CN106348247A - Synthesis method of ternary PtPdCu nano-crystal and application - Google Patents

Synthesis method of ternary PtPdCu nano-crystal and application Download PDF

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Publication number
CN106348247A
CN106348247A CN201610953895.XA CN201610953895A CN106348247A CN 106348247 A CN106348247 A CN 106348247A CN 201610953895 A CN201610953895 A CN 201610953895A CN 106348247 A CN106348247 A CN 106348247A
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ptpdcu
ternary
nanocrystal
ctac
room temperature
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袁强
兰剑
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Guizhou University
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Guizhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a synthesis method of a ternary PtPdCu nano-crystal. The synthesis method is characterized by comprising the following steps: (1) adding CTAC (Cetyltrimethyl Ammonium Chloride) and citric acid monohydrate into water and stirring at a room temperature for 5-8 minutes, wherein the mass ratio of CTAC to citric acid monohydrate ranges from (1 to 2) to (2 to 1) and the amount of the added water enables CTAC and a reducing agent to be completely dissolved; (2) adding precursor solutions of metal platinum salt, palladium salt and copper salt into a mixed solution in the step (1), and stirring at the room temperature for 3-5 minutes; (3) adding ascorbic acid into a mixed solution in the step (2) and stirring at the room temperature for 10-30 minutes, wherein the mass ratio of ascorbic acid to citric acid monohydrate ranges from (1 to 5) to (1 to 8); (4) transferring a mixed solution in the step (3) into a high-pressure reaction kettle and reacting for 2-12 hours, and controlling the temperature to be 150 DEG C-200 DEG C; and (5) after cooling a product in the step (4) and washing, and centrifuging and separating to obtain the ternary PtPdCu nano-crystal.

Description

A kind of synthetic method of ternary ptpdcu nanocrystal and application
Technical field
The present invention relates to a kind of synthetic method of ternary ptpdcu nanocrystal and the application in alcohol fuel battery.
Background technology
Metal pt, pd, cu have not at aspects such as oxidation of alcohols, nitrogen fixation, biomass fuel and liquid fuel batteries Commutable effect.The internal relation of structure and performance determines that the size of metal nanocrystal and morphology control are particularly significant.? Synthesize the synthetic method of poroid ternary ptpdcu nanocrystal in aqueous phase and morphology control technology does not also have case.And due to cu Addition form alloy and not only can strengthen the catalytic performance of catalyst, the cost of catalyst can also be greatly lowered.Therefore Controlledly synthesis ternary ptpdcu nanocrystal is significant.
Content of the invention
The technical problem to be solved in the present invention is: obtains a kind of poroid ternary ptpdcu nanocrystal.This kind of crystal knot Structure is novel, and pattern is unified, and has excellent catalytic performance in alcohol fuel battery.
The technical scheme is that a kind of synthetic method of ternary ptpdcu nanocrystal, comprise the steps: (1) Ctac is added to the water together with citric acid monohydrate, stirs 5～8 minutes under room temperature, ctac with the mass ratio of citric acid monohydrate is 1:2-2:1；Institute's amount of water needs to be completely dissolved ctac and reducing agent；(2) add in step (1) gained mixed solution Metal platinum salt, palladium salt, mantoquita precursor solution, the concentration of slaine presoma is 0.05～0.5mol/l；Under room temperature stirring 3～ 5 minutes；(3) add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 10 ~ 30 minutes, ascorbic acid and The mass ratio of water citric acid is 1:5 ~ 1:8；(4) it is transferred in autoclave to step (3) gained mixed solution and react 2～12 Hour, temperature control is at 150～200 DEG C；(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product three First ptpdcu nanocrystal.
Metal platinum salt precursor liquid solution described in described step (2) is chloroplatinic acid；Metal Palladium salt precursor liquid solution is Potassium chloropalladate；Copper salt precursor solution is copper chloride.
Described in described step (4), in autoclave, reaction temperature controls at 185-195 DEG C, and the response time is 4- 5 hours.
Described ternary ptpdcu nanocrystalline structure is to be made up of the little particle of sub- 5.0 nm, has pore space structure and table Face is rich in defect active sites.
Described ternary ptpdcu nanocrystal is in the application of alcohol fuel battery.
Described alcohol fuel battery is methanol, ethanol or ethylene glycol battery.
Beneficial effects of the present invention: the product morphology of synthesis of ternary ptpdcu nanocrystal can be controlled by the method.Should Plant crystal structure of alloy novelty (being made up of, there is pore space structure), high income the little particle of sub- 5.0 nm, catalytic performance is excellent, There is the possibility replacing the black catalyst of current business pt.
Brief description
Fig. 1 is ternary ptpdcu nanocrystal transmission electron microscope observation result figure；
Fig. 2 is ternary ptpdcu nanocrystal high-energy dispersive x-ray spectrogrph test result figure；
Fig. 3 is ternary ptpdcu Nanoalloy and business platinum black methanol oxidation performance comparison figure；
Fig. 4 is ternary ptpdcu Nanoalloy and business platinum black alcohol catalysis performance comparison figure；
Fig. 5 is ternary ptpdcu Nanoalloy and business platinum black ethylene glycol catalytic performance comparison diagram.
Specific embodiment
Embodiment 1:
A kind of synthetic method of ternary ptpdcu nanocrystal, its feature comprises the steps:
(1) ctac is added to the water together with citric acid monohydrate, stirs 5 minutes under room temperature, the quality of ctac and citric acid monohydrate Than for 1:2；Institute's amount of water needs to be completely dissolved ctac and reducing agent；
(2) metal platinum salt, palladium salt, mantoquita precursor solution are added in step (1) gained mixed solution, slaine presoma Concentration is 0.2mol/l；Stir 3～5 minutes under room temperature；
(3) add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 10 ~ 30 minutes, ascorbic acid and a water The mass ratio of citric acid is 1:6；
(4) it is transferred in autoclave to step (3) gained mixed solution and reacts 4 hours, temperature control is at 190 DEG C；
(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product a kind of ternary ptpdcu nanocrystal. Products therefrom cooling, centrifugation and spend ethanol carry out three times washing after distributed and saved in ethanol solution.
Embodiment 2:
A kind of synthetic method of ternary ptpdcu nanocrystal, its feature comprises the steps:
(1) ctac is added to the water together with citric acid monohydrate, stirs 7 minutes under room temperature, the quality of ctac and citric acid monohydrate Than for 2:1；Institute's amount of water needs to be completely dissolved ctac and reducing agent；
(2) metal platinum salt, palladium salt, mantoquita precursor solution are added in step (1) gained mixed solution, slaine presoma Concentration is 0.5mol/l；Stir 3～5 minutes under room temperature；
(3) add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 20 ~ 30 minutes, ascorbic acid and a water The mass ratio of citric acid is 1:5；
(4) it is transferred in autoclave to step (3) gained mixed solution and reacts 5 hours, temperature control is at 180 DEG C；
(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product a kind of ternary ptpdcu nanocrystal. Products therefrom cooling, centrifugation and spend ethanol carry out three times washing after distributed and saved in ethanol solution.
Embodiment 3:
A kind of synthetic method of ternary ptpdcu nanocrystal, its feature comprises the steps:
(1) ctac is added to the water together with citric acid monohydrate, stirs 8 minutes under room temperature, the quality of ctac and citric acid monohydrate Than for 1:2；Institute's amount of water needs to be completely dissolved ctac and reducing agent；
(2) metal platinum salt, palladium salt, mantoquita precursor solution are added in step (1) gained mixed solution, slaine presoma Concentration is 0.1mol/l；Stir 3～5 minutes under room temperature；
(3) add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 10 ~ 30 minutes, ascorbic acid and a water The mass ratio of citric acid is 1:8；
(4) it is transferred in autoclave to step (3) gained mixed solution and reacts 8 hours, temperature control is at 165 DEG C；
(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product a kind of ternary ptpdcu nanocrystal. Products therefrom cooling, centrifugation and spend ethanol carry out three times washing after distributed and saved in ethanol solution.
Embodiment 4:
A kind of synthetic method of ternary ptpdcu nanocrystal, its feature comprises the steps:
(1) ctac is added to the water together with citric acid monohydrate, stirs 5 minutes under room temperature, the quality of ctac and citric acid monohydrate Than for 1:1；Institute's amount of water needs to be completely dissolved ctac and reducing agent；
(2) metal platinum salt, palladium salt, mantoquita precursor solution are added in step (1) gained mixed solution, slaine presoma Concentration is 0.4mol/l；Stir 3～5 minutes under room temperature；
(3) add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 10 ~ 30 minutes, ascorbic acid and a water The mass ratio of citric acid is 1:6；
(4) it is transferred in autoclave to step (3) gained mixed solution and reacts 7 hours, temperature control is at 200 DEG C；
(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product a kind of ternary ptpdcu nanocrystal. Products therefrom cooling, centrifugation and spend ethanol carry out three times washing after distributed and saved in ethanol solution.
The ternary ptpdcu nanocrystal being obtained by said method, after 1000 circle tests, synthesized ptpdcu receives The activity of meter He Jin is black 2.4,1.8 and 3.0 times of business pt respectively to methanol, ethanol and ethylene glycol.
In addition, the ternary ptpdcu nanocrystal surface that the present invention is obtained is rich in defective bit (drawing from Fig. 1), and have Hole structure (see figure 1).

Claims (6)

1. a kind of synthetic method of ternary ptpdcu nanocrystal it is characterised in that: comprise the steps: (1) by ctac and Water citric acid is added to the water together, stirs 5～8 minutes under room temperature, and ctac is 1:2-2:1 with the mass ratio of citric acid monohydrate；Institute Amount of water needs to be completely dissolved ctac and reducing agent；(2) in step (1) gained mixed solution add metal platinum salt, Palladium salt, mantoquita precursor solution, the concentration of slaine presoma is 0.05～0.5mol/l；Stir 3～5 minutes under room temperature；(3) Add ascorbic acid in the mixed solution of step (2) gained, be stirred at room temperature 10 ~ 30 minutes, ascorbic acid and citric acid monohydrate Mass ratio be 1:5 ~ 1:8；(4) it is transferred in autoclave to step (3) gained mixed solution and react 2～12 hours, temperature Degree controls at 150～200 DEG C；(5) washed after the cooling of step (4) products therefrom, after centrifugation, obtained final product ternary Ptpdcu nanocrystal.
2. a kind of ternary ptpdcu nanocrystal according to claim 1 synthetic method it is characterised in that: step (2) Described in metal platinum salt precursor liquid solution be chloroplatinic acid；Metal Palladium salt precursor liquid solution is potassium chloropalladate；Copper salt forerunner Liquid solution is copper chloride.
3. a kind of ternary ptpdcu nanocrystal according to claim 1 synthetic method it is characterised in that: step (4) Described in autoclave reaction temperature control at 185-195 DEG C, the response time be 4-5 hour.
4. a kind of ternary ptpdcu nanocrystal according to claim 1 synthetic method it is characterised in that: described three First ptpdcu nanocrystalline structure is to be made up of the little particle of sub- 5.0 nm, has pore space structure and surface is rich in defect activity Position.
5. the ternary ptpdcu nanocrystal as described in one of claims 1-4 is in the application of alcohol fuel battery.
6. ternary ptpdcu nanocrystal according to claim 5 alcohol fuel battery application it is characterised in that: institute The alcohol fuel battery stated is methanol, ethanol or ethylene glycol battery.
CN201610953895.XA 2016-10-26 2016-10-26 Synthesis method of ternary PtPdCu nano-crystal and application Pending CN106348247A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107342424A (en) * 2017-06-14 2017-11-10 三峡大学 A kind of preparation method and application of fuel cell PtPdCu elctro-catalysts
CN107543924A (en) * 2017-09-06 2018-01-05 重庆医科大学 Biology sensor detection myeloperoxidase based on copper palladium platinum mesh nanometer material
CN109088079A (en) * 2018-08-06 2018-12-25 安徽师范大学 A kind of method of one-step synthesis platinum-palladium-copper ternary metal nano cubic frame material
CN109599571A (en) * 2017-09-30 2019-04-09 天津大学 Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof
CN110010914A (en) * 2019-04-08 2019-07-12 贵州大学 A kind of one-dimensional PtCuCo alloy nano chain catalyst and synthetic method suitable for methanol fuel cell under high temperature
CN110202127A (en) * 2019-06-17 2019-09-06 贵州大学 The synthetic method and application of sub-10 nano twin icosahedron PdCuPt Nanoalloy

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107342424A (en) * 2017-06-14 2017-11-10 三峡大学 A kind of preparation method and application of fuel cell PtPdCu elctro-catalysts
CN107342424B (en) * 2017-06-14 2019-12-13 三峡大学 Preparation method and application of PtPdCu electrocatalyst for fuel cell
CN107543924A (en) * 2017-09-06 2018-01-05 重庆医科大学 Biology sensor detection myeloperoxidase based on copper palladium platinum mesh nanometer material
CN109599571A (en) * 2017-09-30 2019-04-09 天津大学 Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof
CN109599571B (en) * 2017-09-30 2021-05-14 天津大学 Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof
CN109088079A (en) * 2018-08-06 2018-12-25 安徽师范大学 A kind of method of one-step synthesis platinum-palladium-copper ternary metal nano cubic frame material
CN110010914A (en) * 2019-04-08 2019-07-12 贵州大学 A kind of one-dimensional PtCuCo alloy nano chain catalyst and synthetic method suitable for methanol fuel cell under high temperature
CN110202127A (en) * 2019-06-17 2019-09-06 贵州大学 The synthetic method and application of sub-10 nano twin icosahedron PdCuPt Nanoalloy
CN110202127B (en) * 2019-06-17 2021-08-20 贵州大学 Synthesis method and application of sub-10 nanometer twin-crystal icosahedral PdCuPt nanometer alloy

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Application publication date: 20170125