CN107689456A - A kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, the preparation method of cobalt codope carbon material quantum dot - Google Patents
A kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, the preparation method of cobalt codope carbon material quantum dot Download PDFInfo
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- CN107689456A CN107689456A CN201710742505.9A CN201710742505A CN107689456A CN 107689456 A CN107689456 A CN 107689456A CN 201710742505 A CN201710742505 A CN 201710742505A CN 107689456 A CN107689456 A CN 107689456A
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- fuel cell
- nitrogen
- oxygen reduction
- phosphorus
- carbon material
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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
- H01M4/9041—Metals or alloys
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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
-
- 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
The invention discloses a kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, cobalt codope carbon material quantum dot preparation method, by melamine, pyrophosphoric acid and Co (CH3COO)4•H2O ultrasounds are transferred in hydrothermal reaction kettle after being sufficiently mixed, 20min is reacted in microwave reaction instrument under 1000W and 2.45GHz microwave condition, solid powder i.e. fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, the cobalt codope carbon material quantum dot that particle diameter is 5~6nm will be obtained after the freeze-dried processing of obtained product.The microwave preparation that the present invention uses need not add other additives, one-step synthesis target product, have the advantages of easy to operate and reaction efficiency is high.
Description
Technical field
The invention belongs to the preparing technical field of fuel-cell catalyst, and in particular to a kind of fuel cell oxygen reduction electricity is urged
Agent phosphorus, nitrogen, the preparation method of cobalt codope carbon material quantum dot.
Background technology
Fuel cell technology is a kind of advanced energy technology, and it has, and energy conversion efficiency is high, environment-friendly and energy
The advantages that density is high.But the oxygen reduction reaction of fuel battery negative pole is slow, Cathodic oxygen reduction is to influence fuel cell electricity to urge
An important factor for changing reaction speed.Therefore, oxygen reduction catalyst is one of focus of fuel cell Study of electrocatalysis.
At present, the catalyst of the oxygen reduction reaction of fuel cell substantially uses Pt sills, because being currently known
In metal material, electro catalytic activity highest of the metal platinum to oxygen reduction reaction.To improve reaction rate and conversion efficiency, often need
Substantial amounts of platinum is wanted to be catalyzed the oxygen reduction reaction of acceleration negative electrode.Due to using the cost of platinum too high, fuel cell is seriously constrained
Development.Non-precious metal catalyst cheap, that oxygen reduction catalytic activity is high is researched and developed to urge to substitute the platinum base of main flow
Agent is the only way of fuel cell development.
Doping carbon-supported catalysts have the characteristics that oxygen reduction catalytic activity is high, stability is good, and low with cost of material
It is honest and clean, the advantages that wide material sources.Therefore, doping carbon-supported catalysts very likely substitute platinum based catalyst, there is good application prospect.
But carbon-supported catalysts often have obvious decay by longtime running its performance.Therefore, nano-sized carbon how is further improved to urge
The longtime running stability of agent is one of emphasis of elctro-catalyst research.
It is many to influence the factor of carbon-supported catalysts activity, such as microscopic appearance and state, the reactant and production of catalyst surface
The mass transfer characteristic of thing in catalysis material etc..Wherein the microscopic appearance of catalyst and state and preparation method are closely related, use
Different preparation methods, the pattern state of catalyst are very different, so as to be produced a very large impact to catalyst activity.
Microwave process for synthesizing is a kind of method that target product preparation is realized by microwave heating, is a kind of novel, green
Efficient synthetic method, it can make presoma that carbonization occur, crack so as to reach the purpose quickly prepared rapidly in a short time.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, cobalt codope
The preparation method of carbon material quantum dot, carbon material quantum dot made from this method have good fuel cell oxygen reduction electro-catalysis
Activity.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of fuel cell oxygen reduction electrocatalyst
Phosphorus, nitrogen, the preparation method of cobalt codope carbon material quantum dot, it is characterised in that concretely comprise the following steps:By melamine, pyrophosphoric acid and
Co(CH3COO)4•H2O ultrasounds are transferred in hydrothermal reaction kettle after being sufficiently mixed, under 1000W and 2.45GHz microwave condition
20min is reacted in microwave reaction instrument, the solid powder that particle diameter is 5~6nm will be obtained after the freeze-dried processing of obtained product and is fired
Expect battery oxygen reduction electro-catalyst phosphorus, nitrogen, cobalt codope carbon material quantum dot.
Further preferably, the melamine, pyrophosphoric acid and Co (CH3COO)4•H2The O mass ratio that feeds intake is 1:1:10.
The present invention has the advantages that compared with prior art:
1st, the microwave preparation that the present invention uses need not add other additives, one-step synthesis target product, solve biography
The complicated technical problem of system method preparation process, has the advantages of easy to operate and reaction efficiency is high;
2nd, new fuel cell catalyst produced by the present invention is compared with the nanocarbon catalyst of only N doping, such catalyst
With higher activity, the catalysis material surface that is doped to of phosphorus atoms creates more positively charged sites, enhances to oxygen
Molecular Adsorption, the pi-electron enriched in carbon conjugated system is activated, phosphorus, nitrogen have played the good cooperative effect to carbon material together.
Brief description of the drawings
Fig. 1 is the oxygen reduction reaction polarization curve of catalyst in embodiment 1 and comparative example 1, comparative example 2.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
By 0.01g melamines, 0.01g pyrophosphoric acids and 0.1g Co (CH3COO)4•H2O ultrasounds are transferred to 100mL after being sufficiently mixed
Microwave reaction kettle in, react 20min in microwave reaction instrument under 1000W and 2.45GHz microwave condition, obtained product
Solid powder i.e. fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, cobalt codope carbon material quantum dot are obtained after freeze-dried processing.
Electro-chemical test uses Solartron 1287(Solartron Analytical, England)The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode:Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%(PFSA)Solution, ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result are as shown in Figure 1.
Comparative example 1
0.01g melamines and 0.05g mass concentrations are mixed for 37% formalin with 40mL deionized waters through ultrasonic disperse
Uniform wiring solution-forming;Obtained solution is transferred in autoclave and sealed, 6 h are reacted in 180 DEG C, reaction is natural after terminating
It is cooled to room temperature;By obtained product be washed with deionized until filtrate become colorless, put into vacuum drying chamber in 80 DEG C
Dry to constant weight, then in N22h is calcined in 800 DEG C obtain nitrogen-doped carbon material fuel cell catalyst under atmosphere.
Electro-chemical test uses Solartron 1287(Solartron Analytical, England)The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode:Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%(PFSA)Solution.Ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result are as shown in Figure 1.
Comparative example 2
Take 20% Pt/Xc-72 of JM companies of the business platinum catalyst U.S..
Electro-chemical test uses Solartron 1287(Solartron Analytical, England)The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode:Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%(PFSA)Solution, ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result are as shown in Figure 1.
Fuel-cell catalyst obtained by the present invention has good hydrogen reduction electro catalytic activity.The He of integrated embodiment 1
Comparative example 1-2, it can be seen that in electric performance test result, curve a is the polarization curve of catalyst prepared by embodiment 1 in Fig. 1,
B, c corresponds to comparative example 2, the polarization curve of catalyst prepared by comparative example 1 respectively, and compared with comparative example 1-2, prepared by embodiment 1
Phosphorus, nitrogen, cobalt codope carbon material quantum dot carrying current and half wave potential it is maximum, illustrate that the catalyst has highest oxygen also
Former catalytic activity;It is considered that the catalysis material surface that is doped to of phosphorus atoms creates more positively charged sites, enhance
Oxygen molecule is adsorbed, has activated the pi-electron enriched in carbon conjugated system, phosphorus, nitrogen have played the good collaboration to carbon material together
Effect, show the electro catalytic activity excellent performance of fuel-cell catalyst produced by the present invention, be before one kind has wide application
The fuel-cell catalyst of scape.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. a kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, the preparation method of cobalt codope carbon material quantum dot, its feature exist
In concretely comprising the following steps:By melamine, pyrophosphoric acid and Co (CH3COO)4•H2O ultrasounds are transferred to hydrothermal reaction kettle after being sufficiently mixed
In, 20min is reacted in microwave reaction instrument under 1000W and 2.45GHz microwave condition, by the freeze-dried processing of obtained product
Solid powder i.e. fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen, the cobalt codope carbon material quantum that particle diameter is 5~6nm are obtained afterwards
Point.
2. fuel cell oxygen reduction electrocatalyst phosphorus according to claim 1, nitrogen, the system of cobalt codope carbon material quantum dot
Preparation Method, it is characterised in that:The melamine, pyrophosphoric acid and Co (CH3COO)4•H2The O mass ratio that feeds intake is 1:1:10.
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Citations (3)
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CN104549407A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of platinum based/nitrogen doped carbon quantum dot-carbon nanotube catalyst |
CN105197917A (en) * | 2015-09-11 | 2015-12-30 | 电子科技大学 | Preparation method of nitrogen-doped graphene quantum dot dispersion liquid |
CN105439133A (en) * | 2015-12-18 | 2016-03-30 | 浙江理工大学 | Preparation method of electronegative monolayer graphene |
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- 2017-08-25 CN CN201710742505.9A patent/CN107689456A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104549407A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of platinum based/nitrogen doped carbon quantum dot-carbon nanotube catalyst |
CN105197917A (en) * | 2015-09-11 | 2015-12-30 | 电子科技大学 | Preparation method of nitrogen-doped graphene quantum dot dispersion liquid |
CN105439133A (en) * | 2015-12-18 | 2016-03-30 | 浙江理工大学 | Preparation method of electronegative monolayer graphene |
Non-Patent Citations (2)
Title |
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PHILIPPE SERP,ET AL.: "《Nanostructured Carbon Materials for Catalysis》", 2 March 2015 * |
SHUJUN CHAO,ET AL.: "Template-free synthesis of hierarchical peanut-like Co and N codoped porous carbon with highly efficient catalytic activity for oxygen reduction reaction", 《ELECTROCHIMICA ACTA》 * |
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