CN106179446A - The method of cobalt/nitrating porous carbon composite and preparation method thereof and catalysis silane oxidation - Google Patents
The method of cobalt/nitrating porous carbon composite and preparation method thereof and catalysis silane oxidation Download PDFInfo
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- CN106179446A CN106179446A CN201610536845.1A CN201610536845A CN106179446A CN 106179446 A CN106179446 A CN 106179446A CN 201610536845 A CN201610536845 A CN 201610536845A CN 106179446 A CN106179446 A CN 106179446A
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- nitrating
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- 239000010941 cobalt Substances 0.000 title claims abstract description 235
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 233
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 226
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 150
- 230000000802 nitrating effect Effects 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title abstract description 11
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 229910000077 silane Inorganic materials 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 150000001868 cobalt Chemical class 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013110 organic ligand Substances 0.000 claims abstract description 20
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000000395 magnesium oxide Substances 0.000 claims description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 32
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 241000446313 Lamella Species 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- HCLXLZGAYCTHQJ-UHFFFAOYSA-N 1h-cyclohepta[b]pyridine Chemical compound C1=CC=CC=C2NC=CC=C21 HCLXLZGAYCTHQJ-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940097267 cobaltous chloride Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- TZPUFQUQYUYVQC-UHFFFAOYSA-N phenylsilylmethanamine Chemical compound NC[SiH2]C1=CC=CC=C1 TZPUFQUQYUYVQC-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- JBKICBDXAZNSKA-UHFFFAOYSA-N tcmdc-123507 Chemical compound C1=CC=C2NC(C=3C=CC=C(N=3)C=3NC4=CC=CC=C4N=3)=NC2=C1 JBKICBDXAZNSKA-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
Abstract
The method that the invention provides a kind of cobalt/nitrating porous carbon composite and preparation method thereof and catalysis silane oxidation.This cobalt/nitrating porous carbon composite is through the following steps that prepare: cobalt salt, the nitrogenous organic ligand of cobalt and template are mixed in a solvent, by the mixture after removal solvent 600 1000 DEG C of calcinings, use acid not remove template agent removing and cobalt/cobalt oxide again, obtain cobalt/nitrating porous carbon composite.The method of this catalysis silane oxidation comprises the following steps: using the cobalt of the present invention/nitrating porous carbon composite or do not go the mixture of template agent removing and cobalt/cobalt oxide as catalyst, reacts with organosilan, obtain silanol under the effect of oxidant.The present invention uses the nitrogenous organic ligand of template, cobalt salt and cobalt as raw material, and the nitrating porous carbon composite of the monatomic cobalt of load has been prepared with high-temperature calcination and acid method not, this material has higher specific surface area, mesoporous pore size and bigger pore volume.
Description
Technical field
The present invention relates to a kind of cobalt/nitrating porous carbon composite and preparation method thereof, and a kind of template, cobalt/cobalt oxide
With the mixture of cobalt/nitrating porous carbon composite, and a kind of use this cobalt/nitrating porous carbon composite or this template
The mixture of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as the side of catalyst organosilan oxidation reaction
Method, belongs to porous carbon materials technical field.
Background technology
Silanol is a very important organic molecule of class, is widely used in organic synthesis and pharmaceutical synthesis field, simultaneously
Also it is the important source material of industrial production silicon-containing polymer material.The method of conventional synthesis silanol includes the hydrolysis of chlorosilane, has
Machine highly basic hydrolyzes the anti-and oxidation reaction three major types of silane to silicon ether.In these methods, especially with silane oxidation reaction system
Standby silanol research is more, and its reason essentially consists in relative to chlorosilane and silicon ether, and silane is more cheap and easily-available, and reaction generates silicon
The Atom economy of alcohol is high.
At present the research of silanol is obtained for silane oxidation and specifically include that (1) uses the strong oxidizer of equivalent, such as peroxide
Acid, potassium permanganate, bisoxirane, oxa-acridine etc., but this kind of method toxicity is big, and productivity is the highest, poor selectivity, and can give birth to
Become the by-product of much toxicity；(2) reaction of transition metal-catalyzed silane oxidation is with water or oxygen as oxidant, and hydrogen is unique
By-product, reaction cleaning, overcome disadvantages described above, and cause the extensive attention of people.This kind of transition metal-catalyzed silane oxidation
Method no matter at homogeneous or heterogeneous catalysis system all can with high yield catalysis silane oxidation synthesis silanol, but such
Catalyst used by method is used mostly the noble metal such as Au Ag Pt Pd, ruthenium as active component；Although using noble metal as work
The heterogeneous catalyst of property component has a higher activity and selectivity, but the application of the price limit of costliness catalyst and pushing away
Extensively, it is difficult to realize industrialized production.Base metal has the advantages such as cheap, aboundresources, should as active component
Have a very big significance in organosilan oxidation reaction.
Porous material is because having the characteristics such as the uniform pore passage structure of molecular dimension and big specific surface area, at absorption, ion
Exchange, be particularly widely used in fields such as catalysis.
In numerous porous materials, porous carbon materials is due to the peculiar property having, and synthesis material is abundant and easily obtains
Take, in modern science, therefore there is universal application.Porous carbon materials have high-specific surface area, big pore volume, connection and
The plurality of advantages such as homogeneous duct, adjustable aperture so that it is being catalyzed, adsorb, sense, the aspect such as electrochemistry has and widely should
By value.In order to improve porous carbon materials application in these areas further, generally by hetero atom (such as N, B, S etc.) or contain
Heteroatomic group (amino, nitro, sulfonic group etc.) is doped in surface or the structure of porous carbon materials, makes porous carbon materials
The performance of each side is upgraded and improved.In the middle of numerous doping components, nitrogen is a kind of unit favored by researchers
Element.
After atom N mixes material with carbon element, being entrained in hexagonal carbon grid of atom N produces localised tension, causes carbon to be tied
Structure deforms, and owing to the lone pair electrons of atom N can supply sp2Hydridization carbon skeleton delocalized pi-bond negative charge, thus strengthen electronics
Transmission characteristic and chemical reactivity；The atom N of electron rich of adulterating in material with carbon element can change the band structure of material, makes carbon
The valence band of material reduces, the chemical stability of reinforcing material, increases the electron density on fermi level.
Nitrogen element enters into the nitrogen-doped porous carbon material that the internal structure of porous carbon materials is formed, except having porous carbon
Outside all advantages of material, with features such as the machinery of its uniqueness, electronics, optics, quasiconductor, energy storage character, suitable alkalescence,
Superhard material, adsorb, be catalyzed and the range of application of the aspect such as fuel cell expands further.
Along with the continuous expansion of nitrogen-doped porous carbon material range of application, people are to the synthesis of nitrogen-doped porous carbon material also
Give extensive concern.The method being presently used for nitrogen-doped porous carbon material synthesis has a lot, substantially can be summarized as two classes:
Doping and post processing two kinds in situ.Post processing needs with the nitrogenous gas such as nitrogen or ammonia under the high temperature conditions to pre-synthesis
Carbon material surface is modified, or at the nitrogenous organic group of material surface grafting thus reach to change carbon material surface character
Purpose.In-situ synthesis is typically to introduce nitrogen source or use itself carbon source containing nitrogen element in material with carbon element building-up process,
In the carbonisation of carbon matrix precursor, nitrogen-atoms mixes inside material with carbon element.
In-situ synthesis nitrogen-doped porous carbon material mainly includes template, chemical vapour deposition technique (CVD) and hydro-thermal method
Deng.Template is typically with porous materials such as various porous oxidation silicon materials, porous anodic aluminium oxides as template.According to selected
Template difference can prepare the N doped porous carbon material of various different shape, Different Pore Structures and surface area.
But use template to prepare nitrogen-doped porous carbon material and there is also some technical barriers, first, some nitrogen sources by
In the impact of itself, the nitrogen-doped porous carbon material performance of formation is the best；Secondly, use containing nitride polyporous material as nitrogen source system
Standby then relatively costly, complex；It addition, the selection of template is the most single and expensive.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of cobalt/nitrating porous carbon composite and
Preparation method.The present invention use the nitrogenous organic ligand of template, cobalt salt and cobalt as raw material, and with high-temperature calcination and acid
Method not can prepare the nitrating porous carbon composite loading monatomic cobalt.
The present invention also aims to provide the mixed of a kind of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Compound.
Another object of the present invention is to provide a kind of and use above-mentioned cobalt/nitrating porous carbon composite or above-mentioned template
The mixture of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as the side of catalyst organosilan oxidation reaction
Method.
For reaching above-mentioned purpose, present invention firstly provides the preparation method of a kind of cobalt/nitrating porous carbon composite, its
Comprise the following steps:
(1) by cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent, solvent is then removed,
To a mixture；
(2) make described mixture calcine 0.5～4 hour at 600-1000 DEG C, obtain template, cobalt/cobalt oxide and cobalt/mix
The mixture of nitrogen porous carbon composite；
(3) acid mode not is used to remove the mixing of described template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Template in thing and cobalt/cobalt oxide, obtain described cobalt/nitrating porous carbon composite.
In above-mentioned preparation method, it is preferable that described template includes porous flake hexagon magnesium oxide.It is highly preferred that
The specific surface area of described porous flake hexagon magnesium oxide is 100～300m2/ g, two-dimensional slice footpath a size of 200～400nm.Enter
Preferably, described porous flake hexagon magnesium oxide is through the following steps that prepare: by magnesium oxide powder at water for one step
In boil and keep 8～24 hours, after the solid drying (can be dried 5～12 hours at 80～100 DEG C) that will obtain, then
200～900 DEG C of roastings 0.5～2 hours (this roasting can be carried out in air atmosphere, and heating rate can be 5～15 DEG C/
Min), described porous flake hexagon magnesium oxide is obtained.
In above-mentioned preparation method, it is preferable that described cobalt salt includes the one in cobalt nitrate, cobaltous chloride and cobaltous acetate etc.
Or several combinations.
In above-mentioned preparation method, it is preferable that the nitrogenous organic ligand of described cobalt includes 2,2'-bipyridyl, pyridine, neighbour two
Aza-phenanthrenes, 2,2':6', 2 " combination of one or more in-ter cycloheptapyridine, 2,6-bis-(2-benzimidazolyl) pyridine etc..
In above-mentioned preparation method, it is preferable that cobalt salt, the nitrogenous organic ligand of cobalt and the template used in step (1)
The mass ratio of agent is 1:1:1～1:3:3.
In above-mentioned preparation method, it is preferable that the solvent in step (1) includes ethanol and/or acetone etc..
In above-mentioned preparation method, it is preferable that in step (1) by cobalt salt, the nitrogenous organic ligand of cobalt and template
Mix homogeneously can be in the way of using stirring in a solvent.It is highly preferred that this stirring is magnetic agitation, and magnetic agitation turn
Speed is 300～800r/min, and mixing time is 2～5 hours.It is further preferred that first the nitrogenous organic ligand of cobalt salt, cobalt is existed
In solvent, mix homogeneously (can be in the way of using stirring or ultrasonic disperse), adds template, and in the way of magnetic agitation
Make they mix homogeneously.
In above-mentioned preparation method, cobalt salt, the nitrogenous organic ligand of cobalt and template concentration in a solvent can be by
Those skilled in the art carry out the adjustment of routine, as long as reaction can be made to be smoothed out.
In above-mentioned preparation method, it is preferable that the mode removing solvent in step (1) can be to be dried or rotate to steam
Sending out, and the temperature being dried can be 80～100 DEG C, the time can be 10～12 hours.
In above-mentioned preparation method, it is preferable that the calcining in step (2) is carried out under inert gas shielding, more excellent
Selection of land, described noble gas includes argon etc..
In above-mentioned preparation method, it is preferable that in step (2), with the ramp of 5-15 DEG C/min to 600-1000
℃。
In above-mentioned preparation method, it is preferable that the acid in step (3) does not specifically includes following steps: by described template,
Cobalt/cobalt oxide boils after mixing with acid with the mixture of cobalt/nitrating porous carbon composite and keeps 1～2 hour.Wherein, adopted
Acid can include hydrochloric acid solution etc..Can carry out afterwards filtering or sucking filtration, not wash, be dried, to obtain final product.Its
In, not wash and can use ethanol or acetone etc., the temperature being dried can be 60～80 DEG C, and the time can be 2～5 hours.
It addition, what the preparation method that present invention also offers a kind of above-mentioned cobalt/nitrating porous carbon composite prepared
Cobalt/nitrating porous carbon composite.
Detailed description of the invention according to the present invention, it is preferable that described cobalt/nitrating porous carbon composite containing cobalt amount be
0.2-0.8at%, nitrogen content is 4-10at%, and specific surface area is 400-900m2/ g, aperture is 4-9nm, and pore volume is 0.5-4cm3/
g.This cobalt/nitrating porous carbon composite is by 5～20 layers of nitrating porous graphene lamellas stacking being loaded with monatomic cobalt
Become, and a diameter of the 200 of monolayer lamella～400nm.
The present invention use the nitrogenous organic ligand of template, cobalt salt and cobalt as raw material, and with high-temperature calcination and acid
Method not has prepared the nitrating porous carbon composite of the monatomic cobalt of load.Cobalt/nitrating porous carbon that the present invention provides
Composite and preparation method thereof mainly have following a little: (1) present invention use template porous flake hexagon
Magnesium oxide is cheap, preparation technology is simple, and (specific surface area is 100～300m to have porous flake hexagonal structure2/
G, a diameter of 200～400nm), there is compared with other template the advantage of uniqueness；(2) raw material that the present invention uses is conventional
Industrial chemicals, cost is relatively low, and the requirement to equipment and technology is relatively low simultaneously, by calcining can disposably obtain cobalt/nitrating
Porous carbon composite, preparation technology is simple, it is easy to large-scale production；(3) cobalt of the present invention/nitrating porous carbon composite tool
There is higher specific surface area, mesoporous pore size and bigger pore volume, and there is stable physical and chemical performance and excellent making
Use the life-span.
Additionally, present invention also offers the mixing of a kind of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Thing, it is through the following steps that prepare:
(1) by cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent, solvent is then removed,
To a mixture；
(2) make described mixture calcine 0.5～4 hour at 600-1000 DEG C, obtain described template, cobalt/cobalt oxide with
The mixture of cobalt/nitrating porous carbon composite.
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that described mould
Plate agent includes porous flake hexagon magnesium oxide.It is highly preferred that the specific surface area of described porous flake hexagon magnesium oxide is 100
～300m2/ g, two-dimensional slice footpath a size of 200～400nm.It is further preferred that described porous flake hexagon magnesium oxide is logical
Cross what following steps prepared: boiled in water by magnesium oxide powder and keep 8～24 hours, the solid drying that will obtain
After (can 80～100 DEG C be dried 5～12 hours), then in 200～900 DEG C of roastings 0.5～(this roasting can be at sky in 2 hours
Carrying out under gas atmosphere, heating rate can be 5～15 DEG C/min), obtain described porous flake hexagon magnesium oxide.
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that described cobalt
Salt includes the combination of one or more in cobalt nitrate, cobaltous chloride and cobaltous acetate etc..
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that described cobalt
Nitrogenous organic ligand include 2,2'-bipyridyl, pyridine, phenanthrolene, 2,2':6', 2 "-ter cycloheptapyridine, 2,6-bis-(2-benzene
And imidazole radicals) combination of one or more in pyridine etc..
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that step (1)
The mass ratio of the cobalt salt of middle employing, the nitrogenous organic ligand of cobalt and template is 1:1:1～1:3:3.
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that step (1)
In solvent include ethanol and/or acetone etc..
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that step (1)
In by cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent can by use stirring in the way of.More excellent
Selection of land, this stirring is magnetic agitation, and the rotating speed of magnetic agitation is 300～800r/min, and mixing time is 2～5 hours.Enter
The nitrogenous organic ligand mix homogeneously in a solvent of cobalt salt, cobalt preferably, first (can be used stirring or ultrasonic disperse by one step
Mode), add template, and in the way of magnetic agitation, make they mix homogeneously.
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that step (1)
In the mode removing solvent can be to be dried or rotary evaporation, and dry temperature can be 80～100 DEG C, and the time is permissible
It it is 10～12 hours.
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that step (2)
In calcining carry out under inert gas shielding, it is highly preferred that described noble gas includes argon etc..
In above-mentioned template, the cobalt/cobalt oxide mixture with cobalt/nitrating porous carbon composite, it is preferable that in step
(2) in, with the ramp of 5-15 DEG C/min to 600-1000 DEG C.
On the other hand, present invention also offers a kind of use above-mentioned cobalt/nitrating porous carbon composite or above-mentioned template,
The mixture of cobalt/cobalt oxide and cobalt/nitrating porous carbon composite as the method for catalyst organosilan oxidation reaction,
The method comprises the following steps:
By above-mentioned cobalt/nitrating porous carbon composite or above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite wood
The mixture of material, as catalyst, reacts under the effect of oxidant with organosilan, obtains silanol.
In the above-mentioned methods, it is preferable that consumption is organosilan quality the 1 of described cobalt/nitrating porous carbon composite
～5%, described template, cobalt/cobalt oxide are organosilan quality with the consumption of the mixture of cobalt/nitrating porous carbon composite
10～40%.
In the above-mentioned methods, it is preferable that described oxidant includes the one or several in oxygen gas and water, hydrogen peroxide and methanol etc.
The combination planted.It is highly preferred that described oxidant is ultra-pure water.
In the above-mentioned methods, it is preferable that described reaction is carried out in a solvent, described solvent includes acetone, acetic acid second
The combination of one or more in ester and oxolane etc..
In the above-mentioned methods, it is preferable that reaction temperature is 20～30 DEG C, the response time is 1～8 hour.
The present invention uses cobalt/nitrating porous carbon composite to make or template, cobalt/cobalt oxide and cobalt/nitrating porous carbon are combined
The mixture of material mainly has the advantage that (1) present invention's as the method for catalyst organosilan oxidation reaction
Catalyst, using the monatomic cobalt that is connected with nitrogen as active center, has higher catalysis activity and stability, and without silicon ether
The generation of by-product；(2) comparing with traditional organosilan oxidation catalyst, the catalyst of the present invention has higher specific surface
Long-pending, the beneficially absorption of reactant and the raising of catalysis activity；(3) recycling of the catalyst of the present invention is relatively simple, and
Recycle the catalysis activity that still can keep higher more than 5 times；(4) simultaneously, the report of cobalt-nitrogen-material with carbon element be mostly about
Application in terms of electrochemistry, but the application that the double-doped catalyst of nitrogen, cobalt is in organic molecule converts is rarely reported, and the present invention is to opening up
The exploitation opening up the application of this kind of catalyst and study on mechanism and novel reaction system is significant；(5) present invention
Use and do not go the mixture of template agent removing still to have higher catalysis activity, stability and service life cycle as catalyst.
Accompanying drawing explanation
The preparation method flow chart of the cobalt that Fig. 1 provides for embodiment 1-5/nitrating porous carbon composite.
The scanning electron microscope (SEM) photograph of the cobalt that Fig. 2 provides for embodiment 1/nitrating porous carbon composite.
Fig. 3 a and Fig. 3 b is the transmission electron microscope picture of cobalt/nitrating porous carbon composite that embodiment 1 provides.
The high-resolution-ration transmission electric-lens figure of the cobalt that Fig. 4 provides for embodiment 1/nitrating porous carbon composite.
The mixture of template that Fig. 5 provides for embodiment 1, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite and
The X-ray diffraction spectrogram of cobalt/nitrating porous carbon composite.
The x-ray photoelectron energy spectrogram of the cobalt that Fig. 6 provides for embodiment 1/nitrating porous carbon composite.
The N of the cobalt that Fig. 7 a provides for embodiment 2/nitrating porous carbon composite2Adsorption/desorption curve.
The pore size distribution curve of the cobalt that Fig. 7 b provides for embodiment 2/nitrating porous carbon composite.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of cobalt/nitrating porous carbon composite and preparation method thereof, as it is shown in figure 1, specifically wrap
Include following steps:
(1) being disperseed in deionized water by magnesium oxide powder, backflow is boiled and keeps 24 hours, sucking filtration after cooling, then at
80 DEG C are dried 12 hours, be subsequently placed in Muffle furnace and in air atmosphere with the ramp of 10 DEG C/min to 450 DEG C of roastings
30 minutes, obtaining porous flake hexagon magnesium oxide, its specific surface area is 200m2/ g, two-dimensional slice footpath size is about 300nm；
(2) at room temperature, by 0.5g cobalt nitrate and 0.5g 2,2'-bipyridyl is dissolved in 30mL ethanol in the way of stirring,
It is subsequently added the porous flake hexagon magnesium oxide that 0.5g step (1) obtains, and the rotating speed magnetic agitation 3 with 600 revs/min is little
Time, then solvent is rotated and be evaporated, obtain a mixture；
(3) described mixture is put in tube furnace and under argon shield with the ramp of 10 DEG C/min to 700 DEG C
Calcine 2 hours, obtain the mixture of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite；
(4) described template, cobalt/cobalt oxide are placed in dilute hydrochloric acid solution with the mixture of cobalt/nitrating porous carbon composite
In (according to 37% concentrated hydrochloric acid: the volume ratio preparation of water=10:1), backflow is boiled and keeps 1 hour, after filtering, then uses ethanol
Do not wash, be then dried 5 hours in 60 DEG C, obtain described cobalt/nitrating porous carbon composite.
The scanning electron microscope (SEM) photograph of the cobalt that Fig. 2 provides for the present embodiment/nitrating porous carbon composite, Fig. 3 a and Fig. 3 b are this
The transmission electron microscope picture of cobalt/nitrating porous carbon composite that embodiment provides, the cobalt that Fig. 4 provides for the present embodiment/nitrating porous
The high-resolution-ration transmission electric-lens figure of carbon composite, by Fig. 2-Fig. 4 it can be seen that the cobalt/nitrating porous carbon of the present embodiment offer is multiple
Condensation material has the loose structure of class hexagon magnesium oxide, and lamella is relatively thin.Template that Fig. 5 provides for the present embodiment, cobalt oxidation
The mixture of thing and cobalt/nitrating porous carbon composite and the XRD spectra of cobalt/nitrating porous carbon composite are permissible by Fig. 5
Find out will there be the generation of cobalt/cobalt oxide after cobalt salt, nitrogenous organic ligand and template high-temperature calcination, through peracid non-rear pattern plate agent and
Cobalt/cobalt oxide is all removed, and can obtain loading the composite of monatomic cobalt.The cobalt that Fig. 6 provides for the present embodiment/nitrating porous
The XPS spectrum figure of carbon composite, can substantially observe the peak of C, O, N, Co element, it can be deduced that containing cobalt amount be from Fig. 6
0.55at%, nitrogen content is 8.46at%.
Cobalt/nitrating porous carbon composite that the present embodiment provides is 0.55at% containing cobalt amount, and nitrogen content is
8.46at%, specific surface area is 625m2/ g, average pore size is 6.29nm, and pore volume is 1.18cm3/g.This cobalt/nitrating porous carbon is multiple
Condensation material is to be formed by 5～20 layers of nitrating porous graphene lamellas stacking being loaded with monatomic cobalt, and monolayer lamella is straight
Footpath is 300nm.
It is respectively adopted the cobalt/nitrating porous carbon composite of the present embodiment or mould prepared by the present embodiment step (1)-(3)
The mixture of plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as catalyst organosilan oxidation reaction
Method comprises the following steps:
(1) catalyst and dimethylphenylsilaneand acetone solution and are stirred in reaction bulb；
(2) appropriate ultra-pure water is joined in the solution that step (1) obtains, react 2 hours under 25 DEG C and stirring,
To dimethyl phonyl silanol；
Wherein, when employing cobalt/nitrating porous carbon composite is catalyst, its consumption is dimethylphenylsilaneand quality
2.5%；When the mixture of employing template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is catalyst, its consumption is two
The 25% of aminomethyl phenyl silane quality；The consumption of ultra-pure water is the 132% of dimethylphenylsilaneand quality.
Thin layer chromatography analysis is used to obtain: being respectively adopted two kinds of catalyst reactions after 2 hours, dimethylphenylsilaneand is equal
Reaction completely generates dimethyl phonyl silanol, without the generation of silicon ether by-product.
Proving after tested, after two kinds of catalyst recycle 5 times, catalysis activity is all without substantially reducing.
Embodiment 2
Present embodiments provide a kind of cobalt/nitrating porous carbon composite and preparation method thereof, as it is shown in figure 1, specifically wrap
Include following steps:
(1) being disperseed in deionized water by magnesium oxide powder, backflow is boiled and keeps 24 hours, sucking filtration after cooling, then at
90 DEG C are dried 12 hours, be subsequently placed in Muffle furnace and in air atmosphere with the ramp of 10 DEG C/min to 650 DEG C of roastings
30 minutes, obtaining porous flake hexagon magnesium oxide, its specific surface area is 200m2/ g, two-dimensional slice footpath size is about 300nm；
(2) at room temperature, 0.5g cobaltous acetate and 0.5g pyridine are dissolved in 30mL ethanol in the way of stirring, are subsequently added
The porous flake hexagon magnesium oxide that 0.5g step (1) obtains, and with the rotating speed magnetic agitation 4 hours of 600 revs/min, then
Solvent is rotated and is evaporated, obtain a mixture；
(3) described mixture is put in tube furnace and under argon shield with the ramp of 10 DEG C/min to 800 DEG C
Calcine 3 hours, obtain the mixture of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite；
(4) described template, cobalt/cobalt oxide are placed in dilute hydrochloric acid solution with the mixture of cobalt/nitrating porous carbon composite
In (according to 37% concentrated hydrochloric acid: the volume ratio preparation of water=10:1), backflow is boiled and keeps 1 hour, after filtering, then uses ethanol
Do not wash, be then dried 5 hours in 60 DEG C, obtain described cobalt/nitrating porous carbon composite.
The cobalt that Fig. 7 a provides for the present embodiment/nitrating porous carbon composite is at the N of subzero 200 DEG C2Adsorption/desorption curve,
The pore size distribution curve of the cobalt that Fig. 7 b provides for the present embodiment/nitrating porous carbon composite.Cobalt/nitrating that the present embodiment provides
Porous carbon composite is 0.55at% containing cobalt amount, and nitrogen content is 8.46at%, and specific surface area is 625m2/ g, average pore size
For 6.29nm, pore volume is 1.18cm3/g.This cobalt/nitrating porous carbon composite is to be loaded with mixing of monatomic cobalt by 5～20 layers
Nitrogen porous graphene lamella stacking forms, and a diameter of 300nm of monolayer lamella.
It is respectively adopted the cobalt/nitrating porous carbon composite of the present embodiment or mould prepared by the present embodiment step (1)-(3)
The mixture of plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as catalyst organosilan oxidation reaction
Method comprises the following steps:
(1) catalyst and dimethylphenylsilaneand acetone solution and are stirred in reaction bulb；
(2) appropriate ultra-pure water is joined in the solution that step (1) obtains, react 3 hours under 25 DEG C and stirring,
To dimethyl phonyl silanol；
Wherein, when employing cobalt/nitrating porous carbon composite is catalyst, its consumption is dimethylphenylsilaneand quality
5%；When the mixture of employing template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is catalyst, its consumption is diformazan
The 30% of base phenyl silane quality；The consumption of ultra-pure water is the 160% of dimethylphenylsilaneand quality.
Thin layer chromatography analysis is used to obtain: being respectively adopted two kinds of catalyst reactions after 3 hours, dimethylphenylsilaneand is equal
Reaction completely generates dimethyl phonyl silanol, without the generation of silicon ether by-product.
Proving after tested, after two kinds of catalyst recycle 5 times, catalysis activity is all without substantially reducing.
Embodiment 3
Present embodiments provide a kind of cobalt/nitrating porous carbon composite and preparation method thereof, as it is shown in figure 1, specifically wrap
Include following steps:
(1) being disperseed in deionized water by magnesium oxide powder, backflow is boiled and keeps 24 hours, sucking filtration after cooling, then at
100 DEG C are dried 12 hours, be subsequently placed in Muffle furnace and in air atmosphere with the ramp of 10 DEG C/min to 750 DEG C of roastings
30 minutes, obtaining porous flake hexagon magnesium oxide, its specific surface area is 200m2/ g, two-dimensional slice footpath size is about 400nm；
(2) at room temperature, 0.5g cobalt nitrate and 1g phenanthrolene are dissolved in 30mL ethanol, subsequently in the way of stirring
Add 1g step (1) the porous flake hexagon magnesium oxide that obtains, and with the rotating speed magnetic agitation 4 hours of 600 revs/min, so
After by solvent rotate be evaporated, obtain a mixture；
(3) described mixture is put in tube furnace and under argon shield with the ramp of 10 DEG C/min to 1000 DEG C
Calcine 1 hour, obtain the mixture of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite；
(4) described template, cobalt/cobalt oxide are placed in dilute hydrochloric acid solution with the mixture of cobalt/nitrating porous carbon composite
In (according to 37% concentrated hydrochloric acid: the volume ratio preparation of water=10:1), backflow is boiled and keeps 1 hour, after filtering, then uses ethanol
Do not wash, be then dried 5 hours in 60 DEG C, obtain described cobalt/nitrating porous carbon composite.
Cobalt/nitrating porous carbon composite that the present embodiment provides is 0.44at% containing cobalt amount, and nitrogen content is
6.71at%, specific surface area is 468m2/ g, average pore size is 7.8nm, and pore volume is 1.58cm3/g.This cobalt/nitrating porous carbon is combined
Material is to be formed by 5～20 layers of nitrating porous graphene lamella stacking being loaded with monatomic cobalt, and the diameter of monolayer lamella
For 400nm.
It is respectively adopted the cobalt/nitrating porous carbon composite of the present embodiment or mould prepared by the present embodiment step (1)-(3)
The mixture of plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as catalyst organosilan oxidation reaction
Method comprises the following steps:
(1) catalyst and dimethylphenylsilaneand acetone solution and are stirred in reaction bulb；
(2) appropriate ultra-pure water is joined in the solution that step (1) obtains, react 1 hour under 25 DEG C and stirring,
To dimethyl phonyl silanol；
Wherein, when employing cobalt/nitrating porous carbon composite is catalyst, its consumption is dimethylphenylsilaneand quality
1%；When the mixture of employing template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is catalyst, its consumption is diformazan
The 10% of base phenyl silane quality；The consumption of ultra-pure water is the 160% of dimethylphenylsilaneand quality.
Thin layer chromatography analysis is used to obtain: being respectively adopted two kinds of catalyst reactions after 1 hour, dimethylphenylsilaneand is equal
Reaction completely generates dimethyl phonyl silanol, without the generation of silicon ether by-product.
Proving after tested, after two kinds of catalyst recycle 5 times, catalysis activity is all without substantially reducing.
Embodiment 4
Present embodiments provide a kind of cobalt/nitrating porous carbon composite and preparation method thereof, as it is shown in figure 1, specifically wrap
Include following steps:
(1) being disperseed in deionized water by magnesium oxide powder, backflow is boiled and keeps 24 hours, sucking filtration after cooling, then at
80 DEG C are dried 12 hours, be subsequently placed in Muffle furnace and in air atmosphere with the ramp of 10 DEG C/min to 850 DEG C of roastings
30 minutes, obtaining porous flake hexagon magnesium oxide, its specific surface area is 190m2/ g, two-dimensional slice footpath size is about 200nm；
(2) at room temperature, by 0.5g cobaltous chloride and 1.5g 2,2':6', 2 "-ter cycloheptapyridine by stirring in the way of be dissolved in
In 30mL ethanol, it is subsequently added the porous flake hexagon magnesium oxide that 1.5g step (1) obtains, and with the rotating speed of 600 revs/min
Magnetic agitation 3 hours, then rotates solvent and is evaporated, obtain a mixture；
(3) described mixture is put in tube furnace and under argon shield with the ramp of 10 DEG C/min to 900 DEG C
Calcine 4 hours, obtain the mixture of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite；
(4) described template, cobalt/cobalt oxide are placed in dilute hydrochloric acid solution with the mixture of cobalt/nitrating porous carbon composite
In (according to 37% concentrated hydrochloric acid: the volume ratio preparation of water=10:1), backflow is boiled and keeps 1 hour, after filtering, then uses ethanol
Do not wash, be then dried 5 hours in 60 DEG C, obtain described cobalt/nitrating porous carbon composite.
Cobalt/nitrating porous carbon composite that the present embodiment provides is 0.44at% containing cobalt amount, and nitrogen content is
6.71at%, specific surface area is 468m2/ g, average pore size is 7.8nm, and pore volume is 1.58cm3/g.This cobalt/nitrating porous carbon is combined
Material is to be formed by 5～20 layers of nitrating porous graphene lamella stacking being loaded with monatomic cobalt, and the diameter of monolayer lamella
For 200nm.
It is respectively adopted the cobalt/nitrating porous carbon composite of the present embodiment or mould prepared by the present embodiment step (1)-(3)
The mixture of plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as catalyst organosilan oxidation reaction
Method comprises the following steps:
(1) catalyst and dimethylphenylsilaneand acetone solution and are stirred in reaction bulb；
(2) appropriate ultra-pure water is joined in the solution that step (1) obtains, react 7 hours under 25 DEG C and stirring,
To dimethyl phonyl silanol；
Wherein, when employing cobalt/nitrating porous carbon composite is catalyst, its consumption is dimethylphenylsilaneand quality
4%；When the mixture of employing template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is catalyst, its consumption is diformazan
The 10% of base phenyl silane quality；The consumption of ultra-pure water is the 160% of dimethylphenylsilaneand quality.
Thin layer chromatography analysis is used to obtain: being respectively adopted two kinds of catalyst reactions after 7 hours, dimethylphenylsilaneand is equal
Reaction completely generates dimethyl phonyl silanol, without the generation of silicon ether by-product.
Proving after tested, after two kinds of catalyst recycle 5 times, catalysis activity is all without substantially reducing.
Embodiment 5
Present embodiments provide a kind of cobalt/nitrating porous carbon composite and preparation method thereof, as it is shown in figure 1, specifically wrap
Include following steps:
(1) being disperseed in deionized water by magnesium oxide powder, backflow is boiled and keeps 24 hours, sucking filtration after cooling, then at
100 DEG C are dried 10 hours, be subsequently placed in Muffle furnace and in air atmosphere with the ramp of 10 DEG C/min to 300 DEG C of roastings
30 minutes, obtaining porous flake hexagon magnesium oxide, its specific surface area is 200m2/ g, two-dimensional slice footpath size is about 300nm；
(2) at room temperature, by 0.5g cobalt nitrate and 0.5g 2,6-bis-(2-benzimidazolyl) pyridine is molten in the way of stirring
In 30mL ethanol, it is subsequently added the porous flake hexagon magnesium oxide that 0.5g step (1) obtains, and with 600 revs/min turn
Speed magnetic agitation 4 hours, then rotates solvent and is evaporated, obtain a mixture；
(3) described mixture is put in tube furnace and under argon shield with the ramp of 10 DEG C/min to 600 DEG C
Calcine 2 hours, obtain the mixture of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite；
(4) described template, cobalt/cobalt oxide are placed in dilute hydrochloric acid solution with the mixture of cobalt/nitrating porous carbon composite
In (according to 37% concentrated hydrochloric acid: the volume ratio preparation of water=10:1), backflow is boiled and keeps 1 hour, after filtering, then uses ethanol
Do not wash, be then dried 5 hours in 60 DEG C, obtain described cobalt/nitrating porous carbon composite.
Cobalt/nitrating porous carbon composite that the present embodiment provides is 0.44at% containing cobalt amount, and nitrogen content is
6.71at%, specific surface area is 468m2/ g, average pore size is 7.8nm, and pore volume is 1.58cm3/g.This cobalt/nitrating porous carbon is combined
Material is to be formed by 5～20 layers of nitrating porous graphene lamella stacking being loaded with monatomic cobalt, and the diameter of monolayer lamella
For 300nm.
It is respectively adopted the cobalt/nitrating porous carbon composite of the present embodiment or mould prepared by the present embodiment step (1)-(3)
The mixture of plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as catalyst organosilan oxidation reaction
Method comprises the following steps:
(1) catalyst and dimethylphenylsilaneand acetone solution and are stirred in reaction bulb；
(2) appropriate ultra-pure water is joined in the solution that step (1) obtains, react 3 hours under 25 DEG C and stirring,
To dimethyl phonyl silanol；
Wherein, when employing cobalt/nitrating porous carbon composite is catalyst, its consumption is dimethylphenylsilaneand quality
2.5%；When the mixture of employing template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is catalyst, its consumption is two
The 25% of aminomethyl phenyl silane quality；The consumption of ultra-pure water is the 132% of dimethylphenylsilaneand quality.
Thin layer chromatography analysis is used to obtain: being respectively adopted two kinds of catalyst reactions after 3 hours, dimethylphenylsilaneand is equal
Reaction completely generates dimethyl phonyl silanol, without the generation of silicon ether by-product.
Proving after tested, after two kinds of catalyst recycle 5 times, catalysis activity is all without substantially reducing.
Claims (10)
1. a preparation method for cobalt/nitrating porous carbon composite, it comprises the following steps:
(1) by cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent, then remove solvent, obtain one
Mixture；
(2) make described mixture calcine 0.5～4 hour at 600-1000 DEG C, obtain template, cobalt/cobalt oxide many with cobalt/nitrating
The mixture of hole carbon composite；
(3) acid mode not is used to remove in the mixture of described template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Template and cobalt/cobalt oxide, obtain described cobalt/nitrating porous carbon composite.
The preparation method of cobalt the most according to claim 1/nitrating porous carbon composite, wherein, described template includes
Porous flake hexagon magnesium oxide；Preferably, the specific surface area of described porous flake hexagon magnesium oxide is 100～300m2/ g,
Two-dimensional slice footpath a size of 200～400nm；It is highly preferred that described porous flake hexagon magnesium oxide is through the following steps that prepare
Obtain: magnesium oxide powder is boiled in water and keeps 8～24 hours, by the solid that obtains after drying, then 200～
900 DEG C of roastings 0.5～2 hours, obtain described porous flake hexagon magnesium oxide.
The preparation method of cobalt the most according to claim 1/nitrating porous carbon composite, wherein, described cobalt salt includes nitre
The combination of one or more in acid cobalt, cobaltous chloride and cobaltous acetate.
The preparation method of cobalt the most according to claim 1/nitrating porous carbon composite, wherein, the nitrogenous of described cobalt has
Machine part includes 2,2'-bipyridyl, pyridine, phenanthrolene, 2,2':6', 2 "-ter cycloheptapyridine, 2,6-bis-(2-benzimidazole
Base) combination of one or more in pyridine.
The preparation method of cobalt the most according to claim 1/nitrating porous carbon composite, wherein, uses in step (1)
The ratio of cobalt salt, the nitrogenous organic ligand of cobalt and template is mass ratio 1:1:1～1:3:3.
The preparation method of cobalt the most according to claim 1/nitrating porous carbon composite, wherein, the solvent in step (1)
Including ethanol and/or acetone；
The side that cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent are used stirring in step (1)
Formula；Preferably, this stirring is magnetic agitation, and the rotating speed of magnetic agitation is 300～800r/min, and mixing time is 2～5 little
Time；
Calcining in step (2) is carried out under inert gas shielding, it is preferable that described noble gas includes argon；
In step (2), with the ramp of 5-15 DEG C/min to 600-1000 DEG C；
Acid in step (3) does not specifically includes following steps: described template, cobalt/cobalt oxide are combined with cobalt/nitrating porous carbon
The mixture of material boils after mixing with acid and keeps 1～2 hour；Preferably, the acid used includes hydrochloric acid solution.
7. the cobalt that the preparation method of the cobalt described in an any one of claim 1-6/nitrating porous carbon composite prepares/
Nitrating porous carbon composite.
Cobalt the most according to claim 7/nitrating porous carbon composite, it is 0.2-0.8at% containing cobalt amount, and nitrogen content is
4-10at%, specific surface area is 400-900m2/ g, aperture is 4-9nm, and pore volume is 0.5-4cm3/g；And described cobalt/nitrating is many
Hole carbon composite is to be formed by 5～20 layers of nitrating porous graphene lamella stacking being loaded with monatomic cobalt, and monolayer lamella
A diameter of 200～400nm.
9. a mixture for template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite, it is through the following steps that prepare
Obtain:
(1) by cobalt salt, the nitrogenous organic ligand of cobalt and template mix homogeneously in a solvent, then remove solvent, obtain one
Mixture；
(2) make described mixture calcine 0.5～4 hour at 600-1000 DEG C, obtain described template, cobalt/cobalt oxide and cobalt/
The mixture of nitrating porous carbon composite.
10. the cobalt used described in claim 7 or 8/nitrating porous carbon composite or the template described in claim 9
The mixture of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite is as the side of catalyst organosilan oxidation reaction
Method, the method comprises the following steps:
By described cobalt/nitrating porous carbon composite or described template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Mixture, as catalyst, reacts under the effect of oxidant with organosilan, obtains silanol；
Wherein it is preferred to, the 1-5% that consumption is organosilan quality of described cobalt/nitrating porous carbon composite, described template
The 10-40% that consumption is organosilan quality of the mixture of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite.
Described oxidant includes the combination of one or more in oxygen gas and water, hydrogen peroxide and methanol；
Described reaction is carried out in a solvent, and described solvent includes the one in acetone, ethyl acetate and oxolane or several
The combination planted.
Reaction temperature is 20～30 DEG C, and the response time is 1～8 hour.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477566A (en) * | 2016-12-28 | 2017-03-08 | 山东理工大学 | A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing |
| CN107376970A (en) * | 2017-07-25 | 2017-11-24 | 中国石油大学(北京) | Monatomic porous C catalyst of iron nitrating and preparation method and application |
| CN107413369A (en) * | 2017-06-13 | 2017-12-01 | 中国石油大学(华东) | A kind of simple method for preparing Co Nx/C efficient selective photochemical catalysts |
| CN108270018A (en) * | 2016-12-30 | 2018-07-10 | 上汽通用汽车有限公司 | A kind of cobalt-N doping 2 D mesopore carbon material and its preparation method and application |
| CN108998113A (en) * | 2018-06-14 | 2018-12-14 | 安徽大学 | A kind of monatomic cobalt-based methanol fuel and preparation method thereof |
| CN109248712A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monatomic dopen Nano carbon material catalytic carrier of metal and its preparation method and application |
| CN109939717A (en) * | 2019-04-15 | 2019-06-28 | 中国科学院化学研究所 | The monatomic catalyst and the preparation method and application thereof of the ultra-thin carbon nanosheet load of N doping |
| CN114784297A (en) * | 2022-03-14 | 2022-07-22 | 北京理工大学 | Preparation method of monatomic cobalt ORR catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2476255A1 (en) * | 2002-02-14 | 2003-08-21 | Monsanto Technology Llc | Oxidation catalyst and process for its preparation and process for oxidation using it |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
| CN104624154A (en) * | 2015-01-23 | 2015-05-20 | 南开大学 | Preparation method and application of iron-nitrogen co-doped porous carbon sphere material |
-
2016
- 2016-07-08 CN CN201610536845.1A patent/CN106179446B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2476255A1 (en) * | 2002-02-14 | 2003-08-21 | Monsanto Technology Llc | Oxidation catalyst and process for its preparation and process for oxidation using it |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
| CN104624154A (en) * | 2015-01-23 | 2015-05-20 | 南开大学 | Preparation method and application of iron-nitrogen co-doped porous carbon sphere material |
Non-Patent Citations (1)
| Title |
|---|
| ZHUANGJUN FAN,ET. AL: "Template-Directed Synthesis of Pillared-Porous Carbon Nanosheet Architectures: High-Performance Electrode Materials for Supercapacitors", 《ADV. ENERGY MATER.》 * |
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