CN108652618B - Dendritic platinum modified microelectrode array and preparation method thereof - Google Patents
Dendritic platinum modified microelectrode array and preparation method thereof Download PDFInfo
- Publication number
- CN108652618B CN108652618B CN201710203187.9A CN201710203187A CN108652618B CN 108652618 B CN108652618 B CN 108652618B CN 201710203187 A CN201710203187 A CN 201710203187A CN 108652618 B CN108652618 B CN 108652618B
- Authority
- CN
- China
- Prior art keywords
- platinum
- dendritic
- modified
- microelectrode array
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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]
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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 invention provides a dendritic platinum modified microelectrode array, wherein a dendritic platinum modification layer is arranged on the surface of an electrode of the microelectrode array. The microelectrode array takes dendritic platinum as a surface modification layer, the binding force of the modification layer and a microelectrode substrate is good, the modification layer is not easy to fall off to cause electrode failure, the surface of the modified microelectrode is actively and greatly increased, the electrochemical impedance of the modified microelectrode is obviously reduced, the electrode charge injection capacity and the charge storage capacity are greatly increased, the implanted system power consumption is favorably reduced, the electrical stimulation effect is improved, and meanwhile, the modification layer has good biocompatibility and mechanical stability, so that the application of the modification layer in the field of biomedicine is greatly increased. The invention also provides a preparation method of the dendrite platinum modified microelectrode array. The method has the advantages that the surface of the microelectrode array is modified with a dendritic platinum modification layer in an electrochemical deposition mode, the solution preparation is simple, other toxic substances such as lead and other additives are not contained, and the method is mild in condition, simple and feasible.
Description
Technical Field
The invention relates to the technical field of microelectrode surface modification, in particular to a dendrite platinum modified microelectrode array and a preparation method thereof.
Background
The nerve stimulating/recording electrode is one of the most important implanted micro-devices, is used for stimulating nerve tissues or recording nerve electrical signals (electrocardio, electroencephalogram, cortical electrical signals and the like), is widely used in the life science fields of brain-computer interfaces, neurophysiology, brain science research and the like, and is a very important research and diagnosis and treatment tool.
In order to reduce implantation trauma while providing more stimulation patterns to the clinic and increasing the resolution of electrical stimulation or recording, neurostimulation electrodes/recording are moving towards miniaturization and arraying — microelectrode arrays. However, the reduction in electrode size comes with the problem of increasing electrode impedance and ultimately affects the stimulation efficiency of the electrode. At present, the actual surface area of the electrode is increased and the electrochemical performance of the electrode is improved mainly by means of surface modification without increasing the geometric size of the electrode.
Specifically, the current methods for modifying the surface of the microelectrode array include the following methods: 1. the surface of the electrode is modified with a layer of platinum black (anal. chem.1987,59,217-218), which can reduce the electrochemical impedance of the electrode by at least one order of magnitude, but the mechanical stability is very poor, and meanwhile, the modified layer contains toxic substances such as lead, and the like, so that the electrode is not suitable for application in the biomedical field; 2. the surface of the electrode is modified with a layer of platinum ash (USP patent 6974533,2005), the coating has good mechanical stability and no toxicity, but the surface roughness is not large enough, so that the surface modification of the electrode on the ultrahigh resolution ratio is limited to a certain extent; 3. microelectrodes modified with iridium oxide (Eng. Med. biol. Soc.2004,4153-4156) or conductive polymers (J. biomed. Mater. Res.2001,56,261-272) have excellent electrochemical properties (e.g., high charge injection capability), but these materials have poor adhesion and are easily detached from the electrode surface during stimulation.
Disclosure of Invention
In view of the above, the present invention provides a microelectrode array with a dendritic platinum modification layer as a surface modification layer, wherein the modification layer has a good bonding force with a microelectrode substrate, a large surface area of the microelectrode, a large surface roughness, a good performance stability, and is green and nontoxic.
Specifically, the invention provides a dendritic platinum modified microelectrode array, wherein a dendritic platinum modified layer is arranged on the surface of an electrode of the microelectrode array.
In the invention, the thickness of the dendritic platinum modification layer is 500nm-10 μm. The different thicknesses result in micro-electrodes having different amounts of surface area.
In the invention, the length of the dendritic platinum in the dendritic platinum modification layer is 200 nm-10 μm, the width is 50 nm-2 μm, and the thickness is 5 nm-500 nm.
In the invention, the dendritic platinum modification layer is arranged in an electrodeposition mode. The modification layer arranged on the surface of the electrode in an electrodeposition mode has strong binding force with the surface of the electrode, is not easy to fall off, and has very stable performance.
According to the dendrite platinum modified microelectrode array provided by the first aspect of the invention, dendrite platinum is used as a surface modification layer, the modification layer has good binding force with a microelectrode substrate, the electrode is not easy to fall off to cause electrode failure, the surface of the modified microelectrode is actively and greatly increased, the electrochemical impedance of the modified microelectrode is obviously reduced, the electrode charge injection capacity and the charge storage capacity are greatly increased, the implanted system power consumption is favorably reduced, the electrical stimulation effect is improved, and meanwhile, the modification layer has good biocompatibility and mechanical stability, so that the application of the modified microelectrode array in the biomedical field is greatly increased.
In a second aspect, the invention provides a preparation method of a dendrite platinum modified microelectrode array, which comprises the following steps:
(1) providing a platinum salt solution, adding a proper amount of weak reducing agent into the platinum salt solution, and mixing and uniformly mixing to obtain an electrodeposition solution;
(2) taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, taking a micro-electrode to be modified as a working electrode, forming a three-electrode system with the electrodeposition solution, and connecting the three-electrode system with an electrochemical workstation;
(3) and (3) electrodepositing 3000 s-6000 s at the temperature of 35-60 ℃, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
In the invention, the electrodeposition mode is constant potential deposition, constant current deposition or pulse electrodeposition.
In the invention, the voltage of the constant potential deposition is-0.3V to-0.8V, the current of the constant current deposition is-0.5 muA to-1.5 muA, and the peak current density of the pulse electrodeposition is 0.8A/cm2～2.5A/cm2。
In the invention, the voltage of the constant potential deposition is-0.7V to-0.8V, the current of the constant current deposition is-0.8 muA to-1.5 muA, and the peak current density of the pulse electrodeposition is 1.5A/cm2～2.5A/cm2。
In the invention, the platinum salt solution comprises one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate; in the electrodeposition solution, the concentration of the platinum salt is 1 mmol/L-20 mmol/L.
In the invention, the weak reducing agent comprises one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol and 1,2,4 benzenetriol; in the electrodeposition solution, the concentration of the weak reducing agent is 1 mmol/L-20 mmol/L.
According to the preparation method provided by the second aspect of the invention, a dendritic platinum modification layer is modified on the surface of the microelectrode array in an electro-deposition solution containing platinum salt and a weak reducing agent in an electro-chemical deposition mode, the solution preparation method is simple, other toxic substances (such as additives like lead and the like) are avoided, the conditions are mild, simple and feasible, dendritic platinum can be rapidly modified on the surface of the microelectrode array, the bonding force between the modification layer and a microelectrode substrate is good, the surface roughness of the microelectrode can be rapidly increased, the surface area of the microelectrode is greatly increased, and the microelectrode has very excellent electro-chemical performance, so that the application of the microelectrode array in the field of nerve stimulation is greatly expanded.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIGS. 1-4 are Scanning Electron Microscope (SEM) images of dendritic platinum modification layers of different sizes in accordance with the present invention;
FIG. 5 is a graph showing a comparison of Cyclic Voltammetry (CV) for an array of dendrite platinum modified microelectrodes prepared in example 1 of the present invention and unmodified microelectrodes;
FIG. 6 is a graph comparing Electrochemical Impedance (EIS) of dendrite platinum modified microelectrode arrays prepared according to example 1 of the present invention with unmodified microelectrodes;
FIG. 7 shows the results of electrochemical stability test of dendrite platinum modified microelectrode array prepared in example 1 of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Specifically, the invention provides a dendritic platinum modified microelectrode array, wherein a dendritic platinum modified layer is arranged on the surface of an electrode of the microelectrode array.
The dendritic platinum modification layer provided by the embodiment of the invention contains dendritic platinum, the dendritic platinum comprises a main stem and side branches which sequentially grow along the main stem, the dendritic platinum can be a three-dimensional dendritic structure or a two-dimensional dendritic structure, and when the dendritic platinum is the three-dimensional dendritic structure, the side branches with different lengths grow around the main stem in the three-dimensional direction. When the dendritic platinum is a two-dimensional dendritic structure, the dendritic platinum is a sheet structure. The invention can obtain dendritic platinum with different sizes and different specific shapes by adjusting the preparation process. Specifically, the length of the dendritic platinum in the dendritic platinum modification layer is 200 nm-10 μm, the width is 50 nm-2 μm, and the thickness is 5 nm-500 nm.
The dendritic platinum contains a large number of branch structures, the specific surface area of the dendritic platinum modification layer is greatly increased, and the performance of the dendritic platinum modification layer is stable.
In the invention, the thickness of the dendritic platinum modification layer is 500nm-10 μm. Different dendritic platinum modification layer thicknesses will result in microelectrodes having different sized surface areas.
In the invention, the dendritic platinum modification layer has a three-dimensional nano porous structure. The three-dimensional nano-porous structure can greatly increase the surface area of the microelectrode.
In the invention, the dendritic platinum modification layer is arranged in an electrodeposition mode. The modification layer arranged on the surface of the electrode in an electrodeposition mode has strong binding force with the surface of the electrode, is not easy to fall off, and has very stable performance.
According to the dendrite platinum modified microelectrode array provided by the first aspect of the invention, dendrite platinum is used as a surface modification layer, the modification layer has good binding force with a microelectrode substrate, the electrode is not easy to fall off to cause electrode failure, the surface of the modified microelectrode is actively and greatly increased, the electrochemical impedance of the modified microelectrode is obviously reduced, the electrode charge injection capacity and the charge storage capacity are greatly increased, the implanted system power consumption is favorably reduced, the electrical stimulation effect is improved, and meanwhile, the modification layer has good biocompatibility and mechanical stability, so that the application of the modified microelectrode array in the biomedical field is greatly increased.
In a second aspect, the invention provides a preparation method of a dendrite platinum modified microelectrode array, which comprises the following steps:
(1) providing a platinum salt solution, adding a weak reducing agent into the platinum salt solution, and mixing and uniformly mixing to obtain an electrodeposition solution;
(2) taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, taking a micro-electrode to be modified as a working electrode, forming a three-electrode system with the electrodeposition solution, and connecting the three-electrode system with an electrochemical workstation;
(3) and (3) electrodepositing 3000 s-6000 s at the temperature of 35-60 ℃, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
In the invention, in the step (1), argon is introduced into the electrodeposition solution for 30min-1h to remove air in the solution, prevent the plating layer from being oxidized and contribute to generating a dendritic crystal structure.
In the present invention, before the step (2), the electrode is subjected to surface activation, which is performed as follows:
and (2) taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, taking the micro-electrode to be modified as a working electrode to form a three-electrode system, connecting the three-electrode system with an electrochemical workstation, and circularly scanning for 30-100 circles in a dilute sulfuric acid solution in a CV (cyclic voltammetry) mode within the range of-0.2V-1.2V. The surface of the electrode is activated to remove impurities on the surface of the electrode, so that the subsequent electrodeposition operation is facilitated, and the stability of a plating layer is improved.
In the invention, the platinum salt solution is one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate and potassium chloroplatinate; in the electrodeposition solution, the concentration of the platinum salt is 1 mmol/L-20 mmol/L.
In the invention, the weak reducing agent comprises one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol and 1,2,4 benzenetriol; in the electrodeposition solution, the concentration of the weak reducing agent is 1 mmol/L-20 mmol/L.
The weak reducing agent such as formic acid (HCOOH) added in the invention can react with platinum salt, and the HCOOH can be oxidized to generate carbon dioxide (CO) in the process2) And a porous platinum structure is formed, while the high temperature and high potential (or high current) of the invention can promote the reaction to occur, so that the reduction speed of platinum ions is accelerated, and a more porous platinum structure is formed on the surface of the microelectrode.
In the invention, the deposition temperature in the step (3) is 50-60 ℃.
In the invention, the electrodeposition mode is constant potential deposition, constant current deposition or pulse electrodeposition. Optionally, the potentiostatic deposition voltage is-0.3V to-0.8V, the galvanostatic deposition current is-0.5 muA to-1.5 muA, and the peak current density of the pulsed electrodeposition is 0.8A/cm2～2.5A/cm2. Optionally, the potentiostatic deposition voltage is-0.7V to-0.8V, the galvanostatic deposition current is-0.8 muA to-1.5 muA, and the peak current density of the pulsed electrodeposition is 1.5A/cm2～2.5A/cm2。
In the invention, the thickness of the dendritic platinum modification layer is 500nm-10 μm.
In the invention, the dendritic platinum modification layer has a three-dimensional nano porous structure.
In the present invention, the microelectrode to be modified may be a planar microelectrode, a needle microelectrode or the like.
According to the preparation method of the dendrite platinum modified microelectrode array, provided by the second aspect of the invention, a dendrite platinum modification layer is modified on the surface of the microelectrode array in an electro-deposition solution containing platinum salt and a weak reducing agent in an electro-chemical deposition mode, the solution preparation method is simple, no other toxic substances (such as additives like lead and the like) are contained, the conditions are mild, simple and easy to implement, the three-dimensional dendrite platinum modification layer can be rapidly modified on the surface of the microelectrode array, the binding force between the modification layer and a microelectrode substrate is good, the surface roughness of the microelectrode can be rapidly increased, the surface area of the microelectrode is greatly increased, and the microelectrode array has very excellent electro-chemical properties, so that the application of the microelectrode array in the field of nerve stimulation is greatly expanded.
Example 1
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 1mmol of platinum chloride (PtCl) were added to a vessel at room temperature4) And 5mmol formic acid (HCOOH), gently shaking and mixing uniformly, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing for 3000s at 35 ℃ in a constant potential deposition mode under the condition of-0.3V (vsAg/AgCl), and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode arrays with different sizes.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the dendritic platinum modification layer of the present embodiment, which shows that dendritic platinum with a dendritic structure is formed on the surface of the microelectrode after modification. Fig. 2-4 are Scanning Electron Microscope (SEM) images of dendritic platinum modification layers of different sizes, which can be obtained by adjusting parameters such as deposition time and deposition temperature. The electrodeposition time for dendritic platinum in FIGS. 2-4 was 4000s, 5000s and 6000s, and electrodeposition temperatures of 40 deg.C, 50 deg.C and 60 deg.C, respectively. FIG. 5 is a graph of the Cyclic Voltammetry (CV) of the dendrite platinum modified microelectrode array of this example compared to that of the unmodified microelectrode, where curve 1 is the cyclic voltammetry of the unmodified microelectrode and curve 2 is the cyclic voltammetry of the dendrite platinum modified microelectrode array of this example, and it can be seen from FIG. 4 that the CV of the dendrite platinum modified layer is increased by a factor of about 44 (from 3.7 mC/cm) compared to that of the unmodified microelectrode2Increment of 162.4mC/cm2) Thus showing that the material has more excellent charge storage capacity. FIG. 6 is a graph comparing Electrochemical Impedance (EIS) of the dendrite platinum modified microelectrode array with that of an unmodified microelectrode of this embodiment, wherein curve 1 is an electrochemical impedance curve of an unmodified microelectrode, and curve 2 is an electrochemical impedance curve of the dendrite platinum modified microelectrode array of this embodiment, and it can be seen from FIG. 6 that the dendrite platinum modified layer has a lower electrochemical impedance than an unmodified microelectrode, and the electrochemical impedance at 1KHz can be as low as 1.3k Ω. FIG. 7 is a diagram showing the electrochemical stability test result of the microelectrode array modified by dendrite platinum according to the present embodiment, which is obtained by performing a long-term high-frequency pulse experiment on the microelectrode modified by dendrite platinum and testing the change of the charge storage capacity (obtained by calculating the integral area of the cathode portion in the CV closed curve) before and after the pulse, where curve 1 is a CV curve of the dendrite platinum modification layer without performing the pulse experiment, curve 2 is a CV curve of the dendrite platinum modification layer after 48h of uninterrupted high-frequency pulse, curve 3 is a CV curve of the dendrite platinum modification layer after 96h of uninterrupted high-frequency pulse, and it can be seen from FIG. 7 that the microelectrode array modified by dendrite platinum has undergone a long-term high-frequency pulse (exceeding 2 × 10)6Second), the dendritic platinum modification layer has only small loss (less than 2%) of charge storage capacity, which indicates that the dendritic platinum modification layer prepared by the embodiment of the invention has excellent long-term stability.
The micro-electrode used in this embodiment is fabricated by a series of micro-processing processes such as photolithography (EVG610 uv exposure machine, austria), sputtering, etching, and the like.
Example 2
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 1mmol of platinum nitrate (Pt (NO) were added to a vessel at room temperature3)4) And 10mmol formic acid (HCOOH), gently shaking and mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing for 5000s at 50 ℃ in a constant potential deposition mode under the condition of-0.5V (vsAg/AgCl), and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 3
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 1mmol of chloroplatinic acid (H) were added to a vessel at room temperature2PtCl6) And 8mmol formic acid (HCOOH), gently shaking and mixing uniformly, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing for 3000s at 60 ℃ in a constant current deposition mode at a current of-1.0 muA (vsAg/AgCl), and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 4
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 5mmol of chloroplatinic acid (H) were added to a vessel at room temperature2PtCl6) And 1mmol of formic acid (HCOOH), gently shaking and uniformly mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (2) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and performing pulse electrodeposition at 55 ℃ in a mode of duty ratio of 5 mus: 500 mus, peak current density of 2.5A/cm2The pulse current is used for electrodeposition for 3000s, and a dendritic platinum modification layer is formed on the surface of the microelectrode, so that dendritic platinum modification is obtainedA decorated microelectrode array.
Example 5
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 5mmol of ammonium hexachloroplatinate ((NH)4)2PtCl6) And 5mmol formic acid (HCOOH), gently shaking and mixing uniformly, and introducing argon for 30min to form an electrodeposition solution;
(2) and (2) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and performing pulse electrodeposition at the temperature of 60 ℃ in a mode of duty ratio of 5 mus: 500 mus, peak current density of 1.5A/cm2And (3) carrying out electro-deposition for 5000s by using the pulse current, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 6
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) in a vessel, 1L of water and 5mmol of sodium chloroplatinate (Na) were added at room temperature2PtCl6) And 10mmol formic acid (HCOOH), gently shaking and mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing 3000s at 45 ℃ in a constant potential deposition mode at a potential of-0.8V (vsAg/AgCl) to form a dendritic platinum modification layer on the surface of the microelectrode, and thus obtaining the dendritic platinum modified microelectrode array.
Example 7
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 5mmol of potassium chloroplatinate (K) were added to a vessel2PtCl6) And 20mmol of formic acid (HCOOH), gently shaking and uniformly mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and electrodepositing for 4000s at the temperature of 45 ℃ in a constant potential deposition mode at the potential of-0.6V (vsAg/AgCl) to form a dendritic platinum modification layer on the surface of the microelectrode, thus obtaining the dendritic platinum modified microelectrode array.
Example 8
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 10mmol of potassium chloroplatinate (K) were added to a vessel2PtCl6) And 5mmol formic acid (HCOOH), gently shaking and mixing uniformly, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and electrodepositing 6000s at 50 ℃ in a constant-current deposition mode at a current of-0.5 muA (vsAg/AgCl) to form a dendritic platinum modification layer on the surface of the microelectrode, thereby obtaining the dendritic platinum modified microelectrode array.
Example 9
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 10mmol of potassium chlorosulfite (K) were added to a vessel2PtCl4) And 20mmol of formic acid (HCOOH), gently shaking and uniformly mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing 5000s at 40 ℃ in a constant current deposition mode at a current of-1.5 muA (vsAg/AgCl) to form a dendritic platinum modification layer on the surface of the microelectrode, and obtaining the dendritic platinum modified microelectrode array.
Example 10
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 20mmol of potassium chlorosulfite (K) were added to a vessel2PtCl4) And 5mmol formic acid (HCOOH), gently shaking and mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (2) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and performing pulse electrodeposition at the temperature of 60 ℃ in a mode of duty ratio of 5 mus: 500 mus, peak current density of 0.8A/cm2And (3) carrying out electro-deposition for 6000s by using the pulse current, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 11
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) at room temperature, 1L of water and 20mmol of potassium chlorosulfite (K) were added to a vessel2PtCl4) And 10mmol formic acid (HCOOH), gently shaking and mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (2) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, and performing pulse electrodeposition at 40 ℃ in a mode of duty ratio of 5 mus: 500 mus, peak current density of 2.5A/cm2And (3) carrying out electro-deposition for 5000s by using the pulse current, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 12
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 20mmol of chloroplatinic acid (H) were added to a vessel at room temperature2PtCl6) And 20mmol of formic acid (HCOOH), gently shaking and uniformly mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing 6000s at 50 ℃ in a constant potential deposition mode under the condition of-0.3V (vsAg/AgCl), and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
Example 13
A preparation method of a dendrite platinum modified microelectrode array comprises the following steps:
(1) 1L of water and 20mmol of chloroplatinic acid (H) were added to a vessel at room temperature2PtCl6) And 1mmol of formic acid (HCOOH), gently shaking and uniformly mixing, and introducing argon for 30min to form an electrodeposition solution;
(2) and (3) placing a platinum sheet, an Ag/AgCl reference electrode and a microelectrode in the electrodeposition solution, connecting the electrodeposition solution with an electrochemical workstation, electrodepositing for 3000s in a constant potential deposition mode at 40 ℃ under the condition of-0.8V (vsAg/AgCl), and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain the dendritic platinum modified microelectrode array.
The testing method the same as that in the embodiment 1 is adopted to test the dendrite platinum modified microelectrode array prepared in the embodiments 2-13, and the testing result shows that the prepared modified layer has good bonding force with the microelectrode substrate, low electrochemical impedance, large charge injection and storage capacity, good biocompatibility and good development potential in the nerve stimulation field.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (6)
1. A dendritic platinum modified microelectrode array is used in the field of biomedicine and is characterized in that a dendritic platinum modification layer is arranged on the surface of an electrode of the microelectrode array, dendritic platinum is contained in the dendritic platinum modification layer, and the dendritic platinum is of a three-dimensional dendritic structure; the dendritic platinum comprises a trunk and lateral branches growing orderly along the trunk; the lateral branches grow in different lengths in the three-dimensional direction around the trunk; the dendritic platinum modified microelectrode array is prepared by the following method:
(1) providing a platinum salt solution, adding a weak reducing agent into the platinum salt solution, and mixing and uniformly mixing to obtain an electrodeposition solution;
(2) taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, taking a micro-electrode to be modified as a working electrode, forming a three-electrode system with the electrodeposition solution, and connecting the three-electrode system with an electrochemical workstation;
(3) electrodepositing 3000 s-6000 s at the temperature of 35-60 ℃, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain a dendritic platinum modified microelectrode array; the electrodeposition mode is constant potential deposition, constant current deposition or pulse electrodeposition; the voltage of the constant potential deposition is-0.7V to-0.8V, the current of the constant current deposition is-0.8 muA to-1.5 muA, and the peak current density of the pulse electrodeposition is 1.5A/cm2～2.5A/cm2。
2. The dendrite platinum modified microelectrode array of claim 1, wherein the dendrite platinum modifying layer has a thickness of 500nm to 10 μ ι η.
3. The dendrite platinum modified microelectrode array of claim 1, wherein the dendrite platinum in the dendrite platinum modifying layer has a length of 200nm to 10 μm, a width of 50nm to 2 μm, and a thickness of 5nm to 500 nm.
4. A preparation method of a dendrite platinum modified microelectrode array is characterized by comprising the following steps:
(1) providing a platinum salt solution, adding a weak reducing agent into the platinum salt solution, and mixing and uniformly mixing to obtain an electrodeposition solution;
(2) taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, taking a micro-electrode to be modified as a working electrode, forming a three-electrode system with the electrodeposition solution, and connecting the three-electrode system with an electrochemical workstation;
(3) electrodepositing 3000 s-6000 s at the temperature of 35-60 ℃, and forming a dendritic platinum modification layer on the surface of the microelectrode to obtain a dendritic platinum modified microelectrode array; the electrodeposition mode is constant potential deposition, constant current deposition or pulse electrodeposition; the voltage of the constant potential deposition is-0.7V to-0.8V, and the constant voltage isThe current of flow deposition is-0.8 muA to-1.5 muA, and the peak current density of pulse electrodeposition is 1.5A/cm2～2.5A/cm2。
5. The method of making a dendrite platinum modified microelectrode array of claim 4, wherein the platinum salt solution comprises one or more of platinum nitrate, platinum chloride, chloroplatinic acid, ammonium hexachloroplatinate, sodium chloroplatinate, potassium hexachloroplatinate, and potassium chloroplatinate; in the electrodeposition solution, the concentration of the platinum salt is 1 mmol/L-20 mmol/L.
6. The method of preparing a dendrite platinum modified microelectrode array of claim 4, wherein the weak reducing agent comprises one or more of formic acid, hydroxylamine hydrochloride, citric acid, citrate, ascorbic acid, ascorbate, hydroquinone, pyrogallol, and 1,2,4 benzenetriphenol; in the electrodeposition solution, the concentration of the weak reducing agent is 1 mmol/L-20 mmol/L.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710203187.9A CN108652618B (en) | 2017-03-30 | 2017-03-30 | Dendritic platinum modified microelectrode array and preparation method thereof |
| EP17814509.0A EP3511706B1 (en) | 2016-06-23 | 2017-05-09 | Microelectrode array and manufacturing method therefor |
| PCT/CN2017/083627 WO2017219771A1 (en) | 2016-06-23 | 2017-05-09 | Microelectrode array and manufacturing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710203187.9A CN108652618B (en) | 2017-03-30 | 2017-03-30 | Dendritic platinum modified microelectrode array and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108652618A CN108652618A (en) | 2018-10-16 |
| CN108652618B true CN108652618B (en) | 2021-09-07 |
Family
ID=63785586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710203187.9A Active CN108652618B (en) | 2016-06-23 | 2017-03-30 | Dendritic platinum modified microelectrode array and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108652618B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110314279A (en) * | 2019-07-09 | 2019-10-11 | 深圳先进技术研究院 | A kind of microelectrode and preparation method thereof and nerve prosthesis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643865A (en) * | 2009-05-26 | 2010-02-10 | 西北工业大学 | Silver-copper nano alloy and preparation method thereof |
| CN105386119A (en) * | 2015-10-30 | 2016-03-09 | 西北师范大学 | Preparation method of dendritic silver nanocrystalline coating using electrodeposition |
| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
| CN105908220A (en) * | 2016-05-06 | 2016-08-31 | 上海应用技术学院 | Method for manufacturing micro-nano-silver dendritic crystal through liquid-phase electrodeposition |
| CN106498464A (en) * | 2016-10-24 | 2017-03-15 | 电子科技大学 | A kind of metal receives a micron preparation method for dendrite oldered array |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106108891A (en) * | 2016-06-23 | 2016-11-16 | 中国科学院深圳先进技术研究院 | Microelectrode array that a kind of platinum nano-pillar is modified and preparation method thereof |
-
2017
- 2017-03-30 CN CN201710203187.9A patent/CN108652618B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643865A (en) * | 2009-05-26 | 2010-02-10 | 西北工业大学 | Silver-copper nano alloy and preparation method thereof |
| CN105386119A (en) * | 2015-10-30 | 2016-03-09 | 西北师范大学 | Preparation method of dendritic silver nanocrystalline coating using electrodeposition |
| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
| CN105908220A (en) * | 2016-05-06 | 2016-08-31 | 上海应用技术学院 | Method for manufacturing micro-nano-silver dendritic crystal through liquid-phase electrodeposition |
| CN106498464A (en) * | 2016-10-24 | 2017-03-15 | 电子科技大学 | A kind of metal receives a micron preparation method for dendrite oldered array |
Non-Patent Citations (2)
| Title |
|---|
| 方波电势脉冲法制备金、铂和钯枝晶与多孔金;郭晨;《中国优秀硕士学位论文全文数据库(电子期刊)工程科技Ⅰ辑》;20120515;正文第26-32页 * |
| 温度对电沉积中枝晶分形生长的影响;王桂峰等;《机械科学与技术》;20091015;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108652618A (en) | 2018-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106037719B (en) | Platinum nanowire modified microelectrode array and preparation method thereof | |
| CN108125677B (en) | Microelectrode and preparation method thereof | |
| US6843902B1 (en) | Methods for fabricating metal nanowires | |
| CN104466085B (en) | Lithium ion battery | |
| FI126197B (en) | Method of extracting metal nanoparticles from solutions | |
| CN101172184B (en) | Three-dimensional flexible nervus and preparation method | |
| CN106419906B (en) | Iridium oxide/platinum nano-column composite coating modified microelectrode array and preparation method thereof | |
| Green et al. | Variation in performance of platinum electrodes with size and surface roughness | |
| CN103503101A (en) | Nano-porous electrode for super capacitor and manufacturing method thereof | |
| CN106108891A (en) | Microelectrode array that a kind of platinum nano-pillar is modified and preparation method thereof | |
| CN111060575A (en) | Porous Co-P composite electrode for glucose enzyme-free detection and preparation method and application thereof | |
| Kim et al. | Electrochemical layer-by-layer approach to fabricate mechanically stable platinum black microelectrodes using a mussel-inspired polydopamine adhesive | |
| CN108652618B (en) | Dendritic platinum modified microelectrode array and preparation method thereof | |
| CN109137058B (en) | Method for preparing silver nanoparticle dendritic cluster by cyclic voltammetry | |
| CN105908220A (en) | Method for manufacturing micro-nano-silver dendritic crystal through liquid-phase electrodeposition | |
| Chou et al. | A flexible bioelectrode based on IrO2–coated metallized polypropylene micromembrane | |
| US11401622B2 (en) | Composite array electrode, preparation method thereof and use thereof | |
| EP3511706A1 (en) | Microelectrode array and manufacturing method therefor | |
| CN112481660A (en) | Preparation method of ordered metal nanowire array | |
| CN104404602A (en) | Preparation method of NiTi shape memory alloy with porous surface | |
| CN110257866A (en) | A kind of composite layer modified electrode and its preparation method and application | |
| JP7349747B2 (en) | Dendritic nickel crystal particles and method for producing the same | |
| KR20150046878A (en) | Mesoporous neuronal electrode using surfactant of making the same | |
| CN110820035B (en) | Cobalt hydroxide/foamed nickel composite electrode prepared based on multi-potential cyclic step method and method | |
| CN108588755A (en) | Electrode preparation method and its electrode of preparation is precipitated in three-dimensional vulcanization cobalt oxide based on electro-deposition techniques |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |