CN107845816B - A kind of coarse shape of octahedron PtCoFe alloy particle and preparation method thereof - Google Patents
A kind of coarse shape of octahedron PtCoFe alloy particle and preparation method thereof Download PDFInfo
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- CN107845816B CN107845816B CN201710990620.8A CN201710990620A CN107845816B CN 107845816 B CN107845816 B CN 107845816B CN 201710990620 A CN201710990620 A CN 201710990620A CN 107845816 B CN107845816 B CN 107845816B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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 present invention relates to a kind of coarse octahedron PtCoFe alloy particles and preparation method thereof.The present invention is using chloroplatinic acid and cobalt chloride and ferric trichloride as raw material; think glycine reducing agent and Morphological control agent, using SDS as protective agent, certain content NaI is added; the higher coarse shape of octahedron PtCoFe alloy nano particle of selectivity, the cleaning of preparation method green are prepared under oxygen atmosphere.The coarse octahedron PtCoFe alloy nano particle step atom obtained is more, and active site density is high, is with a wide range of applications.
Description
Technical field
The invention belongs to function nano alloy fields.Specifically, the present invention is that one kind is prepared using hydrothermal synthesis method slightly
Rough shape of octahedron PtCoFe alloy nano particle.
Background technique
Precious metals pt nano-structured calalyst is widely used in industry due to its excellent catalytic performance and thermal stability
Catalysis, bionic, the fields such as electro-catalysis.But due to some restraining factors in practical applications, such as easily poisoning, the service life it is short with
And it is at high price, so that this excellent nanocatalyst can not further genralrlization and application.Research worker is in order to solve this
A little problems substitute Pt frequently with by cheap 3d transition metal element part at present, form Pt base binary/multicomponent alloy and urge
Agent, and controlled by condition, probe into its pattern, the relationship of composition and stable in catalytic performance.
In numerous transition metal elements, Co and Fe respectively as one of transition metal element more abundant on the earth,
It is that Pt base bianry alloy preferably selects.The PtCoFe alloy nano particle of research preparation at present is less, and preparation method all has
As solvent, most of PtCoFe alloy nano particle being synthesized is wrapped up solvent macromolecular by organic matter, and active sites are not
It can expose, can not be in contact with reactant.Therefore it designs and exploitation aqueous solution preparation PtCoFe alloy nano particle is with important
Meaning.A kind of method for preparing coarse octahedron PtCoFe alloy nano particle that the present invention develops, substantially increases Pt's
Step atomicity increases the active site density of PtCoFe alloy.
Fuel cell is considered as the important power device of traditional internal combustion engine alternative in the near future.Proton exchange
Another important feature of membrane cell is that it both can be using clean energy resource such as hydrogen etc. as fuel, also can be with reproducible small
Molecular organic such as formic acid, ethyl alcohol, methanol etc. is fuel.According to before studies have shown that Pt catalyst is proton exchange membrane combustion
Expect the best catalyst of catalytic performance in battery, but the high cost and utilization rate of Pt catalyst limits to a certain extent
The application prospect of fuel cell, therefore prepare to be used to improve the catalyst for improving electrocatalysis characteristic and have become and be currently urgently badly in need of solving
Certainly the problem of.
Summary of the invention
In view of the above technical problems, the present invention solves current Pt nano-structured calalyst and there is easily poisoning, the service life it is short with
And the technical problems such as at high price, a kind of coarse shape of octahedron PtCoFe alloy nano particle of high density active position is prepared,
Improve the catalytic performance of Pt base nanometer.
To achieve the above object, the present invention is achieved by the following technical solutions:
A kind of experimental procedure of coarse octahedron PtCoFe alloy nano particle preparation method is as follows:
The chloroplatinic acid aqueous solution that 1.0mL concentration is 19.3mmol/L is measured, 4.0mL concentration is the cobalt chloride of 1.66mmol/L
Aqueous solution and 3.0mL concentration are the ferric chloride aqueous solutions of 1.66mmol/L in 30ml reaction kettle, be subsequently added into glycine and
Lauryl sodium sulfate SDS and NaI are stirred dissolution with magnetic stirring apparatus, then with air in oxygen discharge reaction kettle
Afterwards, 1.0MPa oxygen is passed through into reaction kettle, then heating is reacted, after reaction by ethyl alcohol centrifuge washing, freezing
The processing steps such as dry, obtain coarse octahedron PtCoFe alloy nano particle.
Preferably, the amount ranges of SDS are 200-250mg, preferably 220mg.
Preferably, the amount ranges of glycine are 100-130mg, preferably 120mg.
Wherein: glycine plays the role of reducing agent and Morphological control agent, and SDS is mainly pattern protective agent, and
The ratio of Na+ ion and I- ion has guiding role to the formation of PtCoFe crystal topology, only when the additional amount of NaI
In the case where for SDS additional amount half, coarse octahedron PtCoFe alloy nano particle of the invention can be just obtained, it is comprehensive one
It rises and reaches unexpected technical effect.
Preferably, the temperature range for heating reaction is 200-210 DEG C.
Further, it should be noted that the oxygen atmosphere of 1.0MPa is also the coarse octahedron of the synthesis present invention under primary condition
The essential factor of PtCoFe alloy nano particle, since oxygen has oxidisability, the present invention constitutes gaseous oxidation-liquid phase
Reduction system is used to synthesize PtCoFe alloy for the first time, and gaseous oxidation tend to preferentially restore on octahedral structure face metal from
And coarse structure is formed, the specific atmosphere of the present invention and other experiment parameters constitute a mutually matched entirety, collaboration
Coarse octahedron PtCoFe alloy of the invention can be just obtained together.
Beneficial effects of the present invention: coarse octahedron PtCoFe alloy nanoparticle of one kind and preparation method thereof is disclosed.
For the present invention with chloroplatinic acid, cobalt chloride and ferric trichloride are raw material, to be to protect with SDS for glycine reducing agent and Morphological control agent
Agent is protected, certain content NaI is added, the higher coarse shape of octahedron PtCoFe alloy of selectivity is prepared under oxygen atmosphere
Nanoparticle, the cleaning of preparation method green.The coarse octahedron PtCoFe alloy nano particle step atom obtained is more, active sites
Density is high, under methanol and the test of formic acid electroxidation, excellent electrocatalytic oxidation activity is shown, before having a wide range of applications
Scape.
Detailed description of the invention
Fig. 1 is the TEM map for the coarse octahedron PtCoFe alloy nano particle that embodiment 1 is prepared；
Fig. 2 is that the first vegetarian noodles for the coarse octahedron PtCoFe alloy nano particle that embodiment 1 is prepared sweeps map；
Fig. 3 is the coarse octahedron PtCoFe alloy nano particle that embodiment 1 is prepared and business Pt/C as methanol
The cyclic voltammetry curve comparison diagram of electro-oxidizing-catalyzing agent；
Fig. 4 is the coarse octahedron PtCoFe alloy nano particle that embodiment 1 is prepared and business Pt/C as formic acid
The cyclic voltammetry curve comparison diagram of electro-oxidizing-catalyzing agent；
Fig. 5 is the TEM map for the PtCoFe alloy nano particle that comparative example 1 is prepared.
Fig. 6 is the TEM map for the PtCoFe alloy nano particle that comparative example 2 is prepared.
Specific embodiment
Below in conjunction with Figure of description, specific embodiment is described in further details.
Embodiment 1
Measure 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration be 1.66mmol/L cobalt chloride solution and
3.0mL concentration is the ferric chloride aqueous solutions of 1.66mmol/L in 30ml reaction kettle, is subsequently added into glycine and dodecyl
Sodium sulphate SDS and NaI are stirred dissolution with magnetic stirring apparatus, are then discharged in reaction kettle after air with oxygen, Xiang Fanying
It is passed through 1.0MPa oxygen in kettle, then heats and is reacted at 210 DEG C, after reaction by ethyl alcohol centrifuge washing, freezing
The processing steps such as dry, obtain coarse octahedron PtCoFe alloy nano particle (as shown in Figs. 1-2), wherein the use of glycine
Amount is 120mg, and the amount ranges of SDS are 220mg, and the additional amount of NaI is 110mg.
The test of methanol (formic acid) electroxidation: anodic oxidation performance test is using conventional three-electrode system, in CHI650D
It is carried out on type electrochemical workstation.It is a platinum filament to electrode with saturated calomel electrode (SCE) for reference electrode, and the electricity that works
Extremely diameter be 3mm glass-carbon electrode (GC).A certain amount of catalyst suspension (holding metal quality is 4 μ g) is taken to drip to GC electrode
Surface on it is dry under infrared lamp, then having one end of sample against UV ozone lamp working electrode drop, (launch wavelength is
185nm and 254nm, power 10W) it is separated by 5mm irradiation 12h to remove the organic molecule of sample surfaces.Then in work electricity
Drip the 0.5wt%Nafion solution (ethyl alcohol dilution) of upper 1.5 μ L in the surface of pole.Catalyst electrochemical activation area is tested with 0.5M
H2SO4Solution first leads to the high-purity N of 30min as electrolyte before experiment2To electrolyte deoxygenation, then followed with 50mV/s rate
Ring volt-ampere (CV) scanning, the scanning range of setting is -0.24~1.0V.It is N that superjacent is kept in experimentation2Atmosphere.First
The test of alcohol (formic acid) electroxidation is in 0.5M H2SO4+2M CH3OH(0.5M H2SO4+ 0.25M HCOOH) it carries out in electrolyte,
Before CV test, lead to high-purity N2Purging 30min is used to remove dissolved oxygen in electrolyte, the scanning range set as -0.2~
1.0V determines that scanning speed is 50mV/s.Current density is with unit catalyst electrochemical activation area (cm on working electrode2) on
Electric current indicate.Each working electrode encloses obtained stable CV curve with the rate loop scan process 50 of 50mV/s.For
Embodiment 1 prepares coarse octahedron PtCoFe nanoparticle, its electricity just sweeping peak and being normalized on electrochemical surface area ECSA
Current density represents the size of the latent active of catalyst, from figs. 3 and 4 it can be seen that coarse octahedron PtCoFe nanoparticle
Highest current density of the son in methanol electro-oxidizing is 3.85mA cm-2Formic acid electroxidation experiment in highest current density be
0.83mA cm-2, the methanol highest current density much higher than commercial Pt/C is 0.47mA cm-2, formic acid highest current density is
0.24mA cm-2。
Comparative example 1
Measure 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration be 1.66mmol/L cobalt chloride solution and
3.0mL concentration be 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into 120mg glycine and
220mg lauryl sodium sulfate SDS and 100mgNaI, are stirred dissolution with magnetic stirring apparatus, are then discharged with oxygen anti-
It answers in kettle after air, 1.0MPa oxygen is passed through into reaction kettle, then heat and reacted at 210 DEG C, passed through after reaction
Cross the processing steps such as ethyl alcohol centrifuge washing, freeze-drying, obtain PtCoFe alloy nano particle (as shown in Figure 5), and using with
The identical test condition of embodiment 1, obtaining its highest current density in methanol electro-oxidizing is 1.59mA cm-2, in formic acid electricity
Highest current density in oxidation experiment is 0.44mA cm-2。
Comparative example 2
Measure 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration be 1.66mmol/L cobalt chloride solution and
3.0mL concentration be 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into 120mg glycine and
220mg lauryl sodium sulfate SDS and 110mgNaI, are stirred dissolution with magnetic stirring apparatus, are then discharged with hydrogen anti-
It answers in kettle after air, 1.0MPa hydrogen is passed through into reaction kettle, then heat and reacted at 210 DEG C, passed through after reaction
Cross the processing steps such as ethyl alcohol centrifuge washing, freeze-drying, obtain PtCoFe alloy nano particle (as shown in Figure 6), and using with
The identical test condition of embodiment 1, obtaining its highest current density in methanol electro-oxidizing is 1.68mA cm-2, in formic acid
Highest current density in electroxidation experiment is 0.35mA cm-2。
Moreover, it relates to arrive multiple groups comparative example, it will not enumerate in view of length, be respectively relative to embodiment 1
Change one or more parametric variables, cannot get this hair in the case where changing one or more variable as the result is shown
Bright coarse shape of octahedron PtCoFe alloy nano particle shows between each technical characteristic of the technical solution of the application and has
There is synergistic effect, and methanol electro-oxidizing-catalyzing activity is respectively less than 2.2mA cm-2, formic acid electro-oxidizing-catalyzing activity is respectively less than 0.5mA
cm-2, far below the catalytic activity of the embodiment of the present invention 1, show no matter the technical solution of the application from alloy pattern or is catalyzed
Unexpected technical effect is reached for activity.
Claims (5)
1. a kind of preparation method of coarse shape of octahedron PtCoFe alloy particle, specific steps are as follows:
The chloroplatinic acid aqueous solution that 1.0mL concentration is 19.3mmol/L is measured, 4.0mL concentration is that the cobalt chloride of 1.66mmol/L is water-soluble
The ferric chloride aqueous solutions that liquid and 3.0mL concentration are 1.66mmol/L are subsequently added into the sweet ammonia of 100-130mg in 30ml reaction kettle
Acid and 200-250mg lauryl sodium sulfate SDS and NaI, the additional amount of NaI are the half dosage of SDS, use magnetic stirring apparatus
Be stirred dissolution, then with after air, 1.0MPa oxygen is passed through into reaction kettle in oxygen discharge reaction kettle, then heat into
Row reaction, passes through ethyl alcohol centrifuge washing, freeze-drying process step after reaction, obtains coarse octahedron PtCoFe alloy and receive
Rice corpuscles.
2. a kind of preparation method of coarse shape of octahedron PtCoFe alloy particle according to claim 1, feature exist
In: the amount ranges of SDS are 220mg.
3. a kind of preparation method of coarse shape of octahedron PtCoFe alloy particle according to claim 1 or 2, feature
Be: the dosage of glycine is 120mg.
4. a kind of preparation method of coarse shape of octahedron PtCoFe alloy particle according to claim 1 or 2, feature
Be: the temperature range for heating reaction is 200-210 DEG C.
5. a kind of coarse octahedron PtCoFe alloy nano particle, it is characterised in that according to claim 1-4
A kind of preparation method of coarse shape of octahedron PtCoFe alloy particle obtains.
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| CN108786845A (en) * | 2018-06-27 | 2018-11-13 | 济南大学 | A kind of preparation method of dendroid Pt-Ni-Cu alloy nanoparticles |
| CN110048132A (en) * | 2019-04-29 | 2019-07-23 | 济南大学 | A kind of three-dimensional preparation method for propping up forked Pt-Cu-Mn alloy nanoparticle |
| CN110048133A (en) * | 2019-04-29 | 2019-07-23 | 济南大学 | A kind of preparation method of cross cube Pt-Cu-Mn alloy nanoparticle |
| CN111230141B (en) * | 2020-03-04 | 2022-10-25 | 王冲 | Preparation method of PtRuCoS alloy nanocrystalline with floccule morphology |
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| CN104451782B (en) * | 2014-12-01 | 2017-08-25 | 上海师范大学 | A kind of octahedral structure nano platinum particle and its synthetic method and application |
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