CN110354888A - A kind of preparation method and applications of the nitrogen-doped carbon composite electrocatalyst of dilval - Google Patents
A kind of preparation method and applications of the nitrogen-doped carbon composite electrocatalyst of dilval Download PDFInfo
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- CN110354888A CN110354888A CN201910756260.4A CN201910756260A CN110354888A CN 110354888 A CN110354888 A CN 110354888A CN 201910756260 A CN201910756260 A CN 201910756260A CN 110354888 A CN110354888 A CN 110354888A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 23
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- -1 iron ion Chemical class 0.000 claims description 23
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of the nitrogen-doped carbon composite electrocatalyst of dilval, including being dispersed in water N doping carbon source to form the first solution, nickel salt and molysite are dispersed in water to form the second solution, the molar ratio of nickel ion and iron ion in the second solution is 1-9:1；First solution and the second solution are mixed to form mixed solution, mixed solution is stood 10-24 hours after mixing evenly at 15-30 DEG C, through centrifuge washing, freeze-drying, obtains solid powder；Solid powder is placed in protective atmosphere, is calcined 2-6 hours at 500-700 DEG C, obtains the nitrogen-doped carbon composite electrocatalyst of dilval.The present invention also provides application of the nitrogen-doped carbon composite electrocatalyst of thus obtained dilval on electrolysis elutriation oxygen.Preparation method process of the invention is simple, economical rationality, preparation efficiency are high, easy large-scale production, and catalyst can be used as the base metal electrolysis water oxygen-separating catalyst of efficient stable.
Description
Technical field
The present invention relates to Modern electrochemistry energy technologys and electrolysis water technical field, relate more specifically to a kind of dilval
Nitrogen-doped carbon composite electrocatalyst preparation method and applications.
Background technique
Electrolysis water technology is that a kind of important method of high-purity clean fuel hydrogen is mass produced.It is directed to four electronics transfers
Oxygen evolution reaction (oxygen evolution reaction, OER) be a half-reaction of electrolysis water reaction and it is main
Rate-limiting step.So far, iridium base and ruthenium-based catalyst are optimal oxygen-separating catalysts under alkaline condition.However, these
The high cost and scarcity of noble metal catalyst greatly limit their extensive use.Therefore exploitation high activity,
The oxygen-separating catalyst of low cost is most important.Domestic and foreign scholars develop a series of base metal oxygen-separating catalysts at present, especially
It is nickel-base catalyst, including oxide, (oxygen) hydroxide, sulfide, phosphide, selenides etc. attract extensive attention.Largely
Studies have shown that adulterating the catalytic efficiency that ferro element is greatly improved oxygen-separating catalyst in nickel-base catalyst.It therefore is further
The catalytic activity of oxygen evolution reaction is improved, the advantage combination of nickel, ferro element is important developing direction.
Wherein, dilval due to naturally contain nickel, ferro element and attract extensive attention.At present to dilval catalyst
Research mainly regulate and control its composition and shape characteristic, and it is it is compound with various carbon materials, to improve its dispersibility and conductive
Property, to improve its oxygen evolution reaction catalytic activity.But develop it is a kind of simple, efficiently, the carbon of dilval that can be mass-produced
Composite material (i.e. dilval/carbon composite) is still a challenge.
Summary of the invention
In order to solve the problems, such as that method in the prior art can not efficiently provide dilval/carbon composite, this hair
A kind of system of the bright nitrogen-doped carbon composite electrocatalyst (i.e. dilval/nitrogen-doped carbon composite electrocatalyst) that dilval is provided
Preparation Method and its application.
The preparation method of the nitrogen-doped carbon composite electrocatalyst of dilval according to the present invention, comprising steps of S1, by one
N doping carbon source is dispersed in water to form one first solution, and a nickel salt and a molysite are dispersed in water to form one second solution,
Wherein, the molar ratio of the nickel ion in second solution and iron ion is 1-9:1；S2, by first solution and second solution
Be mixed to form a mixed solution, which stood 10-24 hours after mixing evenly at 15-30 DEG C, through centrifuge washing,
Freeze-drying, obtains a solid powder；The solid powder is placed in a protective atmosphere by S3, calcines 2-6 at 500-700 DEG C
Hour, obtain the nitrogen-doped carbon composite electrocatalyst of dilval.
Preferably, in the step S1, the N doping carbon source is in imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)
It is at least one.
Preferably, in the step S1, which is completed by ultrasound.
Preferably, in the step S1, the molar concentration of the N doping carbon source in first solution is 0.5-1.0mol/
L.In a preferred embodiment, the molar concentration of the N doping carbon source in first solution is 0.8mol/L.
Preferably, in the step S1, which is selected from least one of nickel nitrate, nickel chloride and nickel acetate.?
In one preferred embodiment, which is Nickel dichloride hexahydrate.
Preferably, in the step S1, which is selected from least one of ferric nitrate, iron chloride and ferric acetate.?
In one preferred embodiment, which is ferric chloride hexahydrate.
Preferably, in the step S1, the molar concentration of the nickel salt in second solution is 0.1-0.5mol/L.It is more excellent
Selection of land, in the step S1, the molar concentration of the nickel salt in second solution are 0.1-0.129mol/L.It is preferred at one
In embodiment, the molar concentration of the nickel ion in second solution is 0.115mol/L.In another preferred embodiment, should
The molar concentration of nickel ion in second solution is 0.129mol/L.In yet another preferred embodiment, in second solution
Nickel ion molar concentration be 0.1mol/L.
Preferably, in the step S1, the molar concentration of the molysite in second solution is 0.001-0.2mol/L.More
Preferably, in the step S1, the molar concentration of the molysite in second solution is 0.015-0.043mol/L.It is excellent at one
In the embodiment of choosing, the molar concentration of the iron ion in second solution is 0.029mol/L.In another preferred embodiment
In, the molar concentration of the iron ion in second solution is 0.015mol/L.In yet another preferred embodiment, this is second molten
The molar concentration of iron ion in liquid is 0.043mol/L.
Preferably, in the step S1, the molar ratio of the nickel ion in second solution and iron ion is 2.33-9:1.
In a preferred embodiment, the molar ratio of the nickel ion in second solution and iron ion is 4:1.It is preferred at another
In embodiment, the molar ratio of nickel ion and iron ion in second solution is 9:1.In yet another preferred embodiment, should
The molar ratio of nickel ion and iron ion in second solution is 2.33:1.
Preferably, step S2 is carried out at room temperature.
Preferably, in the step S2, which is 18 hours.
Preferably, in the step S2, which is yellowish-brown product.
Preferably, in the step S3, which is selected from least one of nitrogen, argon gas and helium.
Preferably, in the step S3,1-5 DEG C/min of heating rate.
The nitrogen-doped carbon composite electrocatalyst for the dilval that preparation method according to the present invention obtains is in electrolysis elutriation oxygen
On application.
Preferably, the nitrogen-doped carbon composite electrocatalyst of the dilval carries out electrochemical activation by cyclic voltammetry scan
It is balanced state.
The present invention is acted on using the coordination precipitation between nickel, iron ion and N doping carbon source (especially imidazole group), in 15-
After being reacted 10-24 hours at 30 DEG C, the solid powder of three's co-precipitation is obtained, which is placed in protective atmosphere,
It is calcined at 500-700 DEG C, so that nickel, ferroalloy and being supported on nitrogen-doped carbon material.Preparation method according to the present invention, system
Standby high-efficient, process is simple, economical rationality, easily realizes large-scale production.In short, the present invention proposes that a kind of process is simple, economical
Rationally, dilval/nitrogen-doped carbon composite electrocatalyst synthetic method of high, the easy large-scale production of preparation efficiency.This hair
The bright native ligands using between nickel, iron ion and imidazole group act on, and by introducing source of iron and nickel source, realize dilval/nitrogen
The synthesis of doped carbon composite electrocatalyst.Dilval provided by the invention/nitrogen-doped carbon composite electrocatalyst can be used as efficiently
Stable base metal electrolysis water oxygen-separating catalyst, is expected to generate good social and economic benefit.
Detailed description of the invention
Fig. 1 be calcined under different temperatures and different nickel ion and iron ion molar ratio under prepare dilval/
The XRD diagram of nitrogen-doped carbon composite electrocatalyst sample；
Fig. 2 is dilval/nitrogen-doped carbon composite electrocatalyst prepared by embodiment 1 after electrochemical activation
TEM figure；
Fig. 3 be calcined under different temperatures and different nickel ion and iron ion molar ratio under prepare dilval/
The electrolysis elutriation oxygen catalytic performance of nitrogen-doped carbon composite electrocatalyst characterizes curve, and wherein Fig. 3 a is linear volt-ampere curve, Fig. 3 b
For Tafel curve；
Fig. 4 is the stability that dilval/nitrogen-doped carbon composite electrocatalyst prepared by embodiment 1 is electrolysed elutriation oxygen
Characterization.
Specific embodiment
With reference to the accompanying drawing, presently preferred embodiments of the present invention is provided, and is described in detail.
Embodiment 1
Selection 2-methylimidazole is carbon source, Nickel dichloride hexahydrate (NiCl2.6H2It O) is nickel salt, ferric chloride hexahydrate
(FeCl3.6H2O it is) molysite, prepares dilval/nitrogen-doped carbon composite electrocatalyst:
2.63g 2-methylimidazole is weighed first and is placed in beaker A and adds water 40mL ultrasonic dissolution, weighs 1.09g
NiCl2.6H2O, 0.31g FeCl3.6H2O is placed in beaker B and adds water 40mL ultrasonic dissolution, and wherein nickel ion concentration is
The molar ratio of 0.115mol/L, iron concentration 0.029mol/L, nickel ion and iron ion is 4.Then by the iron in beaker B
Source and nickel source pour into beaker A and obtain mixed solution, and mixed solution is placed under room temperature (25 DEG C) and is stirred evenly, and it is small to stand 18
Shi Hou, washing centrifugation, freeze-drying obtain yellowish-brown powder.Product after freeze-drying is calcined to 600 DEG C in a nitrogen atmosphere,
Heat preservation 3 hours, resulting product is denoted as Fe0.2Ni0.8/NC-600。
Dilval/nitrogen-doped carbon composite electrocatalyst electrolysis elutriation oxygen performance is the 1M KOH solution being saturated with oxygen
In linear polarisation curves (LSV) assess, electro-chemical test sequentially includes the following steps:
Firstly, weighing the above-mentioned catalyst of 4mg is dispersed in the mixing comprising 2mL isopropanol and 20uL Nafion solution (5%)
In solution, ultrasound obtains finely dispersed suspension, then takes the rotating circular disk glass that the above-mentioned hanging drop of 55uL is 5mm to diameter
On carbon electrode, working electrode can be obtained after natural drying；Electrolysis elutriation oxygen catalytic performance is characterized in electrochemical workstation (CHI
760E, Shanghai Chen Hua) on carry out, using three-electrode system, using the 1M KOH solution of oxygen saturation as electrolyte, graphite rod is pair
Electrode, the Ag/AgCl electrode of 3M KCl solution filling are reference electrode, and the speed of sweeping of linear sweep voltammetry curve is 5mV s-1, real
It tests data and does not carry out IR correction, electrode potential is relative to reversible hydrogen electrode (RHE), and conversion method is as follows: ERHE=EAg/AgCl+
0.059*pH+0.209.Always lead to high purity oxygen gas in Electrochemical Test Procedure, to guarantee that electrolyte oxygen is saturated.It is linear in test
Before polarization curve, catalyst first passes through cyclic voltammetry scan and carries out electrochemical activation, reaches equilibrium state (the linear pole tested
Change curve to be completely coincident).Catalyst after activation is denoted as Fe0.2Ni0.8/NC-600-a。
Embodiment 2
Preparation process and step and above-described embodiment 1 in embodiment 2 is essentially identical, unlike: the calcining temperature of selection
Degree is 500 DEG C, and catalyst obtained is denoted as Fe0.2Ni0.8/NC-500.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is the same as real
Example 1 is applied, and the catalyst after activation is denoted as Fe0.2Ni0.8/NC-500-a。
Embodiment 3
Preparation process and step and above-described embodiment 1 in embodiment 3 is essentially identical, unlike: the calcining temperature of selection
Degree is 700 DEG C, and catalyst obtained is denoted as Fe0.2Ni0.8/NC-700.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is the same as real
Example 1 is applied, and the catalyst after activation is denoted as Fe0.2Ni0.8/NC-700-a。
Embodiment 4
Preparation process and step and above-described embodiment 1 in embodiment 4 is essentially identical, unlike: weigh 1.23g
NiCl2.6H2O, 0.16g FeCl3.6H2O is placed in beaker B and adds water 40mL ultrasonic dissolution, and wherein nickel ion concentration is
The molar ratio of 0.129mol/L, iron concentration 0.015mol/L, nickel ion and iron ion is 9, and catalyst obtained is denoted as
Fe0.1Ni0.9/NC-600.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is with embodiment 1, and the catalyst after activation is denoted as
Fe0.1Ni0.9/NC-600-a。
Embodiment 5
Preparation process and step and above-described embodiment 1 in embodiment 5 is essentially identical, unlike: weigh 0.96g
NiCl2.6H2O, 0.47g FeCl3.6H2O is placed in beaker B and adds water 40mL ultrasonic dissolution, and wherein nickel ion concentration is
The molar ratio of 0.1mol/L, iron concentration 0.043mol/L, nickel ion and iron ion is 2.33, and catalyst obtained is denoted as
Fe0.3Ni0.7/NC-600.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is with embodiment 1, and the catalyst after activation is denoted as
Fe0.3Ni0.7/NC-600-a。
Embodiment 6
Preparation process and step and above-described embodiment 1 in embodiment 6 is essentially identical, unlike: only weigh 1.37g
NiCl2.6H2O is placed in beaker B and adds water 40mL ultrasonic dissolution, and the molar concentration of nickel ion is 0.14mol/L, catalysis obtained
Agent is denoted as Ni/NC-600.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is with embodiment 1, and catalyst is in electrolysis elutriation oxygen mistake
Activation process is not present in journey.
Embodiment 7
Preparation process and step and above-described embodiment 1 in embodiment 7 is essentially identical, unlike: only weigh 1.55g
FeCl3.6H2O is placed in beaker B and adds water 40mL ultrasonic dissolution, and the molar concentration of iron ion is 0.14mol/L, catalysis obtained
Agent is denoted as Fe/NC-700.The electrolysis elutriation oxygen catalytic performance characterization of catalyst is with embodiment 1, and catalyst is in electrolysis elutriation oxygen mistake
Activation process is not present in journey.
Fig. 1 be calcined under different temperatures and different nickel ion and iron ion molar ratio under prepare dilval/
The XRD diagram of nitrogen-doped carbon composite electrocatalyst sample.It will be seen from figure 1 that although nickel ion is different from iron ion molar ratio, system
Standby sample all shows the FeNi of face-centered cubic (FCC)3The diffraction maximum of alloy occurs without the diffraction maximum of other miscellaneous phases.And
And as the increase of iron concentration is (from Fe0.1Ni0.9/ NC-600 to Fe0.3Ni0.7/ NC-600), FeNi3The diffraction maximum of alloy
Mobile to low-angle direction, this is primarily due to the radius of Fe atomSlightly larger than the radius of Ni atomLead to distortion of lattice in excessive Fe atom incorporation Ni lattice.And calcination temperature is improved, the crystalline substance of dilval
Change degree improves.The catalyst n i/NC-600 and Fe/NC-600 that source of iron or nickel source preparation is only added show metallic nickel or gold
Belong to the diffraction maximum of iron.
Fig. 2 is dilval/nitrogen-doped carbon composite electrocatalyst prepared by embodiment 1 after electrochemical activation
TEM figure.From figure 2 it can be seen that dilval particulate load is on nitrogen-doped carbon.
Fig. 3 be calcined under different temperatures and different nickel ion and iron ion molar ratio under prepare dilval/
The electrolysis elutriation oxygen catalytic performance of nitrogen-doped carbon composite electrocatalyst characterizes curve, and wherein Fig. 3 a is linear volt-ampere curve (LSV),
Fig. 3 b is Tafel curve.From Fig. 3 a as can be seen that when current density is 20mA cm-2When, Fe0.2Ni0.8/NC-700-a、
Fe0.2Ni0.8/NC-600-a、Fe0.2Ni0.8/NC-500-a、Fe0.1Ni0.9/NC-600-a、Fe0.3Ni0.7Required for/NC-600-a
Overpotential be respectively 320mV, 290mV, 360mV, 327mV, 310mV, and RuO2In current density 20mAcm-2Under overpotential
For 388mV, illustrate your gold the dilval/catalytic performance of the nitrogen-doped carbon composite electrocatalyst after electrochemical activation is better than
Belong to oxide.As can be seen that Fe from Fig. 3 b0.2Ni0.8/NC-700-a、Fe0.2Ni0.8/NC-600-a、Fe0.2Ni0.8/NC-
500-a、Fe0.1Ni0.9/NC-600-a、Fe0.3Ni0.7/NC-600-a、Fe/NC-600、Ni/NC-600、RuO2Ta Feier it is oblique
Rate is respectively 80mV dec-1、76mV dec-1、93mV dec-1、94mV dec-1、102mV dec-1、126mV dec-1、94mV
dec-1、114mV dec-1, Tafel slope is smaller to be more conducive to reaction progress.
Fig. 4 is dilval/nitrogen-doped carbon composite electrocatalyst sample F e prepared by embodiment 10.2Ni0.8/NC-600
I-t stability test, running in 3h, the current density of the composite electrocatalyst has significantly compared to initial current density
Promotion, show its electrolysis elutriation oxygen catalytic process in there are electrochemical activation processes.In subsequent 5h runing time, electricity
Current density is held essentially constant, and shows that it maintains good stability after activation.
Above-described, only presently preferred embodiments of the present invention, the range being not intended to limit the invention, of the invention is upper
Stating embodiment can also make a variety of changes.Made by i.e. all claims applied according to the present invention and description
Simply, equivalent changes and modifications fall within the claims of the invention patent.The not detailed description of the present invention is
Routine techniques content.
Claims (9)
1. a kind of preparation method of the nitrogen-doped carbon composite electrocatalyst of dilval, which is characterized in that the preparation method includes
Step:
One N doping carbon source is dispersed in water to form one first solution, a nickel salt and a molysite is dispersed in water and is formed by S1
One second solution, wherein the molar ratio of nickel ion and iron ion in second solution is 1-9:1；
First solution and second solution are mixed to form a mixed solution, which are stirred at 15-30 DEG C by S2
10-24 hours are stood after uniformly, through centrifuge washing, freeze-drying, obtains a solid powder；
The solid powder is placed in a protective atmosphere by S3, is calcined 2-6 hours at 500-700 DEG C, is obtained the nitrogen of dilval
Doped carbon composite electrocatalyst.
2. preparation method according to claim 1, which is characterized in that the N doping carbon source be selected from imidazoles, 2-methylimidazole,
At least one of 2- ethyl imidazol(e).
3. preparation method according to claim 1, which is characterized in that the nickel salt is selected from nickel nitrate, nickel chloride and nickel acetate
At least one of.
4. preparation method according to claim 1, which is characterized in that the molysite is selected from ferric nitrate, iron chloride and ferric acetate
At least one of.
5. preparation method according to claim 1, which is characterized in that nickel ion and iron ion in second solution rub
You are than being 2.33-9:1.
6. preparation method according to claim 1, which is characterized in that the protective atmosphere is in nitrogen, argon gas and helium
At least one.
7. preparation method according to claim 1, which is characterized in that in the step S3,1-5 DEG C/minute of heating rate
Clock.
8. the nitrogen-doped carbon composite electro catalytic for the dilval that preparation method described in any one of -7 obtains according to claim 1
Application of the agent on electrolysis elutriation oxygen.
9. application according to claim 8, which is characterized in that the nitrogen-doped carbon composite electrocatalyst of the dilval passes through
Cyclic voltammetry scan carries out electrochemical activation and is balanced state.
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