CN108543545B - A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications - Google Patents

A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications Download PDF

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CN108543545B
CN108543545B CN201810409459.5A CN201810409459A CN108543545B CN 108543545 B CN108543545 B CN 108543545B CN 201810409459 A CN201810409459 A CN 201810409459A CN 108543545 B CN108543545 B CN 108543545B
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catalyst
feni
ncnt
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tri
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CN108543545A (en
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李光兰
陈文雯
袁丽芳
杨贝贝
徐晓存
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Dalian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/33
    • B01J35/40
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9041Metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9075Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications, belong to energy and material and electrochemical field.The catalyst with dicyandiamide be the source C and the source N, ferric citrate, NiCl2·6H2O is source metal, using " one kettle way " be pyrolyzed in two stages a step be made.FeNi metallic in catalyst is largely uniformly wrapped in the carbon nanotube tube wall of " Bamboo-shaped " N doping, is distributed in carbon nanotube tip on a small quantity.Compared with common metal alloy oxygen reduction reaction and oxygen evolution reaction bifunctional catalyst, which also shows good oxygen evolution reaction activity and stability under alkaline condition;And preparation method is simple, it is raw materials used it is at low cost, source is wide;It can be widely applied to the fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery, there is high value of practical.

Description

A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation Method and its application
Technical field
The invention belongs to energy and material and electrochemical fields, are related to a kind of applied to fuel cell, electrolysis water and metal-sky The elctro-catalyst and preparation method of pneumoelectric pond oxygen reduction reaction and oxygen evolution reaction, and in particular to a kind of tri- doped carbon of Fe, Ni, N is received Mitron cladded type FeNi@NCNT catalyst, preparation method and applications.
Background technique
Fuel cell, electrolysis water and metal-air battery etc. are the hot spots of recent domestic scholar research.However, oxygen It is fast that the bottleneck that electrode reaction (oxygen reduction reaction (ORR) and oxygen evolution reaction (OER)) dynamics is slow problem strongly limits it Speed development needs research and development effective catalyst and improves reaction rate, reduces overpotential.Currently, Pt base catalyst is acknowledged as urging Change the most outstanding catalyst of ORR, but its OER performance is poor;IrO2、RuO2Although catalyst OER performance is higher, its ORR Performance is very low.Moreover, these noble metals of Pt, Ir, Ru are expensive, reserves are limited, stability is poor, it is unable to satisfy extensive Commercial applications demand.Therefore, there is an urgent need to develop with high catalytic activity, low cost and good stability ORR and OER it is bis- Function non-precious metal catalyst.
Transition metal (such as Fe, Co, Ni) base elctro-catalyst is lived due to cheap, rich reserves, environmental-friendly, catalysis Property is higher etc., it is considered to be the catalyst of most potential alternative precious metal catalyst ORR and OER.Especially bimetallic base is urged Agent, it is possible to provide variation of valence abundant is of great significance to ORR and OER performance is improved.However, transition metal base is catalyzed It is agent poorly conductive, easy to reunite, need to further increase its catalytic performance.By in the carbon with high-specific surface area and high conductivity Or original position anchor closes the strategy of metal_based material on hetero atom (N, P, S etc.) doping carbon material, can greatly improve catalyst conduction Property while may additionally facilitate the dispersion of metal, improve the mass transfer ability of electronics conduction, molecular/ionic, and Heteroatom doping carbon Material also advantageously improves ORR activity, thus is a kind of very effective side for improving ORR and OER bifunctional catalyst performance Method.
Document [Adv.Sustainable Syst.2017,1,1700020] is coated by solvent structure poly-dopamine Metal precursor (FeM/PDA, M=Ni, Co), then the method for high temperature cabonization has been made FeNi, FeCo and has coupled N doping in situ Porous carbon materials FeM/NPC (M=Ni, Co).The experimental results showed that FeM/NPC (M=Ni, Co) catalyst is in same electrolyte In show good ORR, OER and HER activity.However, time-consuming for the catalyst preparation process, experiment condition is up for into one Step is improved.Fu etc. [Adv.Funct.Mater.2018,28,1705094] using electrostatic spinning technique by polyvinylpyrrolidone, Polyacrylonitrile, Ni (NO3)2·6H2O and Co (NO3)2·6H2Nanofiber is made in the mixed solution of O, and subsequent high temperature pyrolysis is made The N dopen Nano fiber of NiCo alloy modification.The experimental results showed that the catalyst shows higher ORR under alkaline condition With OER Activity and stabill.However, the nanofiber that electrostatic spinning technique is prepared is not readily separated, low yield, intensity difference, And the catalyst preparation process is many and diverse, is unfavorable for large scale preparation.
In conclusion the nitrogen-doped carbon material (MM '/NC) of bimetallic base modification shows good catalysis ORR and OER mistake The potential of journey, but preparation process is up for being further simplified.So simplify preparation process, reduce cost and design be easy to advise greatly The efficient MM ' of mould industrialized production/NC catalyst has important practical significance and application value.
The present invention uses dicyandiamide cheap, that raw material sources are wide for the source C and the source N, ferric citrate and NiCl2· 6H2O is source metal, using a kind of " one kettle way " pyrogenically prepared tri- doped carbon nanometer pipe of Fe, Ni, N of substep under an inert atmosphere FeNi@NCNT catalyst is coated, for being catalyzed ORR and OER process.This method preparation process is simple, low in cost, is easy to amplify Production, it is often more important that the FeNi@NCNT large specific surface area of synthesis, metal are coated by carbon nanotube, are conducive to improve material Catalytic activity and stability.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of tri- doped carbon nanometer pipe cladded type FeNi@of Fe, Ni, N NCNT catalyst, preparation method and applications, the catalyst use cheap dicyandiamide for the source C and the source N, ferric citrate And NiCl2·6H2O is source metal, and using " one kettle way ", substep is pyrogenically prepared under an inert atmosphere.FeNi metal in catalyst Particle is largely uniformly wrapped in the carbon nanotube tube wall of " Bamboo-shaped " N doping, is distributed in point inside carbon nanotube on a small quantity End.FeNi nanoparticle in tube wall facilitates the distribution of regulating catalyst surface electronic, improves catalyst activity;It avoids simultaneously FeNi nanoparticle and electrolyte contacts inhibit the reunion of FeNi nanoparticle, improve the stability of material.On the other hand, N mixes Miscellaneous carbon nanotube can provide high specific surface area and electric conductivity, be conducive to the mass transport process of electronics conduction and reaction species.With it is normal The metal alloy oxygen reduction reaction seen is compared with oxygen evolution reaction bifunctional catalyst, which also shows under alkaline condition Good oxygen evolution reaction activity and stability;And preparation method is simple, it is raw materials used it is at low cost, source is wide, be conducive to scale Production;It can be widely applied to the fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery, it is with higher practical Value.
In order to achieve the above object, of the invention the technical solution adopted is as follows:
A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, the catalyst are unique " ring Shape " carbon nanotube, metal object phase FeNi alloy and Fe3O4It is coated in NCNT, and is mainly dispersed in the tube wall of NCNT Portion, some particles are located at the tip inside pipe, effectively avoid metallic in reaction process from contacting with the direct of electrolyte, help In the stability for improving catalyst.The incorporation of hetero atom N can create more active sites;Bimetallic combination can provide abundant Variation of valence can be catalyzed ORR and OER reaction simultaneously.
The preparation step of above-mentioned tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N is as follows:
1) dissolving metal salts Yu Shuizhong is obtained into solution A, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol is obtained Solution B;Wherein, the molar ratio of dicyandiamide and metal salt (iron and nickel) is 10:1-80:1, and iron nickel molar ratio is 1:0-1:10, water Volume ratio with ethyl alcohol is 20:1-1:20.The metal salt includes ferric citrate ((NH4)3FeC12H10O14, AFC) and NiCl2·6H2O。
2) drying steps 1) resulting solution B, catalyst pyrolytic precursors are made;
3) calcining step 2) in gained catalyst precarsor obtain FeNi@NCNT catalyst
Under inert gas shielding, 1-20 DEG C of min-1Temperature programming is to 400-600 DEG C of calcining 1-4h, then 3-10 DEG C of min-1 It is warming up to after calcining 1-10h at 650-1200 DEG C of pyrolysis temperature, FeNi@NCNT catalyst is obtained after natural cooling.
Ferric citrate described in step 1) or NiCl2·6H2O can be the transition metal such as Mn, Co, Ni, Cu or Zn The mixture of one or more of soluble-salt.
Drying means described in step 2) is vacuum drying, dry, the inert atmosphere drying of air atmosphere etc., drying temperature It is 0-150 DEG C, drying time 3-100h.
Above-mentioned tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N is used as fuel cell, electrolysis water or gold Negative (negative) pole ORR and/or the OER elctro-catalyst of category-air cell.
Compared with prior art, carbon nanotube cladded type FeNi@NCNT catalyst of the present invention and preparation method tool There is following advantage:
1) the tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N prepared using the method for the invention, Pattern is bamboo-like carbon nano tubes, is conducive to provide high specific surface area and electric conductivity, increases catalyst (solid phase), oxygen, electricity The area of liquid three-phase reaction interface is solved,
2) the tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N prepared using the method for the invention, FeNi nanoparticle is mainly dispersed in inside carbon nanotube tube wall, and FeNi nanoparticle on the one hand may be by changing surface The electronics distribution of graphene carbon nanotube walls influences the activity of catalyst, while FeNi active sites can be to avoid electrolyte and electrification The corrosion of process inhibits the reunion of metal nanoparticle, is conducive to the electro-chemical activity and stability that improve catalyst.
3) using the FeNi@NCNT catalyst of the method for the invention preparation, pass through regulation raw material ingredient proportion and preparation Process, such as precursor type, content ratio, calcination temperature, the achievable catalysis dosage form of calcination time of metal source of iron and nickel source The controllable preparation of looks, structure.
4) the FeNi@NCNT catalyst for using the method for the invention to prepare is using dicyandiamide for the source C and the source N, citric acid Iron ammonium and NiCl2·6H2O is source metal, and low in raw material price is easy to get, and helps to be mass produced.
5) using the FeNi@NCNT catalyst of the method for the invention preparation, using " one kettle way ", pyrolysis is primary stage by stage It is prepared, preparation process is simple, economical, safe, reproducible, is conducive to the amplification production of the catalyst.
6) it using the FeNi@NCNT catalyst of the method for the invention preparation, is shown in alkaline electrolyte good ORR catalytic performance, and close to commercialization 20wt.%Pt/C catalyst, it can be used for fuel cell, electrolysis water, metal-air electricity Pond etc. is multi-field.
7) it using the FeNi@NCNT catalyst of the method for the invention preparation, is shown in alkaline electrolyte good OER catalytic performance, and OER performance is better than Pt/C catalyst, can be used as metal-air battery catalyst, apparatus for electrolyzing etc. Catalyst be widely applied.
8) using the FeNi@NCNT catalyst of the method for the invention preparation, excellent ORR and OER catalysis are provided simultaneously with Activity is the double-function catalyzing material that the devices such as chargeable metal-air battery need.
Detailed description of the invention:
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 2.
Fig. 2 is that transmission electron microscope (TEM) photo of sample is made according to embodiment 2 under the conditions of 100nm.
Fig. 3 is that transmission electron microscope (TEM) photo of sample is made according to embodiment 2 under the conditions of 20nm.
Fig. 4 (a) is the isothermal nitrogen adsorption desorption curve (BET) that sample is made according to embodiment 2;Fig. 4 (b) is according to BET The pore distribution curve of sample is made in embodiment 2 obtained by (Fig. 4 (a)) figure.
Fig. 5 (a) is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity The ORR polarization curve in liquid is solved, test voltage range is -0.8~0.2V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 5 (b) is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity The OER polarization curve in liquid is solved, test voltage range is 0~1V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 6 (a) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 6 (b) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH OER polarization curve in electrolyte, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 7 (a) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 7 (b) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH OER polarization curve in electrolyte, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 8 be the sample according to made from embodiment 2 at room temperature, respectively in O2Saturation and N2The 0.1mol L of saturation-1KOH CV figure in electrolyte, sweeps speed: 50mV s-1
Fig. 9 is the sample according to made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte Volt-ampere (LSV) curve is retouched, sweeps speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm.
Figure 10 is Koutecky-Levich (K-L) song obtained according to the LSV curve (Fig. 9) that sample is made in embodiment 2 Line.
Figure 11 is the sample according to made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte In chronoamperogram, revolving speed: 1600rpm, voltage are constant in -0.4V.
Figure 12 (a) is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-18000 circles follow in KOH electrolyte ORR activity comparison diagram after ring, CV scanning range -0.4-0.1V sweep speed: 10mV s-1, revolving speed: 1600rpm;
Figure 12 (b) is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-12000 circles follow in KOH electrolyte OER activity comparison diagram after ring, CV scanning range 0.2-0.7V sweep speed: 10mV s-1, revolving speed: 1600rpm.
Figure 13 is the difference of sample made from embodiment 2 N at room temperature2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation 0.1mol L-1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed: 10mV s-1
Figure 14 be comparative example 1 be commercialized 20wt.%Pt/C catalyst respectively at room temperature, O2The 0.1mol L of saturation-1KOH Electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed: 10mV s-1
Specific embodiment
The present invention is explained in detail below with reference to specific example, but the present invention is not limited only to these specific implementations Example.
Embodiment 1:DA-Fe3(DA is dicyandiamide, Fe to Ni-8003Ni refers to ferric citrate and NiCl in raw material2·6H2O's Molal weight ratio is 3:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.1103g and 0.0178g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath 30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling Obtain Fe3Ni@NCNT-800 catalyst (DA-Fe3Ni-800)。
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 2:DA-FeNi-8002·6H2O's rubs Your mass ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath 30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Embodiment 3:DA-FeNi3- 800 (DA: dicyandiamide, FeNi3Refer to ferric citrate and NiCl in raw material2·6H2O's Molal weight ratio is 1:3, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.0367g and 0.0535g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath 30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling Obtain FeNi3@NCNT-800 catalyst (DA-FeNi3-800)。
Embodiment 4:DA-FeNi-700 (DA: dicyandiamide, Fe3Ni refers to ferric citrate and NiCl in raw material2·6H2O's rubs Your mass ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 700 refer to that pyrolysis temperatures are 700 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath 30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 700 DEG C and calcines 1h again, after natural cooling Obtain FeNi@NCNT-700 catalyst (DA-FeNi-700).
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 5:DA-FeNi-9002·6H2O's rubs Your mass ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 900 refer to that pyrolysis temperatures are 900 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath 30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 900 DEG C and calcines 1h again, after natural cooling Obtain FeNi@NCNT-900 catalyst (DA-FeNi-900).
(DA: dicyandiamide, Fe are ferric citrate, mole 0.15mM, DA and metal to embodiment 6:DA-Fe-800 The molar ratio of Fe is about 79:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
The ferric citrate of 0.0735g is dissolved in 10mL deionized water, solution A is obtained;The dicyandiamide of 1g is weighed again Solution B is obtained in the mixed solution being dissolved in A and 20mL dehydrated alcohol, 30min is stirred at 60 DEG C of oil bath, sufficiently to dissolve It is uniformly mixed;Uniformly mixed solution B is transferred in culture dish, the dry 11h of 60 DEG C of air drying cabinets, before obtaining catalyst Body;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Program liter Temperature is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, Fe@NCNT-800 is obtained after natural cooling and is urged Agent (DA-Fe-800).
(DA: dicyandiamide, Ni refer to NiCl to embodiment 7:DA-Ni-8002·6H2O, mole 0.15mM, DA and metal The molar ratio of Ni is about 79:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
By 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, obtains solution A;The dicyandiamide for weighing 1g again is molten Solution obtains solution B in the mixed solution of A and 20mL dehydrated alcohol, stirs 30min at 60 DEG C of oil bath, with abundant dissolution mixing Uniformly;Uniformly mixed solution B is transferred in culture dish, the dry 11h of 60 DEG C of air drying cabinets obtains catalyst precarsor;It will Drying gained precursor is placed in mortar, and grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming is extremely 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, (DA-Ni-800) catalyst is obtained after natural cooling (DA-Ni-800)。
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 8:DA-FeNi-800-Z2·6H2O's Molal weight ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C, and Z refers to that vacuum is dry It is dry)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath 30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of vacuum ovens are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Embodiment 9:DA19-FeNi-800(DA19- FeNi refers to dicyandiamide and ferric citrate and NiCl2·6H2O is total to rub You are than being about 19:1, and FeNi molar ratio is 1:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.1505g and 0.0713g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath 30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 10:DA-FeNi-800-22·6H2O's Molal weight ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C, and 2 refer to 800 DEG C Lower calcining 2h)
By the ferric citrate of 0.0395g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath 30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry 11h obtains catalyst precarsor;Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 2h again, after natural cooling Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Comparative example 1: commercialization 20wt.%Pt/C catalyst (Alfa Aesar)).
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 2.It is analyzed by the PCPDF card of XRD spectra The metal species for knowing that embodiment 2 is made in sample contain two kinds of crystalline structures: FeNi (43.46 °, 50.38 °, 73.96 ° of diffraction Peak is between Fe (PDF#52-0513) and Ni (PDF#04-0850), it is seen that form FeNi phase be respectively belonging to (111), (200), (220) crystal face), Fe3O4(PDF#75-0033,35.48 ° (3 1 1), 30.12 ° (2 2 0), 62.63 (440)), phase The peak position answered and intensity such as figure mark.In addition, 2 θ=26 ° or so are the characteristic diffraction peak of graphene (002) crystal face, show The material has good carbonization structure.
Fig. 2, Fig. 3 are transmission electron microscope (TEM) photo that sample is made according to embodiment 2.By Fig. 2, Fig. 3 it is found that embodiment 2 Sample obtained is that " Bamboo-shaped " carbon nano tube structure coats FeNi nano particle structure.Carbon nanotube diameter is in 40~130nm It differs, length reaches several microns.Contain black particles in carbon nanotube, may be FeNi or Fe3O4, size is in 15~40nm range. This clad structure can avoid metallic and contact with the direct of electrolyte solution, improve the stability of material.
Fig. 4 (a) is the isothermal nitrogen adsorption desorption curve (BET) that sample is made according to embodiment 2, the specific surface area of catalyst Up to 163m2 g-1.Sample aperture made from embodiment 2 known to Fig. 4 (b) pore size distribution curve be distributed in 3.5nm and 20~ 50nm.Meso-hole structure abundant facilitates the mass transfer of oxygen, to be conducive to the progress of ORR/OER reaction.
Fig. 5 (a) is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity The ORR polarization curve in liquid is solved, test voltage range is -0.8~0.2V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.Fig. 5 (b) It is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1The pole OER in KOH electrolyte Change curve, test voltage range is 0~1V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.By Fig. 5 (a) and Fig. 5 (b) it is found that lemon Lemon acid iron ammonium and NiCl2·6H2The feed ratio of O is affected to the ORR of catalyst.When ferric citrate and feed ratio are 1:1, ORR limiting current density is larger, and value when take-off potential and feed ratio are 3:1 is close;OER performance connects when 1:3 with feed ratio Closely.Consider from the difunctional angle of ORR and OER, when ferric citrate and feed ratio are 1:1, overpotential minimum (△ E=E (jOER=10mA cm -2)-E(jORR=-3mA cm -2)=0.85V), ORR and OER best performance.
Fig. 6 (a) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.Fig. 6 It (b) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1In KOH electrolyte OER polarization curve, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.It will be appreciated from fig. 6 that calcination temperature Be affected to ORR and OER performance, calcine preparation temperature be 800 DEG C when ORR performance half wave potential (- 0.176V) and Limiting current density is maximum, ORR best performance;jOER=10mA cm-2It is maximum to locate voltage, OER best performance.
Fig. 7 (a) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.Fig. 7 It (b) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1In KOH electrolyte OER polarization curve, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.By Fig. 7 (a) it is found that embodiment The half wave potential (- 0.176V) of 2 obtained catalyst, close to commercialization 20wt.%Pt/C catalyst half wave potential (- 0.126V), illustrating the catalyst under alkaline condition has good ORR catalytic performance;By Fig. 7 (b) it is found that embodiment 2 is made Obtain its OER current potential of catalyst (Ej OER=10mA cm -2=0.686V) it is better than 20wt.%Pt/C catalyst, show that the catalyst also has There is good OER catalytic performance.
Fig. 8 is the sample according to made from embodiment 2 at room temperature respectively in O2Saturation and N2The 0.1mol L of saturation-1KOH The CV of electrolyte schemes, and sweeps speed: 50mV s-1.As shown in Figure 8, catalyst made from embodiment 1 is in N2The 0.1mol L of saturation-1KOH There is no ORR in electrolyte, in O2The 0.1mol L of saturation-1There is the peak ORR to go out for -0.18V or so in current potential in KOH electrolyte It is existing.
Fig. 9 is the sample according to made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte Volt-ampere (LSV) curve is retouched, sweeps speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm.As shown in Figure 9, with Revolving speed increase, ORR take-off potential remains unchanged, and Limited diffusion current density constantly increases.
Figure 10 is Koutecky-Levich (K-L) song obtained according to the LSV curve (Fig. 9) that sample is made in embodiment 2 Line.It is 4 or so according to the electron transfer number that K-L equation calculates 2 surface catalysis ORR of embodiment, shows the catalysis obtained of embodiment 2 Agent is catalyzed ORR with 4 electronic processes.
Figure 11 is the sample according to made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte In chronoamperogram, revolving speed: 1600rpm, voltage are constant in -0.4V.By comparison it is found that in the timing electricity by 1800s After flowing stability test, catalyst activity made from embodiment 2 decays to 98.16%;Under the same terms, 20wt.% is commercialized Pt/C catalyst activity decays to 85.43%, illustrates catalyst stability made from embodiment 2 better than comparative example 1.
Figure 12 is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-1The circle of (a) 8000 follows in KOH electrolyte ORR activity comparison diagram after ring, CV -0.4~0.1V of scanning range sweep speed: 10mV s-1, revolving speed: 1600rpm;(b) 2000 circle OER activity comparison diagram after circulation, CV 0.2~0.7V of scanning range sweep speed: 10mV s-1, revolving speed: 1600rpm.By Figure 12 (a) It is found that catalyst made from embodiment 2 is in O2The 0.1moL L of saturation-1In KOH electrolyte solution, after 8000 circle circulations, CV curve shows that catalyst ORR stability made from embodiment 2 is preferable without significant change.By Figure 12 (b) it is found that embodiment 2 is made The catalyst obtained is in O2The 0.1moL L of saturation-1In KOH electrolyte solution, after 2000 circle circulations, CV curve becomes without obvious Change, shows that catalyst OER stability made from embodiment 2 is preferable.
Figure 13 be embodiment 2 made from sample respectively at room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation 3mol L-1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed: 10mV s-1.As shown in Figure 13, embodiment 2 is made Catalyst in the electrolyte solution whether there is or not methanol, CV curve without significant change, show catalyst made from embodiment 2 by Methanol fuel influence is smaller, may be used as methanol fuel cell cathode catalyst.
Figure 14 be comparative example 1 respectively at room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2The 3mol L of saturation- 1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed: 10mV s-1.As shown in Figure 14, commercialization 20wt.%Pt/C is urged There is apparent methanol oxidation current in the electrolyte solution for having methanol in agent, can catalysis methanol oxidation (- 0.4~ 0.2V), show that comparative example 1 is poor to the selectivity of fuel, firing vulnerable to methanol influences.

Claims (4)

1. a kind of preparation method of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, which is characterized in that institute The catalyst stated is unique " Bamboo-shaped " carbon nanotube, is tri- doped carbon nanometer pipe coated catalyst of Fe, Ni, N;Metal object Phase FeNi alloy and Fe3O4It is coated in carbon nanotube NCNT, and is mainly dispersed in inside the tube wall of NCNT, part grain Son is located at the tip inside pipe, can effectively avoid metallic in reaction process from contacting with the direct of electrolyte, improve catalysis The stability of agent;Bimetallic combination is capable of providing variation of valence abundant, is catalyzed ORR and/or OER reaction;
The preparation method the following steps are included:
1) dissolving metal salts Yu Shuizhong is obtained into solution A, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol is obtained into solution B;Wherein, the molar ratio of dicyandiamide and metal salt is 10:1-80:1, and iron nickel molar ratio is 1:0-1:10, the volume of water and ethyl alcohol Than for 20:1-1:20;The metal salt includes ferric citrate and NiCl2·6H2O;
2) drying steps 1) resulting solution B, catalyst pyrolytic precursors are made;
3) calcining step 2) in gained catalyst precarsor obtain FeNi@NCNT catalyst
Under inert gas shielding, room temperature to 400-600 DEG C of calcining 1-4h, then be warming up at 650-1200 DEG C of pyrolysis temperature and forge After burning 1-10h, FeNi@NCNT catalyst is obtained after natural cooling.
2. the preparation of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 1 Method, which is characterized in that drying means described in step 2) is vacuum drying, air atmosphere is dry or inert atmosphere is dry, is done Dry temperature is 0-150 DEG C, drying time 3-100h.
3. tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 1 or 2 Preparation method, which is characterized in that the heating rate that 400-600 DEG C is warming up in step 3) is 1-20 DEG C of min-1;It is warming up to pyrolysis 650-1200 DEG C of temperature of heating rate is 3-10 DEG C of min-1
4. the preparation method of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N described in claim 1 Catalyst obtained is used as fuel cell, electrolysis water or metal-air battery cathode ORR and/or OER elctro-catalyst.
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