CN106179446B - The method of cobalt/nitrating porous carbon composite and its preparation method and catalysis silane oxidation - Google Patents
The method of cobalt/nitrating porous carbon composite and its preparation method and catalysis silane oxidation Download PDFInfo
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- CN106179446B CN106179446B CN201610536845.1A CN201610536845A CN106179446B CN 106179446 B CN106179446 B CN 106179446B CN 201610536845 A CN201610536845 A CN 201610536845A CN 106179446 B CN106179446 B CN 106179446B
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- 239000010941 cobalt Substances 0.000 title claims abstract description 227
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 224
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 224
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 137
- 230000000802 nitrating effect Effects 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 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
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 60
- 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 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013110 organic ligand Substances 0.000 claims abstract description 21
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 56
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 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
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- HCLXLZGAYCTHQJ-UHFFFAOYSA-N 1h-cyclohepta[b]pyridine Chemical class 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 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
- 239000007787 solid Substances 0.000 claims description 3
- 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 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 238000005554 pickling Methods 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 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 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000004087 circulation Effects 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
- 239000006185 dispersion Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 238000010521 absorption reaction 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
- 239000005046 Chlorosilane Substances 0.000 description 2
- 238000002441 X-ray diffraction 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
- 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
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 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
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process 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
- 150000002500 ions Chemical class 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
- 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
- 239000000047 product Substances 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
- 239000004065 semiconductor Substances 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
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 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 present invention provides the methods of a kind of cobalt/nitrating porous carbon composite and its preparation method and catalysis silane oxidation.The cobalt/nitrating porous carbon composite is through the following steps that be prepared: cobalt salt, the nitrogenous organic ligand of cobalt and template mixed in a solvent, mixture after removal solvent is calcined at 600-1000 DEG C, template agent removing and cobalt/cobalt oxide are not gone using acid again, obtain cobalt/nitrating porous carbon composite.The method of the catalysis silane oxidation is reacted under the action of oxidant with organosilan, obtains silanol the following steps are included: using cobalt of the invention/nitrating porous carbon composite or do not go the mixture of template agent removing and cobalt/cobalt oxide as catalyst.The present invention is using 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, material specific surface area with higher, mesoporous pore size and biggish Kong Rong are made in the method for high-temperature calcination and acid not.
Description
Technical field
The present invention relates to a kind of cobalt/nitrating porous carbon composite and preparation method thereof and a kind of templates, cobalt/cobalt oxide
With cobalt/nitrating porous carbon composite mixture and a kind of the use cobalt/nitrating porous carbon composite or the template
Side of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst organosilan oxidation reaction
Method belongs to porous carbon materials technical field.
Background technique
Silanol is a kind of very important organic molecule, is widely used in organic synthesis and pharmaceutical synthesis field, simultaneously
It is also 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 anti-and silane oxidation reaction three categories to silicon ether.In these methods, it is reacted and is made with silane oxidation especially
Standby silanol research is more, and reason is essentially consisted in relative to chlorosilane and silicon ether, and silane is more cheap and easily-available, and is reacted and generated silicon
The Atom economy of alcohol is high.
The research for obtaining silanol for silane oxidation at present specifically includes that (1) uses the strong oxidizer of equivalent, such as peroxide
Acid, potassium permanganate, bisoxirane, oxa- acridine etc., but such methods toxicity is big, yield is not high, poor selectivity, and can give birth to
At the by-product of many toxicity；(2) using water or oxygen as oxidant, hydrogen is unique for transition metal-catalyzed silane oxidation reaction
By-product, reaction cleaning, overcomes disadvantages described above, and causes the extensive attention of people.This kind of transition metal-catalyzed silane oxidation
Method no matter in homogeneous or heterogeneous catalysis system can with high yield be catalyzed silane oxidation synthesize silanol, but such
Catalyst used in method uses the noble metals such as Au Ag Pt Pd, ruthenium as active component mostly；Although using noble metal as work
Property component heterogeneous catalyst activity and selectivity with higher, but the expensive price limit application of catalyst and push away
Extensively, it is difficult to realize industrialized production.Base metal has many advantages, such as cheap, resourceful, answers as active component
For being had a very big significance in organosilan oxidation reaction.
Porous material is because having the characteristics such as the uniform cellular structure of molecular dimension and big specific surface area, in absorption, ion
It exchanges, particularly is widely used in fields such as catalysis.
In numerous porous materials, for porous carbon materials due to the peculiar property having, synthesis material is abundant and is easy to obtain
It takes, therefore there are universal applications in modern science.Porous carbon materials have high-specific surface area, big pore volume, connection and
Many advantages, such as uniform duct, adjustable aperture, make its catalysis, absorption, sensing, in terms of have and widely answer
With value.In order to further improve the application of porous carbon materials in these areas, usually by hetero atom (such as N, B, S etc.) or contain
Heteroatomic group (amino, nitro, sulfonic group etc.) is doped in the surface or structure of porous carbon materials, makes porous carbon materials
The performance of various aspects is upgraded and improved.In numerous doping components, nitrogen is a kind of member most favored by researchers
Element.
After N atom mixes carbon material, being entrained in hexagonal carbon grid for N atom generates localised tension, leads to carbon knot
Structure deformation, and since the lone pair electrons of N atom can supply sp2Hydridization carbon skeleton delocalized pi-bond negative electrical charge, to enhance electronics
Transmission characteristic and chemical reactivity；The N atom that electron rich is adulterated in carbon material can change the band structure of material, make carbon
The valence band of material reduces, the chemical stability of reinforcing material, increases the electron density on fermi level.
Nitrogen enters the nitrogen-doped porous carbon material that the internal structure of porous carbon materials is formed, in addition to porous carbon
Outside all advantages of material, the features such as with its unique machinery, electronics, optics, semiconductor, energy storage property, suitable alkalinity,
The application range further expansion of superhard material, absorption, catalysis and fuel cell etc..
With the continuous expansion of nitrogen-doped porous carbon material application range, synthesis of the people to nitrogen-doped porous carbon material
Give extensive concern.Currently, having much for nitrogen-doped porous carbon material synthetic method, it can substantially be summarized as two classes:
Two kinds of doping and post-processing in situ.Post-processing is needed with nitrogenous gas such as nitrogen or ammonias under the high temperature conditions to pre-synthesis
Carbon material surface is modified, or is grafted nitrogenous organic group on the surface of the material and changed carbon material surface property to reach
Purpose.In-situ synthesis is usually to introduce nitrogen source in carbon material synthesis process or use carbon source containing nitrogen itself,
In the carbonisation of carbon matrix precursor, nitrogen-atoms is mixed inside carbon material.
In-situ synthesis nitrogen-doped porous carbon material mainly includes template, chemical vapour deposition technique (CVD) and hydro-thermal method
Deng.Template is generally using 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 shapes, Different Pore Structures and surface area.
However nitrogen-doped porous carbon material is prepared there is also some technical problems using template, firstly, some nitrogen sources by
It is bad in the nitrogen-doped porous carbon material performance of the influence of itself, formation；Secondly, using nitride polyporous material is contained as nitrogen source system
Standby then higher cost, it is complex；In addition, the selection of template is more single and expensive.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of cobalt/nitrating porous carbon composite and its
Preparation method.The present invention uses the nitrogenous organic ligand of template, cobalt salt and cobalt as raw material, and with high-temperature calcination and acid
The nitrating porous carbon composite for loading monatomic cobalt can be prepared in method not.
It is mixed that the object of the invention is also to provide a kind of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composites
Close object.
Above-mentioned cobalt/nitrating porous carbon composite or above-mentioned template are used another object of the present invention is to provide a kind of
Side of agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst organosilan oxidation reaction
Method.
In order to achieve the above objectives, present invention firstly provides a kind of cobalt/nitrating porous carbon composite preparation method,
The following steps are included:
(1) cobalt salt, the nitrogenous organic ligand of cobalt and template are uniformly mixed in a solvent, then remove solvent, obtains
To a mixture；
(2) it calcines the mixture 0.5~4 hour at 600-1000 DEG C, obtains template, cobalt/cobalt oxide and cobalt/mix
The mixture of nitrogen porous carbon composite；
(3) using acid not by the way of remove the mixing of the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Template and cobalt/cobalt oxide in object obtain the cobalt/nitrating porous carbon composite.
In the above preparation method, it is preferable that the template includes porous flake hexagon magnesia.It is highly preferred that
The specific surface area of the porous flake hexagon magnesia is 100~300m2/ g, two-dimensional slice diameter is having a size of 200~400nm.Into
Preferably, the porous flake hexagon magnesia is through the following steps that be prepared: by magnesium oxide powder in water for one step
In boil and kept for 8~24 hours, by obtained solid after drying (can be 5~12 hours dry at 80~100 DEG C), then
200~900 DEG C roast 0.5~2 hour (roasting can carry out in air atmosphere, heating rate can for 5~15 DEG C/
Min), the porous flake hexagon magnesia is obtained.
In the above preparation method, it is preferable that the cobalt salt includes one of cobalt nitrate, cobalt chloride and cobalt acetate etc.
Or several combination.
In the above preparation method, it is preferable that the nitrogenous organic ligand of the cobalt includes 2,2'- bipyridyl, pyridine, neighbour two
Aza-phenanthrenes, 2,2':6', the combination of one or more of 2 "-ter cycloheptapyridines, 2,6- bis- (2- benzimidazolyl) pyridine etc..
In the above preparation method, it is preferable that the nitrogenous organic ligand and template of the cobalt salt, cobalt that are used in step (1)
The mass ratio of agent is 1:1:1~1:3:3.
In the above preparation method, it is preferable that the solvent in step (1) includes ethyl alcohol and/or acetone etc..
In the above preparation method, it is preferable that in step (1) by cobalt salt, the nitrogenous organic ligand and template of cobalt
Being uniformly mixed in a solvent can be by the way of stirring.It is highly preferred that the stirring be 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
It is uniformly mixed (can be by the way of stirring or ultrasonic disperse) in solvent, adds template, and in a manner of magnetic agitation
It is uniformly mixed them.
In the above preparation method, cobalt salt, cobalt nitrogenous organic ligand and template concentration in a solvent can be by
Those skilled in the art carry out conventional adjustment, as long as reaction can be made to go on smoothly.
In the above preparation method, it is preferable that the mode of the removal solvent in step (1) can steam for dry or rotation
Hair, and dry temperature can be 80~100 DEG C, and the time can be 10~12 hours.
In the above preparation method, it is preferable that the calcining in step (2) carries out under inert gas protection, more excellent
Selection of land, the inert gas include argon gas etc..
In the above preparation method, it is preferable that in step (2), 600-1000 is warming up to the rate of 5-15 DEG C/min
℃。
In the above preparation method, it is preferable that in step (3) acid not specifically includes the following steps: by the template,
Cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture and acid-mixed are boiled and are kept for 1~2 hour after closing.Wherein, it is adopted
Acid may include hydrochloric acid solution etc..It can be filtered or filter later, do not wash, dry, to obtain final product.Its
In, not washing can be able to be 60~80 DEG C using ethyl alcohol or acetone etc., dry temperature, and the time can be 2~5 hours.
In addition, be prepared the present invention also provides a kind of preparation method of above-mentioned cobalt/nitrating porous carbon composite
Cobalt/nitrating porous carbon composite.
Specific embodiment according to the present invention, it is preferable that the cobalt/nitrating porous carbon composite amount containing cobalt is
0.2-0.8at%, nitrogen content 4-10at%, specific surface area 400-900m2/ g, aperture 4-9nm, Kong Rongwei 0.5-4cm3/
g.The cobalt/nitrating porous carbon composite be by 5~20 layers load have monatomic cobalt nitrating porous graphene lamella stack and
At, and the diameter of single layer lamella is 200~400nm.
The present invention uses the nitrogenous organic ligand of template, cobalt salt and cobalt as raw material, and with high-temperature calcination and acid
The nitrating porous carbon composite of the monatomic cobalt of load has been prepared in method not.Cobalt provided by the invention/nitrating porous carbon
Composite material and preparation method mainly has following some a little: (1) the template porous flake hexagon that the present invention uses
Magnesia is cheap, preparation process is simple, and (specific surface area is 100~300m with porous flake hexagonal structure2/
G, diameter are 200~400nm), there is unique advantage compared with other templates；(2) raw material that the present invention uses is common
Industrial chemicals, cost is relatively low, while the requirement to equipment and technology is lower, by calcining can disposably obtain cobalt/nitrating
Porous carbon composite, preparation process is simple, is easy to be mass produced；(3) cobalt of the invention/nitrating porous carbon composite tool
There are higher specific surface area, mesoporous pore size and a biggish Kong Rong, and with stable physical and chemical performance and excellent makes
Use the service life.
In addition, the present invention also provides the mixing of a kind of template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Object, through the following steps that be prepared:
(1) cobalt salt, the nitrogenous organic ligand of cobalt and template are uniformly mixed in a solvent, then remove solvent, obtains
To a mixture；
(2) calcine the mixture 0.5~4 hour at 600-1000 DEG C, obtain the template, cobalt/cobalt oxide with
Cobalt/nitrating porous carbon composite mixture.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that the mould
Plate agent includes porous flake hexagon magnesia.It is highly preferred that the specific surface area of the porous flake hexagon magnesia is 100
~300m2/ g, two-dimensional slice diameter is having a size of 200~400nm.It is further preferred that the porous flake hexagon magnesia is logical
It crosses what following steps were prepared: magnesium oxide powder is boiled in water and kept for 8~24 hours, by obtained solid through drying
After (can be 5~12 hours dry at 80~100 DEG C), then (roasting can be in sky within 0.5~2 hour in 200~900 DEG C of roastings
Carried out under gas atmosphere, heating rate can be 5~15 DEG C/min), obtain the porous flake hexagon magnesia.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that the cobalt
Salt includes the combination of one or more of cobalt nitrate, cobalt chloride and cobalt acetate etc..
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that the cobalt
Nitrogenous organic ligand include 2,2'- bipyridyl, pyridine, phenanthrolene, 2,2':6', 2 "-ter cycloheptapyridines, (the 2- benzene of 2,6- bis-
And imidazole radicals) one or more of pyridine etc. combination.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that step (1)
The mass ratio of the middle cobalt salt used, the nitrogenous organic ligand of cobalt and template is 1:1:1~1:3:3.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that step (1)
In solvent include ethyl alcohol and/or acetone etc..
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that step (1)
In by cobalt salt, the nitrogenous organic ligand of cobalt and template in a solvent be uniformly mixed can using stir by the way of.It is more excellent
Selection of land, which is magnetic agitation, and the revolving speed of magnetic agitation is 300~800r/min, and mixing time is 2~5 hours.Into
Preferably, being first uniformly mixed the nitrogenous organic ligand of cobalt salt, cobalt in a solvent (can be using stirring or ultrasonic disperse for one step
Mode), template is added, and be uniformly mixed them in a manner of magnetic agitation.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that step (1)
In the mode of removal solvent can be dry or rotary evaporation, and dry temperature can be 80~100 DEG C, and the time can be with
It is 10~12 hours.
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that step (2)
In calcining carry out under inert gas protection, it is highly preferred that the inert gas includes argon gas etc..
In above-mentioned template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture, it is preferable that in step
(2) in, 600-1000 DEG C is warming up to the rate of 5-15 DEG C/min.
On the other hand, the present invention also provides it is a kind of using above-mentioned cobalt/nitrating porous carbon composite or above-mentioned template,
Cobalt/cobalt oxide and method of cobalt/nitrating porous carbon composite mixture as catalyst organosilan oxidation reaction,
Method includes 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 reacts under the action of oxidant as catalyst, with organosilan, obtains silanol.
In the above-mentioned methods, it is preferable that the cobalt/nitrating porous carbon composite dosage is the 1 of organosilan quality
~5%, the dosage of the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture is organosilan quality
10~40%.
In the above-mentioned methods, it is preferable that the oxidant includes one of oxygen gas and water, hydrogen peroxide and methanol etc. or several
The combination of kind.It is highly preferred that the oxidant is ultrapure water.
In the above-mentioned methods, it is preferable that the reaction carries out in a solvent, and the solvent includes acetone, acetic acid second
The combination of one or more of ester and tetrahydrofuran etc..
In the above-mentioned methods, it is preferable that reaction temperature is 20~30 DEG C, and the reaction time is 1~8 hour.
The present invention is made using cobalt/nitrating porous carbon composite or template, cobalt/cobalt oxide and cobalt/nitrating porous carbon are compound
The mixture of material mainly has the advantage that (1) is of the invention as the method for catalyst organosilan oxidation reaction
Catalyst is using the monatomic cobalt that is connected with nitrogen as activated centre, catalytic activity and stability with higher, and without silicon ether
The generation of by-product；(2) it is compared with traditional organosilan oxidation catalyst, catalyst of the invention specific surface with higher
Product, conducive to the absorption of reactant and the raising of catalytic activity；(3) recycling of catalyst of the invention is relatively simple, and
It is recycled for 5 times or more and is still able to maintain higher catalytic activity；(4) simultaneously, cobalt-nitrogen-carbon material report be mostly about
Application in terms of electrochemistry, but application of the double-doped catalyst of nitrogen, cobalt in organic molecule transformation is rarely reported, the present invention is to opening up
The exploitation of the application and study on mechanism and novel reaction system of opening up this kind of catalyst is of great significance；(5) of the invention
Using do not go the mixture of template agent removing as catalyst catalytic activity, stability and service life cycle still with higher.
Detailed description of the invention
Fig. 1 is cobalt/nitrating porous carbon composite preparation method flow chart that embodiment 1-5 is provided.
Fig. 2 is cobalt/nitrating porous carbon composite scanning electron microscope (SEM) photograph that embodiment 1 provides.
Fig. 3 a and Fig. 3 b are cobalt/nitrating porous carbon composite transmission electron microscope picture that embodiment 1 provides.
Fig. 4 is cobalt/nitrating porous carbon composite high-resolution-ration transmission electric-lens figure that embodiment 1 provides.
Fig. 5 be template, cobalt/cobalt oxide and cobalt/the nitrating porous carbon composite mixture that provide of embodiment 1 and
Cobalt/nitrating porous carbon composite X-ray diffraction spectrogram.
Fig. 6 is cobalt/nitrating porous carbon composite x-ray photoelectron spectroscopy figure that embodiment 1 provides.
Fig. 7 a is cobalt/nitrating porous carbon composite N that embodiment 2 provides2Adsorption/desorption curve.
Fig. 7 b is cobalt/nitrating porous carbon composite pore size distribution curve that embodiment 2 provides.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of cobalt/nitrating porous carbon composite and preparation method thereof is present embodiments provided, as shown in Figure 1, specific packet
Include following steps:
(1) in deionized water by magnesium oxide powder dispersion, reflux is boiled and is kept for 24 hours, is filtered after cooling, then at
80 DEG C drying 12 hours, be subsequently placed in Muffle furnace and 450 DEG C of roastings be warming up to the rate of 10 DEG C/min in air atmosphere
30 minutes, obtain porous flake hexagon magnesia, specific surface area 200m2/ g, two-dimensional slice diameter size is about 300nm；
(2) at room temperature, by 0.5g cobalt nitrate and 0.5g 2,2'- bipyridyl is dissolved in 30mL ethyl alcohol in a manner of stirring,
The porous flake hexagon magnesia that 0.5g step (1) obtains then is added, and small with 600 revs/min of revolving speed magnetic agitation 3
When, then solvent rotation is evaporated, obtains a mixture；
(3) mixture is put into tube furnace and under protection of argon gas with the rate of 10 DEG C/min and is warming up to 700 DEG C
Calcining 2 hours, obtains template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture；
(4) template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are placed in dilute hydrochloric acid solution
Reflux is boiled and is kept for 1 hour in (according to 37% concentrated hydrochloric acid: water=10:1 volume ratio is prepared), after filtering, then uses ethyl alcohol
It does not wash, it is then 5 hours dry in 60 DEG C, obtain the cobalt/nitrating porous carbon composite.
Fig. 2 is cobalt provided in this embodiment/nitrating porous carbon composite scanning electron microscope (SEM) photograph, and Fig. 3 a and Fig. 3 b are this
Cobalt/nitrating porous carbon composite transmission electron microscope picture that embodiment provides, Fig. 4 are that cobalt/nitrating provided in this embodiment is porous
The high-resolution-ration transmission electric-lens figure of carbon composite, cobalt/nitrating porous carbon provided in this embodiment is answered it can be seen from Fig. 2-Fig. 4
Condensation material has the porous structure of class hexagon magnesia, and lamella is relatively thin.Fig. 5 is template provided in this embodiment, cobalt oxidation
Object and cobalt/nitrating porous carbon composite mixture and cobalt/nitrating porous carbon composite XRD spectra, can be with by Fig. 5
Find out will there is the generation of cobalt/cobalt oxide after cobalt salt, nitrogenous organic ligand and template high-temperature calcination, through the non-rear pattern plate agent of peracid and
Cobalt/cobalt oxide is removed, and can obtain the composite material for loading monatomic cobalt.Fig. 6 is that cobalt/nitrating provided in this embodiment is porous
The XPS spectrum figure of carbon composite can obviously observe the peak of C, O, N, Co element from Fig. 6, it can be deduced that amount containing cobalt is
0.55at%, nitrogen content 8.46at%.
Cobalt provided in this embodiment/nitrating porous carbon composite amount containing cobalt is 0.55at%, and nitrogen content is
8.46at%, specific surface area 625m2/ g, average pore size 6.29nm, Kong Rongwei 1.18cm3/g.The cobalt/nitrating porous carbon is multiple
Condensation material is that have the nitrating porous graphene lamella of monatomic cobalt to stack by 5~20 layers of load, and single layer lamella is straight
Diameter is 300nm.
Cobalt/nitrating the porous carbon composite of the present embodiment or the mould of the present embodiment step (1)-(3) preparation is respectively adopted
Plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are as catalyst organosilan oxidation reaction
Method the following steps are included:
(1) catalyst and dimethylphenylsilaneand acetone solution in reaction flask and are stirred evenly；
(2) appropriate ultrapure water is added in the solution that step (1) obtains, reacts 2 hours, obtains at 25 DEG C and under stirring
To dimethyl phonyl silanol；
Wherein, when using cobalt/nitrating porous carbon composite as catalyst, dosage is dimethylphenylsilaneand quality
2.5%；When using template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst, dosage two
The 25% of aminomethyl phenyl silane quality；The dosage of ultrapure water is the 132% of dimethylphenylsilaneand quality.
It analyzes to obtain using thin-layered chromatography: two kinds of catalyst reactions is respectively adopted after 2 hours, dimethylphenylsilaneand is equal
Reaction generates dimethyl phonyl silanol, the generation of no silicon ether by-product completely.
It proves after tested, using after 5 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 2
A kind of cobalt/nitrating porous carbon composite and preparation method thereof is present embodiments provided, as shown in Figure 1, specific packet
Include following steps:
(1) in deionized water by magnesium oxide powder dispersion, reflux is boiled and is kept for 24 hours, is filtered after cooling, then at
90 DEG C drying 12 hours, be subsequently placed in Muffle furnace and 650 DEG C of roastings be warming up to the rate of 10 DEG C/min in air atmosphere
30 minutes, obtain porous flake hexagon magnesia, specific surface area 200m2/ g, two-dimensional slice diameter size is about 300nm；
(2) at room temperature, 0.5g cobalt acetate and 0.5g pyridine are dissolved in 30mL ethyl alcohol in a manner of stirring, are then added
The porous flake hexagon magnesia that 0.5g step (1) obtains, and with 600 revs/min of revolving speed magnetic agitation 4 hours, then
Solvent rotation is evaporated, a mixture is obtained；
(3) mixture is put into tube furnace and under protection of argon gas with the rate of 10 DEG C/min and is warming up to 800 DEG C
Calcining 3 hours, obtains template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture；
(4) template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are placed in dilute hydrochloric acid solution
Reflux is boiled and is kept for 1 hour in (according to 37% concentrated hydrochloric acid: water=10:1 volume ratio is prepared), after filtering, then uses ethyl alcohol
It does not wash, it is then 5 hours dry in 60 DEG C, obtain the cobalt/nitrating porous carbon composite.
Fig. 7 a is cobalt provided in this embodiment/nitrating porous carbon composite in subzero 200 DEG C of N2Adsorption/desorption curve,
Fig. 7 b is cobalt provided in this embodiment/nitrating porous carbon composite pore size distribution curve.Cobalt/nitrating provided in this embodiment
The amount containing cobalt of porous carbon composite is 0.55at%, nitrogen content 8.46at%, specific surface area 625m2/ g, average pore size
For 6.29nm, Kong Rongwei 1.18cm3/g.The cobalt/nitrating porous carbon composite is that have mixing for monatomic cobalt by 5~20 layers of load
Nitrogen porous graphene lamella stacks, and the diameter of single layer lamella is 300nm.
Cobalt/nitrating the porous carbon composite of the present embodiment or the mould of the present embodiment step (1)-(3) preparation is respectively adopted
Plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are as catalyst organosilan oxidation reaction
Method the following steps are included:
(1) catalyst and dimethylphenylsilaneand acetone solution in reaction flask and are stirred evenly；
(2) appropriate ultrapure water is added in the solution that step (1) obtains, reacts 3 hours, obtains at 25 DEG C and under stirring
To dimethyl phonyl silanol；
Wherein, when using cobalt/nitrating porous carbon composite as catalyst, dosage is dimethylphenylsilaneand quality
5%；When using template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst, dosage is diformazan
The 30% of base phenyl silane quality；The dosage of ultrapure water is the 160% of dimethylphenylsilaneand quality.
It analyzes to obtain using thin-layered chromatography: two kinds of catalyst reactions is respectively adopted after 3 hours, dimethylphenylsilaneand is equal
Reaction generates dimethyl phonyl silanol, the generation of no silicon ether by-product completely.
It proves after tested, using after 5 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 3
A kind of cobalt/nitrating porous carbon composite and preparation method thereof is present embodiments provided, as shown in Figure 1, specific packet
Include following steps:
(1) in deionized water by magnesium oxide powder dispersion, reflux is boiled and is kept for 24 hours, is filtered after cooling, then at
100 DEG C drying 12 hours, be subsequently placed in Muffle furnace and 750 DEG C of roastings be warming up to the rate of 10 DEG C/min in air atmosphere
30 minutes, obtain porous flake hexagon magnesia, specific surface area 200m2/ g, two-dimensional slice diameter size is about 400nm；
(2) at room temperature, 0.5g cobalt nitrate and 1g phenanthrolene are dissolved in 30mL ethyl alcohol in a manner of stirring, then
The porous flake hexagon magnesia that 1g step (1) obtains is added, and with 600 revs/min of revolving speed magnetic agitation 4 hours, so
Solvent rotation is evaporated afterwards, obtains a mixture；
(3) mixture is put into tube furnace and under protection of argon gas with the rate of 10 DEG C/min and is warming up to 1000 DEG C
Calcining 1 hour, obtains template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture；
(4) template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are placed in dilute hydrochloric acid solution
Reflux is boiled and is kept for 1 hour in (according to 37% concentrated hydrochloric acid: water=10:1 volume ratio is prepared), after filtering, then uses ethyl alcohol
It does not wash, it is then 5 hours dry in 60 DEG C, obtain the cobalt/nitrating porous carbon composite.
Cobalt provided in this embodiment/nitrating porous carbon composite amount containing cobalt is 0.44at%, and nitrogen content is
6.71at%, specific surface area 468m2/ g, average pore size 7.8nm, Kong Rongwei 1.58cm3/g.The cobalt/nitrating porous carbon is compound
Material is that have the nitrating porous graphene lamella of monatomic cobalt to stack by 5~20 layers of load, and the diameter of single layer lamella
For 400nm.
Cobalt/nitrating the porous carbon composite of the present embodiment or the mould of the present embodiment step (1)-(3) preparation is respectively adopted
Plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are as catalyst organosilan oxidation reaction
Method the following steps are included:
(1) catalyst and dimethylphenylsilaneand acetone solution in reaction flask and are stirred evenly；
(2) appropriate ultrapure water is added in the solution that step (1) obtains, reacts 1 hour, obtains at 25 DEG C and under stirring
To dimethyl phonyl silanol；
Wherein, when using cobalt/nitrating porous carbon composite as catalyst, dosage is dimethylphenylsilaneand quality
1%；When using template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst, dosage is diformazan
The 10% of base phenyl silane quality；The dosage of ultrapure water is the 160% of dimethylphenylsilaneand quality.
It analyzes to obtain using thin-layered chromatography: two kinds of catalyst reactions is respectively adopted after 1 hour, dimethylphenylsilaneand is equal
Reaction generates dimethyl phonyl silanol, the generation of no silicon ether by-product completely.
It proves after tested, using after 5 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 4
A kind of cobalt/nitrating porous carbon composite and preparation method thereof is present embodiments provided, as shown in Figure 1, specific packet
Include following steps:
(1) in deionized water by magnesium oxide powder dispersion, reflux is boiled and is kept for 24 hours, is filtered after cooling, then at
80 DEG C drying 12 hours, be subsequently placed in Muffle furnace and 850 DEG C of roastings be warming up to the rate of 10 DEG C/min in air atmosphere
30 minutes, obtain porous flake hexagon magnesia, specific surface area 190m2/ g, two-dimensional slice diameter size is about 200nm；
(2) at room temperature, 0.5g cobalt chloride and 2,2':6', 2 "-ter cycloheptapyridine of 1.5g are dissolved in a manner of stirring
In 30mL ethyl alcohol, the porous flake hexagon magnesia that 1.5g step (1) obtains is added, and then with 600 revs/min of revolving speed
Magnetic agitation 3 hours, then solvent rotation is evaporated, obtains a mixture；
(3) mixture is put into tube furnace and under protection of argon gas with the rate of 10 DEG C/min and is warming up to 900 DEG C
Calcining 4 hours, obtains template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture；
(4) template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are placed in dilute hydrochloric acid solution
Reflux is boiled and is kept for 1 hour in (according to 37% concentrated hydrochloric acid: water=10:1 volume ratio is prepared), after filtering, then uses ethyl alcohol
It does not wash, it is then 5 hours dry in 60 DEG C, obtain the cobalt/nitrating porous carbon composite.
Cobalt provided in this embodiment/nitrating porous carbon composite amount containing cobalt is 0.44at%, and nitrogen content is
6.71at%, specific surface area 468m2/ g, average pore size 7.8nm, Kong Rongwei 1.58cm3/g.The cobalt/nitrating porous carbon is compound
Material is that have the nitrating porous graphene lamella of monatomic cobalt to stack by 5~20 layers of load, and the diameter of single layer lamella
For 200nm.
Cobalt/nitrating the porous carbon composite of the present embodiment or the mould of the present embodiment step (1)-(3) preparation is respectively adopted
Plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are as catalyst organosilan oxidation reaction
Method the following steps are included:
(1) catalyst and dimethylphenylsilaneand acetone solution in reaction flask and are stirred evenly；
(2) appropriate ultrapure water is added in the solution that step (1) obtains, reacts 7 hours, obtains at 25 DEG C and under stirring
To dimethyl phonyl silanol；
Wherein, when using cobalt/nitrating porous carbon composite as catalyst, dosage is dimethylphenylsilaneand quality
4%；When using template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst, dosage is diformazan
The 10% of base phenyl silane quality；The dosage of ultrapure water is the 160% of dimethylphenylsilaneand quality.
It analyzes to obtain using thin-layered chromatography: two kinds of catalyst reactions is respectively adopted after 7 hours, dimethylphenylsilaneand is equal
Reaction generates dimethyl phonyl silanol, the generation of no silicon ether by-product completely.
It proves after tested, using after 5 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 5
A kind of cobalt/nitrating porous carbon composite and preparation method thereof is present embodiments provided, as shown in Figure 1, specific packet
Include following steps:
(1) in deionized water by magnesium oxide powder dispersion, reflux is boiled and is kept for 24 hours, is filtered after cooling, then at
100 DEG C drying 10 hours, be subsequently placed in Muffle furnace and 300 DEG C of roastings be warming up to the rate of 10 DEG C/min in air atmosphere
30 minutes, obtain porous flake hexagon magnesia, specific surface area 200m2/ g, two-dimensional slice diameter 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 a manner of stirring
In 30mL ethyl alcohol, the porous flake hexagon magnesia that 0.5g step (1) obtains is added, and then with 600 revs/min of turn
Then solvent rotation is evaporated, obtains a mixture by fast magnetic agitation 4 hours；
(3) mixture is put into tube furnace and under protection of argon gas with the rate of 10 DEG C/min and is warming up to 600 DEG C
Calcining 2 hours, obtains template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture；
(4) template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are placed in dilute hydrochloric acid solution
Reflux is boiled and is kept for 1 hour in (according to 37% concentrated hydrochloric acid: water=10:1 volume ratio is prepared), after filtering, then uses ethyl alcohol
It does not wash, it is then 5 hours dry in 60 DEG C, obtain the cobalt/nitrating porous carbon composite.
Cobalt provided in this embodiment/nitrating porous carbon composite amount containing cobalt is 0.44at%, and nitrogen content is
6.71at%, specific surface area 468m2/ g, average pore size 7.8nm, Kong Rongwei 1.58cm3/g.The cobalt/nitrating porous carbon is compound
Material is that have the nitrating porous graphene lamella of monatomic cobalt to stack by 5~20 layers of load, and the diameter of single layer lamella
For 300nm.
Cobalt/nitrating the porous carbon composite of the present embodiment or the mould of the present embodiment step (1)-(3) preparation is respectively adopted
Plate agent, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are as catalyst organosilan oxidation reaction
Method the following steps are included:
(1) catalyst and dimethylphenylsilaneand acetone solution in reaction flask and are stirred evenly；
(2) appropriate ultrapure water is added in the solution that step (1) obtains, reacts 3 hours, obtains at 25 DEG C and under stirring
To dimethyl phonyl silanol；
Wherein, when using cobalt/nitrating porous carbon composite as catalyst, dosage is dimethylphenylsilaneand quality
2.5%；When using template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture as catalyst, dosage two
The 25% of aminomethyl phenyl silane quality；The dosage of ultrapure water is the 132% of dimethylphenylsilaneand quality.
It analyzes to obtain using thin-layered chromatography: two kinds of catalyst reactions is respectively adopted after 3 hours, dimethylphenylsilaneand is equal
Reaction generates dimethyl phonyl silanol, the generation of no silicon ether by-product completely.
It proves after tested, using after 5 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Claims (16)
1. a kind of using cobalt/nitrating porous carbon composite or template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Method of the mixture as catalyst organosilan oxidation reaction, method includes the following steps:
By the cobalt/nitrating porous carbon composite or the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite
Mixture reacts under the action of oxidant as catalyst, with organosilan, obtains silanol；
Wherein, the cobalt/nitrating porous carbon composite is prepared by method comprising the following steps:
(1) cobalt salt, the nitrogenous organic ligand of cobalt and template are uniformly mixed in a solvent, then remove solvent, obtains one
Mixture；
(2) it calcines the mixture 0.5~4 hour at 600-1000 DEG C, it is more to obtain template, cobalt/cobalt oxide and cobalt/nitrating
The mixture of hole carbon composite；
(3) it is removed by the way of pickling in the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture
Template and cobalt/cobalt oxide, obtain the cobalt/nitrating porous carbon composite；
The template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are through the following steps that be prepared
:
(1) cobalt salt, the nitrogenous organic ligand of cobalt and template are uniformly mixed in a solvent, then remove solvent, obtains one
Mixture；
(2) calcine the mixture 0.5~4 hour at 600-1000 DEG C, obtain template, cobalt/cobalt oxide and the cobalt/
The mixture of nitrating porous carbon composite.
2. according to the method described in claim 1, wherein, the cobalt/nitrating porous carbon composite dosage is organosilan
The 1-5% of quality, the dosage of the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon composite mixture are organosilicon
The 10-40% of alkane quality.
3. according to the method described in claim 1, wherein, the oxidant includes one of oxygen gas and water, hydrogen peroxide and methanol
Or several combination.
4. according to the method described in claim 1, wherein, the reaction carries out in a solvent, the solvent include acetone,
The combination of one or more of ethyl acetate and tetrahydrofuran.
5. the reaction time is 1~8 hour according to the method described in claim 1, wherein, the reaction temperature is 20~30 DEG C.
6. according to the method described in claim 1, wherein, the cobalt/nitrating porous carbon composite amount containing cobalt is 0.2-
0.8at%, nitrogen content 4-10at%, specific surface area 400-900m2/ g, aperture 4-9nm, Kong Rongwei 0.5-4cm3/g；And
And the cobalt/nitrating porous carbon composite is to be loaded to have the nitrating porous graphene lamella of monatomic cobalt to stack by 5~20 layers
It forms, and the diameter of single layer lamella is 200~400nm.
7. according to the method described in claim 1, wherein, the template includes porous flake hexagon magnesia.
8. according to the method described in claim 7, wherein, the specific surface area of the porous flake hexagon magnesia is 100~
300m2/ g, two-dimensional slice diameter is having a size of 200~400nm.
9. according to the method described in claim 8, wherein, the porous flake hexagon magnesia is through the following steps that preparation
It obtains: magnesium oxide powder is boiled in water and kept for 8~24 hours, after drying by obtained solid, then 200~
900 DEG C roast 0.5~2 hour, obtain the porous flake hexagon magnesia.
10. according to the method described in claim 1, wherein, the cobalt salt includes one in cobalt nitrate, cobalt chloride and cobalt acetate
Kind or several combinations.
11. according to the method described in claim 1, wherein, the nitrogenous organic ligand of the cobalt include 2,2'- bipyridyl, pyridine,
Phenanthrolene, 2,2':6', the combination of one or more of 2 "-ter cycloheptapyridines, 2,6- bis- (2- benzimidazolyl) pyridine.
12. according to the method described in claim 1, wherein, the nitrogenous organic ligand of the cobalt salt, cobalt that are used in step (1) and
The ratio of template is mass ratio 1:1:1~1:3:3.
13. according to the method described in claim 1, wherein, the solvent in step (1) includes ethyl alcohol and/or acetone；
The side being uniformly mixed cobalt salt, the nitrogenous organic ligand of cobalt and template in a solvent using stirring in step (1)
Formula；
Calcining in step (2) carries out under inert gas protection；
In step (2), 600-1000 DEG C is warming up to the rate of 5-15 DEG C/min；
Pickling in step (3) is specifically includes the following steps: compound by the template, cobalt/cobalt oxide and cobalt/nitrating porous carbon
The mixture and acid-mixed of material are boiled and are kept for 1~2 hour after closing.
14. according to the method for claim 13, wherein in step (1), the stirring is magnetic agitation, and magnetic force
The revolving speed of stirring is 300~800r/min, and mixing time is 2~5 hours.
15. according to the method for claim 13, wherein in step (2), the inert gas includes argon gas.
16. according to the method for claim 13, wherein in step (3), the acid includes hydrochloric acid solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| Title |
|---|
| Template-Directed Synthesis of Pillared-Porous Carbon Nanosheet Architectures: High-Performance Electrode Materials for Supercapacitors;Zhuangjun Fan,et. al;《Adv. Energy Mater.》;20120206;第2卷(第4期);第419页右栏最后一段，第420页，第421页左栏第一段第421页、右栏第一段，423页左栏第4段、Supporting Information 图S2，S6 |
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