CN109248703A - A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application - Google Patents
A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application Download PDFInfo
- Publication number
- CN109248703A CN109248703A CN201811060200.0A CN201811060200A CN109248703A CN 109248703 A CN109248703 A CN 109248703A CN 201811060200 A CN201811060200 A CN 201811060200A CN 109248703 A CN109248703 A CN 109248703A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- preparation
- pvp
- load
- doped carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title abstract description 68
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000007789 gas Substances 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 35
- 239000002041 carbon nanotube Substances 0.000 abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 33
- 239000002131 composite material Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 15
- 238000010276 construction Methods 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000640 Fe alloy Inorganic materials 0.000 abstract description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 57
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 57
- 239000003054 catalyst Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 10
- 229910001960 metal nitrate Inorganic materials 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000956 alloy Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/399—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
-
- 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
Abstract
The invention discloses a kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application, 1) preparation method is the following steps are included: prepare Ni2+/Fe3+/ PVP mixed sols;2) by the Ni2+/Fe3+/ PVP mixed sols passes through electrostatic spinning, obtains solid fibrous carbon film;3) it after first pre-oxidizing the solid fibrous carbon film in 200~300 DEG C of air atmosphere, is heat-treated in the inert atmosphere at 400~1000 DEG C with temperature programming to get the load Ni3The nitrogen-doped carbon nanocomposite of Fe.Preparation method of the present invention is low in cost, simple general use, and obtained material is one-dimensional composite construction (carbon nano-fiber and carbon nanotube), and Ni3Fe alloy nano particle is uniformly embedded in inside carbon nano-fiber and carbon nanotube, which can have higher activity and excellent stability as the application of electrolysis water Electrocatalytic Activity for Hydrogen Evolution Reaction material.
Description
Technical field
The present invention relates to a kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and
Using belonging to alkaline evolving hydrogen reaction catalyst technical field.
Background technique
With rapidly depleting for fossil energy and becoming increasingly conspicuous for problem of environmental pollution, caused people to cleaning, green,
The urgent need of sustainable energy.Hydrogen Energy is as a kind of important energy source form for replacing fossil fuel, because of its zero-emission, superelevation
Energy density (143kJkg-1), environmental-friendly, sustainable use the advantages that obtained extensive concern.Relative to traditional system
Hydrogen mode, water electrolysis hydrogen production (2H2O→2H2+O2), due to green, efficiently, the advantages that can be mass-produced, it is considered to be it is a kind of
Hydrogen production process with wide application prospect.However, set in electrolysis water reaction and higher reaction energy barrier and biggish overpotential,
This has seriously affected kinetics rate.Therefore, efficient elctro-catalyst is developed to reduce reaction activity and energy barrier, is improved
Kinetics rate is valuable.Currently, the effective catalyst that commercialization produces hydrogen is the precious metal based catalysts such as platinum base,
At high price but due to its reserves rareness, the disadvantages of stability in operational process is poor is serious to be limited its industrialization and answers
With.Therefore, developing novel cheap, efficient base metal elctro-catalyst substitution precious metals pt base catalyst seems particularly critical.
In all kinds of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent, transition metal Ni sill, alloy and its compound-material, such as carbon
Compound, phosphide, sulfide, nitride etc. are more redox site, good anticorrosive due to its reserves abundant
The advantages such as property, are largely studied.Wherein, NiFe alloy shows preferable hydrogen evolution activity (ACS in current research
Nano,2018,12,245;ACS Catalysis,2015,6,580).Although this kind of research has been achieved with certain progress,
It is that there are still biggish limitations for the Hydrogen Evolution Performance of NiFe catalyst.Result of study is shown, by NiFe reactive alloys and nano-sized carbon
Material carries out compound being a kind of key tactics, and nano-carbon material can effectively promote the electric conductivity of catalyst, provide larger
Specific surface area, the stability of active specy.Meanwhile it hetero atom (such as: N, P, S etc.) being doped into carbon matrix can pass through adjusting
The electronic structure of neighbouring carbon atom, effectively promotes Hydrogen Evolution Performance.Therefore, these above-mentioned collaboration superior combinations are got up, is closed
It is a kind of strategy of wisdom at the NiFe alloy that the carbon matrix of Heteroatom doping loads.However, the preparation of usually this kind of material
Often time-consuming is persistently, preparation process is cumbersome, yield is less for journey.
Summary of the invention
Goal of the invention: in order to solve the above technical problems, the purpose of the present invention is to provide a kind of load Ni3The N doping of Fe
The preparation method and its resulting materials of carbon nano-composite material and application.This method simple general use, it is low in cost and obtained
Load Ni3The nitrogen-doped carbon nanocomposite of Fe shows excellent activity and stability as Electrocatalytic Activity for Hydrogen Evolution Reaction agent material.
Technical solution: to achieve the above object of the invention, the invention adopts the following technical scheme:
A kind of load Ni3The preparation method of the nitrogen-doped carbon nanocomposite of Fe, comprising the following steps:
1) Ni is prepared2+/Fe3+/ PVP mixed sols;
2) by the Ni2+/Fe3+/ PVP mixed sols passes through electrostatic spinning, obtains solid fibrous carbon film;
3) after first pre-oxidizing the solid fibrous carbon film in 200~300 DEG C of air atmosphere, existed with temperature programming
It is heat-treated in inert atmosphere at 400~1000 DEG C to get the load Ni3The nitrogen-doped carbon nanocomposite of Fe.
Step 1) the preparation Ni2+/Fe3+The method of/PVP mixed sols, comprising the following steps:
1) PVP is dissolved in DMF and the mixed solution of ethyl alcohol, obtains PVP solution;
2) nickel nitrate and ferric nitrate are added in the PVP solution, after stirring and evenly mixing, obtains the Ni2+/Fe3+/ PVP is mixed
Close colloidal sol.
In the PVP solution, the mass fraction of PVP is 5~10%.
The molar ratio of the nickel nitrate and ferric nitrate is 3:1~1:3.
Inert atmosphere described in step 3) is at least one of nitrogen, argon gas, helium, carbon dioxide.
The heating rate of temperature programming described in step 3) is 1K/min~20K/min, heat treatment time 2-4h.
Load Ni obtained by above-mentioned preparation method3The nitrogen-doped carbon nanocomposite of Fe, can be as alkalinity analysis
Hydrogen catalysts, significant effect.
Reaction principle of the invention are as follows: using nickel nitrate and ferric nitrate as source metal, polyvinylpyrrolidone is carbon nitrogen source, is led to
Cross electrostatic spinning technique, previously prepared Ni2+/Fe3+/ PVP complex fiber material, using its pre-oxidation in air atmosphere and
From in high temperature inert atmosphere, one-dimensional carbon nano-fiber, carbon nanotube loaded Ni is prepared in charing reduction3Fe material.
The material morphology is regular, uniform, Ni therein3Fe alloy nano particle has lesser size, and is uniformly embedded in carbon and receives
Inside rice fiber and carbon nanotube.In addition, N element rich in the carbon nano-fiber and carbon nanotube, due to carbon
Nanofiber, carbon nanotube and active material Ni3Component and structural advantage between Fe, obtained material analysis with higher
Hydrogen activity and excellent stability.
The Ni of prepared one-dimensional carbon nano-fiber and carbon nano tube structure load in the present invention3Fe material has following
Several advantages:
1) Ni of smaller particless size3Fe active metal nanoparticles have excellent electro-chemical activity and more catalysis
Active site;
2) composite construction of one-dimensional carbon nano-fiber and carbon nanotube makes catalyst material have biggish specific surface area,
The meso-hole structure of carbon-based material can effectively promote contact of the electrolyte with catalyst simultaneously, be conducive to the generation of reaction;
3) the quick transmission for the promotion electronics and ion that one-dimensional composite construction can orient, improves rate of catalysis reaction, promotees
Into the reaction of reactant and the quick output of product;
4) one-dimensional carbon matrix material being capable of effective anchoring activity metal material Ni3Fe does not make it during the reaction not
Easily there is a phenomenon where reuniting and falling off, be conducive to the integrality for maintaining one-dimensional composite construction;
5) choosing has the PVP of higher nitrogen content as carbon nitrogen source, and being generated by high temperature carbonization reduction has higher stone
The incorporation of the carbon carrier of blackization degree and better thermal stability, nitrogen can effectively change the electric conductivity of carbon carrier, to improve
The Hydrogen Evolution Performance of material.
Technical effect: compared with the existing technology, present invention has the advantage that
1) it by electrostatic spinning technique easy, that large-scale production can be achieved, is prepared in conjunction with high temperature carbonization thermal reduction one-dimensional
The carbon nano-fiber of composite construction and carbon nanotube loaded Ni3Fe electrocatalyst materials;
2) PVP selected by is cheap and easy to get, compared with the method for tradition preparation electrolysis water Electrocatalytic Activity for Hydrogen Evolution Reaction agent material, the party
Method large-scale production simple for process, low in cost, easy to operate, achievable;
3) product morphology obtained by is regular, Ni3Fe nano-particles size is equably carried on one-dimensional composite carbon nanometer material
In material, thus, the active site of obtained material is more, overpotential is low and it is special with one-dimensional composite construction etc. to have good stability
Point, compared with conventional Ni base alloy material, the one-dimensional composite material load of prepared carbon nano-fiber and carbon nanotube
Ni3Fe has more excellent design feature and component advantage, is a kind of potential electrolysis water Electrocatalytic Activity for Hydrogen Evolution Reaction agent material,
It is expected that having a extensive future in following energy industry.
Detailed description of the invention
Fig. 1 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
Low power SEM spectrum;
Fig. 2 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
The SEM spectrum of amplification;
Fig. 3 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
TEM map;
Fig. 4 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
XRD spectrum;
Fig. 5 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
Raman map;
Fig. 6 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
TG map;
Fig. 7 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material LSV
Curve;
Fig. 8 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
Tafel curve;
Fig. 9 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
The LSV curve comparison of cyclical stability test front and back;
Figure 10 is the nitrogen-doped carbon nano-fiber prepared according to the embodiment of the present invention 1, carbon nanotube loaded Ni3Fe material
Chrono-amperometric test curve;
Figure 11 is the LSV curve comparison for the material that embodiment 1 and comparative example 1~3 obtain in the present invention.
Specific embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment.
Embodiment 1
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
The carbon nano-fiber of the N doping using approach such as TEM, SEM, XRD, Raman and TG prepared by above embodiments and
The Ni of the one-dimensional composite construction load of carbon nanotube3Fe nano material carries out physical characterization.From low power SEM (Fig. 1), it can be seen that
By the more carbon nanotube of EDS maps on one-dimensional carbon nano-fiber, carbon nano-fiber and this one-dimentional structure of carbon nanotube are mutually handed over
Connection composition three-dimensional net structure, while Ni3Fe nanoparticle is evenly distributed on carbon nano-fiber and carbon nanotube, further
The SEM figure (Fig. 2) of amplification is it can be seen that obtained material is this structure, while the diameter of carbon nano-fiber is in 250nm
Left and right.TEM map (Fig. 3) shows Ni3Fe nanoparticle is embedded in inside carbon nano-fiber and carbon nanotube, the structure and SEM
Result it is consistent.By Fig. 4, the diffraction maximum that XRD spectrum can be seen that material can be with Ni3The standard card of Fe fits like a glove
(JCPDS card, 65-3244), it was demonstrated that Ni3The successful preparation of Fe alloy, (002) crystal face corresponds to the diffraction maximum of graphitized carbon simultaneously.
The I of the sample is calculated according to the Raman spectrogram (Fig. 5) of productD/IGValue is 0.85, shows gained carbon material degree of graphitization
It is higher.From thermogravimetric spectrogram (Fig. 6), the content of carbon is 61.18wt% in available material.Fig. 7 is that material is carried out liberation of hydrogen
The LSV figure that performance test obtains.As seen from the figure in 10mA cm-2Current density under the overpotential of the material be only 31mV.
Tafel curve (Fig. 8) shows that the numerical value of the Tafel slope of the material is only 98mV dec-1, this is better than most of alkaline liberation of hydrogen electricity
Catalyst material.Cycle performance tests (Fig. 9), is almost overlapped by the LSV curve before and after 1000 circle CV circulations, shows its tool
There is preferable stability.Figure 10 is the chronoa mperometric plot of the material, and sample is after the long-time test of 40000s, electric current
Density again shows that the material has excellent stable circulation performance almost without decaying.Result above illustrates that the material is made
It is had a good application prospect for alkaline Electrocatalytic Activity for Hydrogen Evolution Reaction agent material.
Embodiment 2
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 0.8g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 3
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 0.7g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 4
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.0mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 5
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 0.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 6
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 0.25mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;At room temperature
By mechanical stirring 12h, it is uniformly mixed it, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 7
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 0.5mmol is added3)2·6H2O and 1.0mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 8
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
200 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 9
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
300 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 600 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 10
A kind of nitrogen-doped carbon nano-fiber, carbon nanotube loaded Ni3The preparation method of Fe material, comprising the following steps:
1)Ni2+/Fe3+The preparation of/PVP mixed sols: 1.0g PVP and 6ml DMF and 6ml C are weighed2H5OH solution is mixed
It closes, the Ni (NO of 1.5mmol is added3)2·6H2O and 0.5mmol Fe (NO3)3·9H2O solid metal nitrate;It passes through at room temperature
Mechanical stirring 12h is crossed, it is uniformly mixed, yellowish-brown Ni can be obtained2+/Fe3+/ PVP colloidal sol;
2) method of electrostatic spinning prepares nitrogen-doped carbon nanocomposite load Ni3Fe composite material: step 1) is obtained
Yellowish-brown Ni2+/Fe3+/ PVP colloidal sol, is handled by electrostatic spinning technique, and obtained solid fibrous carbon thin-film material first passes through
250 DEG C of 3h pre-oxidation treatments in air, then in N2Under atmosphere, 800 DEG C are warming up to the heating rate of 5 DEG C/min and carries out hot place
Reason, and 3h is kept at such a temperature, it then cools to room temperature, final product can be obtained.
Embodiment 11
It is same as Example 1, the difference is that:
In obtained PVP solution, the mass fraction of PVP is 5%;The heating rate of temperature programming be 1K/min, heat at
Managing temperature is 400 DEG C, time 2h.
Embodiment 12
It is same as Example 1, the difference is that:
In obtained PVP solution, the mass fraction of PVP is 10%;The heating rate of temperature programming is 20K/min, heat
Treatment temperature is 1000 DEG C, time 4h.
Comparative example 1
The difference of this comparative example and embodiment 1, which is only that, uses single transition metal Ni as source metal, remaining implements item
Part is constant.
Comparative example 2
The difference of this comparative example and embodiment 1, which is only that, uses single transition metal Fe as source metal, remaining implements item
Part is constant.
Comparative example 3
The difference of this comparative example and embodiment 1 is only that without using transition metal, remaining implementation condition is constant.
The LSV test result for the evolving hydrogen reaction accordingly tested is as shown in figure 11, and the electrocatalysis material of no metal is shown most
Negative initial reduction current potential and the smallest current density, show worst Hydrogen Evolution Performance;Single W metal or Fe are prepared
Electrocatalysis material all show compared with Ni3The poor Hydrogen Evolution Performance of Fe material.Overall performance comparison shows Ni3Fe>Ni>Fe>
The sequence of C.
Claims (8)
1. a kind of load Ni3The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which comprises the following steps:
1) Ni is prepared2+/Fe3+/ PVP mixed sols;
2) by the Ni2+/Fe3+/ PVP mixed sols passes through electrostatic spinning, obtains solid fibrous carbon film;
3) after first pre-oxidizing the solid fibrous carbon film in 200~300 DEG C of air atmosphere, with temperature programming 400
It is heat-treated in inert atmosphere at~1000 DEG C to get the load Ni3The nitrogen-doped carbon nanocomposite of Fe.
2. load Ni according to claim 13The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which is characterized in that
Step 1) the preparation Ni2+/Fe3+The method of/PVP mixed sols, comprising the following steps:
1) PVP is dissolved in DMF and the mixed solution of ethyl alcohol, obtains PVP solution;
2) nickel nitrate and ferric nitrate are added in the PVP solution, after stirring and evenly mixing, obtains the Ni2+/Fe3+/ PVP mixing is molten
Glue.
3. load Ni according to claim 23The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which is characterized in that
In the PVP solution, the mass fraction of PVP is 5~10%.
4. load Ni according to claim 23The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which is characterized in that
The molar ratio of the nickel nitrate and ferric nitrate is 3:1~1:3.
5. load Ni according to claim 13The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which is characterized in that
Inert atmosphere described in step 3) is at least one of nitrogen, argon gas, helium, carbon dioxide.
6. load Ni according to claim 13The preparation method of the nitrogen-doped carbon nanocomposite of Fe, which is characterized in that
The heating rate of temperature programming described in step 3) is 1K/min~20K/min, heat treatment time 2-4h.
7. load Ni obtained by any one of the claim 1-6 preparation method3The nitrogen-doped carbon nanocomposite of Fe.
8. load Ni as claimed in claim 73The nitrogen-doped carbon nanocomposite of Fe is answered as alkaline evolving hydrogen reaction catalyst
With.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811060200.0A CN109248703B (en) | 2018-09-12 | 2018-09-12 | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811060200.0A CN109248703B (en) | 2018-09-12 | 2018-09-12 | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109248703A true CN109248703A (en) | 2019-01-22 |
CN109248703B CN109248703B (en) | 2021-07-27 |
Family
ID=65046735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811060200.0A Active CN109248703B (en) | 2018-09-12 | 2018-09-12 | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109248703B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110075886A (en) * | 2019-05-31 | 2019-08-02 | 中南林业科技大学 | Ni-based-carbon composite electrocatalyst and preparation method thereof |
CN110124713A (en) * | 2019-04-24 | 2019-08-16 | 南京师范大学 | A kind of nitrogen-doped carbon nano-fiber load hollow structure Co3O4/CeO2The preparation method and application of nanometer particle material |
CN110148763A (en) * | 2019-04-24 | 2019-08-20 | 南京师范大学 | A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method and application of carbon-nitrogen material |
CN110142058A (en) * | 2019-05-21 | 2019-08-20 | 大连理工大学 | A kind of three-dimensional porous FeNi-NC bifunctional electrocatalyst and preparation method thereof of F127 induction |
CN110975914A (en) * | 2019-11-29 | 2020-04-10 | 东华大学 | Phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material and preparation method and application thereof |
CN111575836A (en) * | 2020-05-21 | 2020-08-25 | 南京师范大学 | S-doped surface-wrinkled carbon fiber loaded Co and MnO nano particles and preparation method and application thereof |
CN111659439A (en) * | 2020-06-02 | 2020-09-15 | 南京师范大学 | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof |
CN112058293A (en) * | 2020-07-29 | 2020-12-11 | 南京师范大学 | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof |
CN112206805A (en) * | 2020-10-14 | 2021-01-12 | 扬州大学 | Hollow iron-nickel nitride catalyst, preparation method and all-water electrolysis application thereof |
CN113061936A (en) * | 2021-03-25 | 2021-07-02 | 中国科学院上海高等研究院 | Nickel-iron-carbon nanofiber catalyst, preparation method, application method, test method and test system thereof |
CN113945480A (en) * | 2021-11-03 | 2022-01-18 | 辽宁工程技术大学 | Coal secondary oxidation activation energy analysis method based on characteristic temperature division |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634873A (en) * | 2012-04-18 | 2012-08-15 | 江南大学 | Nano titanium dioxide coated carbon nanotube reinforced carbon nanofiber and preparation method thereof |
CN104001518A (en) * | 2014-06-10 | 2014-08-27 | 中国计量学院 | Preparing method for nickel alloy/porous material catalyst |
CN105321728A (en) * | 2014-07-24 | 2016-02-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube composite material, preparation method thereof, electrode and super capacitor |
CN106268636A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | Carbon nano-fiber adsorbing material of aminated carbon nano tube doping and preparation method thereof |
CN106345479A (en) * | 2016-07-27 | 2017-01-25 | 武汉轻工大学 | Porous nanotube or nanofiber type ZnO/ZnFe2O4 composite photocatalyst and electrostatic spinning one-step preparation method thereof |
-
2018
- 2018-09-12 CN CN201811060200.0A patent/CN109248703B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634873A (en) * | 2012-04-18 | 2012-08-15 | 江南大学 | Nano titanium dioxide coated carbon nanotube reinforced carbon nanofiber and preparation method thereof |
CN104001518A (en) * | 2014-06-10 | 2014-08-27 | 中国计量学院 | Preparing method for nickel alloy/porous material catalyst |
CN105321728A (en) * | 2014-07-24 | 2016-02-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube composite material, preparation method thereof, electrode and super capacitor |
CN106345479A (en) * | 2016-07-27 | 2017-01-25 | 武汉轻工大学 | Porous nanotube or nanofiber type ZnO/ZnFe2O4 composite photocatalyst and electrostatic spinning one-step preparation method thereof |
CN106268636A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | Carbon nano-fiber adsorbing material of aminated carbon nano tube doping and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
GENGTAO FU ET AL: "Ni3Fe-N Doped Carbon Sheets as a Bifunctional Electrocatalyst for Air Cathodes", 《ADV. ENERGY MATER.》 * |
YUFEI ZHAO ET AL: "Fe3C@nitrogen doped CNT arrays aligned on nitrogen functionalized carbon nanofibers as highly efficient catalysts for the oxygen evolution reaction", 《J. MATER. CHEM. A》 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110148763B (en) * | 2019-04-24 | 2021-06-11 | 南京师范大学 | Preparation method and application of Fe-doped Mn3O4 carbon-nitrogen material with hollow nano-framework structure |
CN110124713A (en) * | 2019-04-24 | 2019-08-16 | 南京师范大学 | A kind of nitrogen-doped carbon nano-fiber load hollow structure Co3O4/CeO2The preparation method and application of nanometer particle material |
CN110148763A (en) * | 2019-04-24 | 2019-08-20 | 南京师范大学 | A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method and application of carbon-nitrogen material |
CN110124713B (en) * | 2019-04-24 | 2022-06-03 | 南京师范大学 | Nitrogen-doped carbon nanofiber loaded hollow structure Co3O4/CeO2Preparation method and application of nanoparticle material |
CN110142058A (en) * | 2019-05-21 | 2019-08-20 | 大连理工大学 | A kind of three-dimensional porous FeNi-NC bifunctional electrocatalyst and preparation method thereof of F127 induction |
CN110142058B (en) * | 2019-05-21 | 2022-01-04 | 大连理工大学 | F127-induced three-dimensional porous FeNi-NC dual-functional electrocatalyst and preparation method thereof |
CN110075886A (en) * | 2019-05-31 | 2019-08-02 | 中南林业科技大学 | Ni-based-carbon composite electrocatalyst and preparation method thereof |
CN110975914A (en) * | 2019-11-29 | 2020-04-10 | 东华大学 | Phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material and preparation method and application thereof |
CN110975914B (en) * | 2019-11-29 | 2021-12-10 | 东华大学 | Phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material and preparation method and application thereof |
CN111575836B (en) * | 2020-05-21 | 2022-05-31 | 南京师范大学 | S-doped surface-wrinkled carbon fiber loaded Co and MnO nano particles and preparation method and application thereof |
CN111575836A (en) * | 2020-05-21 | 2020-08-25 | 南京师范大学 | S-doped surface-wrinkled carbon fiber loaded Co and MnO nano particles and preparation method and application thereof |
CN111659439A (en) * | 2020-06-02 | 2020-09-15 | 南京师范大学 | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof |
CN111659439B (en) * | 2020-06-02 | 2023-04-07 | 南京师范大学 | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof |
CN112058293A (en) * | 2020-07-29 | 2020-12-11 | 南京师范大学 | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof |
CN112058293B (en) * | 2020-07-29 | 2023-04-07 | 南京师范大学 | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof |
CN112206805A (en) * | 2020-10-14 | 2021-01-12 | 扬州大学 | Hollow iron-nickel nitride catalyst, preparation method and all-water electrolysis application thereof |
CN112206805B (en) * | 2020-10-14 | 2023-05-19 | 扬州大学 | Hollow iron-nickel nitride catalyst, preparation method and full-water electrolysis application thereof |
CN113061936A (en) * | 2021-03-25 | 2021-07-02 | 中国科学院上海高等研究院 | Nickel-iron-carbon nanofiber catalyst, preparation method, application method, test method and test system thereof |
CN113945480A (en) * | 2021-11-03 | 2022-01-18 | 辽宁工程技术大学 | Coal secondary oxidation activation energy analysis method based on characteristic temperature division |
Also Published As
Publication number | Publication date |
---|---|
CN109248703B (en) | 2021-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109248703A (en) | A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application | |
Chang et al. | Dual MOF-derived Fe/N/P-tridoped carbon nanotube as high-performance oxygen reduction catalysts for zinc-air batteries | |
CN106058275B (en) | A kind of used in proton exchange membrane fuel cell carbon carries the preparation method and applications of PtCo intermetallic compound catalyst | |
CN107346826A (en) | A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron | |
CN110124713A (en) | A kind of nitrogen-doped carbon nano-fiber load hollow structure Co3O4/CeO2The preparation method and application of nanometer particle material | |
CN108671948A (en) | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin | |
CN111659439B (en) | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof | |
Wang et al. | Cobalt-gluconate-derived high-density cobalt sulfides nanocrystals encapsulated within nitrogen and sulfur dual-doped micro/mesoporous carbon spheres for efficient electrocatalysis of oxygen reduction | |
CN112058293B (en) | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof | |
WO2021232751A1 (en) | Porous coo/cop nanotubes, preparation method therefor and use thereof | |
Sun et al. | Ce-doped ZIF-67 derived Co3O4 nanoparticles supported by carbon nanofibers: A synergistic strategy towards bifunctional oxygen electrocatalysis and Zn-Air batteries | |
CN103840176B (en) | Three-dimensional grapheme based combined electrode of a kind of area load Au nano particle and its preparation method and application | |
Liu et al. | Modulated FeCo nanoparticle in situ growth on the carbon matrix for high-performance oxygen catalysts | |
CN113289650A (en) | Bimetallic phosphide-carbon electrocatalytic hydrogen evolution material and preparation method thereof | |
CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
CN108649237B (en) | Gel pyrolysis-based cobalt-nitrogen doped carbon composite material and preparation method and application thereof | |
Gong et al. | Prussian blue analogues derived electrocatalyst with multicatalytic centers for boosting oxygen reduction reaction in the wide pH range | |
Wu et al. | In situ growth of copper-iron bimetallic nanoparticles in A-site deficient Sr2Fe1. 5Mo0. 5O6-δ as an active anode material for solid oxide fuel cells | |
Jiang et al. | Metal-organic frameworks derived N, S, O-doped carbon sheets coated CoP/Co3S4 hybrids for enhanced electrocatalytic hydrogen evolution reaction | |
Zhang et al. | Metal-organic-framework-derived bimetallic carbon-based catalysts as efficient oxygen reduction reaction electrocatalysts | |
Yu et al. | Conductive tungsten oxynitride supported highly dispersed cobalt nanoclusters for enhanced oxygen reduction | |
CN113410473B (en) | Iron-nickel polyphenol network nano composite carbon material electrocatalyst based on chitosan modified cellulose aerogel and preparation method thereof | |
Fu et al. | N-doped hollow carbon tubes derived N-HCTs@ NiCo2O4 as bifunctional oxygen electrocatalysts for rechargeable Zinc-air batteries | |
Liu et al. | Surface modification strategy for constructing Fe-Nx species and FeF2/Fe3C nanoparticles co-anchored N, F co-doped carbon nanotubes for efficient oxygen reduction | |
CN112439402B (en) | Preparation method of carbon nanotube loaded with iron-based nanoparticle, carbon nanotube loaded with iron-based nanoparticle and application of carbon nanotube |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |