CN109192999B - Monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material and the preparation method and application thereof - Google Patents
Monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material and the preparation method and application thereof Download PDFInfo
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- CN109192999B CN109192999B CN201810935084.6A CN201810935084A CN109192999B CN 109192999 B CN109192999 B CN 109192999B CN 201810935084 A CN201810935084 A CN 201810935084A CN 109192999 B CN109192999 B CN 109192999B
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
A kind of monodisperse provided by the invention, Pd@Pt core@shell nanometer material of shell thickness controllable precise and the preparation method and application thereof, wherein Pd@Pt core@shell nanometer material be using Pd as core, Pt be constructed by shell at Pd@PtnLCore@core-shell nanoparticles, n are shell number, the Pd@PtnLThe shell thickness of core@core-shell nanoparticles accurately controls, the number of plies that the every increase about 0.7nm of Pt shell thickness corresponds to Pt shell increases by 3 layers, scheme used by the present invention synthesizes is one pot of solvent-thermal method, it is simple and effective, have scalability, simple using equipment, reaction time is short, high-efficient, repdocutbility is good, industrial applications have a extensive future, in addition, Pd@Pt core@shell nanometer material of the invention is supported on commercial activated carbons, its catalytic activity and stability are further increased.
Description
Technical field
The present invention relates to fuel cell material field more particularly to a kind of monodisperses, shell thickness controllable precise Pd@Pt
Core@shell nanometer electrical catalyst and the preparation method and application thereof.
Background technique
As a kind of new energy switch technology, fuel cell is still faced with huge choose in terms of its commercial applications
War, this is mainly due to cathodic oxygen reduction reactions (ORR) to still need a large amount of precious metals pt catalyst.It is used to reduce Pt
Amount improves catalytic performance and stability, Pt bimetallic nanometer electrical catalyst and is concerned, feature are as follows: 1, reduce the use of Pt
Amount；2, catalytic activity is enhanced by the electronics coupled effect between bimetallic and improves stability.The especially double gold of Pd@Pt core@shell
Metal nano-particle, existing pinch effect is that enhancing ORR catalytic activity and improvement are stablized between metal Pd atom and Pt atom
The principal element of property.Up to the present, several methods for preparing Pd@Pt core@core-shell nanoparticles it has been reported that.There is Yuntaek et
Al. NaBH is utilized4Carbon load Pd@Pt core shell nanoparticles (Pd@Pt/C) has been synthesized in water phase system as reducing agent, it is average
Having a size of 4-5nm.Xia's group is prepared in water phase system using ascorbic acid (AA) and ethylene glycol (EG) as reducing agent
Pd@Pt core shell nanoparticles.But that there are preparation process is complicated, cannot accurately control shell thickness, time-consuming, height for the above method
The disadvantages of expense, yield are few.
Also Kun Cao et al. is prepared for the controllable Pd of atom level using area selection atomic layer deposition (ALD) method
Pt core shell nanoparticles.Shangqian Zhu et al. is prepared for Pd Pt nucleocapsid using underpotential deposition (Cu-UPD-Pt) method
Nano particle.Although the above method has the advantages that prepare single layer Pt shell, still have preparation process it is complicated, it is time-consuming,
High cost, yield are few, are unfavorable for the deficiencies of mass preparation.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of monodisperses, shell thickness controllable precise Pd@Pt core@shell
Nano material is shell by core, Pt of Pd, has polymolecularity and high uniformity.
Above-mentioned monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material are utilized the present invention also provides a kind of simultaneously
The Pd@Pt core@shell nanometer electrical catalyst of material.
The technical scheme adopted by the invention is that:
The Pd@Pt core@shell nanometer material of a kind of monodisperse, shell thickness controllable precise, the Pd@Pt core@shell nanometer material
Material be using Pd as core, Pt be constructed by shell at Pd@PtnLCore@core-shell nanoparticles, n are shell number, the Pd@PtnLCore@shell
The shell thickness of nano particle accurately controls.
It further limits, the Pd@PtnLThe Pt shell thickness of core@core-shell nanoparticles and the number of plies of Pt shell are certain former
It is proportional in material ratio range, specifically within the scope of certain raw material proportioning, the Pd@PtnLThe Pt shell of core@core-shell nanoparticles
The number of plies that the every increase about 0.7nm of thickness corresponds to Pt shell increases by 3 layers.
It further limits, the Pd@PtnLThe partial size average-size of core@core-shell nanoparticles is 15.1nm~21.9nm；Wherein
The average thickness of Pt shell is 0.78nm~3.20nm, and the corresponding Pt single layer number of plies is 3.4~13.9.
A kind of Pd@Pt core@shell nanometer electrical catalyst of monodisperse, shell thickness controllable precise comprising absorbent charcoal carrier
With the active component of load on it, the active component is the Pd Pt core of above-mentioned monodisperse, shell thickness controllable precise
Shell nanometer material.
It further limits, the Pd@Pt core@shell nanometer electrical catalyst of the monodisperse, shell thickness controllable precise, feature
Be: the percentage of catalyst gross mass shared by the active component is 7%~11%.
It further limits, the Pd@Pt core@shell nanometer electrical catalyst catalysis oxygen of the monodisperse, shell thickness controllable precise
The best quality activity of gas reduction reaction is 0.95A/mgPt, and highest area specific activity is 1.77mA/cm2, this is than business Pt/C
The mass activity and area specific activity of catalyst want high 5 times and 6 times or more respectively.
The one-pot synthesis method of the Pd@Pt core@shell nanometer material of above-mentioned monodisperse, shell thickness controllable precise, tool
Body is: by platinum presoma, palladium presoma, surfactant and reducing agent helped to be added in reducing agent, disperses above-mentioned mixed liquor,
Solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, puts it into normal drying case, by regulating and controlling temperature control processed
The thickness of shell processed is to setting thickness, to the end of reacting, cooled to room temperature, products therefrom is centrifuged with dehydrated alcohol, rinsed,
It is dry, obtain the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise.
It further limits, within the scope of 140 DEG C~180 DEG C, controls the thickness of shell to setting thickness by regulating and controlling temperature processed
Degree is specifically: reaction temperature is every to increase by 10 DEG C, the Pt shell thickness increase about 0.7nm of Pd@Pt core@core-shell nanoparticles, accordingly
Pt shell number increases by 3 layers.
It further limits, the platinum presoma is acetylacetone,2,4-pentanedione platinum, and palladium presoma is palladium acetylacetonate；The surface-active
Agent is polyvinylpyrrolidone or lauryl sodium sulfate or detergent alkylate sodium sulfonate；Help reducing agent be phenol or benzoic acid or
Sodium benzoate or glucose or citric acid or sodium citrate or ascorbic acid；Reducing agent is dimethylformamide or dimethylacetamide
Amine or dimethylpropionamide.
Above-mentioned monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material as active component in fuel cell
Cathodic oxygen reduction reaction in application.
Monodisperse of the invention, shell thickness controllable precise Pd Pt core shell nanometer material use one pot of solvent heat legal system
Standby, preparation process is simple, mild condition, and with scalability, reaction time is short, high-efficient, repdocutbility is good, industrial applications prospect
Wide, the present invention, which has also been put forward for the first time, realizes monodisperse, shell thickness controllable precise by control reaction temperature, and then realizes not
With the shell thickness of application environment different demands Adaptive Control Pd@Pt core@shell nanometer material, in addition, Pd@Pt of the invention
Core@shell nanometer material has polymolecularity and high uniformity, can further increase catalytic activity using active carbon as carrier,
Its catalytic stability is much better than business Pt/C catalyst.
Detailed description of the invention
Fig. 1 is Pd@PtnLTransmission electron microscope (TEM) photo of core@core-shell nanoparticles；(a~e) is reaction temperature respectively from 140
DEG C~180 DEG C when prepared product.
Fig. 2 is Pd@PtnLCore@core-shell nanoparticles size distribution histogram；Based on the corresponding particle size distribution of Fig. 1 as schemed
(a~e).
Fig. 3 (a~e) is respectively Pd@PtnLThe X-ray energy dispersive line of core@core-shell nanoparticles sweeps (EDS-lines) spectrum；
(f~j) is respectively Pd@PtnLCore@core-shell nanoparticles selectively remove resulting corresponding product after Pd core.
Fig. 4 is the relational graph of reaction temperature and the Pt single layer number of plies.
Fig. 5 is Pd@PtnL/ C and Pt/C catalyst ORR stability test histogram；Test condition is O2Saturation
0.1M HClO4Solution, scanning voltage range are 0.05~1.1V vs.RHE (relative to reversible hydrogen electrode), and sweeping speed is 10mV/
S, revolving speed 1600r/min.
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.
Pd@Pt core@shell nanometer material of the invention be using Pd as core, Pt be constructed by shell at Pd@PtnLCore@shell nanometer
Particle, n are shell number, the Pd@PtnLThe shell thickness of core@core-shell nanoparticles accurately controls, Pd@PtnLCore@shell nanometer
The Pt shell thickness and the number of plies of Pt shell of particle are proportional, i.e., the number of plies that every increase about 0.7nm corresponds to Pt shell increases by 3 layers.
Through detecting, Pd@Pt of the inventionnLThe partial size average-size of core@core-shell nanoparticles is 15.1nm~21.9nm；Wherein
The average thickness of Pt shell is 0.78nm~3.20nm, and the corresponding Pt single layer number of plies is 3.4~13.9, can be used as active component
Application in the cathodic oxygen reduction reaction of fuel cell.
In order to further increase monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material catalytic efficiency,
It can be supported on absorbent charcoal carrier as active component, and active component accounts for the 7%~11% of total weight.
Through detecting, monodisperse, shell thickness controllable precise Pd@Pt core@shell nanometer material be supported on absorbent charcoal carrier
Its best quality activity reaches 0.95A/mg laterPt, and highest area specific activity reaches 1.77mA/cm2。
Embodiment 1: preparation Pd@PtnL/ C catalyst (n=3.4)
(1) the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise is prepared
It weighs 200mg phenol to be added in the n,N-Dimethylformamide of 2mL, acquired solution is labeled as A；Weigh 31mg second
Acyl acetone platinum, 12mg palladium acetylacetonate and 92mg polyvinylpyrrolidone (PVP, number-average molecular weight 58000), are added into
Into 10mL n,N-Dimethylformamide, acquired solution is labeled as B；Solution A is added in solution B, gained mixed solution mark
It is denoted as C, is ultrasonically treated 5 minutes, stirs 10 minutes, C solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, dry
Temperature is begun heat to from room temperature in dry case and reaches 140 DEG C, keeps 8h, and after being cooled to room temperature, centrifugation rinses 3~5 with ethyl alcohol
It is secondary, 12h is kept under 80 DEG C of air atmospheres in drying box, gained black product is monodisperse, shell thickness controllable precise
Pd@Pt core@shell nanometer material.
Through detecting, the partial size average-size of the Pd@Pt core@shell nanometer material of the present embodiment is 15.1nm, and Pt shell is put down
It is 3.4 with a thickness of 0.78nm, Pt single layer number of plies n.
(2) Pd@Pt is preparednL/ C catalyst
It weighs products therefrom in 2mg step (1) and ultrasonic disperse is in the dehydrated alcohol of 9mL, 1mL hexamethylene is added later,
Gained black dispersion liquid is labeled as D；It weighs 17mg carbon black and is dispersed in the dehydrated alcohol of 5mL, 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 the Pd@Pt core@shell nanometer electricity of monodisperse, shell thickness controllable precise
Catalyst (Pd@PtnL/C)。
Embodiment 2: preparation Pd@PtnL/ C catalyst (n=5.3)
(1) the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise is prepared
It weighs 200mg benzoic acid to be added in the n,N-Dimethylformamide (DMF) of 2mL, acquired solution is labeled as A；Claim
31mg acetylacetone,2,4-pentanedione platinum, 12mg palladium acetylacetonate and 92mg lauryl sodium sulfate are taken, is added it in 10mL DMF, institute
It obtains solution and is labeled as B；Solution A is added in solution B, gained mixed solution is labeled as C；Ultrasonic treatment C solution 5 minutes, is stirred
It mixes 10 minutes, C solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, is heated to 150 from room temperature in drying box
DEG C, and 8h is kept, after being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol；It is kept under 80 DEG C of air atmospheres in drying box
12h, gained black product are Pd@Pt core@core-shell nanoparticles.
Through detecting, the particle size of the Pd@Pt core@shell nanometer material of the present embodiment is 20.6nm, the average thickness of Pt shell
Degree is 1.22nm, and Pt single layer number of plies n is 5.3.
(2) Pd@Pt is preparednL/ C catalyst
It weighs products therefrom in 2mg step (1) and ultrasonic disperse is in 9mL dehydrated alcohol, 1mL hexamethylene, institute are added later
It obtains black dispersion liquid and is labeled as D；It weighing 26mg carbon black and is dispersed in the hexamethylene of 5mL, gained black dispersion liquid is labeled as F,
Solution F is added in solution D, then ultrasound 2 hours.It is finally rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, gained
Product 80 DEG C of holding 12h in drying box, obtained black powder are carbon load Pd@Pt core@shell elctro-catalyst.
Embodiment 3: preparation Pd@PtnL/ C catalyst (n=8.2)
(1) the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise is prepared
It weighs 200mg glucose to be added in the dimethyl acetamide of 2mL, acquired solution is labeled as A.Weigh 31mg acetyl
Acetone platinum, 12mg palladium acetylacetonate and 92mg detergent alkylate sodium sulfonate, add it in 10mL dimethyl acetamide, institute
It obtains solution and is labeled as B.Solution A is added in solution B, gained mixed solution is labeled as C.Ultrasonic C solution 5 minutes, stirring 10
Minute, C solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron later, is heated to 160 DEG C from room temperature in drying box, and
8h is kept, after being cooled to room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol.Finally kept under 80 DEG C of air atmospheres in drying box
12h, gained black product are Pd@Pt core@core-shell nanoparticles.
Through detecting, the particle size of the Pd@Pt core@shell nanometer material of the present embodiment is 17.6nm, the average thickness of Pt shell
Degree is 1.90nm, and Pt single layer number of plies n is 8.2.
(2) Pd@Pt is preparednL/ C catalyst
It weighs products therefrom in 2mg step (1) and ultrasonic disperse is in 10mL dehydrated alcohol, gained black dispersion liquid is labeled as
D；It weighing 18mg carbon black and is dispersed in 5mL hexamethylene, gained black dispersion liquid is labeled as F, solution F is added in solution D,
Then ultrasound 2 hours are finally rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, products therefrom 80 DEG C of holdings in drying box
12h, obtained black powder are carbon load Pd@Pt core@shell elctro-catalyst.
Embodiment 4: preparation Pd@PtnL/ C catalyst (n=11.0)
(1) the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise is prepared
It weighs 200mg ascorbic acid to be added in the dimethylpropionamide of 2mL, acquired solution is labeled as A.Weigh 31mg second
Acyl acetone platinum, 12mg palladium acetylacetonate and 92mg PVP, add it in 10mL dimethylpropionamide, acquired solution label
For B.Solution A is added in solution B, gained mixed solution is labeled as C.It Ultrasonic C solution 5 minutes, stirs 10 minutes, later will
C solution is added in polytetrafluoroethylene (PTFE) stainless steel cauldron, 170 DEG C is heated to from room temperature in drying box, and keep 8h, to cold
But to after room temperature, centrifugation is rinsed 3~5 times with ethyl alcohol.12h, gained black are finally kept under 80 DEG C of air atmospheres in drying box
Product is Pd@Pt core@core-shell nanoparticles.
Through detecting, the particle size of the Pd@Pt core@shell nanometer material of the present embodiment is 16.0nm, the average thickness of Pt shell
Degree is 2.52nm, and Pt single layer number of plies n is 11.0.
(2) Pd@Pt is preparednL/ C catalyst
It weighs products therefrom in 2mg step (1) and ultrasonic disperse is in 9mL dehydrated alcohol, 1mL hexamethylene, institute are added later
It obtains black dispersion liquid and is labeled as D；It weighs 18mg carbon black and is dispersed in the dehydrated alcohol of 5mL, gained black dispersion liquid is labeled as
Solution F is added in solution D by F, then ultrasound 2 hours.It is finally rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, institute
Product 80 DEG C of holding 12h in drying box are obtained, obtained black powder is carbon load Pd@Pt core@shell elctro-catalyst.
Embodiment 5: preparation Pd@PtnL/ C catalyst (n=13.9)
(1) the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise is prepared
It weighs 200mg phenol to be added in the DMF of 2mL, acquired solution is labeled as A.Weigh 31mg acetylacetone,2,4-pentanedione platinum, 12mg
Palladium acetylacetonate, 92mg PVP are added it in 10mL DMF, and acquired solution is labeled as B.Solution A is added to solution B
In, gained mixed solution is labeled as C.It Ultrasonic C solution 5 minutes, stirs 10 minutes, C solution is added to polytetrafluoroethylene (PTFE) later
In stainless steel cauldron, 180 DEG C are heated to from room temperature in drying box, and keep 8h, after being cooled to room temperature, are centrifuged, use second
Alcohol rinses 3~5 times.12h is finally kept under 80 DEG C of air atmospheres in drying box, gained black product is Pd@Pt core@shell nanometer
Particle.
Through detecting, the particle size of the Pd@Pt core@shell nanometer material of the present embodiment is 21.9nm, the average thickness of Pt shell
Degree is 3.20nm, and Pt single layer number of plies n is 13.9.
(2) Pd@Pt is preparednL/ C catalyst
It weighs products therefrom in 2mg step (1) and ultrasonic disperse is in 9mL dehydrated alcohol, 1mL hexamethylene, institute are added later
It obtains black dispersion liquid and is labeled as D；It weighs 18mg carbon black and is dispersed in the dehydrated alcohol of 5mL, gained black dispersion liquid is labeled as
Solution F is added in solution D by F, then ultrasound 2 hours.It is finally rinsed 2 times by products therefrom centrifugation, with dehydrated alcohol, institute
Product 80 DEG C of holding 12h in drying box are obtained, obtained black powder is carbon load Pd@Pt core@shell elctro-catalyst.
Raw material palladium presoma, platinum presoma, surfactant in above-described embodiment and reducing agent etc. is helped to select in material
Its quality can be suitably adjusted with reference to the proportion of above-described embodiment after fixed, such as in palladium presoma: platinum presoma: surface-active
Agent: help reducing agent=1: appropriate adjustment in the range of 2~3: 5~8: 16~17 is not limited only to the quality proportioning of above-described embodiment.
Different raw material mass mixture ratios, Pt shell thickness can change, but according to this within the scope of above-mentioned raw materials quality proportioning
The regulation method of invention is that by what shell thickness was precisely controlled.
1~5 data comparison can be seen that through the foregoing embodiment, Pd Pt of the inventionnLThe Pt of core@core-shell nanoparticles
The number of plies of shell thickness and Pt shell is proportional, and is the every increase about 0.7nm of Pt shell thickness, the number of plies of corresponding Pt shell
Increase by 3 layers, therefore can be realized monodisperse, the shell thickness controllable precise of Pd@Pt core@shell nanometer material, specific thickness control
Method processed is:
Thickness to the setting thickness that shell is controlled by regulating and controlling temperature processed is specifically: within the scope of certain raw material proportioning, instead
Answer temperature is every to increase by 10 DEG C, the Pt shell thickness increase about 0.7nm of Pd@Pt core@core-shell nanoparticles, corresponding Pt shell number increases
Add 3 layers.
Help reducing agent can be in phenol, benzoic acid, sodium benzoate, glucose, citric acid, lemon in above-described embodiment 1~5
One kind is arbitrarily selected in lemon acid sodium, ascorbic acid；Surfactant can polyvinylpyrrolidone, lauryl sodium sulfate,
One kind is arbitrarily selected in detergent alkylate sodium sulfonate；Reducing agent can be in dimethylformamide, dimethyl acetamide, dimethyl propylene
One kind is arbitrarily selected in amide.
The catalytic performance and stability of Pd@Pt core@shell nanometer material are further verified by following experiments, had
Body is as follows:
1, using low resolved transmittance Electronic Speculum (TEM) in Pd@Pt core@shell nanometer electrical catalyst obtained by Examples 1 to 5
The pattern of particle is observed, as a result as shown in (a)~(e) of Fig. 1.
Particle it can be seen from (a)~(e) of Fig. 1 in Pd@Pt core@shell nanometer electrical catalyst of the invention has height
Dispersibility and high uniformity.
2, the particle size of Pd@Pt core@shell nanometer electrical catalyst obtained by Examples 1 to 5 is measured, size
Distribution such as Fig. 2 (a)~(e).
The particle mean size in Pd@Pt core@shell nanometer electrical catalyst of the invention it can be seen from (a)~(e) of Fig. 2
Range is 15.1 ± 2.1nm~21.9 ± 3.4nm.
3, the relationship that reaction temperature Yu the Pt single layer number of plies are determined by controlling experimental method, as shown in Figure 3 and Figure 4, in Fig. 3
(a)~(e) is Pd@Pt obtained by Examples 1 to 5nLThe X-ray energy dispersive line of particle is swept in core@shell nanometer electrical catalyst
(EDS-lines) it composes；(f)~(j) is Pd@Pt obtained by Examples 1 to 5 in Fig. 3nLIn core@shell nanometer electrical catalyst
Grain selectivity removes the TEM figure of products therefrom after Pd core.
It can also be seen that the Pt shell of particle in Pd@Pt core@shell nanometer electrical catalyst from (a) in Fig. 3~(e) comparison
Thickness increases with the raising of reaction temperature；In conjunction with (f) in Fig. 3~(j) it is found that Pd@Pt core@shell nanometer electricity of the invention is urged
The shell average-size distribution of particle is 0.78 ± 0.24nm~3.20 ± 0.96nm, corresponding Pt number of monolayers in agent
Range is 3.4 ± 1.0~13.9 ± 4.2.
Fig. 4 urges for the Pt shell nanostructure in foundation Fig. 3 (f)~(j) through counting obtained Pd Pt core shell nanometer electricity
The Pt single layer number of plies of particle and the relational graph of reaction temperature in agent, it can be seen that in Pd@Pt core@shell nanometer electrical catalyst
The shell thickness of grain is accurately controlled by reaction temperature；When reaction temperature successively increases 10 DEG C, active component Pd@PtnLCore@shell
Nano particle Pt shell thickness successively increases about 0.7nm, and corresponding Pt shell number successively increases about 3 single layers.
4, Pd@Pt core@shell nanometer electrical catalyst (Pd@Pt obtained by the embodiment of the present invention 1~5nL/ C) and business Pt/
C catalyst is catalyzed ORR stability test histogram.
Test condition: for O2The 0.1M HClO of saturation4Solution, scanning voltage range are 0.05~1.1V vs.RHE (opposite
In reversible hydrogen electrode), sweeping speed is 10mV/s, revolving speed 1600r/min.
As seen from Figure 5, compared with business Pt/C elctro-catalyst, Pd@PtnL/ C (n=3.4,5.3,8.2,11.0,
13.9) catalyst shows very superior catalytic activity and stability.At 0.9V vs.RHE (relative to reversible hydrogen electrode)
Place, Pd@PtnL/ C (n=3.4) catalyst redox reactions (ORR) mass activity (MA) be it is highest, reach 0.95A/
mgPt, it is business Pt/C catalyst (0.18A/mgPt) 5.3 times.Pd@PtnL/ C (n=11.0) catalyst oxygen reduction is anti-
Answer (ORR) area specific activity (SA) be it is highest, reach 1.77mA/cm2, it is business Pt/C catalyst (0.29mA/cm2) 6.1
Times.After 8000 cyclic voltammetry scans, Pd@PtnL/ C (n=3.4,5.3,8.2,11.0,13.9) catalyst is compared with business Pt/
C catalyst shows extraordinary stability.
Claims (2)
1. a kind of one-pot synthesis method of the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise, the Pd@
Pt core@shell nanometer material be using Pd as core, Pt be constructed by shell at Pd@PtnLCore@core-shell nanoparticles, n are shell number,
It is characterized in that: by acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate, surfactant and helping reducing agent to be added in reducing agent to be mixed
Liquid, wherein helping reducing agent is phenol or benzoic acid or sodium benzoate or glucose or citric acid or sodium citrate；Reducing agent is two
Methylformamide or dimethyl acetamide or dimethylpropionamide；Disperse above-mentioned mixed liquor, solution is added to polytetrafluoro later
In ethylene stainless steel cauldron, normal drying case is put it into, controls the thickness of shell to setting thickness by regulating and controlling temperature processed,
Within the scope of 140 DEG C~180 DEG C, reaction temperature is every to increase by 10 DEG C, and the Pt shell thickness of Pd@Pt core@core-shell nanoparticles increases
0.7nm, corresponding Pt shell number increase by 3 layers；To the end of reacting, cooled to room temperature, products therefrom dehydrated alcohol from
The heart, rinsing, drying obtain the Pd@Pt core@shell nanometer material of monodisperse, shell thickness controllable precise.
2. the one kettle way of the Pd@Pt core@shell nanometer material of monodisperse according to claim 1, shell thickness controllable precise
Synthetic method, it is characterised in that: the surfactant is polyvinylpyrrolidone or lauryl sodium sulfate or dodecyl
Benzene sodium sulfonate.
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| CN102196863A (en) * | 2008-10-30 | 2011-09-21 | 索尼公司 | Platinum-containing catalyst, process for producing the platinum-containing catalyst, electrode, and electrochemical device |
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| Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction;Shuifen Xie et al.;《Nano Lett.》;20140505;第14卷;第3570-3576页 |
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