CN102513109B - Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof - Google Patents
Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof Download PDFInfo
- Publication number
- CN102513109B CN102513109B CN201110423168XA CN201110423168A CN102513109B CN 102513109 B CN102513109 B CN 102513109B CN 201110423168X A CN201110423168X A CN 201110423168XA CN 201110423168 A CN201110423168 A CN 201110423168A CN 102513109 B CN102513109 B CN 102513109B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- carbon
- precious metal
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a double-functional catalyst of carbon-based non-noble-metal oxygen electrode and a preparation method thereof. The catalyst is a composite material composed of metal, metal oxide grains, N-doped graphene, carbon spheres and nanotubes. The preparation method of the catalyst comprises the following steps of: 1) weighing graphite oxide or graphene oxide, the carbon spheres, a metal compound and a nitrogen-containing heterocyclic compound according to ratios; carrying out ultrasonic treatment on the raw materials in a solvent; uniformly agitating and sufficiently drying to obtain a precursor; and 2) carrying out high-temperature pyrolysis in a precursor inert atmosphere to obtain a composite material catalyst. The catalyst provided by the invention not only has the advantages of high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performances, good stability and excellent CH3OH/CO tolerance, but also the cost of the raw materials is low, and the preparation method is simple and is easy to operate.
Description
Technical field
The invention belongs to supply unit catalyst field such as fuel cell and brine electrolysis, relate in particular to a kind of non-precious metal catalyst and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells, methanol fuel cell, electrolytic water device and integral regeneratable fuel cell be it is believed that it is high-energy, high power, the free of contamination supply unit that solves the future source of energy problem.In the technical development, catalyst particularly oxygen electrode catalyst becomes one of its business-like main bottleneck of containment.Take all factors into consideration activity of such catalysts and stability, Pt and alloy catalyst thereof are used to oxygen reduction reaction (ORR), IrO in the electrolytic water device in Proton Exchange Membrane Fuel Cells, the methanol fuel cell at present
2/ RuO
2Be used to oxygen evolution reaction (OER), Pt and alloy catalyst thereof are used to oxygen reduction reaction (ORR), IrO in the integral regeneratable fuel cell
2/ RuO
2Be used to oxygen evolution reaction (OER).Yet the precious metals pt that uses in the catalyst, Ir, Ru are very limited at the occurring in nature reserves, and a large amount of noble metals that use make its cost high in the supply unit.Therefore, direction, especially non-precious metal catalyst that development and exploitation low noble metal and non-precious metal catalyst become this technical field development become the focus that people pay close attention to gradually, are expected for the hope of this technical field quantum jump.Non-precious metal catalyst is with low cost, is applicable to following large-scale development and commercial applications.In recent years, the research of non-precious metal catalyst obtains huge progress gradually, is mainly N doping carbon material, M (metallic elements such as Fe, Co and composition thereof)-N doping carbon material etc.At present, adopt noble metal catalyst in the supply unit, its shortcoming is resource-constrained, expensive, CH
3OH/CO tolerance and long-play poor stability; The non-precious metal catalyst of being expected by people is aboundresources, cheap then, but catalytic activity is far below noble metal catalyst, and catalytic activity and stability remain further to be improved.
Summary of the invention
At the deficiency that prior art exists, the present invention provides a kind of base metal composite oxygen electrode bifunctional catalyst and preparation method thereof in order to reduce the catalyst cost, to improve the base metal catalytic activity.Catalyst of the present invention can also increase catalyst stability, improve the CH of catalyst
3The OH tolerance.
The preparation method of base metal composite oxygen electrode bifunctional catalyst provided by the invention may further comprise the steps:
1) by graphene oxide: carbon ball: metallic compound: nitrogen-containing heterocycle compound mass ratio 1.5～4:1:0.2～1:80 takes by weighing, in solvent ultrasonic agitation evenly after, drying gets presoma, and described metallic compound is that oxide, salt and the organic compound of Fe, Co element is (as FeSO
4.7H
2O, FeCl
3, ferrocene, FePC, CoSO
4Deng) in one or more;
2) with presoma under inert atmosphere, behind 700-1000 ℃ of pyrolysis 0.5-2 h, obtain the base metal composite catalyst.
Above-mentioned graphene oxide (for which floor graphite oxide of individual layer or minority) is prepared by the Hummers chemical oxidization method of modification, graphite oxide or graphene oxide are pale brown color chips shape material, and size 200 ~ 1000 nm(are relevant with degree of oxidation and ultrasonic length power).
Above-mentioned preparation method, described carbon ball is a kind of among conductive black, active carbon, the BP-2000 etc. or composition that they are two or more.
Above-mentioned solvent can be organic solvent or inorganic solvent, as is water, ethanol and other dispersant.
The individual layer that obtains with graphite oxide or graphene oxide high-temperature process among the present invention or several layer graphene are carrier, Graphene has gap structure, big surface area and excellent conducting performance, can effectively disperse various materials, the different in nature element that mixes produces avtive spot; The carbon ball adds can further promote the electric conductivity of material, and makes Graphene better separate the increase effective surface area layer by layer; The adding of nitrogen-containing heterocycle compound helps equally Graphene is separated layer by layer, increases effective surface area, and doping N element and carbon source are provided simultaneously, and high temperature generates new nano tube structure in the presence of metal or metal oxide particle.The final conductivity of composite material that forms can be good, and big specific area produces a large amount of N-C and M-N-C activated centre, promoted ORR and the OER catalytic performance of catalyst greatly.
The preparation-obtained oxygen electrode bifunctional catalyst of the inventive method is the composite of being made up of Graphene, carbon ball, the nanotube of metal and metal oxide particle and N doping.In the catalyst, N-C and M-N-C are activity of such catalysts composition of the present invention.
Prepare in the catalyst, metal and metal oxide particle are nanoscale, and particle diameter is 10 ~ 50 nm, and independently are dispersed on the graphene film, are positioned at the nanotube pipe end or are wrapped in nanotube inside.
Prepare in the catalyst, the Graphene that N mixes is which floor curling tablet of individual layer or minority, is nanoscale or micron order, is of a size of 200 nm ~ 10 um.
Prepare in the catalyst, the carbon ball is nanoscale, and particle diameter is 10 ~ 50 nm, becomes state of aggregation to distribute.
Prepare in the catalyst, nanotube by nitrogen-containing heterocycle compound in the presence of metal or metal oxide, high-purity Ar, N
2Generate Deng high-temperature process in inert gas and the mixed atmosphere thereof, be nanoscale or micron order, caliber 10 ~ 200 nm, pipe range 100 nm ~ 20 um, become straight chain, bending, form such as hook-shaped, nanotube have hollow, end connects or the elongate tubular of interior containing metal or metal oxide particle, ring shape or cucurbit string shape.
Prepare in the catalyst, nanotube and graphene film evenly intersect support distribution.
The inventive method prepares in the catalyst, and metal and metal oxide exist with particle form, about 3 % of mass content, and atomic percent is about 0.7 %; N element atomic percent is 5% ~ 8%, mainly exist with pyridine N, pyrroles N, graphite N and four kinds of forms of N-O, and pyridine N content is the highest.
Compared with prior art, the present invention has following advantage and beneficial effect:
1) base metal oxygen electrode bifunctional catalyst of the present invention, the raw material of use is commercially produced product, is easy to purchase and preparation, and aboundresources is cheap, thereby can reduce the cost of catalyst significantly;
2) base metal oxygen electrode bifunctional catalyst of the present invention has CH preferably
3The OH tolerance, 0.1 M HClO
4Add 0.1 M CH in the electrolyte
3The catalytic activity that the OH test obtains is not decay almost;
3) base metal oxygen electrode bifunctional catalyst of the present invention is a kind of novel three-dimensional composite material, have hydrogen reduction preferably and oxygen simultaneously and separate out activity, the base metal/non-metallic catalyst of research report only has one-side hydrogen reduction activity to have significant advantage at present;
4) base metal oxygen electrode bifunctional catalyst of the present invention is compared with commercial 20 wt.% Pt/C catalyst, and stability obviously improves, and in the long-term use of fuel cell, catalytic activity is kept well;
5) base metal oxygen electrode bifunctional catalyst of the present invention is studied non-precious metal catalyst/non-metallic catalyst of reporting more at present has obviously good oxygen to separate out activity, and the active good mesoporous IrO of bibliographical information in the near future
2Catalytic activity;
6) base metal oxygen electrode bifunctional catalyst preparation method of the present invention is easy, and easy operating is suitable for large-scale production.
Description of drawings
The hydrogen reduction polarization curve that the non-precious metal catalyst N-CNT/N-Graphene that Fig. 1 prepares for embodiment 1 and Pt/C are initial;
The non-precious metal catalyst N-CNT/N-Graphene that Fig. 2 prepares for embodiment 1 and the initial oxygen of Pt/C are separated out polarization curve;
The non-precious metal catalyst N-CNT/N-Graphene that Fig. 3 prepares for embodiment 1 and Pt/C initial with add 0.1 M CH
3Hydrogen reduction polarization curve behind the OH;
Fig. 4 be commercial 20 wt.% Pt/C initial with add 0.1 M CH
3Hydrogen reduction polarization curve behind the OH;
Fig. 5 is non-precious metal catalyst N-CNT/N-Graphene and the Pt/C long-play stability curve (i-t curve) of embodiment 1 preparation;
Fig. 6 is the TEM figure of the non-precious metal catalyst N-CNT/N-Graphene of embodiment 1 preparation.
The specific embodiment
For a better understanding of the present invention, the present invention is described further below in conjunction with embodiment.
The Pt/C catalyst (being designated hereinafter simply as Pt/C) of choosing commercial 20 wt.% in the embodiment of the invention is catalyst as a comparison, and the chemical property of itself and embodiment of the invention gained base metal oxygen electrode bifunctional catalyst is compared.
Embodiment 1
1) contains the preparation of Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains Fe and FeO
xNon-precious metal catalyst.
2) test contains the catalytic performance of Fe non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, ORR and the OER catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show preparation contain the Fe non-precious metal catalyst study more at present the report base metal (nonmetal) catalyst catalytic activity is preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 40 mV(as shown in Figure 1).
The OER polarization curve shows that the more commercial 20 wt.% Pt/C catalyst of Fe non-precious metal catalyst that contain of preparation have obviously good OER activity (as shown in Figure 2).Simultaneously, base metal (nonmetal) catalyst that catalyst is studied report more at present has obviously OER catalytic activity preferably, and the well mesoporous IrO of bibliographical information in the near future of catalytic activity
2Catalytic activity.
3) test contains the methanol tolerance oxidation susceptibility of Fe non-precious metal catalyst
Non-precious metal catalyst and commercially available Pt/C catalyst to preparation have carried out the test of methanol tolerance oxidation susceptibility, and the non-precious metal catalyst of preparation has shown excellent methanol tolerance oxidation susceptibility (as shown in Figure 3).Method of testing only is changed to electrolyte the methyl alcohol mixed liquor of perchloric acid+0.1 mol/L of 0.1 mol/L, the catalytic activity of the identical test down of other conditions oxygen reduction reaction.The oxygen reduction reaction polarization curve shows that the non-precious metal catalyst catalytic activity of preparation is almost without any decay, and strong methanol oxidation peak appears in 20 commercially available wt.% Pt/C catalyst, half wave potential descends more than 200 mv (as shown in Figure 4), about 200 mv of non-precious metal catalyst half wave potential difference of preparation.
4) test contains the stability of Fe non-precious metal catalyst
In addition, non-precious metal catalyst and the Pt/C to preparation carries out long-play stability test (as shown in Figure 5).Method of testing is at O
2In the saturated electrolyte, under the permanent electromotive force of 0.62 V (vs.RHE), the electrode rotating speed is test 100000 s under the 1600 rpm conditions.The i-t curve is the result show, the non-precious metal catalyst for preparing has less initial current than Pt/C, behind the long-play, the electric current of non-precious metal catalyst shows that obviously greater than Pt/C the non-precious metal catalyst for preparing has stability preferably than Pt/C.
Used graphene oxide can be replaced by graphite oxide or Graphene in the present embodiment, vulcan XC-72 carbon black can be replaced by one or both and above mixture in various conductive carbon blacks, the active carbon etc., the ratio 4:1 of graphite oxide or graphene oxide and carbon ball～3:2 is adjustable, FeSO
4.7H
2O can be by the various oxides, salt and the organic compound that contain Fe (as FeSO
4.7H
2O, FeCl
3, ferrocene, FePC etc.) in the mixture of one or more compounds replace, consumption increasing or adding certain amount of surfactant, urea etc. are short molten in the comparable example of nitrogen-containing heterocycle compound amount, and aqueous solvent can add the short dispersion of ethanol or be replaced by other easy dispersion polar solvent.More than replace the every performance that does not all influence the gained catalyst.
1) GO(graphene oxide)/C is the preparation that 4:1 contains the Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 4:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains Fe or FeO
xNon-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 100 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 500 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 80 mV.
Embodiment 3
1) GO/C is the preparation that 3:2 contains the Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:2, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains Fe or FeO
xNon-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 100 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 500 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 80 mV.
Embodiment 4
1) handle to such an extent that contain the preparation of Fe non-precious metal catalyst for 700 ℃
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 700 ℃ of high temperature pyrolysis; time 1 h obtains black and contains the Fe non-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 140 mV.
1) handle to such an extent that contain the preparation of Fe non-precious metal catalyst for 1000 ℃
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 1000 ℃ of high temperature pyrolysis; time 1 h obtains black and contains Fe or FeO
xNon-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 140 mV.
1) M/C is the preparation that 1:5 contains the Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 1:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains the Fe non-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 100 mV.
Embodiment 7
1) M/C is the preparation that 1:1 contains the Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 1:1
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains the Fe non-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 100 mV.
Embodiment 8
1) high temperature 0.5 h must contain the preparation of Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 1:1
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 1000 ℃ of high temperature pyrolysis; time 0.5 h obtains black and contains the Fe non-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 70 mV.
Embodiment 8
1) high temperature 2 h must contain the preparation of Fe non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 1:1
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; times 2 h obtains black and contains the Fe non-precious metal catalyst.
2) catalytic performance of test non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is relatively preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 90 mV.
Embodiment 9
1) contains the preparation of Co non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing CoSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O; take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains black and contains the Co non-precious metal catalyst.
2) test contains the catalytic performance of Co non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show preparation contain the Co non-precious metal catalyst study more at present the report base metal (nonmetal) catalyst catalytic activity is preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 80 mV.
1) contains the preparation of Fe/Co non-precious metal catalyst
Take by weighing two kinds of materials by graphene oxide and vulcan XC-72 carbon black mass ratio 3:1, take by weighing FeSO with the mass ratio with vulcan XC-72 carbon black 2:5
4.7H
2O and CoSO
4.7H
2O(mass ratio 1:1); take by weighing nitrogen-containing heterocycle compound with the mass ratio with vulcan XC-72 carbon black 80:1; above-mentioned substance is scattered in (can add small amount of ethanol urgees to disperse) in the aqueous solvent; it is powerful that ultrasonic to revolve evaporate to dryness dry to stirring back 60 ℃; obtain the Powdered precursor of taupe, precursor is put in high-purity Ar inert gas shielding in the tube furnace, 900 ℃ of high temperature pyrolysis; time 1 h obtains the black non-precious metal catalyst.
2) test contains the catalytic performance of Fe/Co non-precious metal catalyst
The appropriate amount of catalysts powder being dispersed in the aqueous isopropanol of Nafion, is that 120 μ g get the catalyst dispersion liquid and are coated in the glass-carbon electrode surface preparation and become working electrode by the electrode surface catalyst loading.Simultaneously, be that 20 μ gs be coated in glass-carbon electrode surface preparation become working electrode with 20 commercially available wt.% Pt/C catalyst by the electrode surface catalyst loading by above-mentioned same method.
Adopt three-electrode system to test the non-precious metal catalyst of preparation and the chemical property of commercially available Pt/C catalyst respectively, concrete test is as follows: the perchloric acid with 0.1 mol/L is electrolyte, 28 ° of C(± 2 ° C) water-bath temperature control, adopt big platinized platinum conduct to electrode, adopt saturated calomel electrode as reference electrode, reference electrode is placed salt bridge, the salt bridge other end insert electrolytic cell and by capillary tip near working electrode.In the saturated electrolyte of Ar, the hydrogen-oxygen adsorption desorption characteristic curve of the non-precious metal catalyst of 50 mV/s sweep speeds test preparation and commercially available Pt/C catalyst; At O
2In the saturated electrolyte, the ORR catalytic activity of the non-precious metal catalyst of 5 mV/s sweep speeds, electrode rotating speed 1600 rpm test preparation and commercially available Pt/C catalyst.
The ORR polarization curve show the non-precious metal catalyst of preparation study more at present the report base metal (nonmetal) catalyst catalytic activity is preferably arranged, and catalytic activity and commercial 20 wt.% Pt/C catalyst hardly differ the non-precious metal catalyst of preparation (carrying capacity: 600 ug/cm
2) and commercially available Pt/C catalyst loading: (100 ug/cm
2) half wave potential differs ~ 60 mV.
Claims (8)
1. the preparation method of a carbon back base metal oxygen electrode bifunctional catalyst may further comprise the steps:
1) by graphene oxide: carbon ball: metallic compound: nitrogen-containing heterocycle compound mass ratio 1.5～4:1:0.2～1:80 takes by weighing, in solvent ultrasonic agitation evenly after, drying gets presoma, and described metallic compound is one or more in oxide, salt and the organic compound of Fe, Co element;
2) with presoma under inert atmosphere, behind 700-1000 ℃ of pyrolysis 0.5-2 h, obtain carbon back base metal oxygen electrode bifunctional catalyst.
2. preparation method according to claim 1 is characterized in that, described carbon ball is one or both in conductive black, the active carbon.
3. preparation method according to claim 1 and 2 is characterized in that, described solvent is organic solvent or inorganic solvent.
4. preparation method according to claim 1 and 2 is characterized in that, preparation-obtained carbon back base metal oxygen electrode bifunctional catalyst is the composite of being made up of Graphene, carbon ball, the nanotube of metal and metal oxide particle and N doping.
5. preparation method according to claim 4 is characterized in that, in the carbon back base metal oxygen electrode bifunctional catalyst for preparing, metal and metal oxide particle are nanoscale, and particle diameter is 10 ~ 50 nm.
6. preparation method according to claim 4 is characterized in that, in the carbon back base metal oxygen electrode bifunctional catalyst for preparing, the Graphene that N mixes is nanoscale or micron order, is of a size of 200 nm ~ 10 um.
7. preparation method according to claim 4 is characterized in that, in the carbon back base metal oxygen electrode bifunctional catalyst for preparing, the carbon ball is nanoscale, and particle diameter is 10 ~ 50 nm, becomes state of aggregation to distribute.
8. the preparation-obtained carbon back base metal of each described preparation method oxygen electrode bifunctional catalyst in the claim 1～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110423168XA CN102513109B (en) | 2011-12-16 | 2011-12-16 | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110423168XA CN102513109B (en) | 2011-12-16 | 2011-12-16 | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102513109A CN102513109A (en) | 2012-06-27 |
| CN102513109B true CN102513109B (en) | 2013-08-21 |
Family
ID=46284325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110423168XA Expired - Fee Related CN102513109B (en) | 2011-12-16 | 2011-12-16 | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102513109B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165911B (en) * | 2013-02-01 | 2016-08-31 | 武汉理工大学 | There is fuel battery negative pole non-metallic catalyst and the preparation of nanometer sandwich structure |
| CN103094584B (en) * | 2013-02-01 | 2015-09-30 | 武汉理工大学 | Nanometer sandwich structure fuel cell non-precious metal catalyst, membrane electrode and preparation method |
| CN103962139B (en) * | 2013-02-05 | 2016-08-24 | 中国科学院大连化学物理研究所 | The preparation method and application of the base metal eelctro-catalyst that a kind of Graphene supports |
| CN104107729B (en) * | 2013-04-16 | 2017-03-15 | 中国石油化工股份有限公司 | The renovation process of epoxidation catalyst |
| CN103252250B (en) * | 2013-04-25 | 2015-07-08 | 西北师范大学 | Preparation method and application of nitrogen and iron modified carbon material |
| CN104117356B (en) * | 2013-04-26 | 2017-04-12 | 中国科学院大连化学物理研究所 | Preparation method of non-noble metal catalyst used for oxygen reduction reaction |
| CN104174439B (en) * | 2013-05-27 | 2016-12-28 | 中国科学院大连化学物理研究所 | The preparation of a kind of eelctro-catalyst based on transition metal macrocyclic compound and application |
| CN103296292B (en) * | 2013-06-04 | 2015-03-25 | 武汉大学 | Alkaline fuel cell cathode carbon catalyst and preparation method thereof |
| CN103920519B (en) * | 2014-04-23 | 2016-03-30 | 西南大学 | The preparation method of the oxygen reduction electro-catalyst of nitrogen-doped graphene is strengthened based on ferrotungsten bimetallic oxide |
| CN104118874B (en) * | 2014-07-11 | 2016-04-13 | 武汉工程大学 | A kind of preparation method of gac/graphene complex |
| CN104190459B (en) * | 2014-07-29 | 2016-08-17 | 中国科学院合肥物质科学研究院 | A kind of nitrogen-doped graphene is coated with preparation method nanocrystalline for FeCo and the application of prepared product thereof |
| CN105749947B (en) * | 2014-12-16 | 2018-06-26 | 中国科学院大连化学物理研究所 | A kind of non noble metal oxygen reduction catalyst and its preparation and application |
| CN104667869B (en) * | 2015-02-11 | 2016-10-05 | 四川大学 | A kind of single persulfate and load ferro-cobalt two-phase combined oxidation Graphene is utilized to remove the method for incretion interferent in water |
| CN104966842B (en) * | 2015-06-05 | 2018-08-28 | 清华大学 | A kind of water oxidation reaction catalyst and preparation method thereof based on porous carbon materials |
| CN105140531B (en) * | 2015-09-23 | 2017-06-16 | 太原理工大学 | For the three dimensional anodes material and preparation method of water electrolysis hydrogen production |
| CN105289729A (en) * | 2015-11-09 | 2016-02-03 | 中国科学院化学研究所 | Non-precious metal oxygen reduction catalyst and preparing method and application thereof |
| CN106391088B (en) * | 2016-10-24 | 2018-10-23 | 长春理工大学 | A kind of three-dimensional grapheme bi-functional oxygen electrode catalyst and preparation method thereof |
| CN107093746A (en) * | 2017-04-28 | 2017-08-25 | 深圳市航盛新材料技术有限公司 | Iron cobalt carbon composite oxides and preparation method thereof, metal-air battery |
| CN107346826B (en) * | 2017-07-05 | 2020-07-24 | 北京化工大学 | Preparation method of monatomic iron dispersed oxygen reduction electrocatalyst |
| CN110354884A (en) * | 2019-06-27 | 2019-10-22 | 华南师范大学 | A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application |
| CN110544774B (en) * | 2019-09-09 | 2020-11-10 | 长春理工大学 | Transition metal nanocrystalline-nitrogen-doped carbon nanotube composite bifunctional catalyst and preparation method and application thereof |
| CN112002907B (en) * | 2020-07-29 | 2022-06-17 | 天津大学 | Composite electrode material for oxygen reduction reaction and application thereof |
| CN111952603B (en) * | 2020-07-29 | 2022-05-20 | 天津大学 | Preparation method of composite electrode material for oxygen reduction reaction |
| CN112086652B (en) * | 2020-09-15 | 2022-02-25 | 香港科技大学深圳研究院 | Hollow carbon sphere/graphene bifunctional catalyst and preparation method and application thereof |
| CN114318412B (en) * | 2022-01-27 | 2023-04-11 | 江西师范大学 | Limited-domain N-doped Fe nano-particles and preparation method and application thereof |
| CN114824329A (en) * | 2022-05-20 | 2022-07-29 | 南京师范大学 | Iron-containing monatomic catalyst and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184710C (en) * | 2002-09-28 | 2005-01-12 | 中国科学院上海微系统与信息技术研究所 | Electric Pt-multiple wall carbon nanotube catalyst and its prepn |
| US7097933B2 (en) * | 2003-06-09 | 2006-08-29 | Ovonic Battery Company, Inc. | Catalyst for fuel cell oxygen electrodes |
| CN100464841C (en) * | 2006-12-29 | 2009-03-04 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
| CN101811062B (en) * | 2009-02-20 | 2014-03-12 | 中国科学院大连化学物理研究所 | Catalyst based on non-noble metal and preparation method thereof, electrode and fuel cell containing catalyst |
-
2011
- 2011-12-16 CN CN201110423168XA patent/CN102513109B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102513109A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102513109B (en) | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof | |
| Mei et al. | Boosting the ORR active and Zn-air battery performance through ameliorating the coordination environment of iron phthalocyanine | |
| Zhang et al. | Formic acid-reduced ultrasmall Pd nanocrystals on graphene to provide superior electocatalytic activity and stability toward formic acid oxidation | |
| Ren et al. | Pd nanocrystals anchored on 3D hybrid architectures constructed from nitrogen-doped graphene and low-defect carbon nanotube as high-performance multifunctional electrocatalysts for formic acid and methanol oxidation | |
| Han et al. | Fe, Co bimetal activated N-doped graphitic carbon layers as noble metal-free electrocatalysts for high-performance oxygen reduction reaction | |
| CN103537299B (en) | A kind of carbon carries Co core-Pt core/shell nanoparticles Catalysts and its preparation method | |
| Sekar et al. | Ultrathin VS2 nanosheets vertically aligned on NiCo2S4@ C3N4 hybrid for asymmetric supercapacitor and alkaline hydrogen evolution reaction | |
| Cao et al. | Template-free and one-pot synthesis of N-doped hollow carbon tube@ hierarchically porous carbon supporting homogeneous AgNPs for robust oxygen reduction catalyst | |
| Wang et al. | In situ synthesis of Pt/carbon nanofiber nanocomposites with enhanced electrocatalytic activity toward methanol oxidation | |
| CN107029772A (en) | A kind of non-precious metal catalyst and preparation method thereof | |
| Wang et al. | Metal-organic gel-derived Fe-Fe2O3@ nitrogen-doped-carbon nanoparticles anchored on nitrogen-doped carbon nanotubes as a highly effective catalyst for oxygen reduction reaction | |
| CN103252250A (en) | Preparation method and application of nitrogen and iron modified carbon material | |
| Chai et al. | A facile precipitation procedure for synthesis of binary Sn-Co oxide promoting Pd catalyst towards glucose electrooxidation | |
| CN104218250A (en) | PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell | |
| CN103296292B (en) | Alkaline fuel cell cathode carbon catalyst and preparation method thereof | |
| Zhang et al. | Three-dimensional hybrid aerogels built from graphene and polypyrrole-derived nitrogen-doped carbon nanotubes as a high-efficiency Pt-based catalyst support | |
| CN103831103A (en) | Graphene aerogel catalyst and preparation method thereof | |
| Yan et al. | Three-dimensional reduced graphene oxide–Mn3O4 nanosheet hybrid decorated with palladium nanoparticles for highly efficient hydrogen evolution | |
| Zhou et al. | Pt supported on boron, nitrogen co-doped carbon nanotubes (BNC NTs) for effective methanol electrooxidation | |
| Wang et al. | Electrochemical synthesis of Pt nanoparticles on ZrO2/MWCNTs hybrid with high electrocatalytic performance for methanol oxidation | |
| Li et al. | Bimetal-MOF and bacterial cellulose-derived three-dimensional N-doped carbon sheets loaded Co/CoFe nanoparticles wrapped graphite carbon supported on porous carbon nanofibers: An efficient multifunctional electrocatalyst for Zn-air batteries and overall water splitting | |
| Su et al. | Palladium nanoparticles immobilized in B, N doped porous carbon as electrocatalyst for ethanol oxidation reaction | |
| Kang et al. | Activated palladium deposited on defect-rich carbon and cobalt oxide composite materials as bi-functional catalysts for stable rechargeable Zn–air battery | |
| Zhao et al. | A novel support of nano titania modified graphitized nanodiamond for Pt electrocatalyst in direct methanol fuel cell | |
| Wang et al. | Nitrogen-doped mesoporous carbon nanosheet network entrapped nickel nanoparticles as an efficient catalyst for electro-oxidation of glycerol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130821 Termination date: 20141216 |
|
| EXPY | Termination of patent right or utility model |