CN106816614B - The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application - Google Patents

The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application Download PDF

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CN106816614B
CN106816614B CN201510864125.3A CN201510864125A CN106816614B CN 106816614 B CN106816614 B CN 106816614B CN 201510864125 A CN201510864125 A CN 201510864125A CN 106816614 B CN106816614 B CN 106816614B
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porous gold
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CN106816614A (en
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邵志刚
张洪杰
曾亚超
蒋尚峰
白杨芝
衣宝廉
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention provides a kind of fuel cell fine and close platinum monoatomic layer catalysis electrodes and preparation method thereof.Nanoporous gold thin film is obtained using de- alloyage, then by this film transfer in the side of glassy carbon electrode surface or proton exchange membrane for raw material with goldleaf (Au/Ag films) first.Platinum is deposited in mixed electrolytic solution using the method that electrochemistry and chemistry combine in this, as substrate, forms the fine and close platinum single layer catalysis electrode based on nano-porous gold.The method applied in the present invention has many advantages, such as that an environmental-friendly, step is completed, catalyst loading is controllable, monoatomic layer is fine and close.Constructed can be used for fuel cell and other batteries and electrochemical reactor based on nano-porous gold densification platinum single layer catalysis electrode.

Description

The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application
Technical field
The present invention relates to a kind of fine and close platinum monoatomic layer catalysis electrodes and its system for catalytic fuel cell electrode reaction Preparation Method.
Background technique
Fuel cell is a kind of clean, efficient energy conversion device, at present in electric car, distributed power station, boat The multiple fields such as sky, submarine achieve application.Wherein Proton Exchange Membrane Fuel Cells is high with its power density, starting speed is fast, High conversion efficiency, advantages of environment protection have received widespread attention.Electrode is the core component of fuel cell, is that electrochemistry is anti- The place that should occur.In order to realize the commercial applications of fuel cell, at present urgent problem to be solved first is that guarantee activity Under the premise of reduce electrode in noble metal platinum dosage, to reduce cost.
Nano-porous gold (NPG, Nanoporous Gold)) film thickness can in the range of 100nm~1 μm modulation, Furthermore it also has three-dimensional continuous perforation cellular structure, good electric conductivity, biggish specific surface area, can be used for preparing fuel Battery thin layer electrode.
The catalysis that the prior art mainly uses the method for electronation and the method for electrochemical deposition to prepare low platinum carrying capacity is electric Pole.
Patent WO2004021481-A1 describes a kind of nano-porous gold (NPG, nanoporous gold) carried metal The method that Pt is used for Proton Exchange Membrane Fuel Cells.Firstly, using going alloyage to be prepared for nano-porous gold；Then, by nanometer Porous gold is placed in the solution of the presoma containing Pt, and nano-porous gold is made to be laid in liquid level, and hydrazine steam is then passed through into reactor, The presoma of Pt is reduced on the surface of nano-porous gold, ultimately forms the catalysis electrode of NPG load~3nmPt layers.
Patent CN101332425-A describes a kind of inner surface uniform fold platinum metal atomic layer in nano-porous gold Method.This method principle is underpotential deposition.It is specific as follows: 1) removal alloying processing to be carried out to goldleaf with nitric acid, received Meter Duo Kong gold；It 2) is to electrode, SCE as reference electrode for working electrode, graphite flake using porous gold, in containing for abundant deoxygenation Owe potential deposition copper, silver or lead in the acid solution of 0.01~100mM copper, silver or lead ion, the potential range of deposition (- 0.5V, -0.3V) vs.SCE, 1~10min of sedimentation time；3) working electrode is transferred to the platinum metal sun of 0.01~100mM 5~30min is replaced in solion.Catalyst prepared by the patent is mainly used for the Electrocatalytic Oxidation of small organic molecule.
Patent WO2012102712-A1 and WO2012102714-A1 describe a kind of Pt layers of nano-porous gold surface modification Method.The method of nano-porous gold surface modification Pt is dipping-electrochemical reducing.Specific method is: 1) going alloy legal system Standby nano-porous gold；2) nano-porous gold is impregnated in chloroplatinic acid or chloroplatinate solution；3) suction is embathed with deionized water Nano-porous gold with presoma, to control the thickness of platinum layer；3) three-electrode system is used, nano-porous gold is as work electricity Pole, 0.5M H2SO4 is as electrolyte；It is deposited using potentiostatic method or cyclic voltammetric electrodeposition process in nanoporous gold surface Platinum layer；4) it repeats 2), 3) to control platinum layer thickness.
Chemical reduction method refers to by making to react under certain conditions using reducing agent appropriate, surfactant etc. Object occurs specific reduction reaction and prepares platinum layer catalysis electrode.Using hydrazine as reduction in preparation process as described in above-mentioned patent Agent, this have to environment and human body it is potentially hazardous, and this electronation method inconvenience control Pt thickness degree.Electrochemistry is heavy The method that product combines displacement reaction can prepare uniform Pt atomic layer catalysis electrode, but preparation process point multistep carries out, electrode Monoatomic layer is easy to oxidize in transfer process.
Present invention is generally directed to solve the problems, such as the above-mentioned prior art or preparation method, provide a kind of based on nanometer The preparation method of the fine and close platinum monoatomic layer catalysis electrode of porous gold, one step of this method preparation process are completed, platinum list may be implemented Atomic layer, Pt layers of covering densification etc..
Summary of the invention
The principle of preparation method of the present invention are as follows: bivalent cupric ion is in specific potential region, specific substrate table Underpotential deposition (Underpotential Deposition, UPD) can occur for face, that is, be higher than Cu2+/ Cu balance deposition electricity In some specific sections of position, copper ion will be deposited on substrate surface in the form of monoatomic layer, single at the end of UPD process The Cu of atomic layer takes surface, and only potential drop sinks as low as the ontology that just will continue to occur Cu when balancing sedimentation potential at this time Product.It is different using the movable metallic sequence of Cu and Pt after the Cu of monoatomic layer is formed, by displacement reaction, copper by platinum from its It is cemented out in presoma, to obtain the monoatomic layer of platinum.Unlike current all technologies, the process is in a mixing electricity It is carried out in electrolyte solution, a step is completed, and underpotential deposition and displacement reaction are successively carried out continuously, and is avoided in electrode transfer process The oxidation of copper atom.The mixed solution is the copper-bath for being added to platinum presoma and citric acid.The addition of citric acid can be with It prevents from that the underpotential deposition of copper occurs again on the monatomic platinum layer of formation, to form the cluster of platinum and un-densified smooth Platinum monoatomic layer.
To achieve the goals above, the present invention adopts the following technical scheme: with potassium chloroplatinite, dilute sulfuric acid, copper sulphate, lemon The mixed solution of lemon acid is as electrolyte solution.Using platinum plate electrode as to electrode, saturated calomel electrode in three-electrode system As reference electrode, nanoporous gold electrode is as working electrode.It is passed through argon gas in electrolyte solution to being saturated, then uses Cyclic voltammetry, by controlling potential section and scanning speed, a step realizes the Atomic layer deposition and platinum presoma of copper ion Reduction.Finally, being cleaned with deionized water to electrode surface.
Fine and close platinum monoatomic layer catalysis electrode preparation step based on nano-porous gold is as follows:
1) nano-porous gold is using de- alloyage preparation: first by goldleaf (Au/Ag films；12-carat,Sepp LeafProducts, New York) small pieces that are cut to certain area are placed in deionized water, transfer it to dense HNO3 In, corrode 10min-2h under the conditions of 10 DEG C of -60 DEG C of temperature.Ag is removed nano-porous gold (NPG) is made, in deionized water It cleans repeatedly several times, for use.
2) preparation of NPG working electrode: it is 0.1256cm that NPG working electrode, which is divided into area,2With 2 × 2cm2Two kinds.In 1) The NPG prepared is transferred to glass carbon (glass carbon, GC) electrode surface, after sufficiently dry, to the NPG of electrode surface into Row modification, the final GC/NPG electrode only to cover glass carbon part, diameter is 4mm；1) NPG prepared in is transferred to first On mica sheet or metallic substrates, NPG film is transferred to from substrate surface by ion exchange film surface (ion used using pressure sintering Exchange membrane includes proton exchange membrane and anion-exchange membrane), the pressure size that when hot pressing applies is 2~10MPa, time 0.5 ~30min, temperature are 50~200 DEG C, prepare the NPG electrode of 2cm × 2cm.
3) electrolyte solution: the electrolyte solution that preparation method described in this patent uses are as follows: 50mM H is prepared2SO4+50mM CuSO4The K that middle addition concentration is 0.01-10mM2PtCl4The mixed solution for the citric acid solution that solution and concentration are 5-50mM.
4) it prepares densification Pt monoatomic layer catalysis electrode: electrolyte solution being placed in tri- mouthfuls of electrolytic cells of 100ml, Ar is passed through About 30min -1h is extremely saturated.Using three-electrode system, using cyclic voltammetric technology by control of Electric potentials in -0.2-0.6V (vs.SCE) on some section between, scanning speed selection carries out the underpotential deposition and platinum of copper in 1mV/s -50mV/s Monoatomic layer displacement.
Monoatomic layer is controllable, cladding is fine and close, and one step of preparation process is completed.
The method applied in the present invention is completed with an environmental-friendly, step, catalyst loading is controllable, monoatomic layer is fine and close The advantages that.Constructed can be used for fuel cell and other batteries and electricity based on nano-porous gold densification platinum single layer catalysis electrode Chemical reactor.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of nano-porous gold micromorphology.
Fig. 2 is that nano-porous gold is the stereoscan photograph that carrier coats platinum layer rear surface pattern.
Fig. 3 is the CV curve of the naked surface of nano-porous gold (not carrying out Pt layers of cladding).
Fig. 4 is to carry out the CV curve of underpotential deposition Cu in nanoporous gold surface.
Fig. 5 is schematic diagram of the Pt monoatomic layer dense arrangement in nanoporous gold surface.
Fig. 6 is the CV curve after nano-porous gold and surface cladding platinum monoatomic layer.
Fig. 7 is the stability curve after the cladding platinum monoatomic layer of high potential section characterization nano-porous gold surface.
Fig. 8 is the CV curve pair for being commercialized PtC and the Pt monoatomic layer catalyst using the method for the invention preparation According to figure.
Fig. 9 is the ORR curve pair for being commercialized PtC and the Pt monoatomic layer catalyst using the method for the invention preparation According to figure.
Specific embodiment
With reference to the accompanying drawing with embodiment to fine and close platinum monoatomic layer catalysis electrode of the present invention and preparation method thereof It is described further.
Embodiment 1
Specific preparation process:
1) by goldleaf (Au/Ag films；12-carat, Sepp LeafProducts, New York) it is placed in dense HNO3 In, corrode 1 hour under the conditions of 50 DEG C, removes Ag so that nano-porous gold (NPG) is made.；
2) NPG working electrode in step 1) is divided into area is 0.1256cm2 circle and rectangular two kinds of 2 × 2cm2.；It will system The round NPG got ready is transferred to glassy carbon electrode surface, is then modified to the GC/NPG electrode of diameter 4mm stacking；It will preparation Good NPG is transferred in mica sheet substrate, uses pressure sintering (pressure 2MPa, time 25min, temperature are 80 DEG C) by NPG Film is transferred to ion exchange film surface from substrate surface, prepares the rectangular NPG electrode of 2cm × 2cm；
3) preparing addition 2mL concentration in 50mM H2SO4, the 50mM CuSO4 of 100mL is 10mM K2PtCl4,5mL concentration For 10mM citric acid solution mixed solution as electrolyte solution；
4) electrolyte solution is placed in tri- mouthfuls of electrolytic cells of 100ml, is passed through Ar to saturation.Using three-electrode system, respectively It is that cyclic voltammetric is used as reference electrode to electrode, saturated calomel electrode using round and rectangular NPG as working electrode, using platinized platinum Technical controlling potential region is -0.2-0.6V, and scanning speed is that 30mV/s carries out the underpotential deposition of copper and the monoatomic layer of platinum Displacement.
The nano-porous gold of the method for the invention preparation and the microstructure of Supported Pt Nanoparticles monoatomic layer catalyst material Morphology characterization.
Nano-porous gold by taking off alloyage preparation has three-dimensional continuous perforation pore structure, and stephanoporate framework is clear, hole Diameter is within the scope of 30-50nm, and size is uniform, is evenly distributed, and the micromorphology of nano-porous gold is detailed in Figure of description 1. Micromorphology using the nano-porous gold Supported Pt Nanoparticles monoatomic layer catalyst of experimental method of the present invention preparation is detailed See Figure of description 2.From the point of view of the comparison of two width figures, the surface topography of porous gold is substantially change, but its structure is complete Whole property is not destroyed, and fine and close platinum atomic layer has only been coated on original golden skeleton.
Embodiment 2
To the theoretical calculation knot of the nanoporous auri Pt monoatomic layer catalysis electrode using the preparation of this patent the method Fruit.
Figure of description 3 be NPG bare electrode CV curve (electrolyte solution be 0.1M HClO4, scanning speed is 100mV/s), according to the reduction peak (dash area in attached drawing 3) at 1.2V, the active area of NPG is calculated by following formula:
S is the integral area (AV) of dash area in figure, and ν is the scanning speed of CV curve, and Qref is indicated on the surface NPG Absorption electricity (the 400 μ Ccm of unit area-2).Thus the NPG active area ECSA being calculated is 0.6125cm2。
Assuming that Pt atom (diameter 0.225nm) according to single layer dense arrangement on the surface of NPG, such as 5 institute of Figure of description Show, takes (the area S of Red diamonds in figureIIndicate) shown in atom be basic unit.Therefore, completely above-mentioned active face is theoretically occupied Amount (the n of Pt atom species required for product1) are as follows:
n1=ECSA/ (SI×N)
Calculate to obtain n1=0.201 × 10-8Mol, N take 6.02 × 1023。
Figure of description 4 is the underpotential deposition curve of Cu, and current potential shown in arrow is that the UPD of Cu terminates current potential in figure, According to the dash area integral area in figure, the electron number and Cu single layer atom shifted during UPD can be calculated indirectly Number, according to Cu2+Acquire the amount (n for being actually coated on the Pt atom species on the surface NPG in turn with the one-to-one displacement of Pt2) are as follows:
n2=Q/ (2e × N)
N is calculated2=0.204 × 10-8Mol, Q are the device electricity of dash area in Fig. 4, and e is Single Electron electricity 1.6×10-19C。
To n1And n2It compares, n1≈n2, therefore can think that Pt atom is coated in single layer densification to a certain extent The surface NPG.
Embodiment 3
Nano-porous gold and the nano-porous gold Supported Pt Nanoparticles monoatomic layer catalyst prepared using this patent the method Cyclic voltammetric characterization.
Respectively using be loaded with the glass-carbon electrode of nano-porous gold and nanoporous auri platinum single-layer catalyst as working electrode, It is that three-electrode system is formed to electrode by reference electrode, platinum plate electrode of saturated calomel electrode, to lead to N2The 0.1M's of saturation HClO4For electrolyte solution, connects electrochemical workstation and select cyclic voltammetric technology, in potential region 0.05-1.7V, with The scanning speed of 50mV/s carries out scan round test, and acquired results are as shown in Figure of description 6.
Attached drawing 6 is the CV curve of nano-porous gold and nano-porous gold Supported Pt Nanoparticles monoatomic layer in high potential section.Its In, rectangular curve is CV curve of the nano-porous gold in 0.05-1.7V potential range, which starts extremely in 1.4V or so 1.6V terminates, it is continuous go out cash three oxidation peaks, current potential is negative sweep during occur an apparent reduction when lower than 1.2V Peak, the curve are the CV curve of typical nano-porous gold.CV curve is sent out after this patent the method prepares platinum monoatomic layer It has given birth to and has substantially change, as shown in figure intermediate cam shape curve, which loses nanoporous completely under identical testing conditions The typical oxidation peak and reduction peak, especially obvious in 1.2V, the covered disappearance of golden reduction peak, this explanation of gold pass through The platinum monoatomic layer of this method preparation is fine and close to be covered on the skeleton of nano-porous gold.
Attached drawing 7 is nano-porous gold and the catalysis of nano-porous gold Supported Pt Nanoparticles monoatomic layer in the 0.7V-1.6V of high potential section Agent electrode passes through 100,200,500,1000 circles respectively and accelerates attenuation test (attenuation test potential region 0.6V-1.2V, scanning speed Spend 100mV/s) after CV curve.Wherein rectangular curve is the CV curve of typical nano-porous gold, is occurred in 1.2V or so Apparent reduction peak.After Pt atomic layer cladding, this reduction peak disappears, and adds respectively by 100,200,500 and 1000 circulations After fast attenuation test, the reduction peak current at 1.2V is gradually increased, this shows gradually to have the signal of NPG to occur.But pass through After 500 and 1000 circle loop tests, the increase of reduction peak current is not obvious, it is meant that Pt monoatomic layer still can be finer and close Envelope NPG skeleton.After accelerating decaying, starts the signal for gradually appearing NPG on CV curve, think: in 0.7V- When carrying out cyclic voltammetry in this potential region of 1.6V, because the high potential in test section has been more than the dissolution potential of Pt, So the dissolution of Pt is inevitably had, and Pt is monoatomic layer arrangement, therefore will appear the reduction peak of NPG.But Electrode potential can't reach so high in actual application, therefore Pt atomic layer is that densification is coated on the surface NPG.
Embodiment 4
CV and ORR is carried out to the Pt monoatomic layer catalysis electrode based on NPG prepared using this patent the method to characterize.
It is reference that the glass-carbon electrode of NPG base Pt monoatomic layer (NPG/Pt), which is loaded with, as working electrode, saturated calomel electrode Electrode, platinum plate electrode are to form three-electrode system to electrode, connect electrochemical workstation and select cyclic voltammetric technology, to lead to N2It is full The HClO of the 0.1M of sum4It is recycled for electrolyte solution in 0.05-1.2V potential region with the scanning speed of 50mV/s Voltammetric scan test, as a result as shown in Figure of description 8；Linear scan technique is selected, to lead to O2The HClO of the 0.1M of saturation4For Electrolyte solution carries out linear scan test in 0.2-1.0V potential region with the scanning speed of 10mV/s, acquired results are such as Shown in Figure of description 9.
Fig. 8 is NPG, NPG/Pt, is commercialized the CV curve of PtC catalyst, compared with rectangular curve (NPG), by Pt's CV curve is substantially change after monoatomic layer modification, either de- in the suction of H as shown in circular curve (NPG/Pt) in figure Attached area (0.05-0.3V) or all obviously similar to the CV curve of PtC catalyst at the reduction peak of 0.8V or so, figure intermediate cam Shown in shape curve.Illustrate that Pt atom densification is coated on the skeleton of NPG.
Fig. 9 is the ORR curve of nanoporous auri Pt monoatomic layer catalyst (NPG/Pt) and commercialization PtC catalyst, It is intuitively demonstrated by the active size of two kinds of catalyst, from the point of view of half wave potential, NPG/Pt relatively commercialization PtC is higher by~50mV； And the hydrogen reduction take-off potential of NPG/Pt catalysis electrode is close to~1.0V, show to prepare by this patent the method based on receiving The platinum monoatomic layer catalysis electrode of meter Duo Kong gold can be used for fuel cell, and improve platinum utilization.

Claims (5)

1. a kind of fuel cell preparation method of fine and close platinum monoatomic layer catalysis electrode, the steps include:
1) nano-porous gold is using de- alloyage preparation: the goldleaf containing Au/Ag is placed in dense HNO3Middle corrosion removes Ag to make Obtain nano-porous gold；
2) preparation of nanoporous metal working electrode: it is 0.1256cm that nanoporous metal working electrode in step 1), which is divided into area,2 Round and 2 × 2cm2Rectangular two kinds；The preparation of circular electrode: the round nano-porous gold prepared is transferred to glass-carbon electrode table Then face is modified to glass carbon/nanoporous gold electrode of diameter 4mm stacking；The preparation of square-shaped electrode: 1) it will prepare in Nano-porous gold be transferred in mica sheet or metallic substrates first, using pressure sintering by nanoporous gold thin film from substrate surface It is transferred to ion exchange film surface, prepares the rectangular nanoporous gold electrode of 2cm × 2cm；
3) electrolyte solution: the electrolyte solution used are as follows: H is prepared2SO4、CuSO4、K2PtCl4It is molten with the mixing of citric acid solution Liquid；
4) prepare densification Pt monoatomic layer catalysis electrode: electrolyte solution is placed in tri- mouthfuls of electrolytic cells of 100ml, be passed through Ar to satisfy With；Using three-electrode system, the underpotential deposition of copper and the list of platinum are carried out using cyclic voltammetry controlling potential and scanning speed Atomic layer displacement.
2. preparation method according to claim 1, it is characterised in that: the condition that de- alloyage prepares nano-porous gold is 10 Corrode 10min-2h under the conditions of DEG C -60 DEG C of temperature.
3. preparation method according to claim 1, it is characterised in that: by modification, make round 0.1256cm2Electrode be Nano-porous gold is completely covered on the glassy carbon electrode surface that diameter is 4mm just；Pressure sintering prepares the rectangular nanometer of 2cm × 2cm Porous gold electrode, condition be 2~10Mpa of pressure size, 0.5~30min of time, 50~200 DEG C of temperature.
4. preparation method according to claim 1, it is characterised in that: the electrolyte solution is the 50mM H of 100mL2SO4 +50mM CuSO4The K that 200 μ L-2mL concentration of middle addition are 0.01-10mM2PtCl4The lemon that solution and 1-5mL concentration are 5-50mM The mixed solution of lemon acid solution.
5. preparation method according to claim 1, it is characterised in that: the cyclic voltammetry is to use cyclic voltammetric technology By control of Electric potentials on some section between -0.2-0.6Vvs.SCE, scanning speed selection carries out owing for copper in 1-50mV/s The displacement of the monoatomic layer of potential deposition and platinum.
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