CN105413727A - Nano-particle in yolk-eggshell structure and preparation thereof and application thereof - Google Patents

Nano-particle in yolk-eggshell structure and preparation thereof and application thereof Download PDF

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CN105413727A
CN105413727A CN201410486350.3A CN201410486350A CN105413727A CN 105413727 A CN105413727 A CN 105413727A CN 201410486350 A CN201410486350 A CN 201410486350A CN 105413727 A CN105413727 A CN 105413727A
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yolk
nano particle
eggshell structure
particle
nano
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孙公权
谷领峥
姜鲁华
金具涛
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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

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Abstract

The present invention relates to a nano-particle in a yolk-eggshell structure. The nano-particle in the yolk-egg shell structure uses iron and iron carbide (CFex) as a core, and N doped C and a mixture formed of iron and iron carbide (CFex) as a shell. According to the nano-particle of the present invention, the yolk-eggshell structure facilitates increase of active sites of catalyst oxygen reduction; CFex in the yolk and the eggshell, and the nitrogen-doped carbon in the eggshell both facilitate enhancement of activity of oxygen reduction. The preparation method for the yolk-eggshell structure of the present invention is simple and easy to implement. The acid treatment step facilitates removal of impurities in the prepared nano-particle, and the burning step facilitates formation of CFex, and nitrogen doped carbon, so that enhancement of the oxygen reduction activity is facilitated.

Description

A kind of nano particle of yolk-eggshell structure and Synthesis and applications thereof
Technical field
The present invention relates to technical field of nano material, relate to a kind of nano particle of yolk-eggshell structure specifically; The present invention relates to the preparation method and application of this nano particle simultaneously.
Background technology
At present, commercializing fuel cells process is slow, and one of its reason is Cathodic oxygen reduction (ORR) noble metal catalyst used (as Pt and alloy thereof etc.) resource-constrained, and price is higher.Design a kind of there is high activity, the non noble metal oxygen reduction eelctro-catalyst of low cost has profound significance.At present, the studied persons of catalyst of a large amount of non-noble metallic materials Pt as an alternative find, as transition metal macrocyclic compound, and transition metal oxide, the material with carbon element etc. of nitrogen, boron, sulfur doping.Although these researchs achieve greater advance, compared with these catalyst are catalyst based with Pt with in stability in activity, still there is a big difference.
Summary of the invention
The present invention is directed to prior art Problems existing, prepare a kind of nano particle of yolk-eggshell structure.For achieving the above object, the present invention adopts following concrete scheme to realize:
A nano particle for yolk-eggshell structure, with iron or iron and cementite for core, the mixture that the C of N doping and iron and cementite are formed is shell.
In the nano particle of described yolk-eggshell structure, average grain diameter is 250-500nm, and the average diameter of its center is 100-200nm, and the average thickness of shell is 20-50nm.
Described cementite is CFe x, wherein 0.125≤x≤4.
N in the C of described N doping is made up of oxidized form-nitrogen, graphite mould-nitrogen, pyrroles's type-nitrogen, nitrilic type-nitrogen, pyridine type-nitrogen; And the atomic molar content of the nitrogen of said structure respectively is 1-20%, 1-30%, 12-42%, 5-25%, 30-60% of doping N.
Iron in described shell and the average grain diameter of cementite are 10-45nm.
The weight content that in described core, cementite accounts for is 0-3%; The atomic ratio content of described nanoparticle surface element is respectively: the content of C is 60-90%, and the content of fe is the content of 0.05-30%, N is 1-15%; Wherein cementite accounts for 0.01-6%.
The preparation method of the nano particle of described yolk-eggshell structure, comprises the following steps,
1) preparation of precursor dispersion liquid:
In every 100ml absolute ethyl alcohol, add 6-40mL monomer, and be uniformly dispersed;
2) Fe 3o 4the preparation of-P:
A. be the Fe of 0.4-15g/L by concentration 3o 4aqueous dispersions is 10:3 to 35:9 and step 1 by volume) gained precursor dispersion liquid mixes;
B. be 1:10 to 10:1 and step a gained mixed liquor by volume by 4-12mol/L acid solution, after reaction, filter to obtain solid sample;
C. the solid sample of step b gained is disperseed in an acidic solution again, and react;
D. deionized water is adopted to wash to solution in neutral to step b gained reaction solution, dry Fe after filtering 3o 4-P;
3) preparation of the nano particle of yolk-eggshell structure:
By step 2) gained Fe 3o 4-P roasting under inert atmosphere obtains the nano particle of yolk-eggshell structure.
The preparation method of the nano particle of described yolk-eggshell structure,
Described step 1) in monomer be one or more mix monomer in pyrroles, aniline, thiophene;
Described step 2) Fe in a 3o 4particle diameter be 20-300nm;
Described step 2) acid solution is one or more in hydrochloric acid, sulfuric acid, nitric acid in b; Reaction time is 0.5-9h.
Described step 2) acid solution is one or more the mixed acid in sulfuric acid, hydrochloric acid, nitric acid in c; H in described acid solution +concentration be 0.5-2mol/L; The concentration of described solid matter in described acid solution is 1-66g/L; The described reaction time is 0.5-8h;
Described step 2) drying condition in d is under 45-80 DEG C of vacuum condition, dries 5-9h;
Described step 3) in inert atmosphere be N 2, one or more gaseous mixture in Ar, He; Described sintering temperature is 500-1000 DEG C, and roasting time is 0.5-6h.
The nano particle of described yolk-eggshell structure can be used as the oxygen reduction electro-catalyst under alkalescence or acid condition.
Compared with prior art, tool of the present invention has the following advantages:
1. nano particle of the present invention, its yolk-eggshell structure is conducive to catalyst oxygen reduction reaction active site and increases; CFe in yolk and eggshell x, the carbon of N doping is all conducive to the raising of oxygen reduction reaction activity in eggshell.
2. the method for the invention, simply, is easy to realize.Wherein, acid-treated step is conducive to the impurity removed in the nano particle of preparation, and the nano particle of step to preparation of roasting processes further, is conducive to CFe xand the formation of pyridine type-nitrogen in the carbon of N doping and graphite mould-nitrogen, thus be conducive to the raising of oxygen reduction reaction activity.
Accompanying drawing explanation
Fig. 1 is the TEM figure of a kind of yolk-eggshell structure nano particle (sample two) of preparation in embodiment 1.
As can be seen from the figure, in embodiment 1, the pattern of a kind of yolk-eggshell structure nano particle of preparation is yolk-eggshell structure, and its average grain diameter is 300nm.Wherein, the black particle being positioned at nano particle center is core, and the average grain diameter of core is 140nm, and the thickness of shell is 40nm.The average grain diameter being entrained in the black particle in shell is 30nm.
Fig. 2 is the HRTEM figure of the nano particle (sample two) of yolk-eggshell structure prepared by embodiment 1.
As can be seen from the figure, the spacing of lattice of the nano particle of yolk-eggshell structure prepared by embodiment 1, query-relevant data is known, and scheming the spacing of lattice of nano particle a) is 0.273nm, corresponding CFe 2.5(3,1 ,-1) crystal face, figure b) in the spacing of lattice of nano particle be the corresponding respectively CFe of 0.19nm and 0.32nm 2.5(1,1 ,-1), and Fe (1,1,0) crystal face.
Fig. 3 is Fe prepared by comparative example 1 3o 4the XRD characterization result of the nano particle (sample two) of yolk-eggshell structure prepared by-PPy (sample one) and embodiment 1.
As can be seen from the figure, the Fe of comparative example 1 preparation 3o 4-PPy (sample one) is primarily of Fe 3o 4form; And the nano particle (sample two) of yolk-eggshell structure prepared by embodiment 1 is primarily of CFe 2.5form with Fe.This is consistent with HRTEM characterization result conclusion in Fig. 2.
Fig. 4 is the EDX characterization result of the nano particle (sample two) of yolk-eggshell structure prepared by embodiment 1.Wherein, (a) nanoparticle subgraph that is yolk-eggshell structure; B () is carbon distribution map; C () is ferro element distribution map; D () is nitrogen distribution diagram of element.
As can be seen from the figure, the distribution of carbon, nitrogen element is comparatively even, and ferro element mainly concentrates on the position of core, also has short grained ferro element to be distributed in the position of shell in addition.
Fig. 5 is the XPS spectrum figure of N in the nano particle (sample two) of yolk-eggshell structure prepared by embodiment 1.After this spectrogram swarming matching, peak be positioned at 402.2,401,400.2,399.2 and 397.9eV place correspond to oxidized form-nitrogen, graphite mould-nitrogen, pyrroles's type-nitrogen, nitrilic type-nitrogen and pyridine type-nitrogen respectively.
Fig. 6 is Fe prepared by comparative example 1 3o 4the RRDE test result of the nano particle (sample two) of yolk-eggshell structure prepared by-PPy (sample one) and embodiment 1.Test condition is: O 2saturated 0.1mol/LNaOH electrolyte, the interval 0.11V-1.23V (vs.RHE) of electric potential scanning, sweep speed 10mV/s.
The half wave potential of the nano particle of yolk-eggshell structure prepared by embodiment 1 is 0.73V (vs.RHE), and limiting current density is-0.49mA/cm 2, the Fe that its oxygen reduction activity is prepared apparently higher than comparative example 1 3o 4-PPy (sample one).
For the nano particle (sample two) of yolk-eggshell structure prepared by embodiment 1, in 0.12-0.8V (vs.RHE) interval, its HO - 2productive rate is between 0.7-6%, and electron transfer number is between 3.87-3.99.For Fe 3o 4-PPy (sample one), in 0.12-0.6V (vs.RHE) interval, its HO - 2productive rate increases gradually, reaches 54%, and metastatic electron number is now 2.9.
5000 circle senile experiments of the nano particle (sample two) of yolk-eggshell structure prepared by Fig. 7 (a) embodiment 1.Electrochemical Ageing test condition: 0.1mol/LNaOH electrolyte, the interval 0.6V-1.0V (vs.RHE) of electric potential scanning, sweep speed 100mV/s.After 5000 circle scannings, the half wave potential of the nano particle (sample two) of yolk-eggshell structure is negative moves about 42mV.
The nano particle (sample two) of yolk-eggshell structure prepared by Fig. 7 (b) embodiment 1 and the methanol tolerant test result of commodity 20wt.%Pt/C catalyst (JohnsonMatthey company).Test condition is: add 0.1mol/L methyl alcohol in 0.1mol/L NaOH electrolyte, the interval 0.11V-1.23V (vs.RHE) of electric potential scanning, sweep speed 10mV/s.
As can be seen from the figure, after 0.1mol/LNaOH electrolyte adds 0.1mol/L methyl alcohol, the oxygen reduction activity of the nano particle (sample two) of yolk-eggshell structure is substantially constant, and the oxygen reduction activity of 20wt.%Pt/C catalyst sharply declines.This shows relative to 20wt.%Pt/C catalyst, and the nano particle of yolk-eggshell structure has good methanol tolerant performance.
Detailed description of the invention
Embodiment 1:
Take 0.3gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 15min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 15min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, and solid is scattered in 0.5mol/LH again 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, is labeled as sample one.By Fe 3o 4-PPy at 700 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of yolk-eggshell structure, is sample two by Product Labeling.
Embodiment 2:
Take 0.3gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 15min under room temperature.Pipette 3mL aniline monomer, be scattered in 15mL ethanol, ultrasonic disperse 15min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, then is scattered in 0.5mol/LH 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 700 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 3:
Take 0.3gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 15min under room temperature.Pipette 3mL thiophene monomer, be scattered in 15mL ethanol, ultrasonic disperse 15min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, then is scattered in 0.5mol/LH 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 700 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 4:
Take 0.3gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 15min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 15min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, then is scattered in 0.5mol/LH 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 500 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 5:
Take 0.3gFe 3o 4nano particle (20nm particle diameter), is scattered in 170mL deionized water, ultrasonic disperse 1h under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 20min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 1h.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, then uses the hot wash of 60 DEG C, and the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy is at 700 DEG C with the roasting of Ar atmosphere, and roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 6:
Take 0.3gFe 3o 4nano particle (20nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 3h.Reaction terminates rear filtration, then uses the hot wash of 60 DEG C, and the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 700 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 7:
Take 0.3gFe 3o 4nano particle (20nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 3h.Reaction terminates rear filtration.Be scattered in 0.5mol/LH again 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy is at 700 DEG C with the roasting of He atmosphere, and roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 8:
Take 0.3gFe 3o 4nano particle (20nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 6h.Reaction terminates rear filtration.Use the hot wash of 60 DEG C again, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 800 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 9:
Take 0.3gFe 3o 4nano particle (20nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 6h.Reaction terminates rear filtration.Be scattered in 0.5mol/LH again 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 900 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 10:
Take 0.3gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 70mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 3mL pyrrole monomer, be scattered in 15mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 3h.Reaction terminates rear filtration.Be scattered in 0.5mol/LH again 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 700 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 11:
Take 0.6gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 150mL deionized water, ultrasonic disperse 30min under room temperature.Pipette 6mL pyrrole monomer, be scattered in 30mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 6h.Reaction terminates rear filtration.Be scattered in 0.5mol/LHCl solution again, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 800 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 12:
Take 1gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 600mL deionized water, ultrasonic disperse 45min under room temperature.Pipette 10mL pyrrole monomer, be scattered in 50mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 3h.Reaction terminates rear filtration.Be scattered in 0.5mol/LHNO again 3in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 900 DEG C with N 2atmosphere roasting, roasting time is 30min, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Embodiment 13:
Take 1gFe 3o 4nano particle (100-300nm particle diameter), is scattered in 600mL deionized water, ultrasonic disperse 45min under room temperature.Pipette 10mL pyrrole monomer, be scattered in 50mL ethanol, ultrasonic disperse 30min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic reaction 6h.Reaction terminates rear filtration.Be scattered in 0.5mol/LH again 2sO 4in solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 9 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy, by Fe 3o 4-PPy at 1000 DEG C with N 2atmosphere roasting, roasting time is 6h, obtains the nano-particle catalyst of target product yolk-eggshell structure.
Comparative example 1:
Take 0.3gFe3O4 nano particle (100-300nm particle diameter), be scattered in 70mL deionized water, ultrasonic disperse 15min under room temperature.Pipette 3mL pyrrole monomer (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure), be scattered in 15mL ethanol, ultrasonic disperse 15min under room temperature.Pyrroles/ethanolic solution is moved into Fe 3o 4/ H 2in the dispersion liquid of O, ultrasonic disperse 30min.Measure the 15mL6mol/LHCl aqueous solution, move in above-mentioned mixed liquor, ultrasonic 1.5h.Reaction terminates rear filtration, then is scattered in 0.5mol/LH2SO4 solution, ultrasonic 4h.With the hot wash of 60 DEG C, the pH to filtrate reaches neutral, and 75 DEG C of vacuum drying 8 hours, take out, grinding fully, obtains catalyst precarsor Fe 3o 4-PPy (sample one).
Comparative example 2: by commodity 20wt.%Pt/C catalyst (JohnsonMatthey company) as a comparison.

Claims (9)

1. a nano particle for yolk-eggshell structure, is characterized in that: the nano particle of described yolk-eggshell structure is with iron or iron and cementite for core, and the mixture that the C of N doping and iron and cementite are formed is shell.
2. nano particle as claimed in claim 1, it is characterized in that: in the nano particle of described yolk-eggshell structure, average grain diameter is 250-500nm, and the average diameter of its center is 100-200nm, and the average thickness of shell is 20-50nm.
3. nano particle as claimed in claim 1, is characterized in that: described cementite is CFe x, wherein 0.125≤x≤4.
4. nano particle as claimed in claim 1, is characterized in that: the N in the C of described N doping is made up of oxidized form-nitrogen, graphite mould-nitrogen, pyrroles's type-nitrogen, nitrilic type-nitrogen, pyridine type-nitrogen; And the atomic molar content of the nitrogen of said structure respectively is 1-20%, 1-30%, 12-42%, 5-25%, 30-60% of doping N.
5. nano particle as claimed in claim 1, is characterized in that: the iron in described shell and the average grain diameter of cementite are 10-45nm.
6. nano particle as described in as arbitrary in claim 1-5, is characterized in that: the weight content that in core, cementite accounts for is 0-3%; The atomic ratio content of described nanoparticle surface element is respectively: the content of C is 60-90%, and the content of fe is the content of 0.05-30%, N is 1-15%; Wherein cementite accounts for 0.01-6%.
7. a preparation method for the nano particle of the arbitrary described yolk-eggshell structure of claim 1-6, is characterized in that: comprise the following steps,
1) preparation of precursor dispersion liquid:
In every 100ml absolute ethyl alcohol, add 6-40mL monomer, and be uniformly dispersed;
2) Fe 3o 4the preparation of-P:
A. be the Fe of 0.4-15g/L by concentration 3o 4aqueous dispersions is 10:3 to 35:9 and step 1 by volume) gained precursor dispersion liquid mixes;
B. be 1:10 to 10:1 and step a gained mixed liquor by volume by 4-12mol/L acid solution, after reaction, filter to obtain solid sample;
C. the solid sample of step b gained is disperseed in an acidic solution again, and react;
D. deionized water is adopted to wash to solution in neutral to step b gained reaction solution, dry Fe after filtering 3o 4-P;
3) preparation of the nano particle of yolk-eggshell structure:
By step 2) gained Fe 3o 4-P roasting under inert atmosphere obtains the nano particle of yolk-eggshell structure.
8. the preparation method of the nano particle of yolk-eggshell structure as claimed in claim 7, is characterized in that:
Described step 1) in monomer be one or more mix monomer in pyrroles, aniline, thiophene;
Described step 2) Fe in a 3o 4particle diameter be 20-300nm;
Described step 2) acid solution is one or more in hydrochloric acid, sulfuric acid, nitric acid in b; Reaction time is 0.5-9h;
Described step 2) acid solution is one or more the mixed acid in sulfuric acid, hydrochloric acid, nitric acid in c; H in described acid solution +concentration be 0.5-2mol/L; The concentration of described solid matter in described acid solution is 1-66g/L; The described reaction time is 0.5-8h;
Described step 2) drying condition in d is under 45-80 DEG C of vacuum condition, dries 5-9h;
Described step 3) in inert atmosphere be N 2, one or more gaseous mixture in Ar, He; Described sintering temperature is 500-1000 DEG C, and roasting time is 0.5-6h.
9. an application for the nano particle of yolk-eggshell structure as described in as arbitrary in claim 1-6, is characterized in that: this nano particle is used as the oxygen reduction electro-catalyst under alkalescence or acid condition.
CN201410486350.3A 2014-09-22 2014-09-22 Nano-particle in yolk-eggshell structure and preparation thereof and application thereof Pending CN105413727A (en)

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CN105826572A (en) * 2016-05-10 2016-08-03 大连理工大学 N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof
CN109014245A (en) * 2018-09-03 2018-12-18 大连理工大学 A kind of nitrogen-doped carbon coated magnetic Nanocomposites microballoon and preparation method thereof
CN110860275A (en) * 2019-11-19 2020-03-06 南京工程学院 Effective utilization method of kitchen waste

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CN105826572A (en) * 2016-05-10 2016-08-03 大连理工大学 N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof
CN105826572B (en) * 2016-05-10 2018-06-08 大连理工大学 A kind of N, S codope carbon nanotube coat FexC catalyst, preparation method and applications
CN109014245A (en) * 2018-09-03 2018-12-18 大连理工大学 A kind of nitrogen-doped carbon coated magnetic Nanocomposites microballoon and preparation method thereof
CN110860275A (en) * 2019-11-19 2020-03-06 南京工程学院 Effective utilization method of kitchen waste
CN110860275B (en) * 2019-11-19 2022-07-08 南京工程学院 Effective utilization method of kitchen waste

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