CN105449231A - Preparation and application for non-noble metal electro-catalyst with core-shell structure - Google Patents

Preparation and application for non-noble metal electro-catalyst with core-shell structure Download PDF

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CN105449231A
CN105449231A CN201510770346.4A CN201510770346A CN105449231A CN 105449231 A CN105449231 A CN 105449231A CN 201510770346 A CN201510770346 A CN 201510770346A CN 105449231 A CN105449231 A CN 105449231A
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acid
preparation
catalyst
porphyrin
shell structure
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宋玉江
李佳
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Dalian University of Technology
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Dalian University of Technology
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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
    • H01M4/9008—Organic or organo-metallic compounds
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention provides preparation and application for a non-noble metal electro-catalyst with a core-shell structure, and belongs to the field of fuel cells and metal/air cell catalysts. The preparation for the non-noble metal electro-catalyst comprises the steps of dispersing carbon black into an HNO3 solution, performing back flow at a temperature of 20-90 DEG C for 0.5-10h, performing suction filtration, washing until the solution is neutral, and drying; dissolving porphyry into organic solvent, adding pre-processed carbon black, performing ultrasonic dispersion for more than 20 min, and drying the solvent by evaporation; roasting the rest materials in carrier gas at a temperature of 400-1,200 DEG C for 0.5-4h, cooling to room temperature, and adding an acidic water solution, and performing back flow in a water bath at a temperature of 30-90 DEG C for 1-24h, and then performing suction filtration, washing by deionized water until the solution is neutral, and drying to obtain the non-noble metal electro-catalyst with the core-shell structure. The preparation is simple in operation, easy to control, mild in conditions and environment-friendly; and the prepared non-noble metal electro-catalyst with the core-shell structure is quite high in oxygen reduction activity, and can be used for the fuel cells and the metal/air cells.

Description

A kind of preparation of nucleocapsid structure base metal eelctro-catalyst and application thereof
Technical field
The invention belongs to fuel cell and metal-air batteries catalyst field, relate to a kind of He ?the preparation of shell structure base metal eelctro-catalyst and application thereof.
Background technology
Fuel cell owing to having high-energy-density, high efficiency, advantages of environment protection, thus is subject to extensive concern.In fuel cell, negative electrode mainly selects noble metal platinum and alloy thereof as oxygen reduction catalyst, but due to platinum expensive, scarcity of resources, poor durability, easily the shortcoming such as to be poisoned, seriously hinder the commercialization process of fuel cell.Therefore, exploitation oxygen reduction activity is higher, and durability is better, and the lower base metal eelctro-catalyst of cost is most important.
(R.Jasinski after Jasinski discovery Cobalt Phthalocyanine in 1964 has oxygen reduction activity in alkaline system, Nature, 1964,201,1212 ?1213), the macrocyclic compound such as metal phthalocyanine and metalloporphyrin has very high conjugated structure and chemical stability due to it, shows good oxygen reduction activity, becomes the study hotspot of base metal eelctro-catalyst in recent years gradually.Ferriporphyrin is supported the surface of carbon carrier by the method for Dodelet seminar in 2007 dipping, after under 950 DEG C of hot conditionss, use NH 3process sample, the sample obtained has higher oxygen reduction activity, but its durability poor (Charreteur, F., Jaouen, F. & Dodelet, J. ?P, Electrochim.Acta, 2009,54,6622 ?6630).The people such as Adzic take mesoporous silicon as hard template, metalloporphyrin is presoma, remove hard template with HF after high-temperature heat treatment and prepare mesoporous porphyryl base metal eelctro-catalyst, though this catalyst has higher oxygen reduction activity, HF (Cheon, the J.Y.etal environment to harm in its preparation method, are used, Sci.Rep., 2013,3,2715).Patent CN200810040926 adopts ultrasonic method fabricated in situ metalloporphyrin, after supported on carbon carrier, heat treatment obtains base metal eelctro-catalyst, and the oxygen reduction activity of this eelctro-catalyst is poor.
Above-mentioned preparation method is take metalloporphyrin as precursor power base metal eelctro-catalyst, preparation method is comparatively complicated, or use environmentally hazardous reagent in preparation process, and the base metal eelctro-catalyst obtained only has higher oxygen reduction activity in acidity or alkalescence.Above preparation method carries out simplifying and optimizing by the present invention, lower-cost metalloporphyrin is directly selected to be presoma, the method of simple rotary evaporation is adopted to be supported carbon blacksurface, after through simple heat treatment and pickling, namely obtain He ?the base metal eelctro-catalyst of shell structure, and this eelctro-catalyst all shows the oxygen reduction activity of excellence in alkalescence and acid solution.
Summary of the invention
The object of the present invention is to provide a kind of He ?the preparation of shell structure base metal eelctro-catalyst and application thereof, the method abundant raw material source, simple to operate, be easy to control, preparation cost is low.
The invention provides a kind of He ?the preparation method of shell structure base metal eelctro-catalyst, step is as follows:
1) by 1 part of carbon black dispersion in 20 ?500 parts of HNO 3in solution, 20 ?90 DEG C of backflows 0.5 ?10h, suction filtration, deionized water washing, to neutral, dried and is obtained pretreated carbon black, wherein HNO 3the concentration of solution be 1 ?10mol/L;
2) porphyrin is dissolved in organic solvent, adds step 1) pretreated carbon black, more than ultrasonic disperse 20min, then solvent evaporated; Porphyrin concentration be in organic solvent 0.1 ?20mmol/L, the mass ratio of porphyrin and pretreated carbon black be 0.1 ?10:1;
3) by step 2) after solvent evaporated remaining material 400 ?in carrier gas at 1200 DEG C roasting 0.5 ?4h, be cooled to room temperature, add acidic aqueous solution, 30 ?reflux in the water-bath of 90 DEG C 1 ?after 24h, suction filtration, deionized water is washed till neutrality, dry, obtain He ?shell structure base metal eelctro-catalyst.
The particle diameter of described carbon black be 5 ?100nm, specific area be 100 ?2000m 2/ g;
Described porphyrin be meso ?four (4 ?methoxyphenyl) PORPHYRIN IRON, meso ?four (4 ?methoxyphenyl) Cobalt Porphyrin, meso ?four (4 ?methoxyphenyl) zinc porphyrin, meso ?four (4 ?methoxyphenyl) Manganese Porphyrin, meso ?one or more mixtures in four (4 ?methoxyphenyl) Porphyrin Nickel;
Described organic solvent is one or more mixing in chloroform, carrene, tetrachloromethane, benzene,toluene,xylene, carbon tetrachloride, ether, ethyl acetate, n-hexane, in ethanol, ether, methyl alcohol, glycerol, acetone.
Described carrier gas is the mist of one or two or more kinds in helium, neon, argon gas, nitrogen, ammonia.
Described acidic aqueous solution is one or more the mixture in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, hydrofluoric acid, nitric acid and perchloric acid, the concentration of acidic aqueous solution be 0.1 ?10mol/L.
The pattern of the core ?shell structure base metal eelctro-catalyst that the present invention prepares is that graphite carbon-coating is wrapped in carbon blacksurface uniformly, i.e. core ?shell structure, and after improving porphyrin and preliminary treatment, the mass ratio of carbon black can increase the thickness of outer graphite carbon-coating.
The present invention prepare He ?shell structure base metal eelctro-catalyst can be applicable to fuel cell and metal-air batteries.
Compared with the base metal eelctro-catalyst of existing report, the present invention has the following advantages:
A () this method avoids the process adopting ultrasonic method or microwave method synthesis porphyrin, lower-cost anisyl metal porphyrins is directly selected to be raw material, adopt the method for simple rotary evaporation that porphyrin is dispersed in carbon blacksurface, obtained He ?shell structure base metal eelctro-catalyst, in acidity and alkaline solution, all there is very high oxygen reduction activity, its preparation method is simple, be easy to control, Stability Analysis of Structures, fuel cell and Jin Shu ?be with a wide range of applications in air cell.
B base metal eelctro-catalyst that () this method prepares, pattern is that graphite carbon-coating is evenly wrapped in carbon blacksurface, for successfully synthesizing the base metal eelctro-catalyst of the core ?shell structure of carbon bag carbon first, and the thickness of outermost layer graphite carbon-coating can regulate simply by the mass ratio changing porphyrin and pretreated carbon black.And the thickness of graphite carbon-coating directly affects the oxygen reduction activity of this catalyst in acid solution and alkaline solution and durability.
Accompanying drawing explanation
Fig. 1 (a) is transmission electron microscope under 100nm condition (TEM) photo that the embodiment of the present invention 1 prepares product.
Fig. 1 (b) is that the embodiment of the present invention 1 prepares transmission electron microscope (TEM) photo under the 20nm condition of product.
Fig. 2 is that the embodiment of the present invention 1 prepares the redox reactions polarization curve of product in alkaline solution.
Fig. 3 is the redox reactions polarization curve that the embodiment of the present invention 1 prepares before and after the durability test of product in alkaline solution.
Fig. 4 is that the embodiment of the present invention 1 prepares product redox reactions polarization curve in an acidic solution.
Fig. 5 is transmission electron microscope (TEM) photo that the embodiment of the present invention 2 prepares product.
Fig. 6 is that the embodiment of the present invention 2 prepares the redox reactions polarization curve of product in alkaline solution.
Fig. 7 is the redox reactions polarization curve that the embodiment of the present invention 2 prepares before and after the durability test of product in alkaline solution.
Fig. 8 is that the embodiment of the present invention 2 prepares product redox reactions polarization curve in an acidic solution.
Embodiment
The specific embodiment of the invention is illustrated below in conjunction with technical scheme and accompanying drawing.
Embodiment 1:
Take 6g commercial carbon blacks (KetjenEC ?600,20 ?30nm, 1400m 2/ g) be scattered in 600mL3mol/LHNO 3in solution, 80 DEG C of water-bath backflow 1h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 50mgmeso ?four (4 ?methoxyphenyl) PORPHYRIN IRON and 70mL chloroform; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 65 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under argon gas atmosphere protection; temperature programming to 800 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 0.5MH 2sO 4suction filtration after solution stirs 6h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
As Fig. 1, the base metal eelctro-catalyst obtained, pattern is core for dividing with carbon, and graphite carbon-coating is the base metal eelctro-catalyst of the core ?shell structure of shell.
As Fig. 2, redox reactions test employing standard three-electrode method measures chemical property, thin film working electrode made by catalyst, test condition: in the KOH aqueous solution of the 0.1mol/L that at 25 DEG C, oxygen is saturated, 0.1 ?1.1V (vsRHE) voltage under carry out electric potential scanning test, electrode rotary speed is 1600rpm.Polarization curve display embodiment 1 gained base metal eelctro-catalyst has very high oxygen reduction activity in alkaline solution, almost has identical oxygen reduction activity with business Pt/C.
As Fig. 3, durability test condition: in the KOH aqueous solution of the 0.1mol/L that at 25 DEG C, oxygen is saturated, 0.5 ?1.1V (vsRHE) voltage under carry out cyclic voltammetry scan test, sweep speed is 100mVs ?1, the scanning number of turns is 2500 circles.Before and after durability test, polarization curve display embodiment 1 gained base metal eelctro-catalyst has very high endurance quality in alkaline solution, and after 2500 circle durability tests, performance does not almost reduce, and has the durability more more excellent than business Pt/C.
As Fig. 4, redox reactions test employing standard three-electrode method measures chemical property, and thin film working electrode made by catalyst, test condition: the HClO of the 0.1mol/L that oxygen is saturated at 25 DEG C 4in the aqueous solution, 0.1 ?1.1V (vsRHE) voltage under carry out electric potential scanning test, electrode rotary speed is 1600rpm.Polarization curve display embodiment 1 gained base metal eelctro-catalyst has very high oxygen reduction activity in an acidic solution, differs about 150mV with business Pt/C half wave potential.
Embodiment 2:
Take 6g commercial carbon blacks (KetjenEC ?600,20 ?30nm, 1400m 2/ g) be scattered in 600mL3mol/LHNO 3in solution, 80 DEG C of water-bath backflow 1h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 100mgmeso ?four (4 ?methoxyphenyl) PORPHYRIN IRON and 70mL chloroform; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 65 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under argon gas atmosphere protection; temperature programming to 800 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 0.5MH 2sO 4suction filtration after solution stirs 6h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
As Fig. 5, the base metal eelctro-catalyst obtained, pattern is core for dividing with carbon, and graphite carbon-coating is the base metal eelctro-catalyst of the coreshell type structure of shell.
As Fig. 6, redox reactions test employing standard three-electrode method measures chemical property, thin film working electrode made by catalyst, test condition: in the KOH aqueous solution of the 0.1mol/L that at 25 DEG C, oxygen is saturated, 0.1 ?1.1V (vsRHE) voltage under carry out electric potential scanning test, electrode rotary speed is 1600rpm.Polarization curve display embodiment 2 gained base metal eelctro-catalyst has very high oxygen reduction activity in alkaline solution, almost has identical oxygen reduction activity with business Pt/C.
As Fig. 7, durability test condition: in the KOH aqueous solution of the 0.1mol/L that at 25 DEG C, oxygen is saturated, 0.5 ?1.1V (vsRHE) voltage under carry out cyclic voltammetry scan test, sweep speed is 100mVs ?1, the scanning number of turns is 2500 circles.Before and after durability test, polarization curve display embodiment 2 gained base metal eelctro-catalyst has very high endurance quality in alkaline solution, and after 2500 circle durability tests, performance does not almost reduce, and has the durability more more excellent than business Pt/C.
As Fig. 8, redox reactions test employing standard three-electrode method measures chemical property, and thin film working electrode made by catalyst, test condition: the HClO of the 0.1mol/L that oxygen is saturated at 25 DEG C 4in the aqueous solution, 0.1 ?1.1V (vsRHE) voltage under carry out electric potential scanning test, electrode rotary speed is 1600rpm.Polarization curve display embodiment 2 gained base metal eelctro-catalyst has very high oxygen reduction activity in an acidic solution, differs about 120mV with business Pt/C half wave potential.
Embodiment 3:
Take 6g commercial carbon blacks (KetjenEC ?600,20 ?30nm, 1400m 2/ g) be scattered in 600mL3mol/LHNO 3in solution, 80 DEG C of water-bath backflow 1h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 1000mgmeso ?four (4 ?methoxyphenyl) PORPHYRIN IRON and 70mL chloroform; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 65 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under argon gas atmosphere protection; temperature programming to 800 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 0.5MH 2sO 4suction filtration after solution stirs 6h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
The pattern of embodiment 3 gained catalyst is similar to embodiment 1 sample with performance, in alkalescence and acid solution, all have higher oxygen reduction activity.
Embodiment 4:
Take 6g commercial carbon blacks (VXC72,30nm, 254m 2/ g) be scattered in 600mL3mol/LHNO 3in solution, 80 DEG C of water-bath backflow 1h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 100mgmeso ?four (4 ?methoxyphenyl) PORPHYRIN IRON and 70mL chloroform; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 65 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under argon gas atmosphere protection; temperature programming to 1100 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 0.5MH 2sO 4suction filtration after solution stirs 6h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
The pattern of embodiment 4 gained catalyst is similar to embodiment 1 sample with performance, in alkalescence and acid solution, all have higher oxygen reduction activity.
Embodiment 5:
Take 6g commercial carbon blacks (KetjenEC ?600,20 ?30nm, 1400m 2/ g) be scattered in 100mL8mol/LHNO 3in solution, 50 DEG C of water-bath backflow 2h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 100mgmeso ?four (4 ?methoxyphenyl) Cobalt Porphyrin and 70mL chloroform; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 65 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under ammonia atmosphere protection; temperature programming to 800 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 0.5MH 2sO 4suction filtration after solution stirs 6h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
The pattern of embodiment 5 gained catalyst is similar to embodiment 1 sample with performance, in alkalescence and acid solution, all have higher oxygen reduction activity.
Embodiment 6:
Take 6g commercial carbon blacks (KetjenEC ?600,20 ?30nm, 1400m 2/ g) be scattered in 600mL3mol/LHNO 3in solution, 80 DEG C of water-bath backflow 1h, suction filtration, deionized water is washed till neutrality, dries, obtains pretreated carbon black.Add in the round-bottomed flask of 250mL 100mgmeso ?four (4 ?methoxyphenyl) PORPHYRIN IRON and 70mL toluene; the ultrasonic porphyrin that makes all dissolves; after add the pretreated carbon black of 100mg; ultrasonic 30min; 90 DEG C, under 100rpm condition, rotate evaporation of solvent, by the solid that obtains under argon gas atmosphere protection; temperature programming to 800 DEG C, naturally cools to room temperature after steady heat process 2h.Again through 1.0MHClO 4suction filtration after solution stirs 12h under the water-bath of 80 DEG C, is washed to neutrality, vacuumize at 65 DEG C, finally obtains black powder solid.
The pattern of embodiment 6 gained catalyst is similar to embodiment 1 sample with performance, in alkalescence and acid solution, all have higher oxygen reduction activity.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (10)

1. a preparation method for core ?shell structure base metal eelctro-catalyst, it is characterized in that, step is as follows:
1) by 1 part of carbon black dispersion in 20 ?500 parts of HNO 3in solution, 20 ?90 DEG C of backflows 0.5 ?10h, suction filtration, deionized water washing, to neutral, dried and is obtained pretreated carbon black, wherein HNO 3the concentration of solution be 1 ?10mol/L;
2) porphyrin is dissolved in organic solvent, adds step 1) pretreated carbon black, more than ultrasonic disperse 20min, then solvent evaporated; Porphyrin concentration be in organic solvent 0.1 ?20mmol/L, the mass ratio of porphyrin and pretreated carbon black be 0.1 ?10:1;
3) by step 2) after solvent evaporated remaining material 400 ?in carrier gas at 1200 DEG C roasting 0.5 ?4h, be cooled to room temperature, add acidic aqueous solution, 30 ?reflux in the water-bath of 90 DEG C 1 ?24h, suction filtration, deionized water is washed till neutrality, dry, obtain He ?shell structure base metal eelctro-catalyst.
2. preparation method according to claim 1, is characterized in that, the particle diameter of described carbon black be 5 ?100nm, specific area be 100 ?2000m 2/ g.
3. preparation method according to claim 1 and 2, it is characterized in that, described porphyrin be meso ?four (4 ?methoxyphenyl) PORPHYRIN IRON, meso ?four (4 ?methoxyphenyl) Cobalt Porphyrin, meso ?four (4 ?methoxyphenyl) zinc porphyrin, meso ?four (4 ?methoxyphenyl) Manganese Porphyrin, meso ?one or more mixtures in four (4 ?methoxyphenyl) Porphyrin Nickel; Described organic solvent is one or more mixing in chloroform, carrene, tetrachloromethane, benzene,toluene,xylene, carbon tetrachloride, ether, ethyl acetate, n-hexane, in ethanol, ether, methyl alcohol, glycerol, acetone.
4. preparation method according to claim 1 and 2, is characterized in that, described carrier gas is one or more the mist in helium, neon, argon gas, nitrogen, ammonia.
5. preparation method according to claim 3, is characterized in that, described carrier gas is one or more the mist in helium, neon, argon gas, nitrogen, ammonia.
6. the preparation method according to claim 1,2 or 5, it is characterized in that, described acidic aqueous solution is one or more the mixture in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, hydrofluoric acid, nitric acid, perchloric acid, the concentration of acidic aqueous solution be 0.1 ?10mol/L.
7. preparation method according to claim 3, it is characterized in that, described acidic aqueous solution is one or more the mixture in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, hydrofluoric acid, nitric acid, perchloric acid, the concentration of acidic aqueous solution be 0.1 ?10mol/L.
8. preparation method according to claim 4, it is characterized in that, described acidic aqueous solution is one or more the mixture in boric acid, sulfuric acid, benzene sulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, hydrofluoric acid, nitric acid, perchloric acid, the concentration of acidic aqueous solution be 0.1 ?10mol/L.
9. the preparation method described in claim 1,2,5,7 or 8 prepare He ?shell structure base metal eelctro-catalyst for the preparation of fuel cell and metal-air batteries.
10. preparation method according to claim 6 prepare He ?shell structure base metal eelctro-catalyst for the preparation of fuel cell and metal-air batteries.
CN201510770346.4A 2015-11-11 2015-11-11 Preparation and application for non-noble metal electro-catalyst with core-shell structure Pending CN105449231A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654307A (en) * 2017-01-10 2017-05-10 大连理工大学 Preparation method and application of noble metal@graphite layer core-shell structured electro-catalyst
CN106711467A (en) * 2017-01-10 2017-05-24 大连理工大学 Preparation method and application of platinum and core-shell structure carbon composite electrocatalyst
CN109921037A (en) * 2019-03-07 2019-06-21 曲阜师范大学 A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction
CN111530499A (en) * 2020-05-15 2020-08-14 中自环保科技股份有限公司 Synthesis method of core-shell alloy electrocatalyst with controllable structure

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Publication number Priority date Publication date Assignee Title
CN101322948A (en) * 2008-07-24 2008-12-17 上海交通大学 Method for preparing carbon supported metalloporphyrin metalloporphyrin oxygen reduction catalyst
US20130280419A1 (en) * 2008-08-21 2013-10-24 Board Of Trustees Of Michigan State University Novel catalyst for oxygen reduction reaction in fuel cells

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654307A (en) * 2017-01-10 2017-05-10 大连理工大学 Preparation method and application of noble metal@graphite layer core-shell structured electro-catalyst
CN106711467A (en) * 2017-01-10 2017-05-24 大连理工大学 Preparation method and application of platinum and core-shell structure carbon composite electrocatalyst
CN109921037A (en) * 2019-03-07 2019-06-21 曲阜师范大学 A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction
CN111530499A (en) * 2020-05-15 2020-08-14 中自环保科技股份有限公司 Synthesis method of core-shell alloy electrocatalyst with controllable structure

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