CN114057179B - Preparation method of highly ordered nitrogen-doped mesoporous carbon - Google Patents
Preparation method of highly ordered nitrogen-doped mesoporous carbon Download PDFInfo
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- CN114057179B CN114057179B CN202111317892.4A CN202111317892A CN114057179B CN 114057179 B CN114057179 B CN 114057179B CN 202111317892 A CN202111317892 A CN 202111317892A CN 114057179 B CN114057179 B CN 114057179B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002159 nanocrystal Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005642 Oleic acid Substances 0.000 claims abstract description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000012692 Fe precursor Substances 0.000 claims abstract description 6
- DEVYBOZJYUYBMC-KVVVOXFISA-N iron;(z)-octadec-9-enoic acid Chemical compound [Fe].CCCCCCCC\C=C/CCCCCCCC(O)=O DEVYBOZJYUYBMC-KVVVOXFISA-N 0.000 claims abstract description 6
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000002798 polar solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- GPQWKLDEDGOJQH-UHFFFAOYSA-N ethane-1,1,1,2-tetramine Chemical compound NCC(N)(N)N GPQWKLDEDGOJQH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000012296 anti-solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 42
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 239000012071 phase Substances 0.000 description 24
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 7
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of highly ordered nitrogen-doped mesoporous carbon; firstly preparing an oleic acid iron precursor through solvent thermal reflux, and preparing oleic acid modified Fe through pyrolyzing the oleic acid iron 3 O 4 A nanocrystalline; then converting the oleic acid modified nanocrystals into HBF via ligand exchange 4 Modifying the nanocrystals; then the ligand containing nitrogen atoms is blocked to replace HBF on the surface of the nanocrystalline by secondary ligand exchange 4 A ligand; the nano-crystal modified by the nitrogen-containing ligand is subjected to solvent volatilization self-assembly to form a three-dimensional ordered close-packed nano-crystal superlattice; then the superlattice is subjected to high-temperature carbonization and acid etching treatment in sequence, so that the nitrogen-doped mesoporous carbon is obtained; according to the invention, the regulation and control of ordered mesoporous carbon skeleton in dual dimensions of pore size distribution and nitrogen doping level can be realized by controlling the particle size of the nanocrystal and the molecular type of the surface ligand, and the obtained mesoporous carbon material has the characteristics of continuous pore channel structure and high active site exposure, and has good application prospect in electrochemical energy storage.
Description
Technical Field
The invention belongs to the technical field of preparation of electrochemical energy storage materials, and particularly relates to a preparation method of highly ordered nitrogen-doped mesoporous carbon.
Background
The ordered mesoporous carbon material has high surface area and porous structure, narrow pore size distribution, high porosity and controllable pore size, so that the ordered mesoporous carbon material has high charge and discharge speed, is widely applied to the field of energy storage materials, and can effectively improve the surface activity of the mesoporous carbon material and improve the electrochemical performance of the mesoporous carbon by nitrogen doping.
At present, two main methods for synthesizing nitrogen doped mesoporous carbon are: one is a post-treatment doping method, i.e. a heat treatment is carried out on mesoporous carbon by a nitrogen-containing substance, so that nitrogen atoms are immersed into a carbon skeleton; however, further high temperature treatment may cause collapse of the mesoporous carbon structure, thereby reducing the specific surface area; the other is in-situ doping, namely introducing nitrogen-containing substances in the synthesis process of mesoporous carbon; however, the position of the nitrogen atom in the mesoporous carbon obtained by the method is difficult to control accurately, the nitrogen atom is easy to embed in a carbon skeleton, and the mesoporous carbon is difficult to contact with electrolyte solution, so that the improvement of electrochemical performance is limited. In addition, the introduction of the nitrogen-containing substance affects the formation of the mesoporous structure to a certain extent, so that the mesoporous carbon pore structure is difficult to control.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a nitrogen-doped mesoporous carbon material with highly ordered and highly exposed nitrogen atom surface by utilizing in-situ conversion of ligands on the surface of a nanocrystal, and solve the problems of uncontrollable structure, low specific surface and difficult accurate control of the nitrogen atom position of the traditional nitrogen-doped mesoporous carbon.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the highly ordered nitrogen-doped mesoporous carbon specifically comprises the following steps:
(1) Refluxing sodium oleate and an iron precursor in a mixed solvent of water and an organic solvent, and obtaining the iron oleate precursor through extraction and rotary evaporation concentration;
(2) Dissolving an oleic acid iron precursor in an organic solvent, adding oleic acid into the organic solvent, and performing high-temperature pyrolysis to obtain oleic acid coated Fe 3 O 4 A nanocrystalline;
(3) Dissolving the obtained nanocrystalline in a weak polar solvent, adding the polar solvent, and dropwise adding HBF into the two-phase mixture 4 Until the nanocrystalline is transferred from the weak polar phase to the polar phase, adding an antisolvent, centrifuging, and obtaining black precipitate which is HBF 4 The coated nanocrystals are dispersed in a polar solvent;
(4) To HBF 4 Adding a weak polar solvent into a polar solvent for modifying the nanocrystalline, dropwise adding a nitrogen atom-terminated organic ligand into the polar solvent, and oscillating until the nanocrystalline is transferred from a polar phase to a weak polar phase; adding an anti-solvent, centrifuging to obtain nanocrystalline precipitate particles, and dispersing the obtained precipitate particles into a benign solvent;
(5) Performing solvent volatilization self-assembly on the nanocrystals dispersed in the benign solvent in the step (4) to obtain a three-dimensional continuous close-packed ordered superlattice; carbonizing the superlattice at high temperature to convert organic ligand molecules on the surface of the superlattice into a nitrogen-containing carbon layer to obtainCarbon-coated Fe with different nitrogen doping amounts 3 O 4 A superlattice;
(6) Coating the obtained carbon with Fe 3 O 4 And (3) carrying out acid etching treatment on the superlattice to obtain ordered mesoporous carbon frameworks with different nitrogen doping levels.
Preferably, the organic solvent in the step (2) is one or more of benzyl ether, diphenyl ether, octadecene, eicosane and docosane;
preferably, the reaction time of the high-temperature pyrolysis in the step (2) is 0.5-1.5 h;
preferably, the oleic acid coated Fe as described in step (2) 3 O 4 The grain diameter of the nano-crystal is 5-20 nm;
preferably, the weak polar solvent in step (3) and step (4) is one or more of n-hexane, pentane, heptane, octane, nonane, decane; the antisolvent is one or more of methanol, ethanol, propanol, isopropanol, butanol and acetone;
preferably, the polar solvent in the step (3) is one or more of DMF, DMSO, NMP and acetonitrile;
preferably, the benign solvent in step (4) is one or more of n-hexane, chloroform, toluene, cyclohexane, tetrahydrofuran;
preferably, the organic ligand with end capped nitrogen atom in the step (4) may be one or more of oleylamine, dodecylamine, decylamine, nonylamine, octylamine, heptylamine, pentylamine, hexylamine, butylamine and triaminoethylamide;
preferably, in the step (5), the high-temperature carbonization temperature is 300-500 ℃ and the calcination time is 0.5-6 h.
The highly ordered nitrogen doped mesoporous carbon prepared by the preparation method is used as an electrode material and applied to electrochemical energy storage.
Firstly, preparing an oleic acid iron precursor through solvent thermal reflux, and then preparing oleic acid modified Fe through pyrolyzing the oleic acid iron 3 O 4 A nanocrystalline; oleic acid modified nanocrystals are then converted by ligand exchangeIs HBF 4 Modified nanocrystals; then through secondary ligand exchange, the HBF containing nitrogen atom end-capped organic molecular ligand (such as oleylamine, octylamine, butylamine and triaminoethylamine) is used for replacing the surface of the nanocrystal 4 A ligand; performing solvent volatilization self-assembly on the nano-crystal modified by the nitrogen-containing ligand to form a three-dimensional ordered close-packed nano-crystal superlattice; and then carrying out high-temperature carbonization and acid etching treatment on the superlattice in sequence, thus obtaining the highly ordered mesoporous carbon material with different nitrogen doping levels.
Compared with the prior art, the invention has the following advantages:
the invention uses Fe with different amino end caps 3 O 4 The nano-crystal is used as a template, and ligand molecules on the surface of the nano-crystal are simultaneously used as a carbon source and a nitrogen source to prepare the mesoporous carbon skeleton with highly ordered nitrogen doping. On one hand, the invention realizes the accurate control of nitrogen content on the molecular scale by changing the types of ligand molecules; on the other hand, the amino-terminated ligand can keep nitrogen atoms on the inner surface of the carbon layer as much as possible after carbonization, thereby increasing the exposure of the active site; providing the possibility of achieving more excellent electrochemical performance. Meanwhile, the invention adopts the nanocrystalline as a construction unit, and the regulation and control of the pore structure of the nitrogen-doped mesoporous carbon framework material are realized by adjusting the size of the nanocrystalline.
The ordered mesoporous carbon skeleton material with different nitrogen doping levels has the characteristics of continuous pore canal structure and high active site exposure, and is an ideal unit material for researching the structure-activity relationship between nitrogen doping and electrochemical performance.
The method has the advantages of easily obtained raw materials and high flexibility, and the ordered mesoporous carbon skeleton is regulated and controlled in the dual dimension of pore size distribution and nitrogen doping level by controlling the particle size of the nano-crystal and the molecular type of the surface ligand, so that the obtained nitrogen-doped mesoporous carbon material has good application prospect in electrochemical energy storage.
Drawings
FIG. 1 shows oleic acid coated Fe prepared in accordance with the invention 3 O 4 Infrared image spectrogram of the nanocrystalline after two ligand exchanges;
FIG. 2 shows the embodiment of the present inventionExamples preparation of different ligand coated Fe 3 O 4 X-ray diffraction pattern of superlattice;
FIG. 3 is an XPS spectrum of nitrogen-doped mesoporous carbon derived from different ligands prepared in accordance with embodiments of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image and an EDS mapping image of highly ordered nitrogen-doped mesoporous carbon prepared in example 6 according to the present invention using octylamine as ligand;
FIG. 5 is a transmission electron microscope image of highly ordered nitrogen-doped mesoporous carbon obtained by using octylamine as a ligand prepared in example 6 of the present invention;
FIG. 6 is a graph showing the specific surface area and pore size analysis of highly ordered nitrogen-doped mesoporous carbon obtained by using octylamine as a ligand prepared in example 6 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The methods described in the examples are conventional methods unless otherwise specified, and the starting materials described are commercially available unless otherwise specified; while the following examples are provided for illustration of the invention, they should not be construed as limiting the scope of the invention.
Example 1
Preparation of iron oleate:
mixing 36.5 g sodium oleate, 10.8 g ferric chloride, 60 mL water, 80 mL ethanol, 140 mL n-hexane, and stirring uniformly at 60 o Reflux 4 h; separating out organic phase iron oleate by extraction, and removing normal hexane by rotary evaporation to obtain waxy iron oleate;
example 2
Preparation of highly ordered nitrogen-doped mesoporous carbon
(1) 9. 9 g iron oleate (prepared in example 1), 2.3 g oleic acid, 50 g octadecene are placed in a 250 ml three-necked flask and heated to 120 o C, vacuumizing for 0.5 to h, and then introducing argon; heating to 320 in argon atmosphere o C, maintaining 1 h to obtain a mixed solution; washing the mixed solution with ethanol and isopropanol, and centrifuging to obtain14 nm Fe 3 O 4 Nanocrystalline, 14 nm Fe obtained 3 O 4 The nanocrystalline black precipitate is redispersed in n-hexane to prepare n-hexane dispersion of nanocrystalline for standby, wherein the concentration of nanocrystalline is about 40 mg/ml.
(2) Preparation of oleylamine modified nanocrystals: taking out 14 nm Fe in the step (1) of 5 mL 3 O 4 Nanocrystalline n-hexane solution, to which 5 mL of DMF was added, and to this two-phase solution, HBF was added dropwise 4 Simultaneously oscillating until the nanocrystalline is exchanged from the upper normal hexane phase to the lower DMF phase, adding 2 mL methanol, centrifuging to obtain precipitate, and redissolving the precipitate in 5 mL DMF to obtain HBF 4 Modified Fe 3 O 4 A nanocrystalline solution; the second exchange procedure was similar to the procedure described above, with 5 mL HBF 4 Mixing the modified nanocrystalline solution with 5 mL n-hexane, adding oleylamine into the mixture until the nanocrystalline is intersected from DMF at the lower layer to n-hexane at the upper layer, adding methanol, centrifuging to obtain precipitate, and dispersing the precipitate in CHCl 3 And obtaining the oleylamine modified nanocrystalline colloidal solution.
(3) Preparation of an ordered mesoporous carbon skeleton derived from oleylamine as a ligand: naturally volatilizing the obtained nanocrystalline colloid solution at room temperature to obtain the Fe coated with oleylamine 3 O 4 Superlattice. The superlattice is transferred to a tube furnace at 500 o C calcining 2 h; the calcined solid is etched by hydrochloric acid to obtain an ordered nitrogen-doped mesoporous carbon skeleton, wherein the aperture of the mesoporous carbon is 14 nm.
Example 3
Preparation of highly ordered nitrogen-doped mesoporous carbon
(1) 9 g iron oleate (prepared in example 1), 3.45 g oleic acid, 50 g octadecene are placed in a 250 ml three-neck flask and heated to 120 o C, vacuumizing for 0.5 to h, and then introducing argon; heating to 320 in argon atmosphere o C, maintaining the temperature at 0.5 and h to obtain a mixed solution; washing the mixed solution with ethanol and isopropanol, and centrifuging to obtain 8 nm Fe 3 O 4 A nanocrystalline; the obtained Fe with a particle size of 8 nm 3 O 4 The nanocrystalline black precipitate is redispersed in n-hexanePreparing n-hexane dispersion liquid of nano-crystals for later use; wherein the concentration of the nanocrystals was about 40 mg/ml.
(2) Preparation of decylamine modified nanocrystals: taking 8 nm Fe in the step (1) of 5 mL 3 O 4 Nanocrystalline n-hexane solution, to which 5 mL of DMF was added, and to this two-phase solution, HBF was added dropwise 4 Simultaneously oscillating until the nanocrystalline is exchanged from the upper normal hexane phase to the lower DMF phase, adding 2 mL methanol, centrifuging to obtain precipitate, and redissolving the precipitate in 5 mL DMF to obtain HBF 4 Modified Fe 3 O 4 A nanocrystalline solution; the second exchange procedure was similar to the procedure described above, with 5 mL HBF 4 Mixing the modified nanocrystalline solution with 5 mL n-hexane, adding decylamine into the mixture until the nanocrystalline is intersected from lower DMF to upper n-hexane, adding methanol, centrifuging to obtain precipitate, dispersing the precipitate in CHCl 3 The decylamine modified nanocrystalline colloidal solution is obtained.
(3) Preparation of ordered mesoporous carbon skeleton derived from decylamine as ligand: naturally volatilizing the obtained nanocrystalline colloid solution at room temperature to obtain decylamine coated Fe 3 O 4 Superlattice. The superlattice is transferred to a tube furnace at 500 o C calcination 2 h. Etching the calcined solid by hydrochloric acid to obtain an ordered nitrogen-doped mesoporous carbon skeleton, wherein the aperture of the mesoporous carbon is 8 nm;
example 4
Preparation of highly ordered nitrogen-doped mesoporous carbon
(1) 9. 9 g iron oleate (prepared in example 1), 2.3 g oleic acid, 50 g octadecene are placed in a 250 ml three-necked flask and heated to 120 o C, vacuumizing for 0.5 to h, and then introducing argon; heating to 320 in argon atmosphere o C, maintaining 1 h to obtain a mixed solution; washing the mixed solution with ethanol and isopropanol, and centrifuging to obtain 14 nm Fe 3 O 4 Nanocrystalline, black precipitated Fe of 14 nm obtained 3 O 4 The nanocrystals were redispersed in n-hexane to prepare a n-hexane dispersion of nanocrystals for use, wherein the nanocrystal concentration was about 40 mg/ml.
(2) Preparation of butylamine modified nanocrystals: taking out the Fe with the wavelength of 14 nm in the step (1) of 5 mL 3 O 4 Nanocrystalline n-hexane solution, to which 5 mL of DMF was added, and to this two-phase solution, HBF was added dropwise 4 Simultaneously oscillating until the nanocrystalline is exchanged from the upper normal hexane phase to the lower DMF phase, adding 2 mL methanol, centrifuging to obtain precipitate, and redissolving the precipitate in 5 mL DMF to obtain HBF 4 Modified Fe 3 O 4 A nanocrystalline solution; the second exchange procedure was similar to the procedure described above, with 5 mL HBF 4 Mixing the modified nanocrystalline solution with 5 mL n-hexane, adding butylamine into the mixed solution until the nanocrystalline is intersected from DMF at the lower layer to n-hexane at the upper layer, adding methanol into the mixed solution, centrifuging the mixed solution to obtain a precipitate, and dispersing the precipitate in CHCl 3 And (3) obtaining the butylamine modified nanocrystalline colloidal solution.
(3) Preparation of an ordered mesoporous carbon skeleton derived from butylamine as a ligand: naturally volatilizing the obtained nanocrystalline colloid solution at room temperature to obtain the Fe coated with butylamine 3 O 4 Superlattice. The superlattice is transferred to a tube furnace at 400 o C calcination 1 h. The calcined solid is etched by hydrochloric acid to obtain an ordered nitrogen-doped mesoporous carbon skeleton, wherein the aperture of the mesoporous carbon is 14 nm.
Example 5
Preparation of highly ordered nitrogen-doped mesoporous carbon
(1) 9. 9 g iron oleate (prepared in example 1), 1.5 g oleic acid, 50 g eicosane were placed in a 250 ml three-necked flask and warmed to 120 o C, vacuumizing for 0.5 to h, and then introducing argon; heating to 360 deg. C in argon atmosphere o C, maintaining 0.5 to h to obtain a mixed solution; washing the mixed solution with ethanol and isopropanol, and centrifuging to obtain 18 nm Fe 3 O 4 A nanocrystalline; the 18 nm Fe obtained is then 3 O 4 The nanocrystalline black precipitate was redispersed in n-hexane with a nanocrystalline concentration of about 40 mg/ml.
(2) Preparation of a Triaminotthylamine (TREN) modified nanocrystal: taking out 18 nm Fe in the step (1) of 5 mL 3 O 4 Nanocrystalline n-hexane solution, 5 mL of DMF was added thereto, and then the two-phase solution was addedAdding HBF dropwise 4 Simultaneously oscillating until the nanocrystalline is exchanged from the upper normal hexane phase to the lower DMF phase, adding 2 mL methanol, centrifuging to obtain precipitate, and redissolving the precipitate in 5 mL DMF to obtain HBF 4 Modified Fe 3 O 4 A nanocrystalline solution; the second exchange procedure was similar to the procedure described above, with 5 mL HBF 4 Mixing the modified nanocrystalline solution with 5 mL n-hexane, adding triaminoethylamine into the mixed solution until the nanocrystalline is intersected from DMF at the lower layer to the intermediate interface phase, adding methanol into the mixed solution for centrifugation to obtain precipitate, and dispersing the obtained precipitate in tetrahydrofuran, namely the triaminoethylamine modified nanocrystalline colloidal solution.
(3) Preparation of an ordered mesoporous carbon skeleton derived from triaminoethylamine as a ligand: naturally volatilizing the obtained nanocrystalline colloid solution at room temperature to obtain the Fe coated with the tri-aminoethylamine (TREN) 3 O 4 Superlattice. The superlattice is transferred to a tube furnace at 400 o C calcination 1 h. The calcined solid is etched by hydrochloric acid to obtain an ordered nitrogen-doped mesoporous carbon skeleton, wherein the aperture of the mesoporous carbon is 18 nm.
Example 6
Preparation of highly ordered nitrogen-doped mesoporous carbon
(1) 9. 9 g iron oleate (prepared in example 1), 2.3 g oleic acid, 50 g octadecene are placed in a 250 ml three-necked flask and heated to 120 o C, vacuumizing for 0.5 to h, and then introducing argon; heating to 360 deg. C in argon atmosphere o C, maintaining 0.5 to h to obtain a mixed solution; washing the mixed solution with ethanol and isopropanol, and centrifuging to obtain 14 nm Fe 3 O 4 A nanocrystalline; the obtained 14 nm Fe 3 O 4 The nanocrystalline black precipitate was redispersed in n-hexane with a nanocrystalline concentration of about 40 mg/ml.
(2) Preparation of octylamine modified nanocrystals: taking out the Fe with the wavelength of 14 nm in the step (1) of 5 mL 3 O 4 Nanocrystalline n-hexane solution, to which 5 mL of DMF was added, and to this two-phase solution, HBF was added dropwise 4 Simultaneously oscillating until the nanocrystalline is exchanged from the upper normal hexane phase to the lower DMF phase, adding 2 mL methanol, centrifuging to obtain precipitate, and thenThe precipitate is dissolved in 5 mL DMF again to obtain HBF 4 Modified Fe 3 O 4 A nanocrystalline solution; the second exchange procedure was similar to the procedure described above, with 5 mL HBF 4 Mixing the modified nanocrystalline solution with 5 mL n-hexane, adding octylamine into the mixture until the nanocrystalline is intersected from DMF at the lower layer to n-hexane at the upper layer, adding methanol, centrifuging to obtain precipitate, and dispersing the precipitate in CHCl 3 And obtaining the octylamine modified nanocrystalline colloidal solution.
(3) Preparation of an ordered mesoporous carbon skeleton derived from octylamine as a ligand: naturally volatilizing the obtained nanocrystalline colloid solution at room temperature to obtain the Fe coated with octylamine 3 O 4 Superlattice. The superlattice is transferred to a tube furnace at 400 o C calcination 1 h. The calcined solid is etched by hydrochloric acid to obtain an ordered nitrogen-doped mesoporous carbon skeleton, wherein the aperture of the mesoporous carbon is 14 nm.
Characterization analysis
The surface modification and ordered nitrogen doped mesoporous carbon structure of the nanocrystalline prepared in the embodiment of the invention are characterized by means of infrared spectrum, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope analysis, transmission electron microscope analysis and the like, and the specific characterization results are as follows:
(1) Infrared spectroscopic analysis
FIG. 1 shows oleic acid coated Fe prepared in accordance with the invention 3 O 4 Infrared image spectrogram of the nanocrystalline after two ligand exchanges; as can be seen from the figure, oleic acid coated Fe 3 O 4 After ligand exchange, the nanocrystals are in 1053-1070 cm -1 The absorption peak of C-N bond appears at the site, which proves the successful exchange of the nitrogen-containing ligand; in addition, after the exchange, the infrared absorption peak of C-H (2800 to 3000 cm -1 ) Moving to long wave numbers, it is demonstrated that the long carbon chain oleic acid ligand is replaced by a short chain octylamine, butylamine, etc. ligand.
(2) X-ray diffraction analysis
FIG. 2 shows Fe coated with different ligands according to the embodiment of the present invention 3 O 4 X-ray diffraction pattern of superlattice; comparing with standard map, proving that carbonized productThe obtained nanocrystalline phase is still pure ferroferric oxide phase, no other impurity phase is generated, and the main diffraction peaks are (220), (311), (400), (511) and (440) crystal faces respectively.
(3) X-ray photoelectron spectroscopy
FIG. 3 is an XPS spectrum of nitrogen-doped mesoporous carbon derived from different ligands prepared in accordance with embodiments of the present invention; from the figure it can be seen that the amino-terminated ligands can leave nitrogen atoms in the carbon layer after carbonization. The resulting mesoporous carbon has a reduced content of nitrogen elements compared to the proportion of nitrogen atoms in the original ligand molecule, probably due to the fact that part of the nitrogen atoms are removed in gaseous form during carbonization of the ligand; however, as the proportion of nitrogen atoms in the ligand molecules increases, the content of nitrogen elements in the derivatized mesoporous carbon also increases, so that the content of nitrogen elements in the mesoporous carbon can be regulated and controlled by the ligand.
(4) Scanning electron microscope and EDS mapping analysis
FIG. 4 is a Scanning Electron Microscope (SEM) image and an EDS mapping image of highly ordered nitrogen-doped mesoporous carbon prepared in example 6 according to the present invention using octylamine as ligand; as can be seen from the figure, fe 3 O 4 After removal, uniform and regular mesoporous channels are left. By EDS mapping analysis of this region, nitrogen atoms were found to be uniformly distributed on the carbon layer.
(5) Transmission electron microscope analysis
FIG. 5 is a transmission electron microscope image of highly ordered nitrogen-doped mesoporous carbon obtained by using octylamine as a ligand prepared in example 6 of the present invention; from the figure, it can be seen that the mesoporous carbon has a regular and ordered mesoporous structure, which is consistent with the scanning spectrum.
(6) Specific surface and pore size distribution pattern
FIG. 6 is a graph showing the specific surface area and pore size analysis of highly ordered nitrogen-doped mesoporous carbon obtained by using octylamine as a ligand prepared in example 6 of the present invention; typical type IV curves are shown in the map, indicating the presence of a large number of mesopores in the material. The pore size distribution is concentrated at 14 nm, which is consistent with the size of the initial nanocrystal.
Finally, it is to be understood that the foregoing embodiments are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any simple changes or equivalent alternatives of the technical solutions that may be obvious to those skilled in the art within the scope of the present invention are within the scope of the present invention.
Claims (7)
1. The preparation method of the highly ordered nitrogen-doped mesoporous carbon is characterized by comprising the following steps of:
(1) Refluxing sodium oleate and an iron precursor in a mixed solvent of water and an organic solvent, and obtaining the iron oleate precursor through extraction and rotary evaporation concentration;
(2) Dissolving an oleic acid iron precursor in an organic solvent, wherein the organic solvent is one or more of benzyl ether, diphenyl ether, octadecene, eicosane and docosane, adding oleic acid into the organic solvent, and performing high-temperature pyrolysis to obtain oleic acid coated Fe 3 O 4 A nanocrystalline;
(3) Dissolving the obtained nanocrystalline in a weak polar solvent, adding the polar solvent, and dropwise adding HBF into the two-phase mixture 4 Until the nanocrystalline is transferred from the weak polar phase to the polar phase, adding an antisolvent, centrifuging, and obtaining black precipitate which is HBF 4 The coated nanocrystals are dispersed in a polar solvent;
(4) To HBF 4 Adding a weak polar solvent into a polar solvent for modifying the nanocrystalline, dropwise adding a nitrogen atom-terminated organic ligand into the polar solvent, and oscillating until the nanocrystalline is transferred from a polar phase to a weak polar phase, wherein the nitrogen atom-terminated organic ligand is triaminoethylamine; adding an anti-solvent, centrifuging to obtain nanocrystalline precipitate particles, and dispersing the obtained precipitate particles into a benign solvent, wherein the benign solvent is one or more of normal hexane, chloroform, toluene, cyclohexane and tetrahydrofuran;
the weak polar solvent in the step (3) and the step (4) is one or more of hexane, pentane, heptane, octane, nonane and decane; the antisolvent is one or more of methanol, ethanol, propanol, butanol and acetone;
(5) Dissolving the nanocrystals dispersed in the benign solvent in the step (4)Volatilizing and self-assembling the agent to obtain a three-dimensional continuous close-packed ordered superlattice; carbonizing the superlattice at 300-500 deg.C for 0.5-6 hr to convert the organic ligand molecule into nitrogen-containing carbon layer to obtain carbon coated Fe with different nitrogen doping amount 3 O 4 A superlattice;
(6) Coating the obtained carbon with Fe 3 O 4 And (3) carrying out acid etching treatment on the superlattice to obtain ordered mesoporous carbon frameworks with different nitrogen doping levels.
2. The method for preparing highly ordered nitrogen-doped mesoporous carbon according to claim 1, wherein the weak polar solvent in step (3) and step (4) is n-hexane.
3. The method of preparing highly ordered nitrogen doped mesoporous carbon according to claim 1, wherein said antisolvent in step (3) and step (4) is isopropanol.
4. The method for preparing highly ordered nitrogen-doped mesoporous carbon according to claim 1, wherein the reaction time of the pyrolysis in the step (2) is 0.5 to 1.5 hours.
5. The method for preparing highly ordered nitrogen-doped mesoporous carbon according to claim 1, wherein said oleic acid-coated Fe in step (2) 3 O 4 The grain diameter of the nanometer crystal is 5-20 nm.
6. The method of preparing highly ordered nitrogen doped mesoporous carbon according to claim 1, wherein the polar solvent in step (3) is one or more of DMF, DMSO, NMP and acetonitrile.
7. Use of highly ordered nitrogen doped mesoporous carbon prepared by the preparation method of any one of claims 1 to 6 in electrochemical energy storage.
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