CN106744786B - A kind of preparation method of metal-N doping porous carbon microsphere - Google Patents
A kind of preparation method of metal-N doping porous carbon microsphere Download PDFInfo
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- CN106744786B CN106744786B CN201610988843.6A CN201610988843A CN106744786B CN 106744786 B CN106744786 B CN 106744786B CN 201610988843 A CN201610988843 A CN 201610988843A CN 106744786 B CN106744786 B CN 106744786B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004005 microsphere Substances 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 111
- 235000019441 ethanol Nutrition 0.000 claims description 43
- 238000001291 vacuum drying Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- 239000005416 organic matter Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 3
- -1 complexant Substances 0.000 abstract description 3
- 230000000717 retained effect Effects 0.000 abstract description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- 238000013019 agitation Methods 0.000 description 11
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102100028672 C-type lectin domain family 4 member D Human genes 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 101000766905 Homo sapiens C-type lectin domain family 4 member D Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- VTQLKSBTYJTJNF-UHFFFAOYSA-N [N].[O-][N+]1=CC=CC=C1 Chemical compound [N].[O-][N+]1=CC=CC=C1 VTQLKSBTYJTJNF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/90—Other crystal-structural characteristics not specified above
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of metal N doping porous carbon microsphere.The present invention is with 4 vinylpyridine monomers (4VP) for carbon nitrogen source, using different metal salt as initiator, complexant, catalyst and template, by initiator of metal salt 4VP monomers are polymerize at normal temperatures first, metal ion forms metal ligand structure with the nitrogen-atoms in 4VP molecules, forms metallorganic microballoon；Then at high temperature, the metal in microballoon plays the role of catalyst and template again, so that organic matter is converted into carbon, and chondritic is retained, then through pickling up to metal N doping porous carbon microsphere.Source metal of the present invention is alternative wide, and step is simple, and the nitrogen-doped porous carbon material large specific surface area of preparation, nitrogen element content are high.Big specific surface area and high nitrogen element content make this material have huge application prospect in energy stores conversion, catalysis and field of environment protection.
Description
Technical field
The invention belongs to technical field of function materials, specifically, are related to a kind of system of metal-N doping porous carbon microsphere
Preparation Method.
Background technology
Porous carbon has raw material sources wide, and physical and chemical stability is good, large specific surface area, large pore volume, good conductivity, resistance to height
The features such as temperature, acid and alkali-resistance, it is all to be widely used in electrode material, catalysis and catalyst carrier, gas absorption separation and Water warfare etc.
It is multi-field.Studies have shown that the principal element for influencing porous carbon performance has pore structure and surface chemical property.In recent years, porous
Chemically Quality Research becomes hot spot to carbon surface, mainly hetero atom is introduced into carbon skeleton, such as N, O, B, S, P.Carbon skeleton
Middle introducing hetero-atoms make graphite microcrystal plane layer in carbon-coating the lacking with unpaired electron such as generate many dislocations, be bent, off normal
Fall into position；Hetero atom can form local surface functional group simultaneously, so that carbon material surface is had acid-base property, these improve carbon materials jointly
Expect respective performances.Currently, about doping, N doping extensively and is easy to introduce carbon base body and cause numerous researchers' due to nitrogen source
Hobby.
It is different from the combining form of carbon atom according to nitrogen-atoms, the nitrogen-atoms in material can be divided into chemical N doping and knot
Structure N doping.Chemical N doping refers to that there are carbon material surfaces in the form of surface functional group for nitrogen-atoms, and B- alkali is provided for material
Site, such as amino surface nitrogen-containing functional group, such nitrogen-containing functional group alkalinity is strong, is easier to chemically react, but its stability
Difference, high temperature easily decompose easy to fall off.Structure N doping is to be introduced directly into nitrogen-atoms in carbon skeleton and carbon atom bonding, strengthening material
The L- alkalinity of material, such as pyridine nitrogen, pyrroles's nitrogen, graphitization nitrogen, pyridine oxide nitrogen etc., such nitrogen stability are strong.Surface nitrogen doping type
The preparation method of porous carbon is pre-synthesis Carbon Materials, is impregnated with coating material appropriate, is heat-treated, to introduce
Nitrogen-containing functional group, common coating material include：Melamine, urea, NH3Deng.The preparation side of structure N doping type porous carbon
Method is that directly nitrogen-atoms is introduced into carbon skeleton, obtains N doping porous carbon by high temperature cabonization, nitrogen in this method resulting materials
Elemental redistribution is uniform, and mainly exists in the form of structure N doping.Common raw material has acetonitrile, polyacrylonitrile, polypyrrole, trimerization
Cyanamide, aniline, nitrogen containing plasma liquid, chitosan, Glucosamine and rich nitrogen biomass etc..
Invention content
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of simple metal-N doping porous carbons
The preparation method of microballoon.
The present invention for carbon nitrogen source, using various metals salt as initiator, complexant, is urged with 4-vinylpridine monomer (4VP)
Agent and template successfully prepare metal N doping porous carbon microsphere.The implementation process of the present invention is described below：With metal salt
For initiator so that 4VP monomers polymerize at normal temperatures, while metal ion also forms gold with the nitrogen-atoms in 4VP molecules
Category-coordination structure forms metal-organic microballoon through drying.Under hot conditions, the metal in microballoon plays catalyst and mould
The effect of plate agent makes organic matter be converted into carbon, and chondritic is retained, then obtains the N doping containing metal through pickling
Porous carbon microsphere.
The specific technical solution of the present invention is implemented by following steps：
The present invention provides a kind of preparation method of metal-N doping porous carbon microsphere, is as follows：
(1) 4VP/ ethanol solutions are prepared：4-vinylpridine 4VP and absolute ethyl alcohol are mixed, stirring, obtains 4VP/
Ethanol solution；
(2) preparing metal salting liquid：Metal salt and absolute ethyl alcohol are mixed, stir to get metal salt/ethanol solution；
The metal salt is any in molysite, mantoquita, magnesium salts, nickel salt, cobalt salt, cerium salt or lanthanum salt；
(3) preparation of metal-organic microballoon：At room temperature, 4VP/ ethanol solutions and metal salt/absolute ethyl alcohol is molten
Liquid mixes, and forms complex precipitation, is then centrifuged, is dried in vacuo up to metal-organic microballoon；
(4) it is carbonized：Metal-organic microballoon is placed in tube furnace and is carbonized, is taken out after cooling, obtains metal-N doping
Carbosphere；
(5) pickling：It by metal-nitrogen-doped carbon microballoon acid elution, is washed with water, filtering, vacuum drying obtain metal-nitrogen
Adulterate porous carbon microsphere.
In the present invention, in step (1), a concentration of 0.02~0.2mol/L of 4VP/ ethanol solutions.
In the present invention, in step (2), metal salt is iron chloride, copper chloride, magnesium chloride, nickel chloride, cobalt acetate, cerous nitrate
Or the metal salts such as lanthanum nitrate；The concentration of coordinating metal solution is between 0.02~0.2mol/L.
In the present invention, in step (3), the molar ratio of metal ion and 4VP in metal-organic microballoon is 1:4~4:
1。
In the present invention, in step (4), when carbonization, heating schedule is：It is warming up to 400 with the heating rate of 2~5 DEG C/min
~1000 DEG C, heat preservation 4~for 24 hours.
In the present invention, in step (5), acid is the hydrochloric acid or sulfuric acid of 1~2mol/L.
Metal-N doping porous carbon microsphere that the above-mentioned preparation method of the present invention obtains, surface nitrogen content is 2.3~
9.5at%.Preferably, surface nitrogen content is 3.2~8.8at%.
Compared to the prior art, the beneficial effects of the present invention are：Present invention firstly provides closed by carbon nitrogen source of 4VP monomers
At nitrogen-doped carbon material, maximum feature is various metals salt can act on final synthesis N doping porous carbon with 4VP monomers
Microballoon.The present invention has source metal alternative wide, and step is simple, and the characteristics of being suitble to mass produce, and the nitrogen prepared is mixed
Miscellaneous porous carbon materials generally have the advantages that large specific surface area, nitrogen element content are high.And big specific surface area and high nitrogen
Content makes this material have huge application prospect in energy stores conversion, catalysis and field of environment protection.
Description of the drawings
Fig. 1：(A) technology path of the invention；(B) coordination structure of the structural formula of 4VP, 4VP and metal ion.
Fig. 2：(a)Fe3+The scanning electron microscope (SEM) photograph of -4VP-0.25；(b)Cu2+The scanning electron microscope (SEM) photograph of -4VP-0.25；(c)Mg2+-
The scanning electron microscope (SEM) photograph of 4VP-0.5；(d)Ce3+The scanning electron microscope (SEM) photograph of -4VP-1.
Fig. 3：(a) scanning electron microscope (SEM) photograph of Fe-NPCB-0.25-650；(b) scanning electron microscope (SEM) photograph of Cu-NPCB-0.25-550；
(c) scanning electron microscope (SEM) photograph of Mg-NPCB-0.5-700；(d) scanning electron microscope (SEM) photograph of Ce-NPCB-1-500.
Fig. 4：Fe-NPCB-0.25-650；Cu-NPCB-0.25-550；Mg-NPCB-0.5-700；Ce-NPCB-1-500's
N2Adsorption curve.
Fig. 5：(a) the full peaks the XPS of Fe-NPCB-0.25-650 scan spectrogram；(b) the full peaks the XPS of Cu-NPCB-0.25-550
Scan spectrogram；(c) the full peaks the XPS of Mg-NPCB-0.5-700 scan spectrogram；(d) the full peak scanning spectrums of the XPS of Ce-NPCB-1-500
Figure.
Specific implementation mode
Technical scheme of the present invention is further described with reference to specific sample of implementing, but the protection of the present invention
Range is not limited to following embodiments.
The present invention respectively implements various raw materials used in sample, is commercially available unless otherwise specified.
The metal-organic microsphere sample that the present invention respectively implements to prepare in sample is abbreviated as M-4VP-X, and M represents metal
The type of ion；X represents the molar ratio of M and 4VP monomers.
The present invention respectively implements the metal prepared in sample-nitrogen-doped carbon microsphere sample and is abbreviated as M-NCB-X-Y, and M is represented
The type of metal；X represents the molar ratio of M and 4VP monomers；Y represents carburizing temperature.
The present invention respectively implements the metal prepared in sample-N doping porous carbon microsphere sample and is abbreviated as M-NPCB-X-Y, M
Represent the type of metal；X represents the molar ratio of M and 4VP monomers；Y represents carburizing temperature.
Technical scheme of the present invention is as shown in Figure 1.(A) is the technology path of the present invention in Fig. 1, and (B) is 4VP's in Fig. 1
Structural formula
And the coordination structure of metal ion and nitrogen-atoms on 4VP.
Embodiment 1
(1) 4VP/ ethanol solutions are prepared：At room temperature, 1.07ml 4VP monomers is taken to be added in 250ml absolute ethyl alcohols,
Magnetic agitation makes 4VP dissolve to obtain the 4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) FeCl is prepared3/ ethanol solution：Take 1.62g FeCl3It is dissolved in 250ml absolute ethyl alcohols, magnetic agitation
Make FeCl3Dissolving obtains the FeCl of a concentration of 0.04mol/L3/ ethanol solution, for use.
(3)Fe3+The preparation of organic matter microballoon：Under the conditions of room temperature magnetic agitation, 25ml FeCl are taken3/ ethanol solution
It is added in 100ml 4VP/ ethanol solutions, molar ratio Fe3+：4VP=0.25；12h is reacted, it is heavy to form stable complex
It forms sediment, then is centrifuged, 60 DEG C of vacuum drying 12h are up to Fe3+Organic matter microballoon (Fe3+-4VP-0.25℃)。
(4) it is carbonized：By Fe3+- 4VP-0.25 is positioned in quartz boat, and quartz boat is then put into tube type resistance furnace, nitrogen
Protection is warming up to 650 DEG C with the heating rate of 5 DEG C/min, and heat preservation 4h and then natural cooling are up to iron-nitrogen-doped carbon microballoon (Fe-
NCB-0.25-650)。
(5) pickling：100mg Fe-NCB-0.25-650 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L of 100ml
HCl wash 3 times, then washed 3 times through deionization, filtering, 60 DEG C of vacuum drying are for 24 hours up to iron-N doping porous carbon microsphere
(Fe-NPCB-0.25-650)。
Fe is characterized with S-4800 field emission scanning electron microscopes (FE-SEM)3+- 4VP-0.25 and Fe-NPCB-0.25-
The pattern and microstructure of 650 samples, as a result as shown in (a) in (a) in Fig. 2 and Fig. 3：Show that both there is nano-level sphere
Structure；Specific surface area and the aperture point of Fe-NPCB-0.25-650 samples are tested with 3H-2000PM2 specific surfaces and micropore analyzer
Cloth, the results are shown in Figure 4：Fe-NPCB-0.25-650 specific surface areas 842m is obtained according to BET equation calculations2/ g, total pore volume
0.68cm3/g；With AXIS UltaDLDType x-ray photoelectron spectroscopy (XPS) characterizes the surface of Fe-NPCB-0.25-650 samples
Element valence and constituent content, as shown in Figure 5：Show that Fe-NPCB-0.25-650 nitrogen contents reach 6.7at%.With iCPA6300
Inductive coupling plasma emission spectrum (ICP) characterizes the iron content in Fe-NPCB-0.25-650 samples, as a result such as 1 institute of table
Show：Iron content is 0.9374wt%.In conclusion Fe-NPCB-0.25-650 materials have sizable specific surface area and
High surface nitrogen element content makes it have huge application prospect in energy stores conversion, catalysis and field of environment protection.
Table 1 is Fe-NPCB-0.25-650；Cu-NPCB-0.25-550；Mg-NPCB-0.5-700；Ce-NPCB-1-500
Plasma emission spectrum (ICP) data
Embodiment 2
(1) 4VP/ ethanol solutions are prepared：At room temperature, 1.07ml 4VP monomers is taken to be added in 250ml absolute ethyl alcohols,
Magnetic agitation makes 4VP dissolve to obtain the 4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) CuCl is prepared2/ ethanol solution：Take 1.34g CuCl2It is dissolved in 250ml absolute ethyl alcohols, magnetic agitation
Make CuCl2Dissolving obtains the CuCl of a concentration of 0.04mol/L2/ ethanol solution, for use.
(3)Cu2+The preparation of organic matter microballoon：Under the conditions of room temperature magnetic agitation, 25ml CuCl are taken2/ ethanol solution
It is added in 100ml 4VP/ ethanol solutions, molar ratio Cu2+：4VP=0.25；6h is reacted, it is heavy to form stable complex
It forms sediment, then is centrifuged, 60 DEG C of vacuum drying 12h are up to Cu2+Organic matter microballoon (Cu2+-4VP-0.25)。
(4) it is carbonized：By Cu2+- 4VP-0.25 is positioned in quartz boat, and quartz boat is then put into tube type resistance furnace, nitrogen
Protection is warming up to 550 DEG C with the heating rate of 5 DEG C/min, and heat preservation 6h and then natural cooling are up to copper-nitrogen-doped carbon microballoon (Cu-
NCB-0.25-650)。
(5) pickling：100mg Cu-NPCB-0.25-550 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L of 100ml
HCl wash 3 times, then washed 3 times through deionization, filtering, 60 DEG C of vacuum drying are for 24 hours up to copper-N doping porous carbon microsphere
(Cu-NPCB-0.25-550)。
The nitrogen-doped carbon material of above-mentioned gained.Cu is characterized with S-4800 field emission scanning electron microscopes (FE-SEM)2+-
The pattern and microstructure of 4VP-0.25 and Cu-NPCB-0.25-550 samples, as a result as shown in (b) in (b) in Fig. 2 and Fig. 3：
Show both nano-level sphere structures with size uniformity；Cu- is tested with 3H-2000PM2 specific surfaces and micropore analyzer
The specific surface area and pore-size distribution of NPCB-0.25-550 samples, the results are shown in Figure 4：Cu-NPCB- is obtained according to BET equation calculations
0.25-550 specific surface areas 582m2/ g, total pore volume 0.44cm3/g；With AXIS UltaDLDType x-ray photoelectron spectroscopy (XPS)
The surface-element valence state and constituent content of Cu-NPCB-0.25-550 samples are characterized, as shown in Figure 5：Show Cu-NPCB-0.25-
550 nitrogen contents reach 6.1at%.Cu-NPCB-0.25- is characterized with iCPA6300 inductive coupling plasma emission spectrums (ICP)
Copper coin cellulose content in 550 samples, the results are shown in Table 1：Copper coin cellulose content is 1.1213wt%.In conclusion Cu-NPCB-
0.25-550 materials have sizable specific surface area and high surface nitrogen element content make its energy stores conversion, catalysis and
Field of environment protection has huge application prospect.
Embodiment 3
(1) 4VP/ ethanol solutions are prepared：At room temperature, 1.07ml 4VP monomers is taken to be added in 250ml absolute ethyl alcohols,
Magnetic agitation makes 4VP dissolve to obtain the 4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) MgCl is prepared2/ ethanol solution：Take 0.95g MgCl2It is dissolved in 250ml absolute ethyl alcohols, magnetic agitation
Make MgCl2Dissolving obtains the MgCl of a concentration of 0.04mol/L2/ ethanol solution, for use.
(3)Mg2+The preparation of organic matter microballoon：Under the conditions of room temperature magnetic agitation, 50ml MpCl are taken2/ ethanol solution
It is added in 100ml 4VP/ ethanol solutions, molar ratio Mg2+：4VP=0.5；Reaction for 24 hours, it is heavy to form stable complex
It forms sediment, then is centrifuged, 60 DEG C of vacuum drying 12h are up to Mg2+Organic matter microballoon (Mg2+-4VP-0.5)。
(4) it is carbonized：By Mg2+- 4VP-0.5 is positioned in quartz boat, and quartz boat is then put into tube type resistance furnace, and nitrogen is protected
Shield is warming up to 550 DEG C with the heating rate of 5 DEG C/min, and heat preservation 6h and then natural cooling are up to magnesium-nitrogen-doped carbon microballoon (Mg-
NCB-0.5-700)。
(5) pickling：100mg Mg-NCB-0.5-700 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L's of 100ml
HCl is washed 3 times, then is washed 3 times through deionization, filtering, and 60 DEG C of vacuum drying are for 24 hours up to magnesium-N doping porous carbon microsphere (Mg-
NPCB-0.5-700)。
The nitrogen-doped carbon material of above-mentioned gained.Mg is characterized with S-4800 field emission scanning electron microscopes (FE-SEM)2+-
The pattern and microstructure of 4VP-0.5 and Mg-NPCB-0.5-700 samples, as a result as shown in (c) in (c) in Fig. 2 and Fig. 3：Table
Bright Mg2+- 4VP-0.5 samples have micron level spherical structure, and the Mg-NPCB-0.5-700 samples after carbonization, pickling have stratiform
The micron order micro-sphere structure of accumulation；Mg-NPCB-0.5-700 samples are tested with 3H-2000PM2 specific surfaces and micropore analyzer
Specific surface area and pore-size distribution, the results are shown in Figure 4：Mg-NPCB-0.5-700 specific surface areas are obtained according to BET equation calculations
622m2/ g, total pore volume 0.56cm3/g；With AXIS UltaDLDType x-ray photoelectron spectroscopy (XPS) characterizes Mg-NPCB-0.5-
The surface-element valence state and constituent content of 700 samples, as shown in Figure 5：Show that Mg-NPCB-0.5-700 nitrogen contents reach
3.2at%.The magnesium member in Mg-NPCB-0.5-700 samples is characterized with iCPA6300 inductive coupling plasma emission spectrums (ICP)
Cellulose content, the results are shown in Table 1：Magnesium element content is 0.9875wt%.In conclusion Mg-NPCB-0.5-700 materials have
Sizable specific surface area and high surface nitrogen element content make it have in energy stores conversion, catalysis and field of environment protection
Huge application prospect.
Embodiment 4
(1) 4VP/ ethanol solutions are prepared：At room temperature, 1.07ml 4VP monomers is taken to be added in 250ml absolute ethyl alcohols,
Magnetic agitation makes 4VP dissolve to obtain the 4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) Ce (NO are prepared3)3/ ethanol solution：Take 3.26g Ce (NO3)3It is dissolved in 250ml absolute ethyl alcohols, magnetic
Power stirring makes Ce (NO3)3Dissolving obtains the Ce (NO of a concentration of 0.04mol/L3)3/ ethanol solution, for use.
(3)Ce3+The preparation of organic matter microballoon：Under the conditions of room temperature magnetic agitation, 100ml Ce (NO are taken3)3/ absolute ethyl alcohol
Solution is added in 100ml 4VP/ ethanol solutions, molar ratio Ce3+：4VP=1；Reaction for 24 hours, forms stable complex
Precipitation, then be centrifuged, 60 DEG C of vacuum drying 12h are up to Ce2+Organic matter microballoon (Ce3+-4VP-1)。
(4) it is carbonized：By Ce3+- 4VP-1 is positioned in quartz boat, and quartz boat is then put into tube type resistance furnace, and nitrogen is protected
Shield is warming up to 500 DEG C with the heating rate of 2 DEG C/min, and heat preservation 6h and then natural cooling are up to cerium-nitrogen-doped carbon microballoon (Ce-
NCB-1-500)。
(5) pickling：100mg Ce-NCB-1-500 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L's of 100ml
HCl is washed 3 times, then is washed 3 times through deionization, filtering, and 60 DEG C of vacuum drying are for 24 hours up to cerium-N doping porous carbon microsphere (Ce-
NCPB-1-500)。
The nitrogen-doped carbon material of above-mentioned gained.Ce is characterized with S-4800 field emission scanning electron microscopes (FE-SEM)3+-
The pattern and microstructure of 4VP-1 and Ce-NCPB-1-500 samples, as a result as shown in (c) in (c) in Fig. 2 and Fig. 3：Show Ce2 +- 4VP-1 samples have micron level spherical structure, and the Ce-NCPB-1-500 samples after carbonization, pickling have the micro- of stratiform accumulation
Meter level micro-sphere structure；With 3H-2000PM2 specific surfaces and micropore analyzer test Ce-NCPB-1-500 samples specific surface area and
Pore-size distribution, the results are shown in Figure 4：Ce-NCPB-1-500 specific surface areas 786m is obtained according to BET equation calculations2/ g, total pore volume
0.88cm3/g；With AXIS UltaDLDType x-ray photoelectron spectroscopy (XPS) characterizes the surface-element of Ce-NCPB-1-500 samples
Valence state and constituent content, as shown in Figure 5：Show that Ce-NCPB-1-500 nitrogen contents reach 8.8at%.With iCPA6300 inductance couplings
The Ce elements content in plasma emission spectrum (ICP) characterization Ce-NCPB-1-500 samples is closed, the results are shown in Table 1：Ce elements
Content is 1.5378wt%.
In conclusion there is Ce-NCPB-1-500 materials sizable specific surface area and high surface nitrogen element content to make
It has huge application prospect in energy stores conversion, catalysis and field of environment protection.
The foregoing describe the basic principles, principal features and advantages of the present invention, and the present invention is not by above-described embodiment
Limitation, the above embodiments and description only illustrate the principle of the present invention, is not departing from spirit and scope of the invention
Under the premise of, the present invention also has changes and improvements, these changes and improvements are both fallen in claimed the scope of the present invention.
Claims (8)
1. a kind of preparation method of metal-N doping porous carbon microsphere, which is characterized in that be as follows：
(1) 4VP/ ethanol solutions are prepared：4-vinylpridine monomer 4VP and absolute ethyl alcohol are mixed, stirring, obtains 4VP/
Ethanol solution；
(2) preparing metal salting liquid：Metal salt and absolute ethyl alcohol are mixed, stir to get metal salt/ethanol solution；It is described
Metal salt is any in molysite, mantoquita, magnesium salts, nickel salt, cobalt salt, cerium salt or lanthanum salt；
(3) preparation of metal-organic microballoon：At room temperature, 4VP/ ethanol solutions and metal salt/ethanol solution are mixed
It closes, forms complex precipitation, be then centrifuged, be dried in vacuo up to metal-organic microballoon；
(4) it is carbonized：Metal-organic microballoon is placed in tube furnace and is carbonized, is taken out after cooling, it is micro- to obtain metal-nitrogen-doped carbon
Ball；
(5) pickling：It by metal-nitrogen-doped carbon microballoon acid elution, is washed with water, filtering, vacuum drying obtain metal-N doping
Porous carbon microsphere.
2. preparation method according to claim 1, which is characterized in that in step (1), the concentration of 4VP/ ethanol solutions
For 0.02~0.2mol/L.
3. preparation method according to claim 1, which is characterized in that in step (2), metal salt be iron chloride, copper chloride,
It is any in magnesium chloride, nickel chloride, cobalt acetate, cerous nitrate or lanthanum nitrate；The concentration of metal salt/ethanol solution 0.02~
Between 0.2mol/L.
4. preparation method according to claim 1, which is characterized in that in step (3), metal ion in metal salt and
The molar ratio of 4VP is 1:4~4:1.
5. preparation method according to claim 1, which is characterized in that in step (4), when carbonization, heating schedule is：With 2
The heating rate of~5 DEG C/min is warming up to 400~1000 DEG C, and heat preservation 4~for 24 hours.
6. preparation method according to claim 1, which is characterized in that in step (5), acid be 1~2mol/L hydrochloric acid or
Person's sulfuric acid.
7. a kind of preparation method according to one of claim 1-6, which is characterized in that obtained metal-N doping is porous
The surface nitrogen content of carbosphere is 2.3~9.5at%.
8. preparation method according to claim 7, which is characterized in that surface nitrogen content is 3.2~8.8at%.
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| CN108002382A (en) * | 2017-11-29 | 2018-05-08 | 同济大学 | N doping porous carbon loads Fe2O3The preparation method of composite material |
| CN108172413B (en) * | 2017-12-25 | 2020-04-14 | 温州大学新材料与产业技术研究院 | Preparation method and application of three-dimensional spherical nitrogen-doped porous carbon material and nickel/nickel oxide composite material |
| CN108178141B (en) * | 2018-01-17 | 2021-07-16 | 大连理工大学 | Preparation method of microporous carbon with high conductivity, high tap density and high specific surface area |
| WO2019183820A1 (en) * | 2018-03-28 | 2019-10-03 | 中山大学 | Preparation method for nitrogen-doped porous carbon supported metal monoatomic material |
| CN108940336B (en) * | 2018-07-03 | 2020-06-12 | 山西大学 | Nitrogen-doped cobalt-based carbon nano catalyst and preparation method and application thereof |
| CN109387552B (en) * | 2018-10-12 | 2021-04-16 | 温州大学 | Copper-based porous carbon microsphere composite material and preparation method and application thereof |
| CN109970039B (en) * | 2019-04-26 | 2020-08-07 | 陕西科技大学 | Binary transition metal nanoparticle in-situ embedded porous nitrogen-doped carbon sphere and preparation method thereof |
| CN114400302B (en) * | 2021-02-10 | 2023-05-09 | 北京卫蓝新能源科技有限公司 | Porous carbon microsphere and preparation method thereof, carbon-lithium composite material, negative electrode and lithium metal battery |
| CN116037064A (en) * | 2023-02-10 | 2023-05-02 | 北方民族大学 | Nitrogen-doped carbon microsphere material, preparation method and application thereof |
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