CN107394215A - A kind of preparation and application of the functional carbon material of Heteroatom doping - Google Patents

A kind of preparation and application of the functional carbon material of Heteroatom doping Download PDF

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CN107394215A
CN107394215A CN201710572771.1A CN201710572771A CN107394215A CN 107394215 A CN107394215 A CN 107394215A CN 201710572771 A CN201710572771 A CN 201710572771A CN 107394215 A CN107394215 A CN 107394215A
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carbon material
preparation
functional carbon
heteroatom doping
butyl
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CN107394215B (en
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童金辉
马文梅
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Northwest Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a kind of preparation of the functional carbon material of Heteroatom doping, be using N containing hetero atom, B, S, Cl, F ionic liquid as raw material, using Ludox as template, after physical mixed being carried out in transition metal iron, cobalt, nickel salt solution, it is carbonized in nitrogen atmosphere high temperature, removing template is removed with HF again, the functional carbon material of Heteroatom doping is made.The ORR catalytic activity that the functional carbon material has been respectively provided with acid and alkalescence condition, poison performance and good stability with excellent methanol tolerance, and good HER catalytic activity is shown in acid condition, and be free of any noble metal, it is cheap, it is a kind of ORR and HER bifunctional catalysts being expected to instead of business Pt/C, there is extraordinary prospects for commercial application.

Description

A kind of preparation and application of the functional carbon material of Heteroatom doping
Technical field
The present invention relates to a kind of functional carbon material of Heteroatom doping, more particularly to one kind N containing hetero atom, B, S, Cl, F Functional carbon material preparation method, be mainly used as fuel battery negative pole hydrogen reduction catalytic reaction（ORR）And electrolysis water liberation of hydrogen Reaction（HER）Catalyst, also there is certain application prospect in methanol fuel cell technical field.
Background technology
Fuel cell is as energy generation device, due to its potential high efficiency, low stain output and high-energy-density density, Cause extensive concern.Hydrogen is considered as being hopeful one of energy of replacement conventional fossil fuel, as a kind of efficient energy Source and receive much concern.In clean energy resource production, electrolysis water splits water into hydrogen and oxygen dependent on effective elctro-catalyst, to change Learn the form storage energy of fuel.And largely depend on effective in clean energy resource use aspects, fuel cell Hydrogen reduction is water by elctro-catalyst.At present, electrolytic water electric catalyticing research is absorbed in development low cost, high activity and high stable always Property cathode material be used for substitute noble metal（Such as Pt）.And Cathodic oxygen reduction turns into because its reaction rate is slow and restricts fuel electricity The committed step of pond development.Therefore, efficient ORR and HER bifunctional catalysts are developed to have very important significance.
Up to the present, for ORR and HER, catalytic efficiency highest is still platinum-type catalyst.But such The application of catalyst is restricted to a certain extent.On the one hand, platinum-type catalyst methanol tolerance poisons poor-performing, chemistry Stability is poor.On the other hand, the high cost of platinum and its limited supply will certainly hinder the large-scale application of fuel cell.Cause This, it is most active in the current research field and most competitiveness to find base metal and the catalyst without metal ORR and HER Challenge.
Current research more non-platinum class ORR and HER catalyst mainly have transition metal oxide, Heteroatom doping carbon materials Material etc., the activity that these catalyst have closely are even more than the Heteroatom doping such as Pt/C catalyst, especially nitrogen, phosphorus Carbon material, due to being widely used for, as electrode material, urging with high conductivity, excellent chemical stability and catalytic activity Agent support materials and gas separation and hydrogen storage material etc..Traditional method for being used for preparing Heteroatom doping carbon material is general Be be carbonized some have compared with low-steam pressure polymer precursors, such as polyacrylonitrile（PAN）, phenolic resin and some natural materials Etc..And non-polymerized carbon materials material precursor is rarely found because they vapour pressure is difficult control at a higher temperature, it is difficult To form carbon material.But it is to be hardly formed carbon nanometer come one significant drawbacks of carbon material prepared using the presoma of polymerization Composite, the carbon material obtained in addition with this is difficult that carbon yield is relatively low for carrying out high quality parcel, all these all tight Its development and practical application are hindered again.If it is possible to carbon materials are prepared as carbon source using the carbon material of low volatilization, high stability Expect ORR and HER bifunctional catalysts, then can greatly reduce the production cost of carbon material, realize the sustainable development of carbon material Exhibition.
Ionic liquid（ILs）As a kind of organic fuse salt, there is room temperature low volatility, higher ionic conductivity, good There is relatively low vapour pressure under heat endurance well, high temperature.By appropriate MOLECULE DESIGN and combination, ionic liquid can To be used to directly or indirectly prepare various carbon materials and related nano hybridization catalysis material, and gather around and have wide practical use.
Special carrier advantage based on mesoporous silica-base material, using functionalized ion liquid as organic component, passes through grafting Method or the condensation methods of cohydrolysis one are immobilized into mesoporous material, prepare the hybrid mesoporous silica-base material of functionalized ion liquid, make its same When possess the two-fold advantage of mesoporous silica-base material and functionalized ion liquid, be one of the immobilized research of functionalized ion liquid New direction.This material had both had the specific function of functionalized ion liquid, possessed that mesoporous supports specific surface area is big, pore passage structure again The advantage such as regular, it is expected to the catalytic performance of further lifting ionic liquid.
The content of the invention
It is an object of the invention to provide a kind of N containing hetero atom, B, S, Cl, F functional carbon material preparation method；
Contain heteroatomic functional carbon material as catalyst ORR catalyst and HER it is a further object of the present invention to provide above-mentioned Catalyst application.
First, the preparation of the functional carbon material of Heteroatom doping
Because N containing hetero atom, B, S, Cl, F catalytic activity are high, it is strong and recyclable functional that methanol tolerance poisons ability, is expected to replace For Pt/C base metal ORR and HER bifunctional catalyst.Based on considerations above, the functionalized carbon of Heteroatom doping of the present invention The preparation of material, be using N containing hetero atom, B, S, Cl, F ionic liquid as raw material, using Ludox as template；In transition metal Iron, cobalt, nickel salting liquid in after physical mixed, be carbonized, then removing template is removed with HF, product centrifugation, wash in nitrogen atmosphere high temperature Wash, dry, grinding, functional carbon material ORR and the HER bifunctional catalyst of obtained Heteroatom doping.
Wherein, N containing hetero atom, B, S, Cl, F ionic liquid are 1- butyl -3- methylimidazole villaumites（[BMIm]Cl）、1- Butyl -3- methyl imidazolium tetrafluoroborates ([BMIm] [BF4]), 1- butyl -3- methylimidazoles hexafluorophosphates ([BMIm] [PF6]), 1- butyl -3- methylimidazoles trifluoroacetate ([BMIm] [TA]), 1- butyl -3- methylimidazole p-methyl benzenesulfonic acids Salt ([BMIm] [Tos]), 1- butyl sulfonic acid -3- methylimidazole villaumites（[BMIm]Cl）, 1- butyl -3- methylimidazole dintrile amine salt ([BMIm][N(CN)2]), one kind in 1- butyl -3- methylimidazoles rhodanate ([BMIm] [SCN]).N containing hetero atom, B, S, the mass ratio of Cl, F ionic liquid and Ludox is 1:10~1:1.
The transition metal iron, cobalt, nickel salt are iron, cobalt, the chloride of nickel, transition metal iron, cobalt, the concentration of nickel salt solution For 0.05 ~ 0.08M；Transition metal iron, cobalt, the dosage of nickel salt are the 5% ~ 20% of ionic liquid and template gross mass.
Described physical mixed, it is in transition metal iron, cobalt, nickel salt solution by Ludox and ionic liquid ultrasonic disperse In, stir 8 ~ 12h at 50 ~ 65 DEG C.
600 ~ 1000 DEG C of the temperature of the high temperature cabonization, carbonization time are 1 ~ 8h.
Described to be gone with HF etchings in template, HF weight/mass percentage compositions are 10% ~ 50%, and etching temperature is 30 ~ 50 DEG C, during etching Between be 8 ~ 16h.
The functional carbon material of Heteroatom doping prepared by the above method, labeled as aBmimA-T-N-F, wherein a is that silicon is molten Glue and ionic liquid mass ratio, A is ionic liquid anion species, and T is sintering temperature, and N is kinds of transition metals, and F is transition The weight/mass percentage composition that metal salt adds.Fig. 1,2 are respectively carbon material [BMIm] [BF4] -700-Co-20% SEM figure and TEM Figure.Sample is the globular carbide of ionic liquid cladding it can be seen from Fig. 1,2.
2nd, the hydrogen reduction of the functional carbon material of Heteroatom doping and electrolysis water Hydrogen Evolution Performance
With [BMIm] [BF4] exemplified by -700-Co-20%, hydrogen reduction and electrolysis water evolving hydrogen reaction are carried out in three-electrode system, Pt Silk electrode is to electrode, and Ag/AgCl electrodes are reference electrode, 0.1M KOH, 0.5MH2SO4And 0.1MHClO4Respectively it is electrolysed Liquid, when rotating disk electrode (r.d.e) rotating speed is 1600rmp, [BMIm] [BF4] hydrogen reduction starting peak under -700-Co-20% alkalescence conditions Current potential reaches -0.01V, and its hydrogen reduction performance is suitable with 20% business Pt/C catalyst, as shown in Figure 3.Oxygen is also under acid condition Originality can be also suitable with business Pt/C catalyst, as shown in Figure 4.0.5MH2SO4In measure electrolysis water overpotential of hydrogen evolution（10mA/ cm2）For 240mV, Tafel slopes are 166mV/dec, as shown in Figure 5.Using 3M CH3OH and 0.1M KOH mixed liquors are electrolysis When liquid carries out catalyst poisoning performance test, spike potential drops to -0.035 V, as shown in Figure 6.After catalyst scan round 5000 The reduction of hydrogen reduction performance is not notable, such as accompanying drawing 7.So catalyst is a kind of hydrogen reduction function admirable, anti-poisoning ability is good, can Nonexpondable methanol fuel cell cathode oxygen reduction catalyst, there is good prospects for commercial application.
In summary, the present invention using it is low volatilization, high stability room temperature molten salt ionic liquid as primary raw material, it is molten with silicon Glue is template, and using transition metal salt as source metal, by removing removing template with HF after high temperature cabonization, Heteroatom doping is made Functional carbon material, the ORR catalytic activity that the carbon material has been respectively provided with acid and alkalescence condition, has excellent methanol tolerance Poison performance and good stability, and show good HER catalytic activity in acid condition, and your any gold be free of Category, it is cheap, it is a kind of ORR and HER bifunctional catalysts being expected to instead of business Pt/C, there is extraordinary commercial Application Prospect.
Brief description of the drawings
Fig. 1 is catalyst [BMIm] [BF4] -700-Co-20% SEM figure.
Fig. 2 is catalyst [BMIm] [BF4] -700-Co-20% TEM figure.
Fig. 3 is catalyst [BMIm] [BF4] -700-Co-20% and business Pt/C be in alkalescence condition compared with ORR Lsv Figure.
Fig. 4 is catalyst [BMIm] [BF4] -700-Co-20% and business Pt/C be in acid condition（(a).0.5MH2SO4 (b).0.1MHClO4）Middle ORR Lsv compare figure.
Fig. 5 is catalyst [BMIm] [BF4] -700-Co-20% HER (a) Lsv and (b) Tafel slope figures.
Fig. 6 is catalyst [BMIm] [BF4] -700-Co-20% methanol tolerances poison ability Lsv figure.
Fig. 7 is catalyst [BMIm] [BF4] -700-Co-20% stability tests Lsv figure.
Fig. 8 is catalyst 3 [BMIm] [BF4] -700-Co-11% ORR Lsv figure.
Fig. 9 is catalyst 3 [BMIm] [BF4] -700-Co-11% HER (a) Lsv and (b) Tafel slope figure.
Figure 10 is catalyst [BMIm] [BF4] -800-Co-20% ORR Lsv figure.
Figure 11 is catalyst [BMIm] [BF4] -800-Co-20% HER (a) Lsv and (b) Tafel slope figures.
Figure 12 is catalyst [BMIm] Cl-700-Co-20% figures compared with business Pt/C ORR Lsv.
Figure 13 is catalyst [BMIm] Cl-700-Co-20% HER (a) Lsv and (b) Tafel slope figure.
Figure 14 is catalyst [BMIm] Cl-700-Fe-20% figures compared with business Pt/C ORR Lsv.
Figure 15 is that catalyst [BMIm] Cl-700-Fe-20% HER (a) Lsv and (b) Tafel slope ratio are relatively schemed.
Figure 16 is catalyst [BMIm] A-700-Co-20% figures compared with business Pt/C ORR Lsv.
Figure 17 is that catalyst [BMIm] A-700-Co-20% HER (a) Lsv and (b) Tafel slope ratio are relatively schemed.
Embodiment
Make below by preparation of the specific embodiment to catalyst of the present invention and the performance reacted in ORR and HER further Explanation.
Embodiment one
1st, catalyst [BMIm] [BF4] -700-Co-20% preparation
A. the preparation of dopant material：By 1g [BMIm] [BF4] with 1g Ludox ultrasonic dissolution in 30mL 0.07M CoCl2Solution In, the magnetic agitation 12h under the conditions of 60 DEG C, products therefrom drying, produce dopant material product；
b. [BMIm][BF4] -700-Co-20% preparation：By above-mentioned dopant material in nitrogen atmosphere, in 700 DEG C of carbonizations 2h, gained carbon material remove template with HF（Carbon material, which is immersed in the HF that weight/mass percentage composition is 20%, etches 12h）, product centrifugation, Washing, is dried overnight, and grinds, produces [BMIm] [BF4] -700-Co-20% carbon materials.
2nd, hydrogen reduction is tested
Weigh 5mg [BMIm] [BF4] -700-Co-20% adds 0.5mL absolute ethyl alcohols and 10 μ L Nafion（Dupont,5 wt%）Solution, 30min is ultrasonically treated, takes 3 μ L to be coated onto on glass-carbon electrode.Tested in three-electrode system, Pt silk electrodes are To electrode, Ag/AgCl electrodes are reference electrode, and the glass-carbon electrode for scribbling catalyst is working electrode, respectively with 0.1M KOH, 0.5MH2SO4、0.1MHClO4Tested for electrolyte with rotating disk electrode (r.d.e).As shown in Figure 3,4, turn in rotating disk electrode (r.d.e) When speed is 1600rmp, sweep speed is 0.01V/s, when 0.1M KOH are electrolyte, hydrogen reduction take-off potential is -0.01V, 0.5MH2SO4For electrolyte when, hydrogen reduction take-off potential is 0.62V, 0.1MHClO4For electrolyte when, hydrogen reduction take-off potential is 0.6V。
3rd, electrolysis water liberation of hydrogen is tested
Weigh 5mg [BMIm] [BF4] -700-Co-20% adds 0.5mL absolute ethyl alcohols and 10 μ L Nafion（Dupont,5 wt%）Solution, 30min is ultrasonically treated, takes 3 μ L to be coated onto on glass-carbon electrode.Tested in three-electrode system, carbon-point is to electricity Pole, Ag/AgCl electrodes are reference electrode, and the glass-carbon electrode for scribbling catalyst is working electrode, with 0.5MH2SO4Enter for electrolyte Row test.As shown in figure 5, when sweep speed is 0.01V/s, electrolysis water overpotential of hydrogen evolution (10mA/cm2) it is 240mV, Tafel slopes are 166mV/dec.
Embodiment two
1st, catalyst 3 [BMIm] [BF4] -700-Co-11% preparation
A. the preparation of dopant material：By 1g [BMIm] [BF4] with 3g Ludox ultrasonic dissolution in 30mL 0.07MCoCl2Solution In, magnetic agitation 12h, products therefrom are dried under the conditions of 60 DEG C.
b. 3[BMIm][BF4] -700-Co-11% preparation：With embodiment 1.
2nd, hydrogen reduction is tested
With embodiment 1, test result is as shown in Figure 8 for test condition and method.As seen from Figure 8, turn in rotating disk electrode (r.d.e) When speed is 1600rmp, sweep speed is 0.01V/s, when 0.1M KOH are electrolyte, hydrogen reduction take-off potential is -0.03V.
3rd, electrolysis water liberation of hydrogen is tested
With embodiment 1, test result is as shown in Figure 9 for test condition and method.As seen from Figure 9, it is in sweep speed 0.01V/s、0.5MH2SO4For electrolyte when, electrolysis water overpotential of hydrogen evolution (10mA/cm2) it is 340mV, Tafel slopes are 139mV/dec。
Embodiment three
1st, catalyst [BMIm] [BF4] -800-Co-20% preparation
A. the preparation of dopant material：With embodiment 1.
b. [BMIm][BF4] -800-Co-20% preparation：By above-mentioned a resulting materials in nitrogen atmosphere, in 800 DEG C Be carbonized 2h, gained carbon material HF（Carbon material, which is immersed in the HF that weight/mass percentage composition is 20%, etches 12h.）Remove template, product Centrifugation, washing, are dried overnight, and grind, produce [BMIm] [BF4] -800-Co-20% carbon materials.
2nd, hydrogen reduction is tested
With embodiment 1, test result is as shown in Figure 10 for test condition and method.As seen from Figure 10, in rotating disk electrode (r.d.e) When rotating speed is 1600rmp, sweep speed is when being 0.01V/s, when 0.1M KOH are electrolyte, hydrogen reduction take-off potential for- 0.012V。
3rd, electrolysis water liberation of hydrogen is tested
With embodiment 1, test result is as shown in figure 11 for test condition and method.As seen from Figure 11, it is in sweep speed 0.01V/s、0.5MH2SO4For electrolyte when, electrolysis water overpotential of hydrogen evolution (10mA/cm2) it is 316mV, Tafel slopes are 143mV/dec。
Example IV
1st, catalyst [BMIm] Cl-700-Co-20% preparation
A. the preparation of dopant material：By 1g [BMIm] Cl and 1g Ludox ultrasonic dissolution in 30mL 0.07MCoCl2In solution, Magnetic agitation 12h, products therefrom are dried under the conditions of 60 DEG C
B. [BMIm] Cl-700-Co-20% preparation：With embodiment 1.
2nd, hydrogen reduction is tested
With embodiment 1, test result is as shown in figure 12 for test condition and method.As seen from Figure 12, in rotating disk electrode (r.d.e) When rotating speed is 1600rmp, sweep speed is when being 0.01V/s, when 0.1M KOH are electrolyte, hydrogen reduction take-off potential for- 0.015V。
3rd, electrolysis water liberation of hydrogen is tested
With embodiment 1, test result is as shown in figure 13 for test condition and method.As seen from Figure 13, it is in sweep speed 0.01V/s、0.5MH2SO4For electrolyte when, electrolysis water overpotential of hydrogen evolution (10mA/cm2) it is 248mV, Tafel slopes are 115mV/dec。
Embodiment five
1st, catalyst [BMIm] [BF4] -700-Fe-20% preparation
A. the preparation of dopant material：By 1g [BMIm] [BF4] with 1g Ludox ultrasonic dissolution in 30mL 0.07MFeCl3Solution In, magnetic agitation 12h, products therefrom are dried under the conditions of 60 DEG C.
b. [BMIm][BF4] -700-Fe-20% preparation：With embodiment 1.
2nd, hydrogen reduction is tested
With embodiment 1, test result is as shown in figure 14 for test condition and method.As seen from Figure 14, in rotating disk electrode (r.d.e) When rotating speed is 1600rmp, sweep speed is when being 0.01V/s, when 0.1M KOH are electrolyte, hydrogen reduction take-off potential for- 0.002V。
3rd, electrolysis water liberation of hydrogen is tested
With embodiment 1, test result is as shown in figure 15 for test condition and method.As seen from Figure 15, it is in sweep speed 0.01V/s、0.5MH2SO4For electrolyte when, electrolysis water overpotential of hydrogen evolution (10mA/cm2) it is 359mV, Tafel slopes are 203mV/dec。
Embodiment six
1st, catalyst [BMIm] A-700-Co-20% preparation
A. the preparation of dopant material：Respectively by 1g [BMIm] [TA], 1g [BMIm] [PF6] with 1g Ludox ultrasonic dissolution in 30mL 0.07MCoCl2In solution, magnetic agitation 12h, products therefrom are dried under the conditions of 60 DEG C
B. [BMIm] A -700-Co-20% preparation：With embodiment 1.
2nd, hydrogen reduction is tested
With embodiment 1, test result is as shown in figure 16 for test condition and method.As seen from Figure 16, in rotating disk electrode (r.d.e) When rotating speed is 1600rmp, sweep speed is when being 0.01V/s, when 0.1M KOH are electrolyte, [BMIm] [BF4] -700-Co- 20% hydrogen reduction take-off potential is closest to business Pt/C.
3rd, electrolysis water liberation of hydrogen is tested
With embodiment 1, test result is as shown in figure 17 for test condition and method.As seen from Figure 17, it is in sweep speed 0.01V/s、0.5MH2SO4For electrolyte when, [BMIm] [BF4] -700-Co-20% electrolysis water overpotential of hydrogen evolution (10mA/cm2) most Low and Tafel slopes are minimum.

Claims (10)

1. a kind of preparation method of Heteroatom doping functional carbon material, using N containing hetero atom, B, S, Cl, F ionic liquid as original Material, using Ludox as template, after carrying out physical mixed in transition metal iron, cobalt, nickel salt solution, in nitrogen atmosphere high temperature Carbonization, then removing template is removed with HF, the functional carbon material of Heteroatom doping is made.
A kind of 2. preparation method of Heteroatom doping functional carbon material as claimed in claim 1, it is characterised in that：Containing hetero atom N, B, S, Cl, F ionic liquid are 1- butyl -3- methylimidazole villaumites, 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- fourths Base -3- methylimidazoles hexafluorophosphate, 1- butyl -3- methylimidazoles trifluoroacetate, 1- butyl -3- methylimidazoles are to methylbenzene Sulfonate, 1- butyl sulfonic acid -3- methylimidazole villaumites, 1- butyl -3- methylimidazole dintrile amine salt, 1- butyl -3- methylimidazoles One kind in rhodanate.
A kind of 3. preparation method of Heteroatom doping functional carbon material as claimed in claim 1 or 2, it is characterised in that：Containing miscellaneous Atom N, B, S, Cl, F ionic liquid and the mass ratio of Ludox are 1:10~1:1.
A kind of 4. preparation method of the functional carbon material of Heteroatom doping as claimed in claim 1, it is characterised in that：Transition gold It is iron, cobalt, the chloride of nickel to belong to iron, cobalt, nickel salt, and transition metal iron, cobalt, the dosage of nickel salt are ionic liquid and the total matter of template The 5% ~ 20% of amount.
A kind of 5. preparation method of the functional carbon material of Heteroatom doping as claimed in claim 1, it is characterised in that：Transition gold It is 0.05 ~ 0.08M to belong to iron, cobalt, the concentration of nickel salt solution.
A kind of 6. preparation method of the functional carbon material of Heteroatom doping as claimed in claim 1, it is characterised in that：Described Physical mixed, it is by Ludox and ionic liquid ultrasonic disperse in transition metal iron, cobalt, nickel salt solution, in 50 ~ 65 DEG C of stirrings 8~12h。
A kind of 7. preparation method of the functional carbon material of Heteroatom doping as claimed in claim 1, it is characterised in that：The height 600 ~ 1000 DEG C of the temperature of temperature carbonization, carbonization time is 1 ~ 8h.
A kind of 8. preparation method of the functional carbon material of Heteroatom doping as claimed in claim 1, it is characterised in that：The use HF etchings are gone in template, and HF weight/mass percentage compositions are 10% ~ 50%, and etching temperature is 30 ~ 50 DEG C, and etch period is 8 ~ 16h.
9. the functional carbon material of Heteroatom doping prepared by method as claimed in claim 1 is used for fuel cell as catalyst In cathodic oxygen reduction catalytic reaction.
10. the functional carbon material of Heteroatom doping prepared by method as claimed in claim 1 is used for electrolysis water as catalyst In evolving hydrogen reaction.
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CN108439370A (en) * 2018-04-25 2018-08-24 江苏大学 A kind of preparation method and its usage of two dimension porous boron nitrogen codope carbon nanomaterial
CN109494378A (en) * 2018-12-12 2019-03-19 齐齐哈尔大学 A kind of preparation method of the catalyst for catalytic fuel cell cathode reaction
CN112156772A (en) * 2020-09-30 2021-01-01 广州大学 Ion poisoning noble metal catalyst and preparation method and application thereof
CN113839058A (en) * 2021-09-23 2021-12-24 重庆文理学院 Carbon-based oxygen reduction reaction catalyst and preparation method thereof
CN115094479A (en) * 2022-07-25 2022-09-23 福建省清流县东莹化工有限公司 Fluorine oxygen cobalt nickel composite carbon catalyst for electrochemical decomposition water electrode and preparation method thereof

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CN104505524A (en) * 2015-01-13 2015-04-08 哈尔滨工业大学 Preparation method of direct methanol fuel cell platinum-based catalyst carrier with special structure
CN105820123A (en) * 2016-04-13 2016-08-03 东南大学 Preparation method of oxygen reduction catalyst with non-noble metal doped carbon material
CN106115653A (en) * 2016-06-22 2016-11-16 兰州理工大学 A kind of preparation method of the porous carbon materials of Heteroatom doping

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CN102513099A (en) * 2011-11-24 2012-06-27 浙江大学 Novel metal catalyst loaded by mesoporous carbon and preparation method thereof
CN104505524A (en) * 2015-01-13 2015-04-08 哈尔滨工业大学 Preparation method of direct methanol fuel cell platinum-based catalyst carrier with special structure
CN105820123A (en) * 2016-04-13 2016-08-03 东南大学 Preparation method of oxygen reduction catalyst with non-noble metal doped carbon material
CN106115653A (en) * 2016-06-22 2016-11-16 兰州理工大学 A kind of preparation method of the porous carbon materials of Heteroatom doping

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108439370A (en) * 2018-04-25 2018-08-24 江苏大学 A kind of preparation method and its usage of two dimension porous boron nitrogen codope carbon nanomaterial
CN109494378A (en) * 2018-12-12 2019-03-19 齐齐哈尔大学 A kind of preparation method of the catalyst for catalytic fuel cell cathode reaction
CN109494378B (en) * 2018-12-12 2021-08-24 齐齐哈尔大学 Preparation method of catalyst for catalyzing cathode reaction of fuel cell
CN112156772A (en) * 2020-09-30 2021-01-01 广州大学 Ion poisoning noble metal catalyst and preparation method and application thereof
CN113839058A (en) * 2021-09-23 2021-12-24 重庆文理学院 Carbon-based oxygen reduction reaction catalyst and preparation method thereof
CN113839058B (en) * 2021-09-23 2023-05-26 重庆文理学院 Carbon-based oxygen reduction reaction catalyst and preparation method thereof
CN115094479A (en) * 2022-07-25 2022-09-23 福建省清流县东莹化工有限公司 Fluorine oxygen cobalt nickel composite carbon catalyst for electrochemical decomposition water electrode and preparation method thereof
CN115094479B (en) * 2022-07-25 2023-09-05 福建省清流县东莹化工有限公司 Fluorine oxygen cobalt nickel composite carbon catalyst for electrochemical decomposition of water and preparation method thereof

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