CN108817416B - Preparation method and application of Pt nanoparticles - Google Patents
Preparation method and application of Pt nanoparticles Download PDFInfo
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- CN108817416B CN108817416B CN201810738995.XA CN201810738995A CN108817416B CN 108817416 B CN108817416 B CN 108817416B CN 201810738995 A CN201810738995 A CN 201810738995A CN 108817416 B CN108817416 B CN 108817416B
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- B22—CASTING; POWDER METALLURGY
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- 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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- 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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- 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 preparation method of Pt nanoparticles, which utilizes water to enhance the reducing capability of glycol, can reduce platinum salt at room temperature to prepare the Pt nanoparticles, and can regulate the reducing capability of glycol by regulating the volume ratio of water to glycol so as to achieve the purpose of controlling the morphology and the particle size of the nanoparticles. The method has simple process, mild and easily-controlled reaction conditions, is a simple, convenient, high-efficiency and low-energy-consumption Pt nano particle preparation method, and the prepared Pt nano particles can be widely applied to various fields including fuel cell catalysts.
Description
Technical Field
The invention relates to a simple preparation method of Pt nano particles.
Background
The Pt nanoparticles refer to metal Pt particles with the particle size of less than 100nm, and due to the nanometer size effect, the Pt nanoparticles have properties which are very different from those of non-nanoparticles, and have wide application in the aspects of catalysts, electromagnetic functional materials, photoelectric functional materials, biomedical materials and the like. The preparation method of the metal nano-particles comprises a gas phase method, a solid phase method and a liquid phase method. The vapor phase method is generally to heat and evaporate a Pt metal raw material and then condense the Pt metal raw material to obtain metal nano particles, and the method needs complicated equipment and has higher production cost. The solid phase method is difficult to prepare Pt nano particles with the particle size of less than 10nm, and the purity of the product is not high and the particle distribution is not uniform. The liquid phase method is to reduce a Pt precursor into simple substance Pt under the action of a reducing agent and external energy (sound, light, electricity, heat and the like). In contrast, the liquid phase method can carry out material assembly and control at an atomic level, can regulate and control the particle size and morphology of Pt by controlling reaction conditions, and has the advantages of universality, operability, relative simplicity and the like, thereby obtaining extensive research.
At present, sodium borohydride, hydrazine hydrate, ascorbic acid, formic acid, citric acid, formaldehyde, ethylene glycol and the like are common reducing agents for reducing Pt salt in a liquid phase method. Wherein, strong reducing agent (such as sodium borohydride, hydrazine hydrate, etc.) can reduce Pt salt to prepare Pt nano particles under low temperature, but when ethylene glycol is used as the weak reducing agent, the Pt salt can be reduced to prepare Pt nano particles by heating to above 120 ℃. For example, chinese patent CN102476062A describes a method for preparing platinum supported on carbon nanotubes, wherein the preparation process of the Pt nano colloidal solution is as follows: adding soluble platinum compound into ethylene glycol solution, mixing uniformly, adjusting the pH value of the solution to 10-14, heating the solution to 120-190 ℃ under the protection of air or inert gas, keeping the temperature for 30 minutes to 10 hours, and completely reducing platinum. For another example, chinese patent CN105070925A describes preparation and application of a Pt-CrN/graphene complex, wherein platinum salt is dissolved in a solvent ethylene glycol, a certain mass of the CrN/graphene complex is added, the mixture is dispersed uniformly by ultrasonic stirring, and then the mixture is reacted at 120-160 ℃ for 1-3 hours to obtain the Pt-CrN/graphene complex. For another example, chinese patent CN107195913A describes a method for preparing lithium iron phosphate supported platinum, which comprises the following steps: preparing a chloroplatinic acid solution with the concentration of 10g/L, dissolving the chloroplatinic acid solution and the lithium iron phosphate in a bow tie shape in ethylene glycol with the pH value of 10 regulated by 0.1mol/L NaOH, wherein the dosage of the ethylene glycol is 5-10 times of that of the chloroplatinic acid, and refluxing for 3-5h in an oil bath at the temperature of 120-140 ℃ to obtain the lithium iron phosphate loaded platinum composite material. In addition, chinese patent CN1425499A discloses a supported noble metal catalyst and a preparation method thereof, wherein a mixed system of ethylene glycol and water is used to heat and reduce noble metal salt at a certain temperature (60-250 ℃) to obtain the noble metal catalyst, but the PH is adjusted before and after the reaction, and the steps are various.
In the method for preparing the Pt nanoparticles by reducing the Pt salt by using the ethylene glycol, the temperature is at least required to be heated to more than 60 ℃, the energy consumption is high, the PH is required to be adjusted in some reactions, and the steps are relatively various. The invention adopts a simple and feasible glycol room temperature reduction method, skillfully uses water as an accelerant, and greatly enhances the reduction capability of glycol. The method can reduce divalent platinum salt at room temperature to obtain Pt nanoparticles, and can adjust and control the reduction capacity by simply adjusting the volume ratio of water to ethylene glycol, thereby achieving the purpose of controlling the morphology and particle size of the Pt nanoparticles. The method is simple and effective, has low energy consumption, and is a simple, convenient and efficient preparation method of the Pt nano particles.
Disclosure of Invention
The invention aims to provide a simple and efficient preparation method of Pt nanoparticles, which utilizes water to enhance the reducing capability of ethylene glycol and can realize the reduction of platinum salt at room temperature to prepare the Pt nanoparticles; the reducing capacity of the glycol can be regulated and controlled by regulating the volume ratio of the water to the glycol, so as to achieve the purpose of controlling the morphology and the particle size of the Pt nano particles. The purpose of the invention is realized by the following technical scheme: in one aspect, the present invention provides a method for preparing Pt nanoparticles, comprising the steps of:
(1) mixing platinum salt with solvent X to obtain mixture A
(2) Reacting the mixture A at 10-40 ℃ for a period of time to obtain a mixture B (observed as a nanoparticle sol state in an experiment);
(3) adding a solvent Y, centrifugally separating, washing and drying to obtain Pt nano particles;
in the step (1), the step (c),
the solvent X consists of water and ethylene glycol, and the volume ratio of the water to the ethylene glycol is 1: 9-19: 1;
the concentration of the platinum salt in the solvent X is 0.00005 mol/L-0.025 mol/L;
the platinum salt is any one of water-soluble sulfate, nitrate, halide, complex, hydrohalic acid or hydrohalic acid salt of divalent Pt;
in the step (3), the step (c),
the solvent Y is ethanol and/or water.
The reaction time is preferably 0.1-12.0 h.
On the other hand, the invention also provides the Pt nano-particles prepared by the preparation method.
For convenient application, supported Pt nanoparticles can be prepared; firstly, uniformly dispersing a carrier in absolute ethyl alcohol to form a suspension, wherein the concentration of the carrier in the suspension is 1-5 mg/mL; and (3) adding the suspension into the mixture B obtained in the step (2), namely the nanoparticle sol, stirring for at least 2 hours to deposit the Pt nanoparticles on the carrier, and then separating, washing and drying.
Preferably, the carrier is a conductive carbon material, a ceramic material or a polymer material, and the proportion of Pt in the total mass of the carrier and Pt is 1-90%.
In another aspect, the invention further provides the supported Pt nano-particles prepared by the preparation method.
The present invention also provides an application of the above Pt nanoparticles or the above supported Pt nanoparticles as an oxygen reduction catalyst for a fuel cell.
The invention is innovative in that water is used for the first time to enhance the reducing capability of ethylene glycol, and platinum salt can be reduced at room temperature to prepare Pt nanoparticles. The preparation method disclosed by the invention is simple in process, mild and easily controllable in reaction conditions, and is a simple and low-energy-consumption method for synthesizing the Pt nano particles.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In FIG. 1, (a), (b) and (c) are TEM pictures of Pt nanoparticles prepared according to example 1 at different magnifications.
In FIG. 2, (a), (b) and (c) are TEM pictures of Pt nanoparticles prepared according to example 9 at different magnifications.
In FIG. 3, (a), (b) and (c) are TEM pictures of Pt nanoparticles prepared in example 10 at different magnifications.
In FIG. 4, (a), (b) and (c) are TEM pictures of Pt nanoparticles prepared in example 16 at different magnifications.
FIG. 5 shows Pt nanoparticles prepared in example 1 as oxygen reduction (ORR) catalyst and commercial catalystPtblack (HiSPEC 1000) in O2Saturated 0.1MHClO4ORR curves in solution are compared. The electrochemical test conditions were: ensuring that the catalyst loading is the same, the linear scanning speed is 10mV/s, the potential scanning range is 0.2-1.05V (vs. RHE), the forward scanning is carried out, and the rotating speed of the rotating disc electrode is 1600 rpm.
FIG. 6 shows Pt nanoparticles prepared in example 10 as oxygen reduction catalyst (ORR) and commercial catalyst Pt Black (JM) at O2Saturated 0.1MHClO4ORR curves in solution are compared. The electrochemical test conditions were: ensuring that the catalyst loading is the same, the linear scanning speed is 10mV/s, the potential scanning range is 0.2-1.05V (vs. RHE), the forward scanning is carried out, and the rotating speed of the rotating disc electrode is 1600 rpm.
FIG. 7 shows Pt nanoparticles prepared in example 16 as oxygen reduction (ORR) catalyst and commercial catalyst Pt Black (JM) at O2Saturated 0.1MHClO4ORR curves in solution are compared. The electrochemical test conditions were: ensuring that the catalyst loading is the same, the linear scanning speed is 10mV/s, the potential scanning range is 0.2-1.05V (vs. RHE), the forward scanning is carried out, and the rotating speed of the rotating disc electrode is 1600 rpm.
FIG. 8 shows the oxygen reduction (ORR) ratio of Pt nanoparticles obtained in examples 10, 11, 12, 15, 16, 17 and 18 to O2Saturated 0.1MHClO4ORR curves in solution are compared. The electrochemical test conditions were: ensuring that the catalyst loading is the same, the linear scanning speed is 10mV/s, the potential scanning range is 0.2-1.05V (vs. RHE), the forward scanning is carried out, and the rotating speed of the rotating disc electrode is 1600 rpm.
FIG. 9 shows the reaction of XC-72C Pt-loaded nanoparticles prepared in example 19 as oxygen reduction (ORR) catalyst and commercial catalyst Pt/C (JM) at O2Saturated 0.1MHClO4ORR curves in solution are compared. The electrochemical test conditions were: ensuring that the catalyst loading is the same, the linear scanning speed is 10mV/s, the potential scanning range is 0.2-1.05V (vs. RHE), the forward scanning is carried out, and the rotating speed of the rotating disc electrode is 1600 rpm.
Detailed Description
Comparative example 1
(1) Accurately weighing 0.00415g K2PtCl4(0.01mmol), added to 10mL of Ethylene Glycol (EG),
(2) stirring in cold water bath (10 ℃) for 12.0h, wherein the color is unchanged before and after stirring and is light yellow, which indicates that the K cannot be reduced at the temperature of EG10 ℃ alone2PtCl4。
Comparative example 2
(1) 0.01798g of Na are accurately weighed2PtCl4(0.05mmol) was added to 5mL of Ethylene Glycol (EG), and the mixture was dissolved at room temperature for 0.5h with stirring.
(2) After stirring and reacting at room temperature (20 ℃) for 12.0h, the reaction solution did not turn black, so no Pt nanoparticles were generated, indicating that EG alone could not reduce K at room temperature2PtCl4。
Comparative example 3
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 2.5mL of Ethylene Glycol (EG) was added, and the mixture was dissolved at room temperature for 0.5h with stirring.
(2) After stirring and reacting for 12.0h in an oil bath (30 ℃), the reaction solution did not turn black, so no Pt nanoparticles are generated, which indicates whether EG alone cannot reduce K at 30 DEG C2PtCl4。
Comparative example 4
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 1.25mL of Ethylene Glycol (EG) was added, and the mixture was dissolved at room temperature with stirring for 0.5 h.
(2) After stirring and reacting for 12.0h in an oil bath (40 ℃), the reaction solution does not turn black, so no Pt nano particles are generated, which shows that EG alone cannot reduce K at 40 DEG C2PtCl4。
Example 1
(1) Accurately weighing 0.00415g K2PtCl4(0.001mmol), 10mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 10mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 0.5h at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
As can be seen from FIG. 1, the Pt nanoparticles consist of monodisperse nanoflowers (10-15nm) under stirring, and the individual nanoflowers consist of 7-10 Pt particles with diameters of 2-3 nm.
As can be seen from fig. 5: the prepared Pt nanoparticles have better ORR activity than Pt Black, and the mass specific activity of the Pt nanoparticles is 1.7 times of that of Pt Black at 0.9V.
Example 2
(1) Accurately weighing 0.00415g K2PtCl4(0.01mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 1.0 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 1.0h at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 3
(1) Accurately weighing 0.00415g K2PtCl4(0.01mmol), 2.5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 1.5 hours.
(2) 2.5mL of deionized water was added to allow for H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 1.5h at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 4
(1) Accurately weighing 0.00415g K2PtCl4(0.01mmol) was added to a mixture of 1.25mL Ethylene Glycol (EG) and 1.25mL deionized water to allow H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 2.0h at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(2) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 5
(1) 0.00415g are accurately weighed K2PtCl4(0.01mmol), 0.5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 3.5 hours.
(2) 0.5mL of deionized water was added to allow for H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 3.5 hours at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 6
(1) Accurately weighing 0.00415g K2PtCl4(0.01mmol), 0.2mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 6.0 hours.
(2) 0.25mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the mixture is stirred for 6.0h at room temperature (20 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 7
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the mixture is stirred at room temperature (20 ℃) for 3.0 h. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 8
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol) was added to 5mL of deionized water and stirred at room temperature for 0.5 h.
(2) 5mL of Ethylene Glycol (EG) was added to make H2The volume ratio of O to EG is 1:1, and the mixture is stirred at room temperature (20 ℃) for 3.0 h. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 9
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the mixture is kept still for 0.5h at room temperature (17 ℃). Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
As can be seen from FIG. 2, Pt particles with a diameter of 2-3nm constitute nanoflowers with a smaller number of petals (2-4) under a standing condition, and the nanoflowers are mutually connected into a dendritic structure.
Example 10
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 5:5, ultrasonic reaction is carried out for 0.5h, and the water temperature is 26 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
As can be seen from fig. 3, the nanoflower and dendritic structures are completely destroyed under ultrasonic conditions, and the small Pt nanoparticles tend to aggregate into larger particle size particles (2-5 nm).
As can be seen from fig. 6: the prepared Pt nanoparticles have better ORR activity than Pt Black, and the specific mass activity at 0.9V is 1.7 times of that of the Pt Black.
Example 11
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 0.5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 1.0 h.
(2) 9.5mL of deionized water was added to allow for H2The volume ratio of O to EG is 19:1, ultrasonic reaction is carried out for 1.0h, and the water temperature is 33 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 12
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 2mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 1.0 h.
(2) 8mL of deionized water was added to allow H2The volume ratio of O to EG is 8:2, ultrasonic reaction is carried out for 1.0h, and the water temperature is 33 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 13
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 3mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 1.0 h.
(2) Add 7mL of deionized water to let H2The volume ratio of O to EG is 7:3, ultrasonic reaction is carried out for 0.5h, and the water temperature is 26 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 14
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG was 1:1, and the mixture was stirred in a cold water bath (10 ℃ C.) for 12.0 hours. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 15
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 6mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) Add 4mL of deionized water to let H2The volume ratio of O to EG is 4:6, ultrasonic reaction is carried out for 0.5h, and the water temperature is 26 ℃ when the reaction is finished. To obtainBrownish black Pt nanoparticle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 16
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 7mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 3mL of deionized water was added to allow H2The volume ratio of O to EG is 3:7, ultrasonic reaction is carried out for 1.5h, and the water temperature is 37 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
As can be seen from fig. 4, at higher ethylene glycol content, the Pt nanoparticles consist of highly monodisperse extremely small Pt particles with diameters of 1-3nm, indicating that ethylene glycol is more favorable for Pt nanoparticle dispersion.
As can be seen from fig. 7: the prepared Pt nanoparticles have better ORR activity than Pt Black, and the mass specific activity of the Pt nanoparticles is 2.9 times of that of Pt Black at 0.9V.
As can be seen from fig. 8: when the volume fraction of EG was increased from 5% to 70%, the ORR activities (mass specific activities at 0.9V of 33, 36, 69, 75 and 123mA/mg in this order) of Pt nanoparticles prepared in examples 11, 12, 10, 15 and 16 increased as the volume fraction of EG increased; when the volume fraction of EG was further increased from 70% to 90%, the ORR activities (mass specific activities at 0.9V of 123, 71 and 42mA/mg, respectively) of the Pt nanoparticles prepared in examples 16, 17 and 18 decreased as the volume fraction of EG increased, indicating that H2The preferred volume ratio of O to EG is between 8:2 and 3: 7.
Example 17
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 8mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 2mL of deionized water was added to allow H2The volume ratio of O to EG is 2:8, ultrasonic reaction is carried out for 1.5h, and the water temperature is 37 ℃ when the reaction is finished. Obtaining brown black Pt nano particlesAnd (3) sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 18
(1) 0.01798g of Na are accurately weighed2PtCl4(0.05mmol), 9mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 1mL of deionized water was added to allow H2The volume ratio of O to EG is 1:9, and the reaction is stirred in an oil bath (40 ℃) for 0.5 h. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
Example 19
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), 5mL of Ethylene Glycol (EG) was added, and the mixture was stirred at room temperature for 0.5 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, and the reaction is stirred in an oil bath (40 ℃) for 0.1 h. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 4 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
As can be seen from fig. 9: the prepared carbon-supported Pt nanoparticles have better ORR activity than Pt/C (JM), and the mass specific activity of the former is 1.6 times of that of the latter at 0.9V.
Example 20
(1) Accurately weighing 0.02076g K2PtCl4(0.05mmol), added to 5mL Ethylene Glycol (EG), stirred at room temperature for 0.5 h; 0.01463g of XC-72 carbon powder is added, and the mixture is transferred into an ultrasonic pool to be ultrasonically dispersed for 1.0 h.
(2) 5mL of deionized water was added to allow H2The volume ratio of O to EG is 1:1, ultrasonic reaction is carried out for 0.5h, and the water temperature is 35 ℃ when the reaction is finished. Obtaining brownish black Pt nano particle sol.
(3) Adding ethanol for centrifugal separation, and then washing for 5 times by using a mixed solution of deionized water and ethanol to obtain the Pt nano particles.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A preparation method of Pt nano particles is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a platinum salt with a solvent X to obtain a mixture A;
(2) reacting the mixture A at 10-40 ℃ for a period of time to obtain a mixture B;
(3) adding a solvent Y, centrifugally separating, washing and drying to obtain Pt nano particles;
in the step (1), the solvent X consists of water and ethylene glycol, and the volume ratio of the water to the ethylene glycol is 1: 9-19: 1; regulating the ratio of water to glycol to regulate the reducing capacity of glycol;
the concentration of the platinum salt in the solvent X is 0.00005 mol/L-0.025 mol/L;
the platinum salt is any one of water-soluble sulfate, nitrate, halide, complex, hydrohalic acid or hydrohalic acid salt of divalent Pt; in the step (3), the solvent Y is water or water and ethanol.
2. The method for preparing Pt nanoparticles according to claim 1, wherein the reaction time is 0.1-12.0 h.
3. The preparation method of the supported Pt nano particle is characterized by comprising the following steps:
(1) mixing a platinum salt with a solvent X to obtain a mixture A;
(2) reacting the mixture A at 10-40 ℃ for a period of time to obtain a mixture B;
(3) uniformly dispersing a carrier in absolute ethyl alcohol to form a suspension, wherein the concentration of the carrier in the suspension is 1-5 mg/mL;
(4) adding the suspension into the mixture B, stirring for at least 2h to deposit Pt nano particles on a carrier, and then separating, washing and drying;
in the step (1), the solvent X consists of water and ethylene glycol, and the volume ratio of the water to the ethylene glycol is 1: 9-19: 1; regulating the ratio of water to glycol to regulate the reducing capacity of glycol;
the concentration of the platinum salt in the solvent X is 0.00005 mol/L-0.025 mol/L;
the platinum salt is any one of water-soluble sulfate, nitrate, halide, complex, hydrohalic acid or hydrohalic acid salt of divalent Pt.
4. The production method according to claim 3, characterized in that: the carrier is a conductive carbon material, a ceramic material or a polymer material, and the Pt accounts for 1-90% of the total mass of the carrier and the Pt.
5. The method according to claim 3, wherein the reaction time is 0.1 to 12.0 hours.
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