reference electrode, and microelectrode to be finished is working electrode, with the electro-deposition
Solution forms three-electrode system, and is connected with electrochemical workstation；
(3) under the conditions of 35 DEG C~60 DEG C, electro-deposition 3000s~6000s, the microelectrode surface forms dendrite platinum decorative layer,
Obtain the microelectrode array of dendrite platinum modification.
6. the preparation method of the microelectrode array of dendrite platinum modification as claimed in claim 5, which is characterized in that the electro-deposition
Mode be potentiostatic electrodeposition, galvanostatic deposition or pulse electrodeposition.
7. the preparation method of the microelectrode array of dendrite platinum modification as claimed in claim 6, which is characterized in that the constant potential
The voltage of deposition is -0.3V~-0.8V, and the electric current of galvanostatic deposition is -0.5 μ μ A of A~-1.5, the peak value electricity of pulse electrodeposition
Current density is 0.8A/cm2~2.5A/cm2。
8. the preparation method of the microelectrode array of dendrite platinum modification as claimed in claim 7, which is characterized in that the constant potential
The voltage of deposition is -0.7V~-0.8V, and the electric current of galvanostatic deposition is -0.8 μ μ A of A~-1.5, the peak value electricity of pulse electrodeposition
Current density is 1.5A/cm2~2.5A/cm2。
9. the preparation method of the microelectrode array of dendrite platinum modification as claimed in claim 5, which is characterized in that the platinum salt is molten
Liquid includes one kind in platinum nitrate, platinum chloride, chloroplatinic acid, ammonium chloroplatinate, platinic sodium chloride, potassium platinic chloride and potassium chloroplatinite
Or it is a variety of；In the electric depositing solution, a concentration of 1mmol/L~20mmol/L of the platinum salt.
10. the preparation method of the microelectrode array of dendrite platinum as claimed in claim 5 modification, which is characterized in that it is described it is weak also
Former agent include formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol and
It is one or more in 1,2,4 benzenetriols；In the electric depositing solution, a concentration of 1mmol/L of the weak reductant~
20mmol/L。
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