CN108565477A - The method of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N - Google Patents
The method of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 31
- 239000001301 oxygen Substances 0.000 title claims abstract description 31
- 230000009467 reduction Effects 0.000 title claims abstract description 31
- 238000011978 dissolution method Methods 0.000 title claims abstract description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 30
- 239000013082 iron-based metal-organic framework Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- -1 aniline small molecule Chemical class 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 32
- 238000006722 reduction reaction Methods 0.000 description 25
- 238000005303 weighing Methods 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- 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
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to nanocomposite preparing technical fields, and in particular to a method of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe N are built using Polymeric dissolution method.It is precursor that method provided by the invention, which is based on Fe MOF and aniline small molecule, propose " Polymeric dissolution " new strategy, the balance between one effective " aniline polymerization reacts Fe MOF dissolvings " is constructed, the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts (FNCSC) of Fe N of nucleocapsid are prepared for.In the design method of the present invention, Fe MOF serve not only as sacrificing template to build nucleocapsid, while being also that FNCSC introduces Fe, S and N hetero atom.And, the method of the present invention can effectively prepare a series of core-shell material so as to meet different application demands by adjusting " Polymeric dissolution " balances, such as have wide practical use in fuel cell, bio-sensing, ultracapacitor field.Method provided by the invention, process is simple, at low cost, environmental-friendly.
Description
Technical field
The present invention relates to nanocomposite preparing technical fields, and in particular to a kind of polymerization-dissolution method structure Fe-N is equal
The method of the nucleocapsid carbon nanometer oxygen reduction catalyst of even distribution.
Background technology
It is well known that oxygen reduction reaction (ORR) is the committed step in current sustainable energy storage and conversion equipment.
But because of its slow kinetic rate, it is badly in need of developing efficient catalyst to accelerate the progress of reaction.Business can be realized at present
The mainly precious metals pt changed is the catalyst of representative, but its resource is limited, expensive, stability is poor.Thus develop green
Environmentally friendly, cheap, resourceful transition metal base complex carbon material catalyst becomes present research main flow direction.At present
The activity of catalyst is mainly improved by two kinds of strategies：(1) Heteroatom doping carbon material changes its electronic structure and then improves
Activity.So far, compared with the nano-carbon material of transition metal element Co, Ni and Cu doping, the nano-carbon material of Fe element dopings
With higher ORR activity, especially with Fe-N and Fe3C-shaped formula doping complex carbon material performance it is the most excellent [W.Yang,
X.Liu,X.Yue,J.Jia,S.Guo,Journal of the American Chemical Society,2015,137,
1436-1439；C.Zhu,S.Fu,J.Song,Q.Shi,D.Su,M.H.Engelhard,X.Li,D.Xiao,D.Li,
L.Estevez,D.Du,Y.Lin,Small,2017,13,1603407]；(2) microscopic structures of control nano-carbon material are oriented to：
It such as builds the material of hierarchical porous structure load, build the carbon skeleton and core-shell configuration of 3D multichannels, so that it is guaranteed that material has
Higher specific surface area, more active sites, higher catalytic stability [W.Yang, X.Yue, X.Liu, L.Chen,
J.Jia,S.Guo,Nanoscale,2016,8,959-964；M.Zhou,H.-L.Wang,S.Guo,Chemical Society
Reviews,2016,45,1273-1307]。
The nanocomposite of core-shell configuration has become the heat of elctro-catalyst research because of its unique physical and chemical performance
Point [H.Hu, L.Han, M.Yu, Z.Wang, X.W.Lou, Energy＆Environmental Science, 2016,9,107-
111].In general, the nanoparticle core in core-shell configuration can activate the carbon nanometer shell structure of outer layer and increase material
Electric conductivity, and then increase catalytic activity；The carbon nanoshell of outer layer is mainly that can prevent the reunion of nano particle, is avoided in electrification
Etching side effect of the electrolyte to metal nanoparticle during, thus improve stability [Z.Liu, the X.- of material
Y.Yu,U.Paik,Advanced Energy Materials,2016,6,1502318；Q.Zhang,H.Bai,Q.Zhang,
Q.Ma,Y.Li,C.Wan,G.Xi,Nano Research,2016,9,3038-3047]。
More strikingly, recent report is verified in identical carbon substrate, compared to metallic nanoparticle
The metal-doped complex carbon material of the material of son load, the doping of evenly dispersed atom level plays more electro-catalysis process
Important role.Since metallic element is that evenly dispersed there is no the particles of large grained, so that active site density
It greatly increases, the metal-doped Exploration on mechanism for also promoting ORR of atom level is more convenient in addition so that actual sample and theoretical mould
Type more coincide.However, preparing the nanometer nuclear shell nano-structure of transition metal element Uniform Doped as efficient ORR catalyst still
There are still huge challenge [M.H.Naveen, K.Shim, M.S.A.Hossain, J.H.Kim, Y.-B.Shim, Advanced
Energy Materials,2017,7,1602002；Q.-L.Zhu,W.Xia,L.-R.Zheng,R.Zou,Z.Liu,Q.Xu,
ACS Energy Letters,2017,2,504-511]。
Invention content
The object of the present invention is to provide a kind of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer hydrogen reduction of Fe-N to urge
The method of agent.
To achieve the goals above, technical scheme of the present invention is specific as follows：
A kind of method of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N, including with
Lower step：
Aniline solution is scattered in solvent by step 1, is stirred under ice bath；
Fe-MOF is added in step 1 acquired solution by step 2, continues to stir 30min under ice bath；
The mass ratio of the aniline and Fe-MOF are 16:1~1:2；
Step 3, by (NH4)2S2O8It is dissolved in HClO4In, it is added in step 2 acquired solution, continues after cooling in ice bath
Stir 20min~9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, and drying obtains powder material
Material；
Dusty material obtained by step 4 is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, from room temperature liter
Temperature keeps 1-3h, then 700-1000 DEG C is warming up to from 240 DEG C to 240 DEG C, keeps 0.5-3h, obtains the equally distributed cores of Fe-N
Shell carbon nanometer oxygen reduction catalyst.
In the above-mentioned technical solutions, (NH described in step 34)2S2O8Dosage be 0.1334-0.1667g.
In the above-mentioned technical solutions, HClO described in step 34A concentration of 1.0M, dosage 10mL.
In the above-mentioned technical solutions, solvent described in step 1 is HClO4With the mixed solvent of ethyl alcohol.
In the above-mentioned technical solutions, the time stirred described in step 1 is 30min.
In the above-mentioned technical solutions, heating rate is 2 DEG C/min in step 4.
In the above-mentioned technical solutions, the temperature dried described in step 4 is 60 DEG C, and the time is for 24 hours.
The beneficial effects of the invention are as follows：
It is precursor that method provided by the invention, which is based on Fe-MOF and aniline small molecule, it is proposed that " polymerization-dissolving " new plan
Slightly, the balance between one effective " aniline polymerization reaction-Fe-MOF dissolvings " is constructed, the Fe-N for being prepared for nucleocapsid is equal
The nucleocapsid carbon nanometer oxygen reduction catalyst (FNCSC) (such as Fig. 1) of even distribution.In the design method of the present invention, Fe-MOF is not only
Nucleocapsid is built as template is sacrificed, while being also that FNCSC introduces Fe, S and N hetero atom.Also, the method for the present invention
It is different so as to meet a series of core-shell material can effectively to be prepared by adjusting " polymerization-dissolving " balances
Application demand, such as have wide practical use in fuel cell, bio-sensing, ultracapacitor field.
Method provided by the invention, process is simple, at low cost, environmental-friendly.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the design flow diagram of method provided by the invention；
Fig. 2 is the saturating of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 1 method of the embodiment of the present invention
Radio mirror (TEM) figure；
Fig. 3 is the TEM of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 2 method of the embodiment of the present invention
Figure；
Fig. 4 is the TEM of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 3 method of the embodiment of the present invention
Figure；
Fig. 5 is the TEM of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 4 method of the embodiment of the present invention
Figure；
Fig. 6 is that the X of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 4 method of the embodiment of the present invention is penetrated
Ray diffraction diagram；
Fig. 7 is the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of 4 obtained Fe-N of the embodiment of the present invention and business
Change 20%Pt/C, the comparison diagram of the ORR performances in 0.10M KOH；(rotating speed 1600rpm, total number 5mV/s).
Specific implementation mode
The present invention is described in detail below in conjunction with the accompanying drawings.
The present invention provides a kind of side of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N
Method specifically includes following steps：
Step 1, the aniline solution for measuring certain volume, are scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, in ice bath
Lower stirring 30min；
Step 2, the Fe-MOF for weighing certain mass, are slowly added into step 1 acquired solution, continue to stir under ice bath
30min；The mass ratio of the aniline and Fe-MOF are 16:1~1:2；
The step 3, (NH for weighing 0.1334-0.1667g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is cooling in ice bath
After be added in step 2 acquired solution, continue stir 20min~9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry, drying temperature is 60 DEG C, and drying time is for 24 hours, to obtain dusty material；
Dusty material obtained by step 4 is placed in tube furnace by step 5, under nitrogen protection, from room temperature to 240 DEG C,
1-3h is kept, then is warming up to 700-1000 DEG C from 240 DEG C, it is 2 DEG C/min to keep 0.5-3h, heating rate, and it is uniform to obtain Fe-N
The nucleocapsid carbon nanometer oxygen reduction catalyst of distribution.
Method provided by the invention raw materials used predominantly Fe-MOF, aniline molecule and (NH4)2S2O8, it is only necessary to control him
Between ratio, reaction time and HClO4Volume etc., so that it may the composite material of different-shape is made.This method mistake
Journey is simple, at low cost, environmental-friendly, can meet different application prospects.
Embodiment 1
The mass ratio of aniline and Fe-MOF is：6:1, the reaction time is：20min, pattern are shown in attached drawing 2.
Step 1 measures 0.60mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, it is stirred under ice bath
Mix 30min.
Step 2, the Fe-MOF for weighing 0.100g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1334g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 20min；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(1h), 900 DEG C (2h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
Embodiment 2
The mass ratio of aniline and Fe-MOF is：8:1, the reaction time is：3h, pattern are shown in attached drawing 3.
Step 1 measures 0.80mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, it is stirred under ice bath
Mix 30min.
Step 2, the Fe-MOF for weighing 0.100g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1334g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 3h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(2h), 800 DEG C (2h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
Embodiment 3
The mass ratio of aniline and Fe-MOF is：8:1, the reaction time：9h, pattern are shown in attached drawing 4.
Step 1 measures 0.80mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, it is stirred under ice bath
Mix 30min.
Step 2, the Fe-MOF for weighing 0.100g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1667g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(1h), 700 DEG C (2h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
Embodiment 4
The mass ratio of aniline and Fe-MOF is：5:4, reaction time 9h, pattern is shown in attached drawing 5.
Step 1 measures 0.80mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, it is stirred under ice bath
Mix 30min.
Step 2, the Fe-MOF for weighing 1.00g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1667g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(1h), 800 DEG C (2h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
Fig. 2-Fig. 5 is the transmission electron microscope picture (TEM) of acquired target material, before we can be found that by effectively adjusting
The synthesis condition for driving the proportion relation and experiment of body (aniline and Fe-MOF), can effectively adjust the pattern of material by dendritic ellipse
Spherical shape arrives hollow-core construction to nucleocapsid and is changed again.
Fig. 6 is that the X of the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N prepared by 4 method of the embodiment of the present invention is penetrated
Ray diffraction diagram, the classical peak of 26 ° of appearance correspond to the diffraction maximum of (002) of graphited carbon.Other peaks are Fe3The diffraction of C
Peak.In addition, we are by k3The Fourier transformation figure of the EXAFS (full name) on the sides Fe K- of weighting in system it is found that exist apparent
Fe-N keys.
Fig. 7 is the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of 4 obtained Fe-N of the embodiment of the present invention and business
Change 20%Pt/C, the comparison diagram of the ORR performances in 0.10M KOH；We can be found that under alkaline condition material has very
Good catalytic performance, show calibration plays spike potential, half wave potential and limiting current density.
Embodiment 5
The mass ratio of aniline and Fe-MOF is：16:1, reaction time 9h, pattern is shown in attached drawing 5.
Step 1 measures 16mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, is stirred under ice bath
30min。
Step 2, the Fe-MOF for weighing 1.00g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1667g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(3h), 1000 DEG C (0.5h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
The equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N manufactured in the present embodiment, under alkaline condition, material
With good catalytic performance, show calibration plays spike potential, half wave potential and limiting current density.
Embodiment 6
The mass ratio of aniline and Fe-MOF is：1:2, reaction time 9h, pattern is shown in attached drawing 5.
Step 1 measures 1.0mL aniline solutions, is scattered in (1.0M HClO4+ ethyl alcohol) in the mixed solvent, it is stirred under ice bath
Mix 30min.
Step 2, the Fe-MOF for weighing 2.00g, are slowly added into above-mentioned solution, continue to stir 30min under ice bath.
The step 3, (NH for weighing 0.1667g4)2S2O8, it is dissolved in 10mL 1.0M HClO4In, it is added after cooling in ice bath
In above-mentioned mixed solution, continue to stir 9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, is dried in vacuum drying chamber
Dry (60 DEG C, for 24 hours), obtain dusty material.
Obtained dusty material is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, and temperature program 240
(1h), 800 DEG C (3h), heating rate are 2 DEG C/min, obtain the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N.
The equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N manufactured in the present embodiment, under alkaline condition, material
With good catalytic performance, show calibration plays spike potential, half wave potential and limiting current density.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (7)
1. a kind of method of polymerization-dissolution method structure equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N, feature exist
In including the following steps：
Aniline solution is scattered in solvent by step 1, is stirred under ice bath；
Fe-MOF is added in step 1 acquired solution by step 2, continues to stir 30min under ice bath；
The mass ratio of the aniline and Fe-MOF are 16:1~1:2；
Step 3, by (NH4)2S2O8It is dissolved in HClO4In, it is added in step 2 acquired solution after cooling in ice bath, continues to stir
20min~9h；
Step 4, after reaction, is respectively adopted secondary water and ethyl alcohol carries out eccentric cleaning solution, and drying obtains dusty material；
Dusty material obtained by step 4 is placed in tube furnace by step 5, under nitrogen protection, high-temperature calcination, from room temperature to
240 DEG C, 1-3h is kept, then be warming up to 700-1000 DEG C from 240 DEG C, keeps 0.5-3h, obtain the equally distributed nucleocapsid carbon of Fe-N
Nanometer oxygen reduction catalyst.
2. polymerization according to claim 1-dissolution method builds the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N
Method, which is characterized in that (NH described in step 34)2S2O8Dosage be 0.1334-0.1667g.
3. polymerization according to claim 1-dissolution method builds the equally distributed nucleocapsid carbon nanometer oxygen reduction catalysts of Fe-N
Method, which is characterized in that HClO described in step 34A concentration of 1.0M, dosage 10mL.
4. polymerization-dissolution method according to claim 1-3 any one builds the equally distributed nucleocapsid carbon nano oxygens of Fe-N
The method of reducing catalyst, which is characterized in that solvent described in step 1 is HClO4With the mixed solvent of ethyl alcohol.
5. polymerization-dissolution method according to claim 1-3 any one builds the equally distributed nucleocapsid carbon nano oxygens of Fe-N
The method of reducing catalyst, which is characterized in that the time stirred described in step 1 is 30min.
6. polymerization-dissolution method according to claim 1-3 any one builds the equally distributed nucleocapsid carbon nano oxygens of Fe-N
The method of reducing catalyst, which is characterized in that heating rate is 2 DEG C/min in step 4.
7. polymerization-dissolution method according to claim 1-3 any one builds the equally distributed nucleocapsid carbon nano oxygens of Fe-N
The method of reducing catalyst, which is characterized in that the temperature dried described in step 4 is 60 DEG C, and the time is for 24 hours.
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| CN106898786A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of oxygen reduction catalyst and its preparation and application |
| CN107275110A (en) * | 2017-07-21 | 2017-10-20 | 东华大学 | A kind of iron MOF polyaniline composite materials and its preparation method and application |
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| CN106898786A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of oxygen reduction catalyst and its preparation and application |
| CN107275110A (en) * | 2017-07-21 | 2017-10-20 | 东华大学 | A kind of iron MOF polyaniline composite materials and its preparation method and application |
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| WENXIU YANG等: "In situ formed Fe–N doped metal organic framework@carbon nanotubes/graphene hybrids for a rechargeable Zn–air battery", 《CHEM. COMMUN》 * |
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