CN107543849B - The high activity electrode preparation method on two kinds of one step of noble metal modification common metal nanocomposite surfaces - Google Patents
The high activity electrode preparation method on two kinds of one step of noble metal modification common metal nanocomposite surfaces Download PDFInfo
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Abstract
The invention belongs to electrochemical electrode Material Fields, more particularly to a kind of two kinds of one steps of noble metal to modify the preparation method of the high activity electrode on common metal nanocomposite surface.Ni/ graphene composite material is prepared first, is coated onto processed glassy carbon electrode surface, and drying at room temperature obtains Ni/ Graphene electrodes.Then as working electrode, Pt piece is to electrode, saturated calomel electrode is reference electrode, Au and the reduction of mono- step of Pt are deposited into graphene-supported Ni nanoparticle surface in the acid solution containing Au and the presoma of Pt under the conditions of constant potential, prepare the AuPt/Ni/ Graphene electrodes of two kinds of noble metal decorated common metal nanocomposites.The electrode has high catalytic activity to oxidation of glycol reaction in alkaline medium.Electrode prepared by the present invention all has significant advantage in catalytic activity and two aspect of cost, has a extensive future.
Description
Technical field
The invention belongs to electrochemical electrode Material Fields more particularly to a kind of mono- step of Au-Pt to modify Ni/ Graphene electrodes
Preparation method.
Background technique
Alcohol fuel battery is a kind of for moving, fixing and portable electrochemical power source, is had broad application prospects.It grinds
The persons of studying carefully conduct extensive research methanol fuel cell, make great progress.But methanol has toxicity, boiling point
It is low, readily penetrate through the disadvantages of seperation film, therefore, constantly carry out find methanol alternative fuel research.Ethyl alcohol and ethylene glycol are
Most potential substitute, ethylene glycol is due to having the characteristics that low toxicity, higher boiling, high-energy density and high reaction activity by more
Carry out more concerns.
The electrocatalysis oxidation reaction of alcohol carries out in acid and alkaline medium.Under the conditions of acid medium, mainly with platinum and
Two component nanocomposites of platinum base are as electrode material；Under alkaline medium condition, mainly with platinum, palladium and gold and it is based on
Two component nanocomposites of these metals are as electrode material.Platinum, palladium and gold are noble metals, and output is limited, and price is high.
Alcohol electrocatalysis oxidation reaction under the conditions of alkaline media has some apparent advantages, and if reaction speed is fast, corrosivity is low, therefore valence
The metal of lattice relative moderate such as silver and nickel can also use in alkaline medium as electrode material.But the metals such as silver and nickel
Itself is very low to the electro catalytic activity of alcohol oxidation reaction, therefore research is concentrated mainly on M-Ag (its prepared using these elements
Middle M is active metal) etc. on the nanocomposite of two components, the M-Ag alloy or Ag/M core-shell structure that are loaded such as suitable carrier
Nanoparticle, nanometer rods etc., to improve catalytic activity using two intermetallic synergistic effects.
When metal nanoparticle is as catalyst, the metallic atom only on surface serves as active site, and under surface
Metallic atom cannot make full use of, so metal utilization is low.Therefore, for the catalyst of noble metal preparation, Gao Chengben is main
Want defect.The catalyst with core-casing structure for using other metals as core using noble metal as shell is to reduce noble metal usage amount
A kind of approach, but the restriction of many factors is faced for the control of shell thickness, the shell obtained under normal circumstances all compares
Thickness, process are also more complicated.If made by minimal amount of reactive metal deposits on cheap non-noble metal a part of surface
The activity of standby multimetal reforming catalyst is close to or higher than the activity of noble metal itself, then not only in terms of catalytic effect, Er Qie
The utilization rate and drop low cost aspect for improving active metal all have great advantage.It obviously, is to realize to catalyst surface modification
A kind of effective ways of target in this way.
Another metal, which is deposited, on the surface of metal nanoparticle, nanometer rods etc. generallys use chemical method and metal replacement
Method.It is relatively difficult using deposition is controlled when chemical reduction method.It is still relatively more tired using negligible deposition amount is controlled when metal replacement method
Difficulty, but also limited by the oxidation-reduction potential size of two metals.In contrast to this, electrochemical deposition method has apparent excellent
Gesture is easy to control the deposition of trace meter, while not being influenced by metal oxidation reduction current potential.Up to the present to base metal
The research of the different metal deposition modification on surface mainly uses a kind of modified metal, and deposition is bigger.
Summary of the invention
The technical problem to be solved by the present invention is the electro catalytic activity that the nickel as common metal reacts oxidation of glycol
It is very low.In order to solve this problem, catalytic activity is improved by carrying out the modification of different metal to its surface, keeps oxidation of glycol anti-
Ying Feng appears in the region of low potential, and has high peak current density, is conducive to the application on fuel cell, and keeps urging
The low cost of agent, the present invention provide a kind of Ni/ Graphene electrodes with high activity, with minimal amount of gold and platinum modification
Preparation method.The present invention modifies method using a step, and two kinds of gold of Au and Pt are deposited on the sub-fraction surface of Ni/ Graphene electrodes
Belong to, obtains the AuPt/Ni/ Graphene electrodes on two kinds of one step of noble metal modification common metal nanocomposite surfaces.
The technical solution adopted by the present invention to solve the technical problems is: it is general to provide a kind of two kinds of one steps of noble metal modification
The preparation method of the AuPt/Ni/ Graphene electrodes on logical metal nanometer composite material surface, concrete operation step include:
(1) Ni/ Graphene electrodes are prepared
Using Hummers chemical oxidization method, graphite flake is prepared into graphite oxide, then graphite oxide is carried out in water
Ultrasonic treatment obtains graphene oxide solution, adds Ni (NO3)2, with NaBH4For reducing agent, at the same redox graphene and
Ni2+, prepare Ni/ graphene composite material.Ni/ graphene composite material is coated onto glassy carbon electrode surface, drying at room temperature obtains
Ni/ Graphene electrodes；
(2) mono- step of Au-Pt modifies Ni/ Graphene electrodes
With gold chloride, chloroplatinic acid, sulfuric acid and secondary distilled water, the sulfuric acid solution of the presoma containing Au and Pt is prepared.Then, with
Ni/ Graphene electrodes are to electrode as working electrode, Pt piece, and saturated calomel electrode is reference electrode, under the conditions of constant potential
Au and the reduction of mono- step of Pt are deposited into Ni nanoparticle surface, prepare the Ni/ Graphene electrodes of micro Au-Pt modification.Pass through control
Sedimentation time processed obtains the Ni/ Graphene electrodes with different Au-Pt modification amounts, uses AuPt(t)/ Ni/ graphene indicates,
Middle t represents sedimentation time, and unit is the second.
Preferably, in the sulfuric acid solution of the presoma containing Au and Pt described in step (2) gold chloride and chloroplatinic acid it is total dense
Degree is 1.0~2.0mM, and the molar ratio of the two is 1:1, sulfuric acid concentration 0.05M.
Preferably, constant potential described in step (2) is the certain value in+0.35~+0.40V (vs.SCE) range.
Preferably, sedimentation time described in step (2) is 1~2 second.
The present invention also provides the application of AuPt/Ni/ Graphene electrodes, the electrode is anti-for ethylene glycol electrocatalytic oxidation
It answers, method particularly includes:
In the 0.5M sodium hydroxide solution of the ethylene glycol containing 0.1M, AuPt/Ni/ Graphene electrodes prepared by the present invention are made
For working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, carries out cyclic voltammetry, record ethylene glycol electricity
Catalytic oxidation process.
The beneficial effects of the present invention are:
The present invention uses constant potential electrochemical deposition method, and Au and mono- step of Pt are deposited on Ni/ graphene composite material surface,
Prepare the AuPt/Ni/ Graphene electrodes on two kinds of one step of noble metal modification common metal nanocomposite surfaces.Of the invention repairs
Decorations method is simple, and the deposition modification time is short, is easy to carry out the micro control to deposited metal.
It uses graphene as carrier loaded nickel nano particle, prepares Ni/ graphene nanocomposite material, then also by a step
Au and Pt are deposited to Ni nanoparticle surface by former method, are prepared the Ni/ Graphene electrodes of micro Au-Pt modification, are given full play to base
The advantage of synergistic effect and graphene as superior catalytic agent carrier between bottom W metal and modified metal Au and Pt assigns
The Ni/ Graphene electrodes of Au-Pt modification have very high catalytic activity, oxygen to oxidation of glycol reaction under alkaline medium condition
Change peak and appear in low potential region, and there is high peak current density, modification effect is clearly.In addition, since Au and Pt are repaired
Decorations amount is seldom, and Ni price is low, so the preparation cost of the Ni/ Graphene electrodes of Au-Pt modification is very low.Electrode prepared by the present invention
All there is significant advantage in catalytic activity and two aspect of cost, have a extensive future.
With reference to the accompanying drawing, embodiment and comparative example are further described the present invention.
Detailed description of the invention
Fig. 1 is AuPt prepared by embodiment 1(1s)The scanning electron microscope (SEM) photograph on/Ni/ Graphene electrodes surface.
Fig. 2 is AuPt prepared by embodiment 1(1s)AuPt prepared by/Ni/ Graphene electrodes and embodiment 2(2s)/ Ni/ graphite
Cyclic voltammetry curve of the alkene electrode in the 0.5M NaOH solution containing 0.1M ethylene glycol.
Fig. 3 is Ni/ Graphene electrodes and Au prepared by comparative example 1(1s)/ Ni/ Graphene electrodes and comparison are implemented
Pt prepared by example 2(1s)Cyclic voltammetry curve of/Ni/ the Graphene electrodes in the 0.5M NaOH solution containing 0.1M ethylene glycol.
Specific embodiment
The present invention will be described in more detail by embodiment, but protection scope of the present invention is not limited to these realities
Apply example.
Embodiment 1
(1) prepared by Ni/ Graphene electrodes
Using Hummers chemical oxidization method, graphite flake is prepared into graphite oxide, 2mg graphite oxide is then taken to be put in
In 20mL secondary distilled water, ultrasonic oscillation 40min is carried out to it, obtains the graphene oxide solution of dark brown transparence, then plus
Enter 85 μ L 0.1M Ni (NO3)2, continue ultrasonic oscillation 20min, obtain about 20mL and contain Ni (NO3)2With graphene oxide
Solution；40mg NaBH is added into aforesaid liquid under magnetic stirring4, continue to stir 1.5h, transfer the sample into test tube later
Middle standing deposits 10h.After layering, supernatant liquor is removed, raffinate is ultrasonically treated 5min, and obtained 1mL tusche shape liquid is Ni/ stone
Black alkene suspension.Successively with 0.3 μm and 0.05 μm of Al2O3Polishing powder carries out at polishing the glassy carbon electrode surface that diameter is 4mm
Reason, then glass-carbon electrode is cleaned by ultrasonic in secondary distilled water.Then it pipettes the above-mentioned Ni/ graphene suspension of 5 μ L and is coated onto glass
Carbon electrodes, drying at room temperature obtain Ni/ Graphene electrodes, and the Ni load capacity on the basis of glass carbon substrate geometric area is about
20.0μg/cm2。
(2) mono- step of Au-Pt modifies Ni/ Graphene electrodes
20mL HAuCl containing 1mM is prepared with secondary distilled water, gold chloride, chloroplatinic acid and the concentrated sulfuric acid4With 1mM H2PtCl6With
And 0.05M H2SO4Mixed solution, then be passed through nitrogen so that the oxygen wherein dissolved is discharged.Then using Ni/ Graphene electrodes as
Working electrode, Pt piece are to electrode, and saturated calomel electrode is reference electrode, carry out potentiostatic electrodeposition at current potential+0.35V, one
Step reduction deposition Au-Pt prepares AuPt in Ni/ Graphene electrodes surface, sedimentation time 1s(1s)/ Ni/ Graphene electrodes.Root
It is about 0.35 μ g/cm according to the Au-Pt deposition that the quantity of electric charge in deposition process calculates2。AuPt(1s)/ Ni/ Graphene electrodes surface
Scanning electron microscope (SEM) photograph it is as shown in Figure 1.As can be seen that metal nanoparticle is supported on graphene basal plane, distribution uniform, grain in figure
Sub- agglomeration is fewer.
(3)AuPt(1s)/ Ni/ Graphene electrodes are in alkaline medium to the catalytic activity of oxidation of glycol reaction
In the 0.5M sodium hydroxide solution of the ethylene glycol containing 0.1M, by the AuPt of step (2) preparation(1s)/ Ni/ graphene electricity
Pole surface use secondary distilled water to clean after as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, scanning
Speed is 50mV/s, carries out cyclic voltammetry, as a result as shown in Figure 2.AuPt(1s)Oxidation of glycol in/Ni/ Graphene electrodes
The spike potential of reaction is -0.19V, peak current density 24.1mA/cm2。
Embodiment 2
On the basis of embodiment 1, AuPt is prepared(2s)/ Ni/ Graphene electrodes.
(1) prepared by Ni/ Graphene electrodes.It is identical as step (1) in embodiment 1.
(2) mono- step of Au-Pt modifies Ni/ Graphene electrodes.Ni/ Graphene electrodes are as working electrode, Au-Pt sedimentation time
For 2s, other conditions are identical as step (2) in embodiment 1, prepare AuPt(2s)/ Ni/ Graphene electrodes.According to deposition process
In the quantity of electric charge calculate Au-Pt deposition be about 0.70 μ g/cm2。
(3)AuPt(2s)/ Ni/ Graphene electrodes are in alkaline medium to the catalytic activity of oxidation of glycol reaction.Work electricity
Extremely AuPt(2s)/ Ni/ Graphene electrodes, other conditions are identical as step (3) in embodiment 1, as a result as shown in Figure 2.
AuPt(2s)Spike potential-the 0.19V, peak current density 21.7mA/cm that oxidation of glycol reacts in/Ni/ Graphene electrodes2。
Comparative example 1
(1) prepared by Ni/ Graphene electrodes.It is identical as step (1) in embodiment 1.
(2) Au modifies Ni/ Graphene electrodes.20mL, which is prepared, with secondary distilled water, gold chloride and the concentrated sulfuric acid contains 1mM
HAuCl40.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then using Ni/ Graphene electrodes as
Working electrode, Pt piece are to electrode, and saturated calomel electrode is reference electrode, and constant potential reduction deposition is carried out at current potential+0.35V
Au prepares Au in Ni/ Graphene electrodes surface, sedimentation time 1s(1s)/ Ni/ Graphene electrodes.
(3) Ni/ Graphene electrodes and Au(1s)/ Ni/ Graphene electrodes urge oxidation of glycol reaction in alkaline medium
Change activity.In the 0.5M sodium hydroxide solution of the ethylene glycol containing 0.1M, respectively by Ni/ Graphene electrodes and Au(1s)/ Ni/ graphite
Alkene electrode surface use secondary distilled water to clean after as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode,
Scanning speed is 50mV/s, carries out cyclic voltammetry, as a result as shown in Figure 3.Oxidation of glycol reacts in Ni/ Graphene electrodes
Peak very little, appear in the right area of+0.2V；Au(1s)In/Ni/ Graphene electrodes oxidation of glycol react spike potential be+
0.22V, peak current density 9.2mA/cm2.Spike potential is excessively high, the application being unfavorable on fuel cell.These results are obviously not
Such as the result in Fig. 2.
Comparative example 2
(1) prepared by Ni/ Graphene electrodes.It is identical as step (1) in embodiment 1.
(2) Pt modifies Ni/ Graphene electrodes.20mL, which is prepared, with secondary distilled water, chloroplatinic acid and the concentrated sulfuric acid contains 1mM
H2PtCl60.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then with Ni/ Graphene electrodes work
For working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and it is heavy that constant potential reduction is carried out at current potential+0.35V
Product Pt prepares Pt in Ni/ Graphene electrodes surface, sedimentation time 1s(1s)/ Ni/ Graphene electrodes.
(3)Pt(1s)/ Ni/ Graphene electrodes are in alkaline medium to the catalytic activity of oxidation of glycol reaction.Containing 0.1M
In the 0.5M sodium hydroxide solution of ethylene glycol, by Pt(1s)/ Ni/ Graphene electrodes surface use secondary distilled water to clean after as work
Make electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and scanning speed 50mV/s carries out cyclic voltammetry,
As a result as shown in Figure 3.Pt(1s)The cyclic voltammogram of/Ni/ Graphene electrodes is compared with the cyclic voltammogram of Ni/ Graphene electrodes
Relatively show Pt modification without the effect of raising catalytic activity.
Comparative example 3
Using step deposition, first deposition modification Au, rear deposition modification Pt prepare Pt(1s)/Au(1s)/ Ni/ graphene electricity
Pole, the catalytic effect for examining the electrode to react oxidation of glycol.Detailed process is as follows:
(1) prepared by Ni/ Graphene electrodes.It is identical as step (1) in embodiment 1.
(2) Au modifies Ni/ Graphene electrodes.20mL, which is prepared, with secondary distilled water, gold chloride and the concentrated sulfuric acid contains 1mM
HAuCl40.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then using Ni/ Graphene electrodes as
Working electrode, Pt piece are to electrode, and saturated calomel electrode is reference electrode, and constant potential reduction deposition is carried out at current potential+0.35V
Au prepares Au in Ni/ Graphene electrodes surface, sedimentation time 1s(1s)/ Ni/ Graphene electrodes.
(3) Pt modifies Au(1s)/ Ni/ Graphene electrodes.20mL, which is prepared, with secondary distilled water, chloroplatinic acid and the concentrated sulfuric acid contains 1mM
H2PtCl60.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then with Au(1s)/ Ni/ graphene electricity
Pole is to electrode as working electrode, Pt piece, and saturated calomel electrode is reference electrode, carries out constant potential also at current potential+0.35V
Pt is in Au for original deposition(1s)/ Ni/ Graphene electrodes surface, sedimentation time 1s prepare Pt(1s)/Au(1s)/ Ni/ Graphene electrodes.
(4)Pt(1s)/Au(1s)The catalytic activity that/Ni/ Graphene electrodes react oxidation of glycol in alkaline medium.Containing
In the 0.5M sodium hydroxide solution of 0.1M ethylene glycol, by Pt(1s)/Au(1s)/ Ni/ Graphene electrodes surface is cleaned with secondary distilled water
It is used as working electrode afterwards, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and scanning speed 50mV/s is recycled
Voltammetric measuring.The result shows that Pt(1s)/Au(1s)Spike potential is -0.19V (vs.SCE), peak current density in/Ni/ Graphene electrodes
For 6.7mA/cm2, the AuPt of catalytic effect and the preparation of embodiment 1(1s)/ Ni/ graphene is relatively low compared to obvious.This illustrates first to sink
Product Au, what the rear Ni/ Graphene electrodes for depositing Pt modification modified mono- step of catalytic activity ratio Au-Pt that oxidation of glycol reacts
The catalytic activity of Ni/ Graphene electrodes is low, it was demonstrated that the Ni/ Graphene electrodes of Au-Pt mono- step decorations and Au and Pt substep modification
For Ni/ Graphene electrodes compared to having a clear superiority, not only catalytic activity is stronger, also reduces electrode preparation step.
Comparative example 4
Using step deposition, first deposition modification Pt, rear deposition modification Au prepare Au(1s)/Pt(1s)/ Ni/ graphene electricity
Pole, the catalytic effect for examining the electrode to react oxidation of glycol.Detailed process is as follows:
(1) prepared by Ni/ Graphene electrodes.It is identical as step (1) in embodiment 1.
(2) Pt modifies Ni/ graphene composite material.20mL, which is prepared, with secondary distilled water, chloroplatinic acid and the concentrated sulfuric acid contains 1mM
H2PtCl60.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then with Ni/ Graphene electrodes work
For working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and it is heavy that constant potential reduction is carried out at current potential+0.35V
Product Pt prepares Pt in Ni/ Graphene electrodes surface, sedimentation time 1s(1s)/ Ni/ Graphene electrodes.
(3) Au modifies Pt(1s)/ Ni/ Graphene electrodes.20mL, which is prepared, with secondary distilled water, gold chloride and the concentrated sulfuric acid contains 1mM
HAuCl40.05M H2SO4Solution, then nitrogen is passed through so that the oxygen wherein dissolved is discharged.Then with Pt(1s)/ Ni/ graphene electricity
Pole is to electrode as working electrode, Pt piece, and saturated calomel electrode is reference electrode, carries out constant potential also at current potential+0.35V
Au is in Pt for original deposition(1s)/ Ni/ Graphene electrodes surface, sedimentation time 1s prepare Au(1s)/Pt(1s)/ Ni/ Graphene electrodes.
(4)Au(1s)/Pt(1s)The catalytic activity that/Ni/ Graphene electrodes react oxidation of glycol in alkaline medium.Containing
In the 0.5M sodium hydroxide solution of 0.1M ethylene glycol, by Au(1s)/Pt(1s)/ Ni/ graphene surface is made after being cleaned with secondary distilled water
For working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and scanning speed 50mV/s carries out cyclic voltammetric
Measurement.The result shows that Au(1s)/Pt(1s)Spike potential is -0.14V (vs.SCE) in/Ni/ Graphene electrodes, and peak current density is
14.1mA/cm2, the AuPt of catalytic effect and the preparation of embodiment 1(1s)/ Ni/ graphene is relatively low compared to obvious.This illustrates first to deposit
Pt, the Ni/ for mono- step of the catalytic activity ratio Au-Pt modification that the rear Ni/ Graphene electrodes for depositing Au modification react oxidation of glycol
The catalytic activity of Graphene electrodes is low, it was demonstrated that the Ni/ Graphene electrodes of Au-Pt mono- step modification and Pt and Au substep modification
For Ni/ Graphene electrodes compared to having a clear superiority, not only catalytic activity is stronger, also reduces electrode preparation step.
Comparative example 5
On the basis of embodiment 1, carrier is done with carbon black substitution graphene, prepares AuPt(1s)/ Ni/ charcoal black electrode is examined
Catalytic effect of the carbon black as carrier.Detailed process is as follows:
(1) prepared by Ni/ charcoal black electrode.It takes 2mg carbon black to be put in 20mL secondary distilled water, carries out ultrasonic oscillation 40min,
Carbon black suspension is obtained, the Ni (NO that 85 μ L concentration are 0.1M is then added3)2, then ultrasonic vibration 20min, it obtains about 20mL and contains
Ni(NO3)2With the suspension of carbon black.10mg NaBH is added into aforesaid liquid under magnetic stirring4, continue to stir 40min, it
After transfer the sample into test tube stand deposition 10h.After layering, supernatant liquor is removed, raffinate is ultrasonically treated 5min, obtains 1mL
Ni/ carbon black suspension.It pipettes 5 μ L therein and is coated onto the glassy carbon electrode surface that diameter is 4mm, drying at room temperature obtains Ni/ carbon black
Electrode, the Ni load capacity on the basis of glass carbon substrate geometric area are about 20.0 μ g/cm2。
(2) mono- step of Au-Pt modifies Ni/ charcoal black electrode.It is prepared with secondary distilled water, gold chloride, chloroplatinic acid and the concentrated sulfuric acid
20mL HAuCl containing 1mM4With 1mM H2PtCl6And 0.05M H2SO4Mixed solution, then be passed through nitrogen and wherein dissolved with being discharged
Oxygen.Then using Ni/ charcoal black electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, in electricity
One step of constant potential reduction deposition Au and Pt is carried out under+the 0.35V of position in Ni/ carbon black electrode surface, sedimentation time 1s, preparation
AuPt(1s)/ Ni/ charcoal black electrode.
(3)AuPt(1s)/ Ni/ charcoal black electrode is in alkaline medium to the catalytic activity of oxidation of glycol reaction.Containing 0.1M
In the 0.5M sodium hydroxide solution of ethylene glycol, by AuPt(1s)/ Ni/ carbon black electrode surface use secondary distilled water to clean after as work
Make electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode, and scanning speed 50mV/s carries out cyclic voltammetry.
The result shows that AuPt(1s)Oxidation of glycol reaction peak goes out the peak of very little in current potential+0.21V (vs.SCE) in/Ni/ charcoal black electrode,
Peak point current is only 1.6mA/cm2, with AuPt(1s)Peak in/Ni/ Graphene electrodes is compared, no matter in reaction potential or electric current
Density has very big difference.This shows graphene in the present invention as the effect of carrier better than carbon black.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (3)
1. the preparation method of the high activity electrode on two kinds of one step of noble metal modification common metal nanocomposite surfaces, feature
Be: the concrete operation step of the preparation method includes:
(1) Ni/ Graphene electrodes are prepared
Graphite oxide is prepared by raw material of graphite flake, then graphite oxide is ultrasonically treated in water to obtain graphene oxide
Solution adds Ni (NO3)2, with NaBH4For reducing agent, while redox graphene and Ni2+, it is compound to prepare Ni/ graphene
Material；Ni/ graphene composite material obtained is coated onto glassy carbon electrode surface, drying at room temperature obtains Ni/ Graphene electrodes；
(2) mono- step of Au-Pt modifies Ni/ Graphene electrodes
With gold chloride, chloroplatinic acid, sulfuric acid and secondary distilled water, the sulfuric acid solution of the presoma containing Au and Pt is prepared, then with Ni/ stone
Black alkene electrode is as working electrode, and Pt piece is to electrode, and saturated calomel electrode is reference electrode, under the conditions of constant potential by Au and
The reduction of mono- step of Pt deposits to Ni nanoparticle surface, prepares the Ni/ Graphene electrodes of micro Au-Pt modification；The constant potential
For a value in+0.35~+0.40Vvs.SCE range；
The electrode is used for the ethylene glycol electrocatalysis oxidation reaction under alkaline condition.
2. the high activity electrode on two kinds of noble metals as described in claim 1, one step modification common metal nanocomposite surface
Preparation method, it is characterised in that: gold chloride and chloroplatinic acid is total dense in Au and Pt precursor mixed solution described in step (2)
Degree is 1.0~2.0mM, and the molar ratio of the two is 1:1, sulfuric acid concentration 0.05M.
3. the high activity electrode on two kinds of noble metals as described in claim 1, one step modification common metal nanocomposite surface
Preparation method, it is characterised in that: sedimentation time described in step (2) be 1~2 second.
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