WO2020119607A1 - 一种铂纳米锥阵列结构的制备方法及其应用 - Google Patents

一种铂纳米锥阵列结构的制备方法及其应用 Download PDF

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WO2020119607A1
WO2020119607A1 PCT/CN2019/123749 CN2019123749W WO2020119607A1 WO 2020119607 A1 WO2020119607 A1 WO 2020119607A1 CN 2019123749 W CN2019123749 W CN 2019123749W WO 2020119607 A1 WO2020119607 A1 WO 2020119607A1
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platinum
array structure
nano
cone array
electrodeposition
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吴天准
曾齐
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells

Definitions

  • the present invention requires the prior application priority of the application number 201811504013.7 of the invention titled "Preparation Method and Application of a Platinum Nanocone Array Structure” submitted on December 10, 2018.
  • the content of the foregoing prior application is by way of introduction Incorporated into this text.
  • the invention relates to the technical field of nanomaterials, in particular to a preparation method and application of a platinum nanocone array structure.
  • Platinum is widely used in the field of catalysts due to its excellent electrocatalytic performance. In the application process, it was found that the morphology and structure of platinum will further affect its catalytic performance, while platinum nanostructures show better catalytic performance due to their unique structural characteristics. At present, by adjusting the thermodynamic and kinetic conditions, the morphology and structure of platinum can be adjusted to improve its catalytic performance. For example: using acrylic acid and polyacrylate to prepare a platinum structure with tetrahedrons and cubes in a colloidal system, but the prepared microscopic shape The appearance uniformity is not uniform (Petroski J. MJ Phys. Chem.
  • the present invention provides a method for preparing a platinum nano-cone array structure.
  • a suitable crystal form accelerator to control the morphology of the platinum nano-array formed during the electrodeposition process
  • platinum nano-crystals with uniform morphology are prepared
  • the cone array structure improves its electrochemical performance and catalytic performance; no toxic and harmful substances are added during the preparation process, which ensures biocompatibility; the preparation method is simple and suitable for preparing platinum nano-cone array structures on the surface of devices of various specifications. Improve its application in the field of sensors, catalysis and neural interface.
  • the present invention provides a method for preparing a platinum nano-cone array structure, including:
  • a conductive substrate is provided, the conductive substrate is placed in the electrodeposition solution, and a platinum nano-cone array structure is prepared on the surface of the conductive substrate by an electrodeposition method.
  • a promoter with a special selection for platinum micro-morphology is selected from many inorganic and organic crystalline accelerators, so that during the electrodeposition process, the crystalline accelerator can guide the generation of platinum nanocones while avoiding other Nanostructures are generated, such as nanowires, nanopillars, etc., and the structural morphology of the prepared platinum nanocone array is uniform.
  • the inorganic ammonium salt includes at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium hypochlorite, and ammonium nitrite.
  • the organic amines include at least one of fatty amines, alcohol amines and alicyclic amines.
  • the crystal form accelerator is an inorganic ammonium salt.
  • both the inorganic ammonium salt and the organic amine can promote the formation of the platinum nano-cone array structure to achieve the effect of the present invention, and the inorganic ammonium salt is more conducive to the formation of the platinum nano-cone array structure than the organic amine.
  • the solute of the platinum salt solution is platinum chloride, ammonium hexachloroplatinate, potassium hexachloroplatinate, sodium hexachloroplatinate, chloroplatinic acid, platinum nitrate, platinum sulfate, potassium tetrachloroplatinate, One or more of ammonium tetrachloroplatinate.
  • the concentration of the platinum salt is 1 mmol/L-20 mmol/L. Further, the concentration of the platinum salt is 3mmol/L-18mmol/L. Specifically, the concentration of the platinum salt may be, but not limited to, 7 mmol/L, 10 mmol/L, or 15 mmol/L.
  • the molar ratio of the platinum salt in the platinum salt solution to the crystal form promoter is 1: (0.1-10). Further, the molar ratio of the platinum salt to the crystal form promoter in the platinum salt solution is 1: (0.2-8). Specifically, the molar ratio of the platinum salt to the crystal form promoter in the platinum salt solution may be, but not limited to, 1:0.5, 1:1, 1:5, or 1:7.
  • the pH of the electrodeposition solution is not less than 7.
  • the height of the platinum Pt nanocones nanocone array structure is 1nm-10 ⁇ m, tip diameter of less than 10 nm, a base diameter of 100nm-300nm, a density of 10 / ⁇ m -2 -300 a / ⁇ m - 2 .
  • the height of the platinum nano-cones in the platinum nano-cone array structure is 2 nm-8 ⁇ m, the diameter of the tip is less than 8 nm, the diameter of the bottom is 120 nm-200 nm, and the density is 50 pcs/ ⁇ m -2 -280 pcs/ ⁇ m -2 .
  • the prepared platinum nanocone array structure has a large surface area of nanocones, which can effectively improve the electrochemical performance of the overall structure.
  • the electrodeposition method is constant potential deposition, constant current deposition, or pulse electrodeposition.
  • the voltage in the constant potential deposition is -0.5V ⁇ -0.75V
  • the current in the constant current deposition is -0.1 ⁇ A ⁇ -0.7 ⁇ A
  • the voltage in the pulse electrodeposition is -0.5V ⁇ -0.75V
  • the on-off ratio is (2ms-100ms): (200ms-1000ms).
  • the electrodeposition time is 5-60 minutes. Further, the electrodeposition time is 10 min-50 min.
  • the electrodeposition method includes taking a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, the conductive substrate as a working electrode, forming a three-electrode system with the electrodeposition solution, and interacting with an electrochemical workstation Connect for electrodeposition.
  • the electrodeposition process can control the specific morphology of the platinum nano-cones, adjust the electrodeposition process conditions to change the morphology of the platinum nano-cones according to actual needs, and work with the crystal form accelerator to produce platinum with a uniform morphology Nano cone array structure.
  • the conductive substrate includes at least one of a micro-electrode array, a metal wire, a metal sheet, a metal ring, a conductive plastic, and a conductive rubber.
  • a metal wire a metal wire
  • a metal sheet a metal sheet
  • a metal ring a conductive plastic
  • a conductive rubber a conductive rubber
  • it may be, but not limited to, platinum wire, cochlear implant, platinum sheet, and platinum ring.
  • the preparation method provided by the present invention is suitable for devices of various specifications, from microelectrode arrays to filaments, sheets or rings, etc., without being affected by the specifications of the devices, platinum nanocones with uniform morphology can be prepared on the surface thereof Array structure.
  • the conductive substrate may also deposit a layer of conductive material on the surface of the non-conductive substrate.
  • a layer of metal material may be deposited on the surface of the silicon wafer as the conductive substrate.
  • the method before placing the conductive substrate in the electrodeposition solution, the method further includes:
  • the conductive substrate is placed in an acetone or ethanol solution for ultrasonic cleaning, and scanned by cyclic voltammetry to ensure that the conductive substrate is cleaned.
  • the first aspect of the present invention provides a method for preparing a platinum nano-cone array structure.
  • a platinum nano-cone array structure By adding a suitable crystal form accelerator to control the crystal growth of platinum during the electrodeposition process, a platinum nano-cone array structure with a uniform appearance is prepared .
  • the preparation method is simple and easy, the production cost is low, the operability is strong, the repeatability is good, the conditions are mild, and no toxic and harmful substances are added.
  • the prepared platinum nano-cone array structure has low impedance, high charge storage capacity and charge injection capacity Excellent electrochemical performance and biocompatibility.
  • the present invention provides a microelectrode including a microelectrode substrate and a platinum nanocone array structure disposed on the microelectrode substrate, the platinum nanocone array structure is composed of the platinum nanocone described in the first aspect
  • the preparation method of the array structure is prepared.
  • the height of the platinum Pt nanocones nanocone array structure is 1nm-10 ⁇ m, tip diameter of less than 10 nm, a base diameter of 100nm-300nm, a density of 10 / ⁇ m -2 -300 a / ⁇ m - 2 .
  • the height of the platinum nano-cones in the platinum nano-cone array structure is 2 nm-8 ⁇ m, the diameter of the tip is less than 8 nm, the diameter of the bottom is 120 nm-200 nm, and the density is 50 pcs/ ⁇ m -2 -280 pcs/ ⁇ m -2 .
  • the surface area of the nano-cones in the platinum nano-cone array structure is large, which can effectively improve the electrochemical performance of the overall structure.
  • the present invention provides an application of the microelectrode described in the second aspect in the field of sensors, catalysis, and neural interface.
  • the invention provides a method for preparing a platinum nano-cone array structure.
  • a platinum nano-cone array structure By adding a suitable crystal form accelerator to control the growth of platinum in the electrodeposition process, a platinum nano-cone array structure with a uniform appearance is prepared.
  • the preparation method is simple and easy, the production cost is low, the operability is strong, the repeatability is good, the conditions are mild, and no toxic and harmful substances are added.
  • the prepared platinum nano-cone array structure has low impedance, high charge storage capacity and charge injection capacity Excellent electrochemical performance and biocompatibility.
  • the preparation method of the present invention can be realized on conductive substrates of various specifications, has strong binding force, is not easy to fall off, and has wide application prospects in the field of sensors, catalysis, and neural interfaces.
  • Example 1 is an electron micrograph of a micro-electrode array with a platinum nano-cone array structure prepared in Example 1 of the present invention
  • Example 2 is an electron micrograph of a metal wire with a platinum nano-cone array structure prepared in Example 2 of the present invention
  • Example 3 is an electron micrograph of a metal ring with a platinum nano-cone array structure prepared in Example 3 of the present invention
  • FIG. 4 is an electron micrograph of a metal sheet with a platinum nano-cone array structure prepared in Example 5 of the present invention, where FIG. 4(A) is an electron micrograph at a scale of 50 ⁇ m, and FIG. 4(B) is in The scale is the electron micrograph under 1 ⁇ m;
  • FIG. 6 is a comparison diagram of electrochemical impedance and cyclic voltammetry of a metal sheet with a platinum nanoarray structure prepared in Example 5 of the present invention and a comparative example, where FIG. 6(A) is a comparison diagram of electrochemical impedance, and FIG. 6 (B) Cyclic voltammetry comparison chart.
  • microelectrode arrays of different specifications placed in electrodeposition solution, using platinum sheet as counter electrode, Ag/AgCl as reference electrode, microelectrode array as working electrode, and connected with electrochemical workstation, deposited with constant potential
  • electrochemical workstation deposited with constant potential
  • electrochemical workstation electrodeposited for 5 minutes to form a platinum nano-cone array structure on the surface of the micro-electrode array.
  • a layer of platinum nano-particles with a uniform appearance was prepared In the cone array structure, the height of the platinum nano-cone is about 1 ⁇ m, the diameter of the tip is less than 10 nm, the diameter of the bottom is about 300 nm, and the density is 100 pcs/ ⁇ m -2 .
  • metal wire place it in acetone or ethanol solution for ultrasonic cleaning, and scan by cyclic voltammetry to ensure that it is cleaned before placing it in the electrodeposition solution.
  • platinum sheet as counter electrode
  • Ag/AgCl as reference electrode
  • metal wire as working electrode
  • electrochemical workstation in the way of constant current deposition, under -0.3 ⁇ A, electrodeposition for 30min, on the surface of the wire
  • a platinum nano-cone array structure is formed, and the scanning result of electron microscope is shown in FIG.
  • a layer of platinum nano-cone array structure is evenly distributed on the surface of the metal wire, wherein the height of the platinum nano-cone is about 3 ⁇ m, the diameter of the tip is less than 10 nm, and the diameter of the bottom It is about 100 nm, and the density is 160 pcs/ ⁇ m -2 .
  • a platinum nano-cone array structure was formed on the surface of the metal ring.
  • a layer of platinum nano-cone array structure was evenly distributed on the surface of the metal wire, where the height of the platinum nano-cone It is about 50nm, the diameter of the tip is less than 10nm, the diameter of the bottom is about 180nm, and the density is 50 pcs/ ⁇ m -2 .
  • Electrochemical impedance and cyclic voltammetry test experiments were carried out on the metal sheet with platinum nanoarray structure prepared in Example 5 and the comparative example, and the untreated metal sheet (blank group). The results are shown in FIG. 6. It can be seen from FIG. 6(A) that, compared with the blank group and the comparative example, the impedance value of the platinum nanocone array structure obtained in Example 5 is lower, about 2 k ⁇ (1 kHz). The reduction of the impedance value can greatly reduce the energy consumption of the later implantation stimulation. As can be seen from FIG.
  • the CV area of the platinum nano-cone array structure obtained in Example 5 is significantly increased relative to the blank group and the comparative example, which is about 60 times that of the comparative example, and the repeatability is good. It shows that it has more excellent charge storage capacity. Therefore, the platinum nano-cone array structure obtained by the method provided by the present invention has a large surface area and excellent charge storage capacity, is conducive to improving electrical stimulation and catalytic efficiency, and has a wide range of fields in the field of sensors, catalysis, and neural interfaces. Application prospects.

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Abstract

一种铂纳米锥阵列结构的制备方法，包括：提供铂盐溶液，向所述铂盐溶液中加入晶型促进剂，混合均匀后形成电沉积溶液，其中，所述晶型促进剂包括无机铵盐和有机胺类中的至少一种；提供导电基体，将所述导电基体置于所述电沉积溶液中，采用电沉积的方法在所述导电基体表面制得铂纳米锥阵列结构。通过加入合适的晶型促进剂，控制电沉积过程中形成的铂纳米阵列形貌，制得形貌均匀一致的铂纳米锥阵列结构，提高其电化学性能和催化性能，同时保证了生物兼容性；该制备方法简单，适用于在各种规格的器件表面制备铂纳米锥阵列结构，提高器件在传感器领域、催化领域以及神经接口领域中的应用。

Description

一种铂纳米锥阵列结构的制备方法及其应用
本发明要求2018年12月10日递交的发明名称为“一种铂纳米锥阵列结构的制备方法及其应用”的申请号201811504013.7的在先申请优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明涉及纳米材料技术领域，特别涉及一种铂纳米锥阵列结构的制备方法及其应用。
背景技术
铂因其优异的电催化性能被广泛地应用于催化剂领域。在应用过程中发现，铂的形貌结构会进一步影响其催化性能，而铂纳米结构由于其独特的结构特征而表现出更好的催化性能。目前，通过调节热力学和动力学条件可以调节铂的形貌结构，提高其催化性能，例如：用丙烯酸和聚丙烯酸酯在胶体体系中制备具有四面体和立方体的铂结构，但制备出的微观形貌均匀性不太统一(PetroskiJ.M.J.Phys.Chem.2001,105,5542-5547)；在体系中加入少量的二价/三价的铁离子来调节铂的还原速率(Lee E.P.Adv.Mater.2006,18,3271-3274)；加入铜离子，采用电位置换法制备立方体和球形的铂结构(Qu L.T.J.Am.Chem.Soc.2006,128,5523)。虽然上述方法在一定程度上可以调节铂的形貌结构，但是制备时间长，制得的形貌结构均一性差，且制备过程中会加入有毒有害物质，制得的铂纳米结构不能够应用于具有生物兼容要求的神经接口方向。
因此，亟需一种形貌可控、均匀一致并且能够应用于传感器领域、催化领域以及神经接口领域中铂纳米结构。
发明内容
有鉴于此，本发明提供了一种铂纳米锥阵列结构的制备方法，通过加入合适的晶型促进剂，控制电沉积过程中形成的铂纳米阵列形貌，制得形貌均匀一 致的铂纳米锥阵列结构，提高其电化学性能和催化性能；制备过程中无有毒有害物质的加入，保证了生物兼容性；该制备方法简单，适用于在各种规格的器件表面制备铂纳米锥阵列结构，提高其在传感器领域、催化领域以及神经接口领域中的应用。
第一方面，本发明提供了一种铂纳米锥阵列结构的制备方法，包括：
提供铂盐溶液，向所述铂盐溶液中加入晶型促进剂，混合均匀后形成电沉积溶液，其中，所述晶型促进剂包括无机铵盐和有机胺类中的至少一种；
提供导电基体，将所述导电基体置于所述电沉积溶液中，采用电沉积的方法在所述导电基体表面制得铂纳米锥阵列结构。
在本发明中，从众多无机和有机的晶型促进剂中选择对铂微观形貌有特殊选择的促进剂，使得在电沉积过程过程中，晶型促进剂可以引导生成铂纳米锥而避免其他纳米结构生成，如纳米线、纳米柱等，且制得的铂纳米锥阵列结构形貌均匀一致。
可选的，所述无机铵盐包括硫酸铵、氯化铵、硝酸铵、次氯酸铵、亚硝酸铵中的至少一种。
可选的，所述有机胺类包括脂肪胺类、醇胺类和脂环胺类中的至少一种。
进一步的，所述晶型促进剂为无机铵盐。在本发明中，无机铵盐和有机胺类均可以促进铂纳米锥阵列结构的形成，达到本发明的效果，且无机铵盐比有机胺类更加有利于铂纳米锥阵列结构的形成。
可选的，所述铂盐溶液的溶质为氯化铂、六氯铂酸铵、六氯铂酸钾、六氯铂酸钠、氯铂酸、硝酸铂、硫酸铂、四氯铂酸钾、四氯铂酸铵中的一种或多种。
可选的，所述铂盐的浓度为1mmol/L-20mmol/L。进一步的，所述铂盐的浓度为3mmol/L-18mmol/L。具体的，所述铂盐的浓度可以但不限于为7mmol/L、10mmol/L或15mmol/L。
可选的，在所述电沉积溶液中，所述铂盐溶液中铂盐与所述晶型促进剂的摩尔比1:(0.1-10)。进一步的，所述铂盐溶液中铂盐与所述晶型促进剂的摩尔比1:(0.2-8)。具体的，所述铂盐溶液中铂盐与所述晶型促进剂的摩尔比可以但不限于为1:0.5、1：1、1：5或1:7。
可选的，所述电沉积溶液的pH不小于7。
可选的，所述铂纳米锥阵列结构中的铂纳米锥的高度为1nm-10μm，尖部直径小于10nm，底部直径为100nm-300nm，密度为10个/μm -2-300个/μm -2。进一步的，所述铂纳米锥阵列结构中的铂纳米锥的高度为2nm-8μm，尖部直径小于8nm，底部直径为120nm-200nm，密度为50个/μm -2-280个/μm -2。
在本发明中，制得的铂纳米锥阵列结构中纳米锥的表面积大，能够有效提高整体结构的电化学性能。
可选的，所述电沉积的方法为恒电位沉积、恒电流沉积或脉冲电沉积。
可选的，所述恒电位沉积中的电压为-0.5V～-0.75V，所述恒电流沉积中的电流为-0.1μA～-0.7μA，所述脉冲电沉积中的电压为-0.5V～-0.75V，通断比为(2ms-100ms)：(200ms-1000ms)。
可选的，所述电沉积的时间为5min-60min。进一步的，所述电沉积的时间为10min-50min。
可选的，所述电沉积的方法包括以铂片为对电极，Ag/AgCl为参比电极，所述导电基体为工作电极，与所述电沉积溶液形成三电极体系，并与电化学工作站连接进行电沉积。
在本发明中，电沉积工艺可以控制铂纳米锥的具体形貌，根据实际需要调节电沉积工艺条件改变铂纳米锥的形貌，并与晶型促进剂共同作用制得具有均一形貌的铂纳米锥阵列结构。
可选的，所述导电基体包括微电极阵列、金属丝、金属片、金属环、导电塑料和导电橡胶中的至少一种。具体的，可以但不限于为铂线、人工耳蜗、铂片、铂环。
本发明提供的制备方法适用于各种规格的器件，从微电极阵列到丝状、片状或环状等，不受器件规格的影响，均可以在其表面制得形貌均一的铂纳米锥阵列结构。
在本发明中，所述导电基体也可以为不导电基体表面沉积一层导电材料，如在硅片表面沉积一层金属材料即可作为导电基体使用。
可选的，在将所述导电基体置于所述电沉积溶液中之前，还包括：
将所述导电基体置于丙酮或乙醇溶液中超声清洗，并通过循环伏安扫描，确保所述导电基体清洗干净。
本发明第一方面提供了一种铂纳米锥阵列结构的制备方法，通过加入合适的晶型促进剂，控制电沉积过程中铂的晶型生长，制得形貌均匀一致的铂纳米锥阵列结构。该制备方法简单易行、生产成本低、可操作性强、重复性好、条件温和、无有毒有害物质的加入，制得的铂纳米锥阵列结构具有低阻抗、高电荷存储能力和电荷注入能力等优异的电化学性能和生物相容性。
第二方面，本发明提供了一种微电极，包括微电极基体以及设置在所述微电极基体上的铂纳米锥阵列结构，所述铂纳米锥阵列结构由第一方面所述的铂纳米锥阵列结构的制备方法制备得到。
可选的，所述铂纳米锥阵列结构中的铂纳米锥的高度为1nm-10μm，尖部直径小于10nm，底部直径为100nm-300nm，密度为10个/μm -2-300个/μm -2。进一步的，所述铂纳米锥阵列结构中的铂纳米锥的高度为2nm-8μm，尖部直径小于8nm，底部直径为120nm-200nm，密度为50个/μm -2-280个/μm -2。
在本发明中，铂纳米锥阵列结构中纳米锥的表面积大，能够有效提高整体结构的电化学性能。
第三方面，本发明提供了一种如第二方面所述的微电极在传感器领域、催化领域以及神经接口领域中的应用。
本发明的有益效果：
本发明提供了一种铂纳米锥阵列结构的制备方法，通过加入合适的晶型促进剂，控制电沉积过程中铂的晶型生长，制得形貌均匀一致的铂纳米锥阵列结构。该制备方法简单易行、生产成本低、可操作性强、重复性好、条件温和、无有毒有害物质的加入，制得的铂纳米锥阵列结构具有低阻抗、高电荷存储能力和电荷注入能力等优异的电化学性能和生物相容性。本发明的制备方法能够在各种规格的导电基体上实现且结合力强、不易脱落，在传感器领域、催化领域以及神经接口领域中具有广泛的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
图1为本发明实施例1制得的具有铂纳米锥阵列结构的微电极阵列的电镜图；
图2为本发明实施例2制得的具有铂纳米锥阵列结构的金属丝的电镜图；
图3为本发明实施例3制得的具有铂纳米锥阵列结构的金属环的电镜图；
图4为本发明实施例5制得的具有铂纳米锥阵列结构的金属片的电镜图，其中，图4中(A)是在标尺为50μm下的电镜图，图4中(B)是在标尺为1μm下的电镜图；
图5为对比例制得的具有铂纳米阵列结构的金属片的电镜图；
图6为本发明实施例5和对比例制得的具有铂纳米阵列结构的金属片的电化学阻抗和循环伏安对比图，其中图6中(A)为电化学阻抗对比图，图6中(B)为循环伏安对比图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种微电极的制备方法
在容器中加入1L水、1mmol/L的六氯铂酸钾和5mmol/L的硫酸铵，混合均匀后形成电沉积溶液。
提供不同规格的微电极阵列，分别置于电沉积溶液中，以铂片为对电极，Ag/AgCl为参比电极，微电极阵列为工作电极，并与电化学工作站连接，以恒电位沉积的方式，在-0.5V条件下，电沉积5min，在微电极阵列表面形成铂纳米锥阵列结构，经过电镜扫描结果如图1所示，微电极阵列表面制得了一层形貌均匀一致的铂纳米锥阵列结构，其中，铂纳米锥的高度约为1μm，尖部直径小于10nm，底部直径约为300nm，密度为100个/μm -2。
实施例2
一种铂纳米锥阵列结构的制备方法
在容器中加入1L水、5mmol/L的氯铂酸和5mmol/L的次氯酸铵，混合均匀后形成电沉积溶液。
提供金属丝，将其置于丙酮或乙醇溶液中超声清洗，并通过循环伏安扫描，确保清洗干净后再置于电沉积溶液中。以铂片为对电极，Ag/AgCl为参比电极，金属丝为工作电极，并与电化学工作站连接，以恒电流沉积的方式，在-0.3μA条件下，电沉积30min，在金属丝表面形成铂纳米锥阵列结构，经过电镜扫描结果如图2所示，金属丝表面均匀分布了一层铂纳米锥阵列结构，其中，铂纳米锥的高度约为3μm，尖部直径小于10nm，底部直径约为100nm，密度为160个/μm -2。
实施例3
一种铂纳米锥阵列结构的制备方法
在容器中加入1L水、20mmol/L的硫酸铂和2mmol/L的三烷基胺，混合均匀后形成电沉积溶液。
提供金属环，并置于电沉积溶液中，以铂片为对电极，Ag/AgCl为参比电极，金属环为工作电极，并与电化学工作站连接，以恒电位沉积的方式，在-0.1V条件下，电沉积30min，在金属环表面形成铂纳米锥阵列结构，经过电镜扫描结果如图3所示，金属丝表面均匀分布了一层铂纳米锥阵列结构，其中，铂纳米锥的高度约为50nm，尖部直径小于10nm，底部直径约为180nm，密度为50个/μm -2。
实施例4
一种铂纳米锥阵列结构的制备方法
在容器中加入1L水、15mmol/L的硝酸铂和5mmol/L的硝酸铵，混合均匀后形成电沉积溶液。
提供金属丝，将其置于丙酮或乙醇溶液中超声清洗，并通过循环伏安扫描，确保清洗干净后再置于电沉积溶液中。以铂片为对电极，Ag/AgCl为参比电极，金属丝为工作电极，并与电化学工作站连接，以脉冲电沉积的方式，在-0.6V，通断比为5ms：200ms条件下，电沉积20min。经检测发现，在金属丝表面形成一层均匀分布的铂纳米锥阵列结构，且铂纳米锥的形貌均匀一致，其中，铂纳米锥的高度约为5μm，尖部直径小于10nm，底部直径约为300nm，密度为 250个/μm -2。
实施例5
一种铂纳米锥阵列结构的制备方法
在容器中加入1L水、10mmol/L的氯化铂和5mmol/L的氯化铵，混合均匀后形成电沉积溶液。
提供金属片，将其置于丙酮或乙醇溶液中超声清洗，并通过循环伏安扫描，确保清洗干净后再置于电沉积溶液中。以铂片为对电极，Ag/AgCl为参比电极，金属片为工作电极，并与电化学工作站连接，以恒电位沉积的方式，在-0.7V条件下，电沉积15min，在金属片表面形成铂纳米锥阵列结构。经过电镜扫描，结果如图4所示，其中图4中(A)可以看出在金属片的表面均匀覆盖一层铂纳米锥阵列结构，图4中(B)可以看出该铂纳米锥阵列结构中纳米锥的形貌结构相同，没有其他杂质生成，纳米锥均匀分布在金属片的表面，铂纳米锥的高度约为1.5μm，尖部直径小于8nm，底部直径约为220nm，密度为200个/μm -2。
对比例
在容器中加入1L水和10mmol/L的氯化铂，混合均匀后形成电沉积溶液。
提供金属片，将其置于丙酮或乙醇溶液中超声清洗，并通过循环伏安扫描，确保清洗干净后再置于电沉积溶液中。以铂片为对电极，Ag/AgCl为参比电极，金属片为工作电极，并与电化学工作站连接，以恒电位沉积的方式，在-0.7V条件下，电沉积15min，在金属片表面形成铂纳米阵列结构。经过电镜扫描，结果如图5所示，可以看出，铂纳米阵列结构由铂纳米花组成，没有铂纳米锥的生成，且铂纳米花大小不同、形貌不均一。可以看出，本发明提供的合适的晶型促进剂能够在电沉积过程中控制铂的晶型生长，促进形貌均一的纳米锥的生成。
效果实施例
将实施例5和对比例制得的具有铂纳米阵列结构金属片，以及没有处理的金属片(空白组)进行电化学阻抗和循环伏安测试实验，结果如图6所示。从图6中(A)可以看出，相对于空白组和对比例，实施例5制得的铂纳米锥阵列结构的阻抗值更低，约2kΩ(1kHz)。阻抗值的降低很大程度上可以减少后期植入刺激的能耗。从图6中(B)可以看出，相对于空白组和对比例，实 施例5制得的铂纳米锥阵列结构的CV面积明显增加，大致为对比例的60倍左右，且重复性好，表明其具有更为优异的电荷存储能力。因此，采用本发明提供的方法制得的铂纳米锥阵列结构具有大的表面积和优异的电荷存储能力，有利于提升电刺激和催化效率，在传感器领域、催化领域以及神经接口领域中具有广泛的应用前景。
以上所述是本发明的优选实施方式，但并不能因此而理解为对本发明专利范围的限制。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。

Claims (10)

  1. 一种铂纳米锥阵列结构的制备方法，其特征在于，包括：
    提供铂盐溶液，向所述铂盐溶液中加入晶型促进剂，混合均匀后形成电沉积溶液，其中，所述晶型促进剂包括无机铵盐和有机胺类中的至少一种；
    提供导电基体，将所述导电基体置于所述电沉积溶液中，采用电沉积的方法在所述导电基体表面制得铂纳米锥阵列结构。
  2. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，所述无机铵盐包括硫酸铵、氯化铵、硝酸铵、次氯酸铵、亚硝酸铵中的至少一种，所述有机胺类包括脂肪胺类、醇胺类和脂环胺类中的至少一种。
  3. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，在所述电沉积溶液中，所述铂盐溶液中的铂盐与所述晶型促进剂的摩尔比1:(0.1-10)。
  4. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，所述铂盐溶液中的铂盐包括氯化铂、六氯铂酸铵、六氯铂酸钾、六氯铂酸钠、氯铂酸、硝酸铂、硫酸铂、四氯铂酸钾、四氯铂酸铵中的一种或多种。
  5. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，所述铂纳米锥阵列结构中的铂纳米锥的高度为1nm-10μm，尖部直径小于10nm，底部直径为100nm-300nm，密度为10个/μm -2-300个/μm -2。
  6. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，所述电沉积的方法为恒电位沉积、恒电流沉积或脉冲电沉积。
  7. 如权利要求6所述的铂纳米锥阵列结构的制备方法，其特征在于，所述恒电位沉积中的电压为-0.5V～-0.75V，所述恒电流沉积中的电流为 -0.1μA～-0.7μA，所述脉冲电沉积中的电压为-0.5V～-0.75V，通断比为(2ms-100ms)：(200ms-1000ms)。
  8. 如权利要求1所述的铂纳米锥阵列结构的制备方法，其特征在于，所述导电基体包括微电极阵列、金属丝、金属片、金属环、导电塑料和导电橡胶中的至少一种。
  9. 一种微电极，其特征在于，包括微电极基体以及设置在所述微电极基体上的铂纳米锥阵列结构，所述铂纳米锥阵列结构由权利要求1-8任一项所述的铂纳米锥阵列结构的制备方法制备得到。
  10. 如权利要求9所述的微电极在传感器领域、催化领域以及神经接口领域中的应用。
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CN106835219A (zh) * 2017-01-19 2017-06-13 中国科学院深圳先进技术研究院 一种超疏水不锈钢表面涂层及其制备方法
CN108360026A (zh) * 2017-12-29 2018-08-03 郑州轻工业学院 一种直接电沉积制备金属纳米管阵列的方法
CN109468668A (zh) * 2018-12-10 2019-03-15 深圳先进技术研究院 一种铂纳米锥阵列结构的制备方法及其应用

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