CN112864404A - Three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode - Google Patents

Three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode Download PDF

Info

Publication number
CN112864404A
CN112864404A CN201911192286.7A CN201911192286A CN112864404A CN 112864404 A CN112864404 A CN 112864404A CN 201911192286 A CN201911192286 A CN 201911192286A CN 112864404 A CN112864404 A CN 112864404A
Authority
CN
China
Prior art keywords
electrode
ito
nickel
modified
gold
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.)
Granted
Application number
CN201911192286.7A
Other languages
Chinese (zh)
Other versions
CN112864404B (en
Inventor
孙晶
曹猛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University
Original Assignee
Dalian University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian University filed Critical Dalian University
Priority to CN201911192286.7A priority Critical patent/CN112864404B/en
Publication of CN112864404A publication Critical patent/CN112864404A/en
Application granted granted Critical
Publication of CN112864404B publication Critical patent/CN112864404B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode, belonging to the technical field of electrochemistry. The main technical scheme is as follows: using surface tape (PDDA/PSS)6The ITO glass of the electrostatic self-assembly layer is used as a substrate, and the Ni-Au/ITO electrode with the nano structure is prepared by utilizing underpotential deposition. And preparing the Au-Ni-Pt/ITO electrode with the multilevel nano structure by using an etching growth-particle self-assembly method. And (4) adopting a scanning electron microscope to represent the secondary flower-like morphology of the modified electrode under different gold deposition conditions. The novel electrode combines the advantages of the nano material and has the advantages ofThe catalyst has high specific surface area, high catalytic activity and high stability, can be used as a non-enzyme fuel cell anode to replace enzyme as a catalyst to solve the problem of specificity of the enzyme, is favorable for promoting the commercialization of the biofuel cell, and has good application prospect.

Description

Three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode
Technical Field
The invention relates to a three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode, belonging to the field of biofuel cells.
Background
The nano material has the advantages of large specific surface area, easy functionalization, various shapes, controllable composition, simple preparation method and the like, and is widely applied to the fields of electrochemical catalysis, electrochemical sensors, biological imaging and the like. Recent developments in nanotechnology have also brought a new turn of opportunities and developments in the field of biofuel cells. The nano material can be used as an electrode substrate in an enzyme biofuel cell to promote an electron transfer process between an enzyme and an electrode. Importantly, various types of nanomaterials have proven to be good alternatives to enzymatic catalysts to improve BFC performance, particularly stability issues. The application of the nano material in the biofuel cell has the following advantages: 1. the nano material can provide larger specific surface area, thereby providing more redox sites; 2. the nano material has low resistance and high conductivity, and is favorable for promoting the transfer of electrons and the catalytic process of the surface of an electrode; 3. the nano material shows higher stability, which is beneficial to the fuel cell to keep normal operation for a long time. In addition, the nanomaterial, instead of an enzyme, as a catalyst solves the problem of specificity of the enzyme, thereby contributing to the promotion of commercialization of the biofuel cell.
The methods for preparing the nano-electrode are roughly classified into an electrochemical deposition method, a sol-gel method, an emulsion method, a chemical etching method, a vapor deposition method, a self-assembly method and the like. The electrochemical deposition method is very economical and simple, has low cost, high purity and small granularity, and is suitable for large-scale production. The nano material prepared by electrochemistry has better application prospect in the aspects of corrosion resistance, catalysis, hydrogen storage, electrochemical sensors and the like.
Disclosure of Invention
The invention aims to provide a three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode which has the characteristics of high sensitivity, high selectivity and quick response, can be used as a non-enzyme fuel cell anode, replaces enzyme as a catalyst to solve the specificity problem of the enzyme, is favorable for promoting the commercialization of a biofuel cell, and is widely applied to the field of the biofuel cell.
The technical scheme adopted by the invention is as follows: a three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode is prepared according to the following method:
(1) the method comprises the steps of (1) taking ITO conductive glass as a substrate, and carrying out pretreatment and self-assembly operation on the ITO conductive glass to obtain a modified ITO electrode;
(2) performing flower-like nano gold deposition on the modified ITO electrode by adopting an electrochemical method: using a three-electrode system with H2SO4(0.5M) and KAuCl4(1mg/mL) mixed solution is an electrolyte solution, the modified ITO electrode is a working electrode, the counter electrode is a platinum electrode, the reference electrode is Ag/AgCl, and the voltage is set to be-0.2V.
(3) Preparing an Au-Ni-Pt/ITO composite electrode by adopting an electrochemical method: a three-electrode system is adopted, a nickel sulfate solution is taken as an electrolyte solution, Au/ITO glass with a nano structure is taken as a working electrode, and an Ag/AgCl electrode and a platinum wire electrode are taken as reference electrodes. Setting electrodeposition parameters of an electrochemical workstation by adopting a chronoamperometry method: voltage-1V, time 500 s. Immediately taking out the electrode, washing with deionized water for multiple times, quickly transferring to a newly prepared potassium tetrachloroplatinate solution, and standing for 100 s;
further, the modified ITO glass in the step (1) is provided with a surface tape (PDDA/PSS)6ITO glass of the electrostatic self-assembly layer. The pretreatment operation in the step (1) is to cut the ITO glass into pieces with the specification size of 1cm multiplied by 2cm, then sequentially ultrasonically clean the cut ITO glass in deionized water, acetone and ethanol for 30min, and then clean the cut ITO glass with ozone for 30 min.
Further, the nickel sulfate solution in step (3) is NiSO4(0.02M) and Na2SO4(0.1M).
The invention has the following beneficial effects:
(1) when the gold deposition conditions are different, the shapes of the final multi-stage Au-Ni-pt alloy nanoflowers are changed due to the fact that the grain sizes of the nano golden flowers are different. The reason is that the time for depositing gold is long, the formed nano golden flowers are dense, the interatomic self-assembly effect is obvious, and the similar small aggregations can be connected with each other; on the contrary, when the deposition time is shorter, the distance between the nano golden flowers is sparser, so that the aggregates formed by self-assembly of atoms are more regularly and uniformly distributed. When the nano particle aggregates on the composite electrode are uniformly distributed, the electrochemical performance is particularly outstanding.
(2) The multilayer nano structure enables the surface of the electrode to have a high specific surface area; meanwhile, the electrode is composed of three metals, the nano golden flower is used as a basic framework, non-noble metal nickel is deposited, and finally platinum is used for replacing the nickel, so that the noble metal platinum loading capacity is low, the cost of the electrode is reduced, and the catalytic activity of nano platinum particles is improved.
Drawings
FIG. 1 is a diagram of an experimental setup;
wherein: 1. a reference electrode; 2. working electrode, 3, counter electrode, 4, carbohydrate alkaline solution.
FIG. 2 is a graph of nano-gold cluster deposition;
wherein: a is a curve of 400 s; b is a curve of 800 s; c is a 1600s curve.
FIG. 3 Scanning Electron Microscope (SEM) of nano-gold clusters formed on a modified ITO electrode by electrochemical deposition;
wherein: a. deposit gold 400s (2 μm) b deposit gold 800s (2 μm) c deposit gold 800s (1 μm) d deposit gold 1600s (2 μm).
FIG. 4 is an electron microscope representation of the Au-Ni-Pt nanocomposite electrode;
wherein: a. SEM images of composite nanoelectrodes with time to deposit gold at 400s (4 μm), b SEM images of composite nanoelectrodes with time to deposit gold at 800s, c SEM images of composite nanoelectrodes with time to deposit gold at 1600s (4 μm).
FIG. 5 contact angles of the original ITO electrode and the Au-Ni-Pt/ITO electrode;
wherein: a. contact angle of original ITO electrode, b.
FIG. 6 electrochemical characterization of the pretreated ITO electrode surface;
wherein: A.ITO, B.ITO/(PDDA)/(PSS).
FIG. 7Fe (CN)63-/4-Performing electrochemical behavior on the surface of the nano composite modified electrode;
wherein: Au-Ni-Pt/ITO, B.5mM Fe (CN)63-/4-Cyclic voltammograms in solution.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the specific embodiments, but the present invention is not limited to the embodiments in any way. In the examples, unless otherwise specified, the experimental methods are all conventional methods; unless otherwise indicated, the experimental reagents and materials were commercially available.
Example 1
A three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode is prepared according to the following method:
(1) the method comprises the steps of (1) taking ITO conductive glass as a substrate, and carrying out pretreatment and self-assembly operation on the ITO conductive glass to obtain a modified ITO electrode; the modified ITO electrode is a surface tape (PDDA/PSS)6ITO glass of the electrostatic self-assembly layer.
(2) Performing flower-like nano gold deposition on the modified ITO electrode by adopting an electrochemical method: using a three-electrode system at 0.5M H2SO4And 1mg/mL KAuCl4The mixed solution of (1) is electrolyte solution, the modified ITO electrode is a working electrode, the counter electrode is a platinum electrode, the reference electrode is Ag/AgCl, and the voltage is set to be-0.2V;
(3) preparing an Au-Ni-Pt/ITO composite electrode by adopting an electrochemical method: a three-electrode system is adopted, a nickel sulfate solution is taken as an electrolyte solution, Au/ITO glass with a nano structure is taken as a working electrode, an Ag/AgCl electrode and a platinum wire electrode are taken as reference electrodes, a timing current method is adopted, and electro-deposition parameters of an electrochemical workstation are set: voltage-1V and time 500 s; immediately taking out the electrode, washing with deionized water for multiple times, transferring to a newly-prepared potassium tetrachloroplatinate solution, and standing for 100s to prepare a nano composite electrode; NiSO with nickel sulfate solution of 0.02M4And 0.1M of Na2SO4The two are mixed to form a solution.
The gold-nickel-platinum modified nano composite electrode has a non-close-packed three-dimensional structure and has a finer secondary flower-like nano structure on the basis of the three-dimensional structure, as shown in the attached figures 1 to 4.
Example 2
Contact angle experiments were used to evaluate the surface hydrophilicity of the original ITO electrode and the Au-Ni-Pt/ITO electrode. The contact angles of the original ITO electrode and the Au-Ni-Pt/ITO electrode are respectively 37.3 degrees and 2.7 degrees. As shown in fig. 5. The decrease in contact angle indicates that the hydrophilicity of the ITO-based electrode is improved by the modification of the three metals. The increase in hydrophilicity is beneficial for the reaction of the electroactive material on the electrode surface.
Example 3
Electrochemical properties of the nanocomposite electrode:
and (3) characterizing the electrochemical properties of the electrodes before and after self-assembly by using cyclic voltammetry. Electrodes before and after self-assembly were set at 0.05M H2SO4The cyclic voltammetry behavior of the solution was investigated. Potential: -0.6-1.2V, and the sweep rate is 100 mV/s. The conductivity of the ITO glass before and after modification is obviously improved, and the further electrochemical deposition is facilitated. As shown in fig. 6.
Example 4
And (3) characterizing the electrochemical performance of the nano composite modified electrode by cyclic voltammetry. By Fe (CN)6 3-/4-And modifying the electron transfer condition on the electrode to characterize the electrochemical behavior of the surface of the electrode. Fe (CN)6 3-/4-The solution was 5mM, the set potential was: -0.2-1.2V, sweep speed: 100 mV/s. After nano modification, the reversibility of the electrode surface is better, and the conductivity is increased to some extent. As shown in fig. 7.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (3)

1. A three-dimensional flower-like gold-nickel-platinum modified nano composite electrode is characterized by being prepared according to the following method:
(1) the method comprises the steps of (1) taking ITO conductive glass as a substrate, and carrying out pretreatment and self-assembly operation on the ITO conductive glass to obtain a modified ITO electrode;
(2) performing flower-like nano gold deposition on the modified ITO electrode by adopting an electrochemical method: using a three-electrode system at 0.5M H2SO4And 1mg/mL KAuCl4The mixed liquid of (A) is electricityThe electrolyte solution, the modified ITO electrode is a working electrode, the counter electrode is a platinum electrode, the reference electrode is Ag/AgCl, and the voltage is set to be-0.2V;
(3) preparing an Au-Ni-Pt/ITO composite electrode by adopting an electrochemical method: a three-electrode system is adopted, a nickel sulfate solution is taken as an electrolyte solution, Au/ITO glass with a nano structure is taken as a working electrode, an Ag/AgCl electrode and a platinum wire electrode are taken as reference electrodes, a timing current method is adopted, and electro-deposition parameters of an electrochemical workstation are set: voltage-1V and time 500 s; and immediately taking out the electrode, washing the electrode with deionized water for multiple times, transferring the electrode into a newly prepared potassium tetrachloroplatinate solution, and standing the electrode for 100 seconds to prepare the nano composite electrode.
2. The three-dimensional flower-like gold-nickel-platinum modified nano composite electrode as claimed in claim 1, wherein the modified ITO electrode of step (1) is surface coated with (PDDA/PSS)6ITO glass of the electrostatic self-assembly layer.
3. The three-dimensional flower-like gold-nickel-platinum modified nano composite electrode as claimed in claim 1, wherein the nickel sulfate solution in the step (3) is 0.02M NiSO4And 0.1M of Na2SO4The two are mixed to form a solution.
CN201911192286.7A 2019-11-28 2019-11-28 Three-dimensional flower-like gold-nickel-platinum modified nano composite electrode Active CN112864404B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911192286.7A CN112864404B (en) 2019-11-28 2019-11-28 Three-dimensional flower-like gold-nickel-platinum modified nano composite electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911192286.7A CN112864404B (en) 2019-11-28 2019-11-28 Three-dimensional flower-like gold-nickel-platinum modified nano composite electrode

Publications (2)

Publication Number Publication Date
CN112864404A true CN112864404A (en) 2021-05-28
CN112864404B CN112864404B (en) 2023-06-02

Family

ID=75995647

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911192286.7A Active CN112864404B (en) 2019-11-28 2019-11-28 Three-dimensional flower-like gold-nickel-platinum modified nano composite electrode

Country Status (1)

Country Link
CN (1) CN112864404B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115029751A (en) * 2022-05-06 2022-09-09 南昌航空大学 Pt/MoS 2 Electroplating preparation method of nanosheet

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130056876A1 (en) * 2010-05-07 2013-03-07 Thomas HARVEY Composite electrode and method of manufacture thereof
US20140113127A1 (en) * 2011-05-13 2014-04-24 Masato Tominaga Carbon nanotube composite electrode and method for manufacturing the same
CN105680063A (en) * 2016-04-06 2016-06-15 湖北大学 Composite nano gold-platinum material, preparation method thereof and an application of composite nano gold-platinum material in direct methanol fuel cell anode catalyst
CN108982632A (en) * 2018-07-26 2018-12-11 大连大学 A kind of flexible electrode and preparation method thereof based on flower-like nanometer gold structure
CN109273728A (en) * 2018-09-27 2019-01-25 北京工业大学 A kind of pulse electrodeposition prepares Platinum Nanoparticles/cobalt titanium dioxide nanotube composite electrode method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130056876A1 (en) * 2010-05-07 2013-03-07 Thomas HARVEY Composite electrode and method of manufacture thereof
US20140113127A1 (en) * 2011-05-13 2014-04-24 Masato Tominaga Carbon nanotube composite electrode and method for manufacturing the same
CN105680063A (en) * 2016-04-06 2016-06-15 湖北大学 Composite nano gold-platinum material, preparation method thereof and an application of composite nano gold-platinum material in direct methanol fuel cell anode catalyst
CN108982632A (en) * 2018-07-26 2018-12-11 大连大学 A kind of flexible electrode and preparation method thereof based on flower-like nanometer gold structure
CN109273728A (en) * 2018-09-27 2019-01-25 北京工业大学 A kind of pulse electrodeposition prepares Platinum Nanoparticles/cobalt titanium dioxide nanotube composite electrode method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨朝晖;吴敏;秦艳涛;张俊颉;孙岳明;: "电化学沉积四氨基酞菁镍敏化纳米TiO_2电极", 东南大学学报(自然科学版), no. 02 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115029751A (en) * 2022-05-06 2022-09-09 南昌航空大学 Pt/MoS 2 Electroplating preparation method of nanosheet

Also Published As

Publication number Publication date
CN112864404B (en) 2023-06-02

Similar Documents

Publication Publication Date Title
Solmaz et al. The Ni-deposited carbon felt as substrate for preparation of Pt-modified electrocatalysts: Application for alkaline water electrolysis
Guo et al. Amorphous Ni-P with hollow dendritic architecture as bifunctional electrocatalyst for overall water splitting
CN106669739A (en) Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof
CN108722453B (en) Molybdenum phosphide/carbon composite nano material for alkaline electro-catalysis hydrogen evolution
CN102024955B (en) Three-dimensional mesh nano porous palladium-ruthenium electrode material for fuel cell and preparation method thereof
CN107863538A (en) A kind of electrode and its application for alcohol catalysis
CN111370716B (en) Superfine three-dimensional platinum nanowire array growing on substrate under control of strong ligand and method thereof
Wen et al. CoP nanoplates dotted with porous Ni3S2 nanospheres for the collaborative enhancement of hydrogen production via urea-water electrolysis
Elrouby Electrochemical applications of carbon nanotube
CN102703953B (en) Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition
CN107543849B (en) The high activity electrode preparation method on two kinds of one step of noble metal modification common metal nanocomposite surfaces
CN100421787C (en) Platinum icosahedron nano crystal catalyst, its preparing method and use
Telli et al. Investigation of noble metal loading CoWZn electrode for HER
CN108273524B (en) Carbon composite material modified by chalcogenide and transition metal and preparation method and application thereof
CN112864404B (en) Three-dimensional flower-like gold-nickel-platinum modified nano composite electrode
CN113174599B (en) Nickel-based hierarchical structure integrated electrode for water electrolysis and preparation method thereof
Du et al. Preparation Ru, Bi monolayer modified Pt nanoparticles as the anode catalyst for methanol oxidation
CN107910562B (en) Low-cost high-activity trimetal nanocomposite electrode preparation method
CN108538645A (en) A kind of preparation method of carbon/transition metal based combined electrode and products thereof and purposes
Wu et al. An alkaline-acid asymmetric electrolyzer using NiCoP/CoP/Co3O4 multi-shell hollow nanoflakes as cathode and Ag as anode to realizing energy efficient production of hydrogen and shape controllable silver oxide
CN110841646B (en) Preparation method of hydrophilic monodisperse magnetic NiFe @ NiFeO nanoparticle modified foamed nickel electrode
Dmitriev et al. Morphology-dependent impedance and electrocatalytic activity of Ni-Co nanocoatings
CN109326799B (en) Preparation method of nano porous platinum ruthenium catalyst
CN110368992A (en) A kind of preparation method of metal-organic framework elctro-catalyst
Liu et al. Low-Pt-loading electrocatalyst derived from the reduction of hydrogenated MoO3 for highly efficient hydrogen evolution reaction

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