CN107331874A - NiCu films load the preparation method of Pt nano particle electroxidation ethanol composite catalyst - Google Patents
NiCu films load the preparation method of Pt nano particle electroxidation ethanol composite catalyst Download PDFInfo
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- CN107331874A CN107331874A CN201710458638.3A CN201710458638A CN107331874A CN 107331874 A CN107331874 A CN 107331874A CN 201710458638 A CN201710458638 A CN 201710458638A CN 107331874 A CN107331874 A CN 107331874A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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Abstract
The invention discloses the preparation method that a kind of NiCu films load Pt nano particle electroxidation ethanol composite catalyst, comprise the following steps：By mantoquita and nickel salt using mol ratio as 0.01~11：1 is soluble in water, and NiCu bimetallic thin films are prepared using constant potential electrochemical co-deposition method；1~10g/L platinum acid chloride solution is added dropwise in NiCu bimetallic thin films, the mixed-alkali solution of 0.005~0.5mol/L reducing agent and 0.01~0.5mol/L stabilizer is added dropwise again, by chemical reduction method in NiCu bimetallic thin films supporting Pt noble metal, NiCu films load Pt nano particle electroxidation ethanol composite catalyst is made.Ni and Cu of the present invention are in electrocatalytic oxidation ethanol process, and oxide or/and the hydroxide such as NiOOH and CuO of generation are conducive to the intermediate product generated in Ethanol Oxidation further to aoxidize, while reducing noble metal poisoning；Precious metals pt loading content is relatively low and high degree of dispersion, is conducive to giving full play to activity, reduces noble metal usage amount.
Description
Technical field
It is the research field of small molecule fuel cell, specifically one the invention belongs to electro-catalysis catalyst technical field
Plant the preparation method that NiCu films load Pt nano particle electroxidation ethanol composite catalyst.
Background technology
Ethanol is a kind of regenerative resource, has preferable application prospect in organic molecule fuel cell, existing straight
Connect alcohol fuel cell (DEFC) appearance.In Direct Ethanol Fuel Cell, catalyst is an important influence factor, at present
The catalyst mainly used is noble metal catalyst, and noble metal catalyst such as platinum based catalyst are used for during ethanol electrooxidation,
Being also easy to produce CO intermediate products makes platinum based catalyst be poisoned, and activity is substantially reduced；The price of noble metal is high simultaneously, is unfavorable for industry and pushes away
Extensively use.Multiplex catalyst can trigger the change of interface electronic structure due to being contacted between its metal, and then electro-catalysis is lived
Property increases.In addition, never there is the method combined using electrochemical deposition method with chemical reduction method to prepare electroxidation ethanol
Composite catalyst, different preparation method can make the specific surface area of composite catalyst, surface chemical property produce larger difference,
Influence the catalytic activity of catalyst.
The Chinese patent of Application No. 201610025501.4 disclose " a kind of preparation method of Pt/Cu-Ni catalyst and
The method of its catalytic oxidation of alcohol and application ", the patent is prepared for Pt/NiCu composite catalyzings using electrochemical deposition method twice
Agent, it uses electrochemical deposition method, Cu-Ni bimetallic alloys, and cleaning electrode is deposited in ITO working electrode surfaces first；
There is the ITO electro-conductive glass of Cu-Ni bimetallic alloys to deposit afterwards as working electrode, again using electrochemical deposition method, obtain
Deposition has the working electrode of Pt/Cu-Ni products, and working electrode is washed to, dried, collected the product on surface afterwards, Pt/ is obtained
Electrochemical deposition method supporting Pt is needed to use during supporting Pt in Cu-Ni composite catalysts, the patent, electrochemical energy need to be additionally consumed
And other devices such as electrolytic cell are needed, operating process is complex.
The content of the invention
It is an object of the invention to provide the preparation side that a kind of NiCu films load Pt nano particle electroxidation ethanol composite catalyst
Constant potential electrochemical co-deposition method and chemical reduction method are combined and prepare composite catalyst by method, this law, use the amount of noble metal platinum
Controllable, the composite catalyst of preparation is high compared to Pt/Ni or Pt/Cu double bases catalyst its electroxidation ethanol activity, during supporting Pt
It is simple to operate.
To achieve the above object, the technical solution adopted by the present invention is：A kind of NiCu films load Pt nano particle electroxidation second
The preparation method of alcohol composite catalyst, comprises the following steps：
1) by mantoquita and nickel salt using mol ratio as 0.01~11：1 is soluble in water, using constant potential electrochemical co-deposition legal system
Standby NiCu bimetallic thin films；
2) 1~10g/L 0.05~0.21ml of platinum acid chloride solution is added dropwise in NiCu bimetallic thin films, then is added dropwise 0.005
Mixed-alkali 0.01~15ml of solution of~0.5mol/L reducing agent and 0.01~0.5mol/L stabilizer, by chemistry also
Former method supporting Pt noble metal in NiCu bimetallic thin films, is made NiCu films load Pt nano particle electroxidation ethanol composite catalyzing
Agent.
Specifically, the step 1) in mantoquita be copper chloride, copper sulphate, copper nitrate or copper acetate in one kind；Nickel salt
For one kind in nickel chloride, nickel sulfate, nickel nitrate and nickel acetate.
Further, the step 1) in constant potential chemical coprecipitation area method electrolyte be mantoquita and nickel salt mixing it is water-soluble
Liquid, negative electrode is electro-conductive glass or titanium sheet, and anode is platinum electrode, and sedimentation potential is -0.5~-1.3V, electrodeposition time is 300~
1200s。
Preferably, the mol ratio of the mantoquita and nickel salt is 0.2~1：1；Sedimentation potential is -0.6~-0.9V, electro-deposition
Time is 300~600s.
Specifically, the step 2) in reducing agent be NaBH4、KBH4Or one kind in hydrazine hydrate；Stabilizer be NaOH or
KOH。
Further, the step 2) in reducing agent and stabilizer mol ratio be 0.5~1：1.
Further, mantoquita：Nickel salt：The mol ratio of chloroplatinic acid is 0.01~11：1：1.2×10-6。
Most preferably, the present invention uses mantoquita and nickel salt using mol ratio as 0.5：The mixed solution of 1 formation soluble in water is made
For electrolyte, using electro-conductive glass as negative electrode, platinum electrode is anode, and in the case where sedimentation potential is -0.6V, electrodeposition time is 600s,
NiCu bimetallic thin films are co-deposited on electro-conductive glass by constant potential electrochemical co-deposition method；Dripped in NiCu bimetallic thin films
Plus 10g/L platinum acid chloride solution 0.05ml, then 0.05ml 0.02mol/L sodium borohydride and 0.05mol/L hydrogen-oxygen is added dropwise
Change sodium mixed-alkali solution, by chemical reduction method in NiCu bimetallic thin films supporting Pt noble metal, NiCu films are made and bear
Carry Pt nano particle electroxidation ethanol composite catalyst.
1) present invention uses constant potential electrochemical co-deposition method combination chemical reduction method, when formation NiCu bimetallic thin films
Afterwards, directly film surface slightly can be cleaned with deionized water, and be added dropwise on film the platinum acid chloride solution prepared, reducing agent and
Pt/NiCu catalyst films are then obtained after stabilizer reaction, it is simple to operate, it is not necessary to extra corollary equipment；2) Ni and Cu are in electricity
During catalytic oxidation of alcohol, oxide or/and the hydroxide such as NiOOH and CuO of generation are conducive to Ethanol Oxidation
The further oxidation of the intermediate product of middle generation, but also noble metal poisoning can be reduced, repeatedly it is used for electrocatalytic oxidation ethanol
After remain to keep high activity；3) Ni nanoparticle Cu bimetallics on the one hand can as Pt nano particles carrier, make precious metals pt height
It is scattered；On the other hand at the interface of NiCu bimetallics and Pt, due to the close contact between nano particle, Pt sheet electrons can be changed
Structure, improves its electro catalytic activity；Electrochemical reaction occur at the interface of NiCu bimetallics and Pt, loading content it is relatively low and height
Scattered Pt is conducive to giving full play to Pt activity, reduces the bullion content used in alcohol fuel cell.
Brief description of the drawings
Fig. 1 loads the XRD spectra of Pt nano particle electroxidation ethanol composite catalyst for NiCu films prepared by the present invention.
Fig. 2 loads the SEM spectrograms of Pt nano particle electroxidation ethanol composite catalyst for NiCu films prepared by the present invention.
Fig. 3 loads the EDS spectrograms of Pt nano particle electroxidation ethanol composite catalyst for NiCu films prepared by the present invention.
Fig. 4 loads Pt nano particle electroxidation ethanol composite catalyst, comparative example in 1mol/ for NiCu films prepared by the present invention
L NaOH and 1mol/L C2H5In OH solution and NiCu films load Pt nano particle electroxidation ethanol composite catalyst in 1mol/L
The cyclic voltammetry curve comparison diagram that NaOH is tested as blank solution.
Fig. 5 loads many of Pt nano particle electroxidation ethanol composite catalyst electroxidation ethanol for NiCu films prepared by the present invention
Secondary cyclic voltammetry curve figure.
Fig. 6 loads the electricity of Pt nano particle electroxidation ethanol composite catalyst electroxidation ethanol for NiCu films prepared by the present invention
Flow time plot.
Embodiment
The present invention is described in further detail with reference to preferred embodiment, is easy to more clearly understand this
Invention, but the present invention is not limited to following embodiments.
A kind of NiCu films of the present invention load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, including following step
Suddenly：
1) by mantoquita and nickel salt using mol ratio as 0.01~11：1 is soluble in water, and the mol ratio of preferably mantoquita and nickel salt is
0.2~1:1, NiCu bimetallic thin films are prepared using constant potential electrochemical co-deposition method；Wherein mantoquita be copper chloride, copper sulphate,
One kind in copper nitrate or copper acetate；Nickel salt is one kind in nickel chloride, nickel sulfate, nickel nitrate and nickel acetate；Wherein constant potential
Electrolyte is the mixed aqueous solution of mantoquita and nickel salt in chemical coprecipitation area method, and negative electrode is electro-conductive glass or titanium sheet, and anode is platinum electricity
Pole, sedimentation potential is -0.5~-1.3V, and preferred deposition current potential is -0.6~-0.9V, and electrodeposition time is 300~1200s, excellent
Select 300~600s；
2) the electrode taking-up for there are NiCu bimetallic thin films will be deposited and slightly cleaned with deionized water, afterwards using liquid-transfering gun
1~10g/L 0.05~0.21ml of platinum acid chloride solution is added dropwise in NiCu bimetallic thin films, then 0.005~0.5mol/L is added dropwise
Reducing agent and 0.01~0.5mol/L stabilizer mixed-alkali 0.01~15ml of solution, by chemical reduction method in NiCu
Supporting Pt noble metal in bimetallic thin film, is made NiCu films load Pt nano particle electroxidation ethanol composite catalyst；Wherein reduce
Agent is NaBH4、KBH4Or one kind in hydrazine hydrate；Stabilizer is NaOH or KOH；Mantoquita：Nickel salt：The mol ratio of chloroplatinic acid is
0.01~11：1：1.2×10-6；The mol ratio of reducing agent and stabilizer is 0.5~1：1.
The bimetallic alloy of different ambrose alloy ratios can be made in different electrodeposition times.
It is streamlined sequentially more equal in the entire surface of NiCu bimetallic thin films in second step carried noble metal Pt
Platinum acid chloride solution and reducing agent and stabilizer are added dropwise evenly.
When the apparent area of working electrode is 1.5 square centimeters, mantoquita：Nickel salt：The mol ratio of chloroplatinic acid is 0.01~11：
1：1.2×10-6。
The mantoquita used in following examples is copper sulphate, and copper chloride, copper nitrate or copper acetate have suitable effect,
Do not repeated in embodiment；The nickel salt used is nickel sulfate, and nickel chloride, nickel nitrate and nickel acetate have suitable effect, in reality
Apply in example and do not repeat；Negative electrode selects electro-conductive glass, and titanium sheet has suitable effect, do not repeated in embodiment；Reducing agent
NaBH is selected4Or KBH4, hydrazine hydrate has suitable effect, do not repeated in embodiment, when selecting NaBH4When, it is corresponding
Stabilizer selects NaOH, when selecting KBH4When, corresponding stabilizer selects KOH, if from hydrazine hydrate, corresponding stabilizer choosing
Use NaOH.
Embodiment 1
1) 0.02mol/L CuSO is prepared4With 0.04mol/L NiSO4Mixed aqueous solution, at 70 DEG C stir and point
Dissipate and be uniformly used as electrolyte；In the case where sedimentation potential is -0.6V, electrodeposition time is 600s, and NiCu is co-deposited on electro-conductive glass
Bimetallic thin film；
2) 10g/L platinum acid chloride solution 0.05mL is added dropwise in NiCu bimetallic thin films, is added dropwise 0.05mL's immediately after
0.02mol/L sodium borohydrides and 0.05moL/L sodium hydroxide mixed-alkali solution, can obtain NiCu films load Pt nano particle electroxidation
The mol ratio of ethanol composite catalyst, copper ion and nickel ion is 0.5：1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 1 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel learns its electrocatalytic oxidation alcohol performance, measures spike potential for 0.250V, peak current is 163.5mA/mgPt。
Embodiment 2
With reference to the method for embodiment 1, the difference is that using concentration for 0.01mol/L CuSO4With 0.05mol/L NiSO4
Mixed aqueous solution, finally obtained NiCu films load Pt nano particle electroxidation ethanol composite catalyst, copper ion and nickel ion rub
You are than being 0.2：1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 2 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel learns its electrocatalytic oxidation alcohol performance, measures spike potential for 0.638V, peak current is 167.0mA/mgPt。
Embodiment 3
With reference to the method for embodiment 1, the difference is that using concentration for 0.03mol/L CuSO4With 0.03mol/L NiSO4
Mixed aqueous solution, finally obtained NiCu films load Pt nano particle electroxidation ethanol composite catalyst, copper ion and nickel ion rub
You are than being 1：1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 3 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel learns its electrocatalytic oxidation alcohol performance, measures spike potential for 0.528V, peak current is 200.8mA/mgPt。
Embodiment 4
With reference to the method for embodiment 1, the difference is that using concentration for 0.055mol/L CuSO4With 0.005mol/L's
NiSO4Mixed aqueous solution, sedimentation potential use -0.9V, reducing agent uses potassium borohydride, and stabilizer uses potassium hydroxide, finally
The mol ratio of obtained NiCu films load Pt nano particle electroxidation ethanol composite catalyst, copper ion and nickel ion is 11：1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 4 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.580V, peak current is 186.9mA/mgPt。
Embodiment 5
1) 0.005mol/L CuSO is prepared4With 0.5mol/L NiSO4Mixed aqueous solution, at 70 DEG C stir and point
Dissipate and be uniformly used as electrolyte；In the case where sedimentation potential is -0.5V, electrodeposition time is 1200s, and NiCu is co-deposited on electro-conductive glass
Bimetallic thin film；
2) 1g/L platinum acid chloride solution 0.21mL is added dropwise in NiCu bimetallic thin films, is added dropwise 15mL's immediately after
0.005mol/L potassium borohydrides and 0.005moL/L potassium hydroxide mixed-alkali solution, can obtain the electric oxygen of NiCu films load Pt nano particle
The mol ratio of change ethanol composite catalyst, copper ion and nickel ion is 0.01：1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 5 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.450V, peak current is 119.3mA/mgPt。
Embodiment 6
1) 0.055mol/L CuSO is prepared4With 0.5mol/L NiSO4Mixed aqueous solution, at 70 DEG C stir and point
Dissipate and be uniformly used as electrolyte；In the case where sedimentation potential is -1.3V, electrodeposition time is 300s, and NiCu is co-deposited on electro-conductive glass
Bimetallic thin film；
2) 10g/L platinum acid chloride solution 0.21mL is added dropwise in NiCu bimetallic thin films, is added dropwise 0.01mL's immediately after
0.5mol/L sodium borohydrides and 0.5moL/L sodium hydroxide mixed-alkali solution, can obtain NiCu films load Pt nano particle electroxidation second
The mol ratio of alcohol composite catalyst, copper ion and nickel ion is 0.11:1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 6 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.350V, peak current is 84.8mA/mgPt。
Embodiment 7
1) 0.02mol/L CuSO is prepared4With 0.04mol/L NiSO4Mixed aqueous solution, at 70 DEG C stir and point
Dissipate and be uniformly used as electrolyte；In the case where sedimentation potential is -0.7V, electrodeposition time is 1000s, and NiCu is co-deposited on electro-conductive glass
Bimetallic thin film；
2) 5g/L platinum acid chloride solution 0.05mL is added dropwise in NiCu bimetallic thin films, is added dropwise 0.1mL's immediately after
0.03mol/L potassium borohydrides and 0.01moL/L potassium hydroxide mixed-alkali solution, can obtain NiCu films load Pt nano particle electroxidation
The mol ratio of ethanol composite catalyst, copper ion and nickel ion is 0.5:1.
NiCu films load Pt nano particle electroxidation ethanol composite catalyst made from above-described embodiment 7 is dried at room temperature
Afterwards 1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, by test loop volt-ampere curve and
Current-time curvel measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.592V, peak current is 68.9mA/mgPt。
Comparative example 1
1) 0.06mol/L NiSO is prepared4The aqueous solution, stir and be uniformly dispersed as electrolyte at 70 DEG C；Heavy
Product current potential is co-deposited Ni films under -1.0V, electrodeposition time is 300s on electro-conductive glass；
2) 10g/L platinum acid chloride solution 0.05mL is added dropwise on Ni films, 0.05mL 0.02mol/L is added dropwise immediately after
Sodium borohydride and 0.05moL/L sodium hydroxide mixed-alkali solution, can obtain that Ni films load Pt nano particle electroxidation ethanol is compound to urge
Agent.
After Ni films load Pt nano particle electroxidation ethanol composite catalyst is dried at room temperature made from above-mentioned comparative example 1
1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, pass through test loop volt-ampere curve and electricity
Stream time graph measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.418V, peak current is 49.5mA/mgPt。
Comparative example 2
1) 0.06mol/L CuSO is prepared4The aqueous solution, stirs and is uniformly dispersed as electrolyte at 70 DEG C；In deposition
Current potential is co-deposited Cu films under -0.6V, electrodeposition time is 600s on electro-conductive glass；
2) 10g/L platinum acid chloride solution 0.05mL is added dropwise on Cu films, 0.05mL 0.02mol/L is added dropwise immediately after
Sodium borohydride and 0.05moL/L sodium hydroxide mixed-alkali solution, can obtain that Cu films load Pt nano particle electroxidation ethanol is compound to urge
Agent.
After Cu films load Pt nano particle electroxidation ethanol composite catalyst is dried at room temperature made from above-mentioned comparative example 2
1mol/L NaOH+1mol/L C are put into as working electrode5H6In OH mixed solutions, pass through test loop volt-ampere curve and electricity
Stream time graph measures its electrocatalytic oxidation alcohol performance, measures spike potential for 0.290V, peak current is 31.1mA/mgPt。
Compared with comparative example 1 and comparative example 2, the electric current of the elctro-catalyst electroxidation ethanol prepared by embodiment 1~7 compared with
Greatly, spike potential is relatively large.In elctro-catalyst electro-oxidation process, the elctro-catalyst prepared by the present invention is due to larger
Oxidation of ethanol electric current, so that electrode surface generation more nonconducting hydroxide or/and oxide, add electrode
Resistance, so as to result in the need for occurring oxidation of ethanol peak under higher current potential.In general, spike potential is more negative, and peak current is bigger,
Elctro-catalyst activity is higher.Embodiment 1 shows larger peak current and smaller spike potential.NiCu films made from embodiment 1
Load Pt nano particle electroxidation ethanol composite catalyst can be used as most preferred Catalysts for Electrocatalytic Oxidation ethanol.
Tested using the NiCu films load Pt nano particle electroxidation ethanol composite catalyst obtained by embodiment 1 as sample,
Measure XRD, SEM figures, EDS spectrograms, cyclic voltammetry curve comparison diagram, multiple cyclic voltammetry curve figure, current-time curvel figure
Be described as follows：
Such as Fig. 1, NiCu films, which are loaded, shows Cu elements and Ni members in the XRD of Pt nano particle electroxidation ethanol composite catalyst
The wider diffraction maximum of element, shows that the catalyst is main by Cu and Ni metal phase compositions, and it shows as amorphous phase or particle is smaller.
Not it was observed that the diffraction maximum related to Pt, shows that Pt content is smaller.Such as Fig. 2, NiCu films load Pt nano particle electroxidation ethanol
Show that catalyst granules is smaller in the SEM figures of composite catalyst, and it is scattered more uniform, and there is tiny loose structure on surface.
Such as Fig. 3, NiCu films load in the EDS spectrograms of Pt nano particle electroxidation ethanol composite catalyst and further show catalysis
Tri- kinds of elements of Pt, Cu and Ni are mainly contained in agent, and Cu and Ni content of the total content than Pt is big, elctro-catalyst is successfully made
It is standby.
Such as Fig. 4, NiCu films load Pt nano particle electroxidation ethanol composite catalyst in blank solution 1mol/L NaOH solutions
In, NiCu films load Pt nano particle electroxidation ethanol composite catalyst ((Pt/NiCu)) in 1mol/L NaOH and 1mol/L
C2H5OH mixed solutions, comparative example 1 (Pt/Ni) and comparative example 2 (Pt/Cu) are in 1mol/L NaOH and 1mol/L C2H5OH is mixed
Cyclic voltammogram in solution is shown, compared with the cyclic voltammetry curve in blank solution, and embodiment 1 is in ethanol water
Cyclic voltammetry curve has obvious double positive oxidation peaks, shows that the catalyst prepared by embodiment 1 has catalytic oxidation of alcohol work
Property；Compared with comparative example 1 (Pt/Ni) and comparative example 2 (Pt/Cu), the elctro-catalyst prepared by embodiment 1 is in forward scan process
In, substantially high oxidation of ethanol peak current is shown, illustrates that the catalyst activity prepared by embodiment 1 is substantially better than comparative example 1
With catalyst obtained in contrast 2.
The NiCu films prepared in such as Fig. 5, embodiment 1 load Pt nano particle electroxidation ethanol composite catalyst in 1mol/L
NaOH and 1mol/L C2H5Multiple cyclic voltammetry curve figure in OH mixed solutions, with the increase of scanning times, positive ethanol
Oxidation peak current does not weaken, and shows the NiCu films load Pt nano particle electroxidation ethanol composite catalyst prepared by embodiment 1
With preferable electrocatalytic oxidation ethanol activity, while indicating the NiCu films load Pt nano particle electricity in electrocatalytic oxidation ethanol
The poisoning of Oxidation of Alcohol composite catalyst is lighter, and electro catalytic activity can be kept for a long time.
Such as Fig. 6, oxidation of ethanol current density dramatic decrease in 200s, this mainly due to caused by pseudocapacity electric current,
With the continuous extension in reaction time, current density reduction is slower, shows that NiCu films load Pt nano particle electroxidation ethanol is answered
Close catalyst has preferable stability during the electro-catalysis in later stage.
Unspecified content is prior art known to a person of ordinary skill in the art in this specification.
Above-described embodiment is only schematical, and one of ordinary skill in the art is in NiCu of the present invention
Under the enlightenment of the preparation method of film load Pt nano particle electroxidation ethanol composite catalyst, present inventive concept and right are not being departed from
It is required that under the ambit protected, can also derive many forms, these are within protection scope of the present invention.
Claims (8)
1. a kind of NiCu films load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, it is characterised in that including with
Lower step：
1) by mantoquita and nickel salt using mol ratio as 0.01~11：1 is soluble in water, is prepared using constant potential electrochemical co-deposition method
NiCu bimetallic thin films；
2) it is added dropwise 1~10g/L 0.05~0.21ml of platinum acid chloride solution in NiCu bimetallic thin films, then it is added dropwise 0.005~
Mixed-alkali 0.01~15ml of solution of 0.5mol/L reducing agent and 0.01~0.5mol/L stabilizer, passes through electronation
Method supporting Pt noble metal in NiCu bimetallic thin films, is made NiCu films load Pt nano particle electroxidation ethanol composite catalyst.
2. NiCu films according to claim 1 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：The step 1) in mantoquita be copper chloride, copper sulphate, copper nitrate or copper acetate in one kind；Nickel salt is chlorination
One kind in nickel, nickel sulfate, nickel nitrate and nickel acetate.
3. NiCu films according to claim 2 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：The step 1) in constant potential chemical coprecipitation area method electrolyte be mantoquita and nickel salt mixed aqueous solution, negative electrode
For electro-conductive glass or titanium sheet, anode is platinum electrode, and sedimentation potential is -0.5~-1.3V, and electrodeposition time is 300~1200s.
4. NiCu films according to claim 3 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：The mol ratio of the mantoquita and nickel salt is 0.2~1：1；Sedimentation potential is -0.6~-0.9V, and electrodeposition time is
300~600s.
5. NiCu films according to claim 1 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：The step 2) in reducing agent be NaBH4、KBH4Or one kind in hydrazine hydrate；Stabilizer is NaOH or KOH.
6. NiCu films according to claim 5 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：The step 2) in reducing agent and stabilizer mol ratio be 0.5~1：1.
7. NiCu films according to claim 5 load the preparation method of Pt nano particle electroxidation ethanol composite catalyst, its
It is characterised by：Mantoquita：Nickel salt：The mol ratio of chloroplatinic acid is 0.01~11：1：1.2×10-6。
8. Pt nano particle electroxidation ethanol composite catalyst is loaded according to NiCu films according to any one of claims 1 to 7
Preparation method, it is characterised in that：The present invention uses mantoquita and nickel salt using mol ratio as 0.5：The mixed solution of 1 formation soluble in water
As electrolyte, using electro-conductive glass as negative electrode, platinum electrode is anode, and in the case where sedimentation potential is -0.6V, electrodeposition time is
600s, NiCu bimetallic thin films are co-deposited by constant potential electrochemical co-deposition method on electro-conductive glass；It is thin in NiCu bimetallics
10g/L platinum acid chloride solution 0.05ml is added dropwise on film, then 0.05ml 0.02mol/L sodium borohydride and 0.05mol/L is added dropwise
Sodium hydroxide mixed-alkali solution, by chemical reduction method in NiCu bimetallic thin films supporting Pt noble metal, be made NiCu
Film loads Pt nano particle electroxidation ethanol composite catalyst.
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Cited By (6)
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| CN108796544A (en) * | 2018-05-04 | 2018-11-13 | 四川大学 | A kind of electrochemistry mineralising CO2Prepare the devices and methods therefor of magnesium carbonate |
| CN110833840A (en) * | 2018-08-16 | 2020-02-25 | 现代自动车株式会社 | Method for producing electrocatalysts by single-step electrodeposition and electrocatalysts produced thereby |
| CN110988074A (en) * | 2019-12-20 | 2020-04-10 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN112886023A (en) * | 2019-11-29 | 2021-06-01 | 大连大学 | CuO-NiNPs/PET-ITO electrode and application thereof |
| CN113130952A (en) * | 2019-12-30 | 2021-07-16 | 大连大学 | PdNPs/NiNPs/ITO electrode and method for constructing ethanol fuel cell by electrocatalytic oxidation of ethanol solution |
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| CN108796544A (en) * | 2018-05-04 | 2018-11-13 | 四川大学 | A kind of electrochemistry mineralising CO2Prepare the devices and methods therefor of magnesium carbonate |
| CN110833840A (en) * | 2018-08-16 | 2020-02-25 | 现代自动车株式会社 | Method for producing electrocatalysts by single-step electrodeposition and electrocatalysts produced thereby |
| CN112886023A (en) * | 2019-11-29 | 2021-06-01 | 大连大学 | CuO-NiNPs/PET-ITO electrode and application thereof |
| CN112886023B (en) * | 2019-11-29 | 2022-07-12 | 大连大学 | CuO-NiNPs/PET-ITO electrode and application thereof |
| CN110988074A (en) * | 2019-12-20 | 2020-04-10 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN110988074B (en) * | 2019-12-20 | 2021-12-21 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
| CN113130952A (en) * | 2019-12-30 | 2021-07-16 | 大连大学 | PdNPs/NiNPs/ITO electrode and method for constructing ethanol fuel cell by electrocatalytic oxidation of ethanol solution |
| CN113140740A (en) * | 2021-06-22 | 2021-07-20 | 成都大学 | Pd @ Ni0.7Cu0.3/NiOOH/CuO mixed crystal methanol oxidation composite electrode and preparation method thereof |
| CN113140740B (en) * | 2021-06-22 | 2021-08-17 | 成都大学 | Pd @ Ni0.7Cu0.3/NiOOH/CuO mixed crystal methanol oxidation composite electrode and preparation method thereof |
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