CN109494376A - Regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness and the preparation method and application thereof - Google Patents
Regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness and the preparation method and application thereof Download PDFInfo
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- CN109494376A CN109494376A CN201811313466.1A CN201811313466A CN109494376A CN 109494376 A CN109494376 A CN 109494376A CN 201811313466 A CN201811313466 A CN 201811313466A CN 109494376 A CN109494376 A CN 109494376A
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to fuel cell material technical fields, a kind of shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness and the preparation method and application thereof are provided, Pd@Pt-Ni core@shell nanometer material is the Pd@Pt being built into as core, Pt-Ni alloy by shell using PdyNi core@core-shell nanoparticles, y are the atom ratio of Pt/Ni in alloy shell, when reacted between since 1h when every increases 2h, alloy shell atom ratio y accordingly reduces 0.3, alloy shell thickness increase about 0.25nm, alloy shell number increase by 1；It is one pot of solvent-thermal method that the present invention, which synthesizes the scheme used, it has the characteristics that simple and effective, simple using equipment, reaction time is short, high-efficient, repdocutbility is good, there is scalability, industrial applications to have a extensive future, Pd@Pt-Ni core@shell nanometer material of the invention is supported on commercial activated carbons, its catalytic activity and stability can be enhanced.
Description
Technical field
The present invention relates to fuel cell material field more particularly to the regulatable Pd@Pt-Ni of a kind of shell component, thickness
Core@shell nanometer electrical catalyst and the preparation method and application thereof.
Background technique
The new energy for finding alternative traditional energy is one of the important decision of countries in the world realization sustainable development.Combustion
Expect that battery is a kind of device that chemical energy is converted into electric energy, because of its high efficiency, high reliablity, environmental-friendly, adaptation energy
The advantages that power is strong and be concerned.Business carbon supporting Pt nano particle (Pt/C) is business-purpose fuel cell elctro-catalyst at present, but
Because the factors such as its Pt scarcity of resources, expensive constrain the commercial applications of fuel cell.A large number of studies show that Pt- base transition
Metal alloy or core-shell nanostructure are expected to substitution Pt/C catalyst and answer as a kind of novel achievable commercializing fuel cells
Elctro-catalyst, because the catalyst can not only reduce the dosage of Pt, but also can be interatomic by different metal
Ligand effect, electronic effect and geometric effect enhance the catalytic activity of fuel molecule and improve its stability.
Up to the present, the preparation of Pd@Pt-Ni core@core-shell nanoparticles has been reported, but used synthetic method
That seed assists growth method or two-step synthesis method: that is, researcher is first with solvent structure Pd nano particle, and by its
As seed；Then it pipettes a small amount of Pd seed and weighs suitable platinum presoma and nickel presoma simultaneously, utilize solvent again
Process for thermosynthesizing can prepare Pd@Pt-Ni core@core-shell nanoparticles.However, there are preparation process to answer for above-mentioned synthetic method
It is miscellaneous, time-consuming, yield is low, be unfavorable for mass preparation the deficiencies of.Therefore, it is necessary to develop a kind of novel synthetic method to prepare
The regulatable Pd@Pt-Ni core@core-shell nanoparticles of shell component, thickness, and as fuel cell active component, study it
The influence of shell component, thickness to anode of fuel cell methanol oxidation catalytic performance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of shell components, the regulatable Pd@Pt-Ni core@shell of thickness
Nano material, with good dispersibility and uniformity, high catalytic activity.
The present invention provides one kind to be precisely controlled Pt/Ni atom ratio y and shell by the control reaction time simultaneously
The preparation method of the Pd@Pt-Ni core@shell nanometer material of thickness and the Pd@Pt-Ni core@shell nanometer material are as active component
Application in the anodic methanol oxidation reaction of fuel cell.
The technical scheme adopted by the invention is that:
A kind of shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness, the Pd@Pt-Ni core@shell nanometer
Material be using Pd as core, Pt-Ni alloy be constructed by shell at Pd@PtyNi core@core-shell nanoparticles, y are Pt/ in alloy shell
The atom ratio of Ni, the Pd@PtyThe atom ratio of Pt/Ni is in the range of y=2.1~1.2 in Ni core@core-shell nanoparticles
Controllable, Pt-Ni alloy shell thickness is controllable in the range of 0.25nm~1.00nm, corresponding alloy shell number
It is controllable in the range of 1~4.
It further limits, the Pd@PtyThe atom ratio of Pt/Ni can be in y=2.1~1.2 in Ni core@core-shell nanoparticles
In the range of it is controllable, specifically: the Pd@PtyWhen synthesising reacting time every increase since 1h in Ni core@core-shell nanoparticles
When 2h, corresponding alloy shell atom ratio y reduces 0.3.
It further limits, the Pd@PtyThe thickness of alloy shell is in 0.25nm~1.00nm in Ni core@core-shell nanoparticles
In the range of it is controllable, specifically: the Pd@PtyWhen synthesising reacting time every increase since 1h in Ni core@core-shell nanoparticles
When 2h, corresponding shell thickness increase about 0.25nm, corresponding shell number increases by 1.
It further limits, the Pd@PtyThe partial size average-size of Ni core@core-shell nanoparticles is 13.8nm~15.3nm.
A kind of shell component, the regulatable Pd@Pt-Ni core@shell nanometer electrical catalyst of thickness, the Pd@Pt-Ni core@shell
Nanometer electrical catalyst includes the active component of active carrier and load on it, and the active component is described in claim 1
The regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness, the percentage of catalyst gross mass shared by the active component
Than being 6%~13%.
It further limits, the active carrier is active carbon.
The one-pot synthesis method of above-mentioned shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness, be by
Acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate, nickel acetylacetonate and surfactant are added in reducing agent, disperse above-mentioned mixed liquor,
Solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, puts it into drying box, the reaction time is 1~7 hour,
Pt/Ni atom ratio y and shell thickness are controlled by the control reaction time in Pt-Ni alloy shell, to Pt/Ni atomic ratio
Rate y and shell thickness reach sets requirement, and reaction was completed, cooled to room temperature, and products therefrom is centrifuged with dehydrated alcohol, is rushed
It washes, dry, obtain the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness.
It further limits, the Pt/Ni atom ratio y and shell thickness of the Pt-Ni alloy shell pass through control reaction
Time controls, and specific method is, the molar ratio of palladium acetylacetonate and acetylacetone,2,4-pentanedione platinum, nickel acetylacetonate be 1:1~2:1~
In the range of 2, when reacted between since 1h when every increase 2h, corresponding Pt/Ni atom ratio y reduces 0.3, the thickness of shell
Increase about 0.25nm, y=2.1~1.2.
It further limits, the surfactant is cetyl trimethylammonium bromide or double ten alkyl trimethyl ammonium bromides
Or double dodecyl trimethyl ammonium bromide；Reducing agent is dimethylformamide or dimethyl acetamide or dimethylpropionamide.
The regulatable Pd@Pt-Ni core@shell nanometer material of above-mentioned shell component, thickness is as active component in fuel cell
Anodic methanol oxidation reaction in purposes can be according to different application environment different demands adaptability control with scalability
The alloy shell component and thickness of Pd@Pt-Ni core@shell nanometer material processed, meet the diversified demand of fuel cell, and its highest
Mass activity reaches 1554mA/mgPt。
Shell component of the invention, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness have good dispersibility and
Uniformity, especially alloy shell element Pt's and Ni is evenly distributed, and using active carbon as carrier, shell Pt-Ni alloy is activity
Component can increase substantially catalytic activity, and catalytic stability is much better than business Pt/C catalyst, and the present invention is to use
One pot of solvent-thermal method preparation, within the scope of raw material mass mixture ratio, the Pt/Ni atom ratio y and shell of Pt-Ni alloy shell are thick
Degree can be precisely controlled by the control reaction time, and then realize different application environment different demands Adaptive Control Pd@Pt-
The alloy shell component and thickness of Ni core@shell nanometer material, compared with the synthetic technology of the prior art, preparation process letter of the invention
Single, mild condition, with scalability, high income, reaction time is short, high-efficient, repdocutbility is good, industrial applications have a extensive future.
Detailed description of the invention
Fig. 1 is Pd@PtyTransmission electron microscope (TEM) photo of Ni core@core-shell nanoparticles；(a~d) is respectively
Prepared product when 1h~7h.
Fig. 2 is Pd@PtyNi core@core-shell nanoparticles histogram of particle size distribution；Such as based on the corresponding particle size distribution of Fig. 1
Scheme (a~d).
Fig. 3 (a) is Pd@PtyThe X-ray energy dispersive line of Ni (y=1.2) core@core-shell nanoparticles sweeps (EDS-lines)
Spectrum；It (b) is Pd@PtyAlloy shell Pt/Ni atom ratio and the relation curve between the reaction time in Ni core@core-shell nanoparticles；
It (c) is Pd@PtyAlloy shell thickness and the relation curve between the reaction time in Ni core@core-shell nanoparticles.
Fig. 4 (a) is Pd@PtyNi/C and Pt/C catalyst methanol oxidation activity curve figure；Test condition is N2
The 0.5M H of saturation2SO4+1.0M CH3OH solution, 0~1.1V of scanning voltage vs.RHE (relative to reversible hydrogen electrode), scanning
Speed is 50mV/s.It (b) is stability test curve；Test condition is at constant voltage 0.75V vs.RHE, in N2Saturation
0.5M H2SO4+1.0M CH3In OH solution, the stability of catalyst is detected by chronoamperometry (i-t curve).
Specific embodiment
Technical solution of the present invention is further described now in conjunction with drawings and examples, but the present invention is not limited only to
Following implementation situations.
It is core, Pt-Ni alloy for shell that Pd@Pt-Ni core@shell nanometer material prepared by method proposed by the present invention, which is using Pd,
It is constructed at Pd@PtyNi core@core-shell nanoparticles, y are the atom ratio of Pt/Ni in alloy shell, wherein Pd@PtyNi core@shell
The atom ratio of Pt/Ni can be in y=2.1~1.2 in nano particle, and shell thickness is accurate in the range of 0.25nm~1.00nm
It is adjustable, specifically: between when reacted since 1h when every increase 2h, the atom ratio y of corresponding Pt/Ni reduces 0.3, and shell is thick
Degree successively increases about 0.25nm, and corresponding shell number successively increases about 1 single layer.
Through detecting, the average-size of Pd@Pt-Ni core@core-shell nanoparticles of the invention is 13.8nm~15.3nm；It can make
It is applied in the anodic methanol oxidation reaction of fuel cell for active component.
It, can be by it in order to further increase the catalytic efficiency of the regulatable Pd@Pt-Ni core@shell nanometer material of shell component
It is supported on absorbent charcoal carrier as active component, and active component accounts for the 6%~13% of total weight.
Through detecting, the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is supported on absorbent charcoal carrier it
Its best quality activity reaches 1554mA/mg afterwardsPt。
Embodiment 1: preparation Pd@PtyNi/C catalyst (y=2.1)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 12mg nickel acetylacetonate, 17mg acetylacetone,2,4-pentanedione platinum, 71mg cetyl trimethyl bromine
Change ammonium and add it in the beaker containing 10mL dimethylformamide, seals ultrasound 10min, then mixed solution is added
Into stainless steel ptfe autoclave, temperature is begun heat to from room temperature in drying box and reaches 170 DEG C, keeps 1h, to
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 12h under 80 DEG C of air atmospheres in drying box, gained black produces
Object is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 13.8nm, alloy shell Pt/
Ni atom ratio y is 2.1, and shell thickness is about 0.25nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=2.1)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 35mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 2h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom is dry
80 DEG C of holding 12h in dry case, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer electricity
Catalyst (Pd@PtyNi/C)。
Embodiment 2: preparation Pd@PtyNi/C catalyst (y=1.8)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 12mg nickel acetylacetonate, 17mg acetylacetone,2,4-pentanedione platinum, 71mg cetyl trimethyl bromine
Change ammonium and add it in the beaker containing 10mL dimethylformamide, seals ultrasound 10min, then mixed solution is added
Into stainless steel ptfe autoclave, temperature is begun heat to from room temperature in drying box and reaches 170 DEG C, keeps 3h, to
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 12h under 80 DEG C of air atmospheres in drying box, gained black produces
Object is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 14.2nm, alloy shell Pt/
Ni atom ratio y is 1.8, and shell thickness is about 0.45nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=1.8)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 40mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 2h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom is dry
80 DEG C of holding 12h in dry case, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer electricity
Catalyst (Pd@PtyNi/C)。
Embodiment 3: preparation Pd@PtyNi/C catalyst (y=1.5)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 12mg nickel acetylacetonate, 17mg acetylacetone,2,4-pentanedione platinum, 71mg cetyl trimethyl bromine
Change ammonium and add it in the beaker containing 10mL dimethylformamide, seals ultrasound 10min, then mixed solution is added
Into stainless steel ptfe autoclave, temperature is begun heat to from room temperature in drying box and reaches 170 DEG C, keeps 5h, to
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 12h under 80 DEG C of air atmospheres in drying box, gained black produces
Object is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 14.7nm, alloy shell Pt/
Ni atom ratio y is 1.5, and shell thickness is about 0.70nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=1.5)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 56mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 2h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom is dry
80 DEG C of holding 12h in dry case, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer electricity
Catalyst (Pd@PtyNi/C)。
Embodiment 4: preparation Pd@PtyNi/C catalyst (y=1.2)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 12mg nickel acetylacetonate, 17mg acetylacetone,2,4-pentanedione platinum, 71mg cetyl trimethyl bromine
Change ammonium and add it in the beaker containing 10mL dimethylformamide, seals ultrasound 10min, then mixed solution is added
Into stainless steel ptfe autoclave, temperature is begun heat to from room temperature in drying box and reaches 170 DEG C, keeps 7h, to
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 12h under 80 DEG C of air atmospheres in drying box, gained black produces
Object is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 15.3nm, alloy shell Pt/
Ni atom ratio y is 1.2, and shell thickness is about 1.01nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=1.2)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 72mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 2h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom is dry
80 DEG C of holding 12h in dry case, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer electricity
Catalyst (Pd@PtyNi/C)。
Embodiment 5: preparation Pd@PtyNi/C catalyst (y=1.3)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 24mg nickel acetylacetonate, 34mg acetylacetone,2,4-pentanedione platinum, the bis- ten alkyl trimethyls bromines of 92mg
Change ammonium and add it in the beaker containing 10mL dimethyl acetamide, seals ultrasound 20min, then mixed solution is added
Into stainless steel ptfe autoclave, temperature is begun heat to from room temperature in drying box and reaches 200 DEG C, keeps 4h, to
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 15h under 75 DEG C of air atmospheres in drying box, gained black produces
Object is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 14.9nm, alloy shell Pt/
Ni atom ratio y is 1.3, and shell thickness is about 0.92nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=1.3)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 60mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 1.5h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom exists
75 DEG C of holding 15h in drying box, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer
Elctro-catalyst (Pd@PtyNi/C)。
Embodiment 6: preparation Pd@PtyNi/C catalyst (y=1.7)
(1) the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness is prepared
Weigh 13mg palladium acetylacetonate, 12mg nickel acetylacetonate, 17mg acetylacetone,2,4-pentanedione platinum, the bis- trimethyls of 80mg
Ammonium bromide simultaneously adds it in the beaker containing 10mL dimethylpropionamide, seals ultrasound 15min, then adds mixed solution
Enter into stainless steel ptfe autoclave, begin heat to temperature from room temperature in drying box and reach 180 DEG C, keep 2h,
After being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol, keeps 15h, gained black under 80 DEG C of air atmospheres in drying box
Product is monodisperse shell component, the regulatable Pd@Pt-Ni core@shell nanometer material of thickness.
Through detecting, the partial size average-size of the Pd@Pt-Ni core@shell nanometer material of the present embodiment is 14.4nm, alloy shell
Pt/Ni atom ratio y is 1.7, and shell thickness is about 0.67nm.
(2) Pd@Pt is preparedyNi/C catalyst (y=1.7)
It weighs products therefrom in 5mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 10mL, 5mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 60mg carbon black and is dispersed in the dehydrated alcohol of 10mL, gained black dispersion liquid label
For F, solution F is added in solution D, ultrasonic 2h, is rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom is dry
80 DEG C of holding 15h in dry case, obtained black powder are shell component, the regulatable Pd@Pt of thicknessyNi core@shell nanometer electricity
Catalyst (Pd@PtyNi/C)。
1~6 data comparison can be seen that through the foregoing embodiment, Pd Pt-Ni core core-shell nanoparticles of the invention
Alloy shell component, thickness can be controllable.Specific control method is:
Alloy shell component and thickness are controlled by regulating and controlling the reaction time processed, specifically: within the scope of raw material mass mixture ratio,
The atom ratio of Pt/Ni can accurately control in the range of y=2.1~1.2, while shell thickness is 0.25nm~1.00nm's
It is accurate adjustable in range, i.e., when reacted between since 1h when every increases 2h, the atom ratio y reduction 0.3 of corresponding Pt/Ni,
Shell thickness successively increases about 0.25nm simultaneously, and corresponding shell number successively increases about 1 single layer, can basis
Different demands and application environment set required shell thickness and alloy shell component proportion, and then pass through the control reaction time
To control alloy shell component and thickness.
Surfactant is cetyl trimethylammonium bromide or double ten alkyl trimethyls brominations in above-described embodiment 1~6
Ammonium or double dodecyl trimethyl ammonium bromide can be replaced mutually between them；Reducing agent is dimethylformamide or dimethyl
Acetamide or dimethylpropionamide can also be replaced mutually.
Its mole can after material is selected for raw material palladium presoma, platinum presoma, surfactant in above-described embodiment etc.
It is suitably adjusted with the proportion with reference to above-described embodiment, such as in palladium presoma: platinum presoma: nickel presoma: surfactant
Appropriate adjustment in the range of=1: 1~2: 1~2: 5~7 is not limited only to the proportion of above-described embodiment.Different raw material proportionings,
Alloy shell component Pt/Ni atom ratio and shell thickness can change, but within the scope of above-mentioned raw materials quality proportioning
Regulation method according to the invention can be achieved on alloy shell constituent atoms ratio and shell thickness is precisely controlled.
By taking Examples 1 to 4 as an example, by following experiments to the catalytic performance of Pd@Pt-Ni core@shell nanometer material and steady
Qualitative further verifying, specific as follows:
1, using transmission electron microscope (TEM) in Pd@Pt-Ni core@shell nanometer electrical catalyst prepared by Examples 1 to 4
The microscopic appearance of grain is observed, as a result as shown in figure 1 shown in (a)~(d).
Particle tool it can be seen from (a)~(d) in Fig. 1 in Pd@Pt-Ni core@shell nanometer electrical catalyst of the invention
There are good dispersibility and uniformity.
2, the particle size in Pd@Pt-Ni core@shell nanometer electrical catalyst prepared by Examples 1 to 4 is measured,
Its particle diameter distribution such as Fig. 2 (a)~(d).
Particle is averaged in Pd@Pt-Ni core@shell nanometer electrical catalyst of the invention it can be seen from (a)~(d) of Fig. 2
Particle size range is 13.8 ± 1.2nm~15.3 ± 1.9nm.
3, it is composed by X-ray energy dispersive and inductively coupled plasma atomic emission spectrum (ICP-AES) determines Pd@
Component Pt/Ni atom ratio in the crystal structure and alloy shell of particle in Pt-Ni core@shell nanometer electrical catalyst, such as Fig. 3 institute
Show.Fig. 3 (a) is Pd@Pt prepared by embodiment 4yThe X-ray energy of particle in Ni (y=1.2) core@shell nanometer electrical catalyst
Scattered rays sweeps (EDS-lines) spectrum；Fig. 3 (b) is that particle alloy shell Pt/Ni is former in Pd@Pt-Ni core@shell nanometer electrical catalyst
The graph of relation of sub- ratio and reaction time；Fig. 3 (c) is particle alloy shell in Pd@Pt-Ni core@shell nanometer electrical catalyst
The graph of relation of thickness and reaction time.
From Fig. 3 (a) as can be seen that particle is by Pd core and Pt-Ni alloy shell institute structure in Pd@Pt-Ni nanometer electrical catalyst
The core-shell nanostructure built up.From Fig. 3 (b) as can be seen that according to ICP-AES as a result, Pd@Pt- prepared by Examples 1 to 4
The alloy shell component Pt/Ni atom ratio of particle shows monotone decreasing with the reaction time in Ni core@shell nanometer electrical catalyst
Relationship, and when reacted between since 1h when every increase 2h, corresponding shell atom ratio y reduces 0.3.It can be with from Fig. 3 (c)
Find out, according to the alloy of particle in Pd@Pt-Ni core@shell nanometer electrical catalyst prepared by statistical result showed Examples 1 to 4
Shell thickness shows monotonic increase relationship with the reaction time, and when reacted between since 1h when every increase 2h, accordingly
Shell thickness successively increases about 0.25nm, and corresponding alloy shell number successively increases about 1 single layer.
4, Pd@Pt prepared by the embodiment of the present invention 1~4yNi core@shell nanometer electrical catalyst (Pd@Pty) and quotient Ni/C
The activity and stability test curve graph of industry Pt/C catalyst methanol oxidation.
Active testing condition: N2The 0.5M H of saturation2SO4+1.0M CH3OH solution, 0~1.1V of scanning voltage vs.RHE
(relative to reversible hydrogen electrode), scanning speed 50mV/s.Stability test condition: at constant voltage 0.75V vs.RHE,
In N2The 0.5M H of saturation2SO4+1.0M CH3The stabilization of catalyst is detected in OH solution by chronoamperometry (i-t curve)
Property.
It can be seen from Fig. 4 (a) compared with business Pt/C catalyst, Pd@PtyNi/C (y=2.1,1.8,1.5,
1.2) catalyst shows very superior methanol oxidation catalytic activity；Pd@Pt simultaneouslyyNi/C (y=1.2) catalyst is aobvious
Highest catalytic activity is shown, 1553.5mA/mg is reachedPt；From Fig. 4 (b) as can be seen that during 3000s stability test,
Pd@PtyNi/C (y=2.1,1.8,1.5,1.2) catalyst shows extraordinary stability compared with business Pt/C catalyst.
Claims (10)
1. the regulatable Pd@Pt-Ni core@shell nanometer material of a kind of shell component, thickness, it is characterised in that: the Pd@Pt-Ni
Core@shell nanometer material be using Pd as core, Pt-Ni alloy be constructed by shell at Pd@PtyNi core@core-shell nanoparticles, y is alloy
The atom ratio of Pt/Ni in shell, the Pd@PtyThe atom ratio of Pt/Ni is in y=2.1~1.2 in Ni core@core-shell nanoparticles
In the range of it is controllable, Pt-Ni alloy shell thickness is controllable in the range of 0.25nm~1.00nm, corresponding alloy
Shell number is controllable in the range of 1~4.
2. the regulatable Pd@Pt-Ni core@shell nanometer material of shell component as described in claim 1, thickness, it is characterised in that: institute
State Pd@PtyThe atom ratio of Pt/Ni can be controllable in the range of y=2.1~1.2 in Ni core@core-shell nanoparticles, specifically:
The Pd@PtyIn Ni core@core-shell nanoparticles as synthesising reacting time every increase 2h since 1h, corresponding alloy shell is former
Sub- ratio y reduces 0.3.
3. the regulatable Pd@Pt-Ni core@shell nanometer material of shell component as described in claim 1, thickness, it is characterised in that: institute
State Pd@PtyThe thickness of alloy shell is controllable in the range of 0.25nm~1.00nm in Ni core@core-shell nanoparticles, specifically:
The Pd@PtyIn Ni core@core-shell nanoparticles as synthesising reacting time every increase 2h since 1h, corresponding shell thickness increases
Add about 0.25nm, while corresponding shell number increases by 1.
4. the regulatable Pd@Pt-Ni core@shell nanometer material of shell component as described in claim 1, thickness, it is characterised in that: institute
State Pd@PtyThe partial size average-size of Ni core@core-shell nanoparticles is 13.8nm~15.3nm.
5. the regulatable Pd@Pt-Ni core@shell nanometer electrical catalyst of a kind of shell component, thickness, it is characterised in that: the Pd@
Pt-Ni core shell nanometer electrical catalyst includes the active component of active carrier and load on it, and the active component is wanted for right
The regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness described in asking 1, catalyst shared by the active component are total
The percentage of quality is 6%~13%.
6. the regulatable Pd@Pt-Ni core@shell nanometer electrical catalyst of shell component as claimed in claim 5, thickness, feature exist
In: the active carrier is active carbon.
7. the one-pot synthesis side of the regulatable Pd@Pt-Ni core@shell nanometer material of shell component described in claim 1, thickness
Method, it is characterised in that: acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate, nickel acetylacetonate and surfactant are added in reducing agent,
Disperse above-mentioned mixed liquor, solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, put it into drying box, when reaction
Between be 1~7 hour, Pt/Ni atom ratio y and shell thickness are controlled by the control reaction time in Pt-Ni alloy shell,
Reach sets requirement to Pt/Ni atom ratio y and shell thickness, reaction was completed, cooled to room temperature, and products therefrom is with anhydrous
Ethyl alcohol centrifugation, rinsing, drying, obtain the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness.
8. the one-pot synthesis of the regulatable Pd@Pt-Ni core@shell nanometer material of shell component according to claim 7, thickness
Method, it is characterised in that；The Pt/Ni atom ratio y and shell thickness of the Pt-Ni alloy shell pass through the control reaction time
It controls, it is 1:1~2:1~2 in the molar ratio of palladium acetylacetonate and acetylacetone,2,4-pentanedione platinum, nickel acetylacetonate that specific method, which is,
In range, when reacted between since 1h when every increase 2h, the thickness that corresponding Pt/Ni atom ratio y reduces by 0.3, shell increases
Add about 0.25nm, y=2.1~1.2.
9. the one-pot synthesis of the regulatable Pd@Pt-Ni core@shell nanometer material of shell component according to claim 7, thickness
Method, it is characterised in that: the surfactant be cetyl trimethylammonium bromide or double ten alkyl trimethyl ammonium bromides or
Double dodecyl trimethyl ammonium bromide；Reducing agent is dimethylformamide or dimethyl acetamide or dimethylpropionamide.
10. the regulatable Pd@Pt-Ni core@shell nanometer material of shell component, thickness described in claim 1 exists as active component
Purposes in the anodic methanol oxidation reaction of fuel cell.
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