CN108817416A - A kind of preparation method and application of Pt nanoparticle - Google Patents
A kind of preparation method and application of Pt nanoparticle Download PDFInfo
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- CN108817416A CN108817416A CN201810738995.XA CN201810738995A CN108817416A CN 108817416 A CN108817416 A CN 108817416A CN 201810738995 A CN201810738995 A CN 201810738995A CN 108817416 A CN108817416 A CN 108817416A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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 invention discloses a kind of Pt nanoparticle preparation methods, utilize water to the reducing power of enhancing ethylene glycol, platinum salt can be restored at room temperature, and Pt nanoparticle is made, and the reducing power of ethylene glycol can be regulated and controled by adjusting the volume ratio of water and ethylene glycol, to achieve the purpose that control the pattern and partial size of nanoparticle.The method of the present invention simple process, reaction condition is mild, easily-controllable, is a kind of easy, efficient, low energy consumption Pt nanoparticle preparation method, and prepared Pt nanoparticle can be widely applied to the numerous areas including fuel-cell catalyst.
Description
Technical field
The present invention relates to a kind of simple preparation methods of Pt nanoparticle.
Background technique
Pt nanoparticle refers to that partial size is less than the Pt metal particle of 100nm, due to nanometer size effect, they have with it is non-
The very different property of nanoparticle, catalyst, electromagnetic functional material, photoelectric functional material, in terms of
Tool has been widely used.The preparation method of metal nanoparticle includes vapor phase method, solid phase method and liquid phase method.Vapor phase method is usually will
Pt raw metal heating evaporation, which then condenses, obtains metal nanoparticle, and this method needs complex device, and production cost is higher.And
Solid phase method is difficult to prepare 10nm or less Pt nanoparticle, and the purity of product is not high, and distribution of particles is also uneven.Liquid phase method is
Under reducing agent and external energy (sound, light, electricity, heat etc.) effect, Pt precursor is reduced to simple substance Pt.In contrast, liquid phase
Method can carry out substance assembly and control on atomic level, and the partial size and shape of Pt can be regulated and controled by the control of reaction condition
Looks have many advantages, such as versatility, operability and relatively easy, thus obtain extensive research.
Currently, restoring the common reducing agent of Pt salt in liquid phase method has sodium borohydride, hydrazine hydrate, ascorbic acid, formic acid, lemon
Acid, formaldehyde and ethylene glycol etc..Wherein strong reductant (such as sodium borohydride, hydrazine hydrate) can restore Pt salt system under cryogenic
Pt nanoparticle, but when this weak reductant of spent glycol, it usually needs Pt salt system can be restored by being heated to 120 DEG C or more
Obtain Pt nanoparticle.For example, a kind of preparation method that platinum is supported with carbon nanotube is described in Chinese patent CN102476062A,
Wherein the preparation process of Pt nano-sized colloidal solution is：In ethylene glycol solution, soluble platinum compounds is added after mixing, adjusts
Section solution ph is 10-14, is kept under conditions of solution is then heated to 120-190 DEG C under air or inert gas shielding
30 minutes -10 hours restored platinum completely.For another example, a kind of Pt-CrN/ is described in Chinese patent CN105070925A
The CrN/ of certain mass is added it is mentioned that platinum salt is dissolved in solvent ethylene glycol in the preparation and application of graphene complex
Graphene complex, ultrasound, stirring make it be uniformly dispersed, then in 120~160 DEG C of 1~3h of reaction, obtain Pt-CrN/ graphite
Alkene complex.For another example, a kind of preparation method of LiFePO 4 Supported Pt Nanoparticles is described in Chinese patent CN107195913A, is made
Standby process is as follows：Compound concentration is the platinum acid chloride solution of 10g/L, under an inert atmosphere, by platinum acid chloride solution and bowknot shape
LiFePO 4, being dissolved in and adjusting solution with 0.1mol/L NaOH is in the ethylene glycol of pH=10, and wherein the dosage of ethylene glycol is
5-10 times of chloroplatinic acid, flow back 3-5h in 120-140 DEG C of oil bath, and LiFePO 4 Supported Pt Nanoparticles composite material can be obtained.This
Outside, a kind of solid supported noble metal catalyst and preparation method thereof is disclosed in Chinese patent CN1425499A, using ethylene glycol and
The mixed system of water heats reduction precious metal salt under certain temperature (60-250 DEG C) and obtains noble metal catalyst, but before reacting
After to adjust PH, step is various.
Reduction of ethylene glycol Pt salt utilized above is prepared in the method for Pt nanoparticle, at least requires heat to 60 DEG C or more,
Energy consumption is high, and some reactions will also adjust PH, and step is more various.The present invention is using a kind of simple and easy ethylene glycol room temperature reduction
Method dexterously uses water as promotor, greatly strengthens the reducing power of ethylene glycol.The method can be restored in room temperature condition
Divalent platinum salt obtains Pt nanoparticle, and can regulate and control also proper energy by simply adjusting the volume ratio of water and ethylene glycol
Power achievees the purpose that control Pt nanoparticle pattern and partial size.The method of the present invention is simple and effective, and low energy consumption, is a kind of easy, high
The preparation method of the Pt nanoparticle of effect.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of easy, efficient Pt nanoparticle, which is utilized water to
The reducing power for enhancing ethylene glycol may be implemented to restore the obtained Pt nanoparticle of platinum salt under room temperature；And it can be by adjusting water
Regulate and control the reducing power of ethylene glycol, with the volume ratio of ethylene glycol to achieve the purpose that control Pt nanoparticle pattern and partial size.
Specific the object of the invention is achieved through the following technical solutions：, the one side present invention provides a kind of Pt nanoparticle preparation method, wraps
Include following steps：
(1) platinum salt is mixed with solvent X, obtains mixture A
(2) mixture A is reacted to a period of time at 10~40 DEG C, mixture B is obtained and (it is molten to be viewed as nanoparticle in experiment
Colloidal state)；
(3) solvent Y, centrifuge separation is added, washing, drying obtain Pt nanoparticle；
In step (1),
The solvent X is made of water and ethylene glycol, with volume basis, water:Ethylene glycol=1:9~19:1；
Concentration of the platinum salt in solvent X is 0.00005mol/L~0.025mol/L；
The platinum salt is water soluble sulfate, nitrate, halide, complex compound, halogen acids or the halogen acid salt of divalent Pt
Any one of；
In step (3),
The solvent Y is ethyl alcohol and/or water.
Described reaction a period of time is preferably 0.1~12.0h.
On the other hand, the present invention also provides Pt nanoparticles made from above-mentioned preparation method.
For loaded Pt nanoparticle can be prepared convenient for application；Method is first to disperse carrier in dehydrated alcohol
It is even, suspension is formed, concentration of the carrier in suspension is 1~5mg/mL；Then the suspension is added to the step
(2) mixture B is obtained, i.e., in nanoparticle sol, stirring at least 2h then divides so that Pt nanoparticle deposits on carrier
From, washing, dry.
Preferably, the carrier is conductive carbon material, ceramic material or polymer material, and Pt accounts for carrier and Pt gross mass
Ratio be 1~90%.
In another aspect, the present invention also provides loaded Pt nanoparticles made from above-mentioned preparation method.
The present invention also provides the applications of above-mentioned Pt nanoparticle or above-mentioned loaded Pt nanoparticle, are catalyzed as hydrogen reduction
Agent is used for fuel cell.
The novelty of the present invention is utilizing water to the reducing power of enhancing ethylene glycol for the first time, platinum can be restored at room temperature
Pt nanoparticle is made in salt.Preparation method simple process of the present invention, reaction condition is mildly easily-controllable, is a kind of succinct, low energy
The method of the synthesis Pt nanoparticle of consumption.
Detailed description of the invention
Attached drawing provides a further understanding of the present invention, and constitutes part of specification, with following specific implementation
Mode is used to explain the present invention together, but is not construed as limiting the invention.
(a), (b) and (c) are by transmission of the Pt nanoparticle under different amplification obtained by embodiment 1 in Fig. 1
Electron microscopic picture.
(a), (b) and (c) are by transmission of the Pt nanoparticle under different amplification obtained by embodiment 9 in Fig. 2
Electron microscopic picture.
(a), (b) and (c) are by transmission of the Pt nanoparticle under different amplification obtained by embodiment 10 in Fig. 3
Electron microscopic picture.
(a), (b) and (c) are by transmission of the Pt nanoparticle under different amplification obtained by embodiment 16 in Fig. 4
Electron microscopic picture.
Fig. 5 is by Pt nanoparticle obtained by embodiment 1 as hydrogen reduction (ORR) catalyst and commercial catalysts Pt
Black (HiSPEC 1000) is in O2The 0.1MHClO of saturation4ORR curve comparison figure in solution.Electro-chemical test condition is：It protects
Card catalyst load amount is identical, and linear scanning velocity 10mV/s, electric potential scanning range is 0.2~1.05V (vs.RHE), and forward direction is swept
It retouches, rotating disk electrode (r.d.e) revolving speed is 1600rpm.
Fig. 6 is to urge (ORR) agent and commercial catalysts as hydrogen reduction by Pt nanoparticle obtained by embodiment 10
Pt Black (JM) is in O2The 0.1MHClO of saturation4ORR curve comparison figure in solution.Electro-chemical test condition is：Guarantee catalysis
Agent load amount is identical, linear scanning velocity 10mV/s, and electric potential scanning range is 0.2~1.05V (vs.RHE), forward scan, rotation
Turning disk electrode revolving speed is 1600rpm.
Fig. 7 is by Pt nanoparticle obtained by embodiment 16 as hydrogen reduction (ORR) catalyst and commercial catalysts
Pt Black (JM) is in O2The 0.1MHClO of saturation4ORR curve comparison figure in solution.Electro-chemical test condition is：Guarantee catalysis
Agent load amount is identical, linear scanning velocity 10mV/s, and electric potential scanning range is 0.2~1.05V (vs.RHE), forward scan, rotation
Turning disk electrode revolving speed is 1600rpm.
Fig. 8 is by embodiment 10, embodiment 11, embodiment 12, embodiment 15, embodiment 16, embodiment 17 and embodiment
Pt nanoparticle obtained by 18 is as hydrogen reduction (ORR) catalyst in O2The 0.1MHClO of saturation4ORR curve pair in solution
Than figure.Electro-chemical test condition is：Guarantee catalyst load amount is identical, linear scanning velocity 10mV/s, and electric potential scanning range is
0.2~1.05V (vs.RHE), forward scan, rotating disk electrode (r.d.e) revolving speed are 1600rpm.
Fig. 9 is that Pt nanoparticle is supported by XC-72C obtained by embodiment 19 as hydrogen reduction (ORR) catalyst and quotient
Product catalyst Pt/C (JM) is in O2The 0.1MHClO of saturation4ORR curve comparison figure in solution.Electro-chemical test condition is：It protects
Card catalyst load amount is identical, and linear scanning velocity 10mV/s, electric potential scanning range is 0.2~1.05V (vs.RHE), and forward direction is swept
It retouches, rotating disk electrode (r.d.e) revolving speed is 1600rpm.
Specific embodiment
Comparative example 1
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol) is added in 10mL ethylene glycol (EG),
(2) 12.0h is stirred in cold bath (10 DEG C), stirring front and back color is unchanged, be it is light yellow, illustrate individual
K cannot be restored at EG10 DEG C2PtCl4。
Comparative example 2
(1) 0.01798g Na is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
Dissolve 0.5h.
(2) there is no blackening for reaction solution after being stirred to react 12.0h in room temperature (20 DEG C), therefore it is raw to have no Pt nanoparticle
At illustrating that individual EG can not restore K in room temperature2PtCl4。
Comparative example 3
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 2.5mL ethylene glycol (EG), stirs at room temperature
Dissolve 0.5h.
(2) there is no blackening for reaction solution after being stirred to react 12.0h in oil bath (30 DEG C), therefore it is raw to have no Pt nanoparticle
At illustrating individual EG at 30 DEG C or cannot restore K2PtCl4。
Comparative example 4
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 1.25mL ethylene glycol (EG), stirs at room temperature
Mix dissolution 0.5h.
(2) there is no blackening for reaction solution after being stirred to react 12.0h in oil bath (40 DEG C), therefore it is raw to have no Pt nanoparticle
At illustrating that individual EG cannot still restore K at 40 DEG C2PtCl4。
Embodiment 1
(1) 0.00415g K is accurately weighed2PtCl4(0.001mmol) is added in 10mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 10mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 0.5h at room temperature.?
To the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
It will be seen from figure 1 that Pt nanoparticle is made of mono-dispersed nano flower (10-15nm) under stirring condition, individually
Pt particle of the nano flower then by 7-10 diameter in 2-3nm forms.
As seen from Figure 5：Pt nanoparticle obtained has ORR activity more preferably than Pt Black, at the 0.9V before
The quality specific activity of person is 1.7 times of the latter.
Embodiment 2
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
1.0h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 1.0h at room temperature.It obtains
The Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 3
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol) is added in 2.5mL ethylene glycol (EG), stirs at room temperature
1.5h。
(2) 2.5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 1.5h at room temperature.?
To the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 4
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol), is added to 1.25mL ethylene glycol (EG) and 1.25mL is gone
In the mixed liquor of ionized water, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 2.0h at room temperature.Obtain the Pt of brownish black
Nanoparticle sol.
(2) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 5
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol) is added in 0.5mL ethylene glycol (EG), stirs at room temperature
3.5h。
(2) 0.5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 3.5h at room temperature.?
To the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 6
(1) 0.00415g K is accurately weighed2PtCl4(0.01mmol) is added in 0.2mL ethylene glycol (EG), stirs at room temperature
6.0h。
(2) 0.25mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 6.0h at room temperature.
Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 7
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 3.0h at room temperature.It obtains
The Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 8
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL deionized water, stirs at room temperature
0.5h。
(2) 5mL ethylene glycol (EG) is added, so that H2The volume ratio of O and EG is 1:1, (20 DEG C) stirring 3.0h at room temperature.?
To the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 9
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, (17 DEG C) standing 0.5h at room temperature.It obtains
The Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
From figure 2 it can be seen that diameter forms petal number less (2-4) in the Pt particle of 2-3nm under static conditions
Nano flower, and dendritic structure is interconnected between nano flower.
Embodiment 10
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 5:5, ultrasonic reaction 0.5h, water at the end of reaction
Temperature is 26 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
From figure 3, it can be seen that nano flower and dendritic structure are entirely destroyed under ultrasound condition, small Pt nanometer
Grain tends to be gathered into the bigger particle of partial size (2-5nm).
As seen from Figure 6：Pt nanoparticle obtained has ORR activity more preferably than Pt Black, at 0.9V
Quality specific activity is 1.7 times of the latter.
Embodiment 11
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 0.5mL ethylene glycol (EG), stirs at room temperature
1.0h。
(2) 9.5mL deionized water is added, so that H2The volume ratio of O and EG is 19:1, ultrasonic reaction 1.0h, reaction terminates
Shi Shuiwen is 33 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 12
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 2mL ethylene glycol (EG), stirs at room temperature
1.0h。
(2) 8mL deionized water is added, so that H2The volume ratio of O and EG is 8:2, ultrasonic reaction 1.0h, water at the end of reaction
Temperature is 33 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 13
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 3mL ethylene glycol (EG), stirs at room temperature
1.0h。
(2) 7mL deionized water is added, so that H2The volume ratio of O and EG is 7:3, ultrasonic reaction 0.5h, water at the end of reaction
Temperature is 26 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 14
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, cold bath (10 DEG C) is middle to stir 12.0h.
Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, obtained Pt nanometer
Particle.
Embodiment 15
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 6mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 4mL deionized water is added, so that H2The volume ratio of O and EG is 4:6, ultrasonic reaction 0.5h, water at the end of reaction
Temperature is 26 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 16
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 7mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 3mL deionized water is added, so that H2The volume ratio of O and EG is 3:7, ultrasonic reaction 1.5h, water at the end of reaction
Temperature is 37 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Figure 4, it is seen that Pt nanoparticle is by the monodispersed diameter of height in 1- when the content of ethylene glycol is higher
The Minimal P t particle of 3nm forms, and illustrates that ethylene glycol is more advantageous to the dispersion of Pt nanoparticle.
As seen from Figure 7：Pt nanoparticle obtained has ORR activity more preferably than Pt Black, at the 0.9V before
The quality specific activity of person is 2.9 times of the latter.
As seen from Figure 8：When the volume fraction of EG is increased to 70% by 5%, by embodiment 11,12,10,15 and 16
The ORR of obtained Pt nanoparticle active (quality specific activity is followed successively by 33,36,69,75 and 123mA/mg at 0.9V) is with EG
Volume fraction increases and increases；When the volume fraction of EG further rises to 90% by 70%, by 16,17 and 18 institute of embodiment
The ORR of Pt nanoparticle obtained active (quality specific activity is followed successively by 123,71 and 42mA/mg at 0.9V) is then with EG volume point
Number increases and reduces, and illustrates H2The preferred volume ratio of O and EG is 8:2 to 3:Between 7.
Embodiment 17
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 8mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 2mL deionized water is added, so that H2The volume ratio of O and EG is 2:8, ultrasonic reaction 1.5h, water at the end of reaction
Temperature is 37 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 18
(1) 0.01798g Na is accurately weighed2PtCl4(0.05mmol) is added in 9mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 1mL deionized water is added, so that H2The volume ratio of O and EG is 1:9,0.5h is stirred to react in oil bath (40 DEG C).
Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
Embodiment 19
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h。
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1,0.1h is stirred to react in oil bath (40 DEG C).
Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 4 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
As seen from Figure 9：Carbon obtained, which carries Pt nanoparticle, has ORR activity more preferably than Pt/C (JM), in 0.9V
The quality specific activity for locating the former is 1.6 times of the latter.
Embodiment 20
(1) 0.02076g K is accurately weighed2PtCl4(0.05mmol) is added in 5mL ethylene glycol (EG), stirs at room temperature
0.5h；0.01463g XC-72 carbon dust is added, moves into ultrasonic disperse 1.0h in ultrasonic pond.
(2) 5mL deionized water is added, so that H2The volume ratio of O and EG is 1:1, ultrasonic reaction 0.5h, water at the end of reaction
Temperature is 35 DEG C.Obtain the Pt nanoparticle sol of brownish black.
(3) plus ethyl alcohol is centrifugated, and is then washed 5 times with the mixed solution of deionized water and ethyl alcohol, is obtained Pt nanoparticle
Son.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of Pt nanoparticle, it is characterised in that：
Include the following steps：
(1) platinum salt is mixed with solvent X, obtains mixture A
(2) mixture A is reacted to a period of time at 10~40 DEG C, obtains mixture B；
(3) solvent Y, centrifuge separation is added, washing, drying obtain Pt nanoparticle；
In step (1),
The solvent X is made of water and ethylene glycol, with volume basis, water:Ethylene glycol=1:9~19:1；
Concentration of the platinum salt in solvent X is 0.00005mol/L~0.025mol/L；
The platinum salt is in water soluble sulfate, nitrate, halide, complex compound, halogen acids or the halogen acid salt of divalent Pt
It is any；
In step (3), the solvent Y is water or is water and ethyl alcohol.
2. Pt nanoparticle preparation method according to claim 1, which is characterized in that described reaction a period of time is 0.1
~12.0h.
3. Pt nanoparticle made from preparation method as claimed in claim 1 or 2.
4. Pt nanoparticle according to claim 3, which is characterized in that Pt nanoparticle forms nanometer flower structure.
5. Pt nanoparticle according to claim 3, which is characterized in that the diameter of Pt nanoparticle is 1-5nm.
6. Pt nanoparticle according to claim 3, which is characterized in that the diameter of Pt nanoparticle is 1-3nm.
7. the preparation method of loaded Pt nanoparticle, it is characterised in that：Carrier is uniformly dispersed in dehydrated alcohol first, is formed
Suspension, concentration of the carrier in suspension are 1~5mg/mL；Then the suspension is added to step described in claim 1
Suddenly (2) obtain in mixture B, stir at least 2h, so that Pt nanoparticle deposits on carrier, then separate, wash, is dry.
8. preparation method according to claim 3, it is characterised in that：The carrier is conductive carbon material, ceramic material
Or polymer material, it is 1~90% that Pt, which accounts for carrier and the ratio of Pt gross mass,.
9. loaded Pt nanoparticle made from preparation method described in claim 4.
10. Pt nanoparticle as claimed in claim 3 or loaded Pt nanoparticle as claimed in claim 6 are urged as hydrogen reduction
Agent is used for fuel cell.
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