CN106238080B - The method of p-doped porous graphene and preparation method thereof and catalysis benzylamine oxidation - Google Patents
The method of p-doped porous graphene and preparation method thereof and catalysis benzylamine oxidation Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 128
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title abstract description 7
- 238000006555 catalytic reaction Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- WYSRMZBCJRNZKB-UHFFFAOYSA-N N-benzylidenebutanamide Chemical compound C(C1=CC=CC=C1)=NC(CCC)=O WYSRMZBCJRNZKB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 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 44
- 239000000395 magnesium oxide Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 230000005291 magnetic effect Effects 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims 3
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- -1 phosphorus organic compound Chemical class 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- MUEHGEQAMLEEID-UHFFFAOYSA-N 1-pentyl-2-phenylbenzene Chemical group CCCCCC1=CC=CC=C1C1=CC=CC=C1 MUEHGEQAMLEEID-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
- B01J27/14—Phosphorus; Compounds thereof
-
- 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
- B01J27/20—Carbon compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Carbon And Carbon Compounds (AREA)
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Abstract
The present invention provides the methods of a kind of p-doped porous graphene and preparation method thereof and catalysis benzylamine oxidation.The p-doped porous graphene is prepared by the following method to obtain: template is mixed with the dispersion liquid containing organic carbon, phosphorus source; remove the solvent in mixed liquor; by obtained mixture under inert gas protection, 200~700 DEG C calcine 2~5 hours; then template agent removing is removed by the way of pickling, obtains p-doped porous graphene.The method of catalysis benzylamine oxidation reacts under the action of oxidant with benzylamine the following steps are included: using the mixture of p-doped porous graphene of the invention or template and p-doped porous graphene as catalyst, obtains N- benzylidenebutyramide.The present invention controls pattern using template, and using carbon containing, phosphorus organic compound simultaneously as carbon source and phosphorus source, directly synthesize p-doped porous graphene in the method for roasting, have many advantages, such as it is quick, convenient, can one-step synthesis, easy be mass produced.
Description
Technical field
The present invention relates to a kind of p-doped porous graphenes and preparation method thereof and a kind of template and p-doped porous graphene
Mixture and it is a kind of using the mixture of the p-doped porous graphene or the template and p-doped porous graphene as urging
The method that agent is catalyzed benzylamine oxidation reaction, belongs to grapheme material technical field.
Background technique
N- benzylidenebutyramide chemical industry and in terms of have a wide range of applications, the synthesis of N- benzylidenebutyramide is usually
Oxidation based on benzylamine.But the oxidation process of benzylamine needs to match using the more difficult metal for separating and being recycled is organic at present
Object is closed as catalyst, and is also possible to need higher reaction temperature or uses the solvent toxic to environment.Therefore, development is high
The approach for imitating the synthesis N- benzylidenebutyramide of green is still very big challenge.
It is most in the synthesis of existing N- benzylidenebutyramide to use noble metal catalyst such as rhodium, ruthenium, iridium and palladium, it is expensive at
Originally it is unfavorable for its industrial application.Cheap transition-metal catalyst even non-metallic catalyst is developed to have a very big significance.
Since being found from graphene in 2004, just always by the universal blueness from physics and Material Field researcher
It looks at.Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in the flat film of honeycomb lattice.Although graphite
Only one carbon atomic layer thickness of alkene, and be one kind most thin in known materials, however but unusual rigid.Graphene
It is to be currently known the most outstanding material of electric conductivity.In addition, there are many more excellent performances for graphene: such as higher Young's modulus,
Thermal conductivity, huge specific surface area etc..Due to the property of graphene, it electronics, optics, magnetics, biomedicine,
Sensor, energy storage etc. are widely used.
In recent years, similar with graphene-structured to contain conjugation sp2The stratiform carbon material of carbon atom is also applied to be catalyzed
Process.On the one hand, they are good metallic carriers, and distinctive electronic structure is capable of the reactivity worth of Effective Regulation metal,
For example, graphite oxide has Fischer-Tropsch synthesis as the iron catalyst of carrier better compared to common active carbon
Catalytic activity, graphene support iron material and also show excellent catalytic performance to alcohol oxidation reaction；On the other hand, they can also
To participate in chemically reacting as catalyst, such as nitrobenzene reduction, benzene oxidatoin, oxidation of alcohols and carbon carbon coupling reaction.
However, π-π effect strong in graphene, so that being stacked mutually between graphene sheet layer, to reduce surface area
And active site.Studies have shown that doping is to change the effective way of graphene electronic structure and chemical property.Heteroatom is (such as
N, P, S, B etc.) graphene-doped lattice, band gap not only can be effectively introduced, but also the defect and local of graphene can be increased
Reactivity.
In addition, the research hotspot of graphene defect functionalization also focuses on the research aspect of porous graphene in recent years.It is more
Hole graphene refers to the carbon material on two-dimentional basal plane with nanoscale hole.It is excellent that porous graphene not only remains graphene
Property, and compare inert graphene surface, the presence in hole promotes the raising of matter transportation efficiency.Importantly,
The introducing in hole also effectively opens the band gap of graphene, promotes graphene in the application of every field.
Currently, containing, heteroatomic graphene mainly passes through chemical vapour deposition technique and prepared by ion implantation.But
It is that requirement of the above two method to equipment and technology is harsh, preparation cost is high, is unfavorable for large-scale production.And porous graphite
The preparation method of alkene mainly includes catalysis etching method, chemical vapour deposition technique, wet etching and carbothermic method.These porous stones
The preparation process of black alkene is relatively complicated, and the period is longer.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of p-doped porous graphene and its preparation sides
Method.The present invention prepares p-doped porous graphene using template and organic carbon, phosphorus source, have it is quick, convenient, can a step close
At, easily large-scale production the advantages that.
The object of the invention is also to provide the mixtures of a kind of template and p-doped porous graphene.
Another object of the present invention is to provide a kind of using above-mentioned p-doped porous graphene or above-mentioned template and p-doped
Method of the mixture of porous graphene as catalyst benzylamine oxidation reaction.
In order to achieve the above objectives, present invention firstly provides a kind of preparation methods of p-doped porous graphene comprising with
Lower step:
(1) template is uniformly mixed with the dispersion liquid containing organic carbon, phosphorus source, obtains a mixed liquor, then described in removal
Solvent in mixed liquor, obtains precursor mixture；
(2) precursor mixture is calcined 2~5 hours at 200~700 DEG C, obtains template and p-doped porous stone
The mixture of black alkene；
(3) template in the mixture of the template and p-doped porous graphene is removed by the way of pickling, is obtained
To the p-doped porous graphene.
In above-mentioned preparation method, it is preferable that the template includes porous flake hexagon magnesia.It is highly preferred that institute
The specific surface area for stating porous flake hexagon magnesia is 100~300m2/ g, two-dimensional slice diameter is having a size of 200~400nm.Into one
Preferably, the porous flake hexagon magnesia is through the following steps that be prepared: in water by magnesium oxide powder for step
It boils and is 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 organic carbon, phosphorus source include 2- dicyclohexyl phosphorus -2', 4', 6'- tri- different
The combination of one or more of the bis- diphenylphosphine -9,9- xanthphos of pentylbiphenyl, 4,5- and triphenylphosphine etc..
In the above preparation method, it is preferable that the dispersion liquid containing organic carbon, phosphorus source is by by organic carbon, phosphorus source
It is added in the solvent, and through obtained from ultrasonic disperse.Wherein, ultrasonic power is 50~100kHz, at ultrasonic disperse
The time of reason can be 10~30 minutes.It is described containing organic carbon, phosphorus source dispersion liquid in solvent may include ethyl alcohol and/or third
Ketone etc..The concentration of organic carbon, phosphorus source in above-mentioned dispersion liquid can be carried out conventional adjusting by those skilled in the art, generally may be used
Think 0.01~0.3g/mL.
In the above preparation method, it is preferable that the mass ratio of the template used in step (1) and organic carbon, phosphorus source for
10:1~1:10, the mass ratio are more preferably 1:1~1:4.
In the above preparation method, it is preferable that template in step (1) is mixed with the dispersion liquid containing organic carbon, phosphorus source
Conjunction carries out under magnetic stirring, and the revolving speed of magnetic agitation is 300~800r/min, and mixing time is 2~5 hours.
In the above preparation method, it is preferable that the solvent in the removal mixed liquor in step (1) can use drying
Mode, and dry temperature is 80~100 DEG C, and the time is 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), be warming up to 200~700 with the rate of 5-15 DEG C/min
℃。
In the above preparation method, it is preferable that the pickling in step (3) is specifically includes the following steps: by the template
It boils and is kept for 1~2 hour after being closed with the mixture and acid-mixed of p-doped porous graphene.Wherein, used acid may include
Hydrochloric acid solution etc..It can be filtered or filter later, wash, dry, to obtain final product.Wherein, washing can adopt
With ethyl alcohol or acetone etc., dry temperature can be 60~80 DEG C, and the time can be 2~5 hours.
In addition, the present invention also provides the p-doped that a kind of preparation method of above-mentioned p-doped porous graphene is prepared is porous
Graphene.
Specific embodiment according to the present invention, it is preferable that the p-doped porous graphene with a thickness of 1~5nm, two dimension
For piece diameter having a size of 200~400nm, phosphorus content is 1~2at%, and specific surface area is 1000~1800m2/ g, aperture are 3~5nm.
The present invention controls pattern using template, and using carbon containing, phosphorus organic compound simultaneously as carbon source and phosphorus source, with
P-doped porous graphene is prepared in the method for calcining.The preparation method of p-doped porous graphene provided by the invention mainly has
Following characteristics: (1) using the preparation approach entirely different with traditional preparation method, participates in without graphene or graphene oxide
Reaction, but carbon containing, phosphorus organic compound is used to be used as carbon source and phosphorus source, directly synthesis p-doped porous graphene simultaneously, more
To be quick, convenient, and can be with one-step synthesis；(2) have price low as template using porous flake hexagon magnesia
Honest and clean, the advantages that preparation process is simple, and the template has special porous flake hexagonal structure (specific surface area 100
~300m2/ g, diameter are 200~400nm), there is unique advantage compared with other templates；(3) raw material used is normal
Industrial chemicals, cost is relatively low, while the requirement to equipment and technology is lower, and it is more disposably to obtain p-doped by calcining
Hole graphene, it is easy to operate, it is easy to be mass produced；(4) lattice that can be effectively graphene-doped by P atom, and then effectively
Band gap is introduced, and P is former in the p-doped porous graphene for increasing the defect of graphene and the reactivity of local, and being prepared
Son is evenly distributed, and doping concentration is adjustable, so as to meet the application of graphene different field；(5) p-doped being prepared is more
Hole graphene has porous structure, has preferable self-supporting energy, while specific surface area with higher, and have and stablize
Physical and chemical performance and excellent service life.
In addition, being by following step the present invention also provides the mixture of a kind of template and p-doped porous graphene
Suddenly it is prepared:
(1) template is uniformly mixed with the dispersion liquid containing organic carbon, phosphorus source, obtains a mixed liquor, then described in removal
Solvent in mixed liquor, obtains precursor mixture；
(2) precursor mixture is calcined 2~5 hours at 200~700 DEG C, obtains the template and p-doped
The mixture of porous graphene.
In the mixture of above-mentioned template and p-doped porous graphene, 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.It is further preferred that the porous flake hexagon magnesia is through the following steps that be prepared into
To: magnesium oxide powder is boiled in water and is kept for 8~24 hours, it (can be at 80~100 DEG C through drying by obtained solid
It is 5~12 hours dry) after, then (roasting can carry out in air atmosphere, heating within 0.5~2 hour in 200~900 DEG C of roastings
Rate can be 5~15 DEG C/min), obtain the porous flake hexagon magnesia.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that the organic carbon, phosphorus source include 2- bis-
Cyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl, the bis- diphenylphosphine -9,9- xanthphos of 4,5- and triphenylphosphine etc.
One or more of combination.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that the dispersion containing organic carbon, phosphorus source
Liquid is by the way that organic carbon, phosphorus source to be added in the solvent, and through obtained from ultrasonic disperse.Wherein, ultrasonic power is
50~100kHz, the time of ultrasonic disperse processing can be 10~30 minutes.It is described containing organic carbon, phosphorus source dispersion liquid in it is molten
Agent may include ethyl alcohol and/or acetone etc..The concentration of organic carbon, phosphorus source in above-mentioned dispersion liquid can be by those skilled in the art
Conventional adjusting is carried out, generally can be 0.01~0.3g/mL.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that the template used in step (1) with
Organic carbon, phosphorus source mass ratio be 10:1~1:10, which is more preferably 1:1~1:4.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that template in step (1) with contain
The mixing of dispersion liquid of machine carbon, phosphorus source carries out under magnetic stirring, and the revolving speed of magnetic agitation is 300~800r/
Min, mixing time are 2~5 hours.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that the removal mixed liquor in step (1)
In solvent can be by the way of dry, and dry temperature is 80~100 DEG C, and the time is 10~12 hours.
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that the calcining in step (2) is in inertia
It is carried out under gas shield, it is highly preferred that the inert gas includes argon gas etc..
In the mixture of above-mentioned template and p-doped porous graphene, it is preferable that in step (2), with 5-15 DEG C/
The rate of min is warming up to 200~700 DEG C.
On the other hand, it is more using above-mentioned p-doped porous graphene or above-mentioned template and p-doped that the present invention also provides a kind of
Method of the mixture of hole graphene as catalyst benzylamine oxidation reaction, method includes the following steps:
Using the mixture of above-mentioned p-doped porous graphene or above-mentioned template and p-doped porous graphene as catalyst, with
Benzylamine reacts under the action of oxidant, obtains N- benzylidenebutyramide.
In the above-mentioned methods, it is preferable that the dosage of the p-doped porous graphene is the 8~12% of benzylamine quality, described
The dosage of p-doped porous graphene is the 8~12% of benzylamine quality in the mixture of template and p-doped porous graphene.
In the above-mentioned methods, it is preferable that the oxidant includes oxygen and/or hydrogen peroxide etc..
In the above-mentioned methods, it is preferable that reaction temperature is 80~100 DEG C, and the reaction time is 10~12 hours.
For the present invention using p-doped porous graphene as catalyst benzylamine oxidation reaction, which is to belong to no gold
Metal catalyst, and non-metal catalyst meets the requirement of Green Chemistry, it is pollution-free, environmentally friendly, stability is good, repeatable
It utilizes, recycles activity preferably.It is provided by the invention using the mixed of p-doped porous graphene or template and p-doped porous graphene
Closing the method that object is aoxidized as catalyst benzylamine can carry out in the absence of solvent, p-doped porous graphene or template
The mixture of agent and p-doped porous graphene is used as heterogeneous catalyst in benzylamine oxidation reaction, and the processing of solvent is omitted, this
It is the another factor to reduce environmental pollution.The combination of non-metal catalyst and solvent-free catalysis that the present invention uses is to industrial production
It makes great sense.
Detailed description of the invention
Fig. 1 is the preparation method flow chart for the p-doped porous graphene that embodiment 1-3 is provided.
Fig. 2 is the scanning electron microscope (SEM) photograph for the p-doped porous graphene that embodiment 1 provides.
Fig. 3 is the transmission electron microscope picture for the p-doped porous graphene that embodiment 1 provides.
Fig. 4 is the N for the p-doped porous graphene that embodiment 1 provides2Adsorption/desorption curve.
Fig. 5 is the Raman curve for the p-doped porous graphene that embodiment 1 provides.
Fig. 6 is the x-ray photoelectron spectroscopy figure for the p-doped porous graphene that embodiment 1 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 p-doped porous graphene is present embodiments provided, through the following steps that be prepared, such as Fig. 1 institute
Show:
(1) magnesium oxide powder is flowed back in water and boils and is kept for 8 hours, it is 12 hours dry in 80 DEG C after cooling, suction filtration,
It is placed in Muffle furnace again and is warming up to 500 DEG C in air atmosphere with the rate of 10 DEG C/min and roasted 2 hours, obtain porous flake
Hexagon magnesia, specific surface area 195m2/ g, two-dimensional slice diameter size is about 300nm；
(2) by 0.5g 4, bis- diphenylphosphine -9, the 9- xanthphos of 5- are added in 30mL ethyl alcohol, ultrasonic disperse 0.5
Hour, and the power of ultrasound is 80kHz, obtains the dispersion liquid containing organic carbon, phosphorus source；
(3) by the porous flake hexagon magnesia that 0.5g step (1) obtains be added to that step (2) obtains containing organic
Carbon, phosphorus source dispersion liquid in, with revolving speed magnetic agitation 2 hours of 600r/min, a mixed liquor is obtained, then by the mixed liquor
It is 12 hours dry in 80 DEG C, obtain precursor mixture；
(4) precursor mixture is placed in quartz boat, and with 10 DEG C/min in tube furnace under protection of argon gas
Rate be warming up to 700 DEG C calcine 2 hours, after dropping to room temperature, obtain the mixture of template Yu p-doped porous graphene；
(5) by the mixture of the template and p-doped porous graphene be placed in dilute hydrochloric acid solution (according to 37% concentrated hydrochloric acid:
Water=10:1 volume ratio prepare) in reflux boil and kept for 1 hour, obtain black powder after filtering, washed later with ethyl alcohol
It washs, it is 5 hours dry then at 60 DEG C, obtain the p-doped porous graphene.
Fig. 2 is the scanning electron microscope (SEM) photograph of p-doped porous graphene provided in this embodiment, as can see from Figure 2 apparent piece
Shape hexagonal structure, two-dimensional slice diameter size substantially 300nm.Fig. 3 is the transmission of p-doped porous graphene provided in this embodiment
Electron microscope still can see sheet hexagonal structure from Fig. 3, and be observed that the presence for having a large amount of neat arrangement holes, and
There are many folds.Fig. 4 is p-doped porous graphene provided in this embodiment in subzero 200 DEG C of N2Adsorption/desorption curve, can
To obtain the specific surface area (SSA) of the p-doped porous graphene for 1546m2/ g, and can be seen that there is a large amount of mesoporous presence.Figure
5 be the Raman curve of p-doped porous graphene provided in this embodiment, as can see from Figure 5 the apparent peak D and the peak G, it was demonstrated that
Product is graphene, and defect and degree of graphitization are preferable.Fig. 6 is the XPS of p-doped porous graphene provided by the embodiment
Spectrogram can obviously observe the peak of C, O, P element, it can be deduced that phosphorus content 1.8at% from Fig. 6.
The thickness of p-doped porous graphene manufactured in the present embodiment is about 4nm, and two-dimensional slice diameter size is about 300nm, phosphorous
Amount is 1.8at%, specific surface area 1546m2/ g, average pore size 3.8nm.
The template prepared using p-doped porous graphene manufactured in the present embodiment and the present embodiment step (1)-(4) with
The mixture of p-doped porous graphene respectively as catalyst benzylamine oxidation reaction method the following steps are included:
(1) a certain amount of catalyst is placed in microscale reactor；
(2) then, a certain amount of benzylamine is added in the reactor, and is inserted into oxygen bag in the reactor
(1atm)；
(3) make the reactor be warming up to 90 DEG C to react 12 hours, obtain N- benzylidenebutyramide；
Wherein, the dosage of the p-doped porous graphene is the 10% of benzylamine quality, the template and p-doped porous stone
The dosage of p-doped porous graphene is the 10% of benzylamine quality in the mixture of black alkene.
It analyzes to obtain using thin-layered chromatography and there was only product point using two kinds of catalyst respectively, produced using filtration method
Object is simultaneously concentrated, and the yield for using two kinds of catalyst manufactured in the present embodiment to be catalyzed benzylamine oxidation reaction respectively is calculated and is
98%.
It proves after tested, using after 8 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 2
A kind of p-doped porous graphene is present embodiments provided, through the following steps that be prepared, such as Fig. 1 institute
Show:
(1) magnesium oxide powder is flowed back in water and boils and is kept for 8 hours, it is 10 hours dry in 90 DEG C after cooling, suction filtration,
It is placed in Muffle furnace again and is warming up to 800 DEG C in air atmosphere with the rate of 10 DEG C/min and roasted 2 hours, obtain porous flake
Hexagon magnesia, specific surface area 197m2/ g, two-dimensional slice diameter size is about 300nm；
(2) 1g 2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl is added in 30mL ethyl alcohol, ultrasonic disperse
0.5 hour, and the power of ultrasound is 80kHz, obtains the dispersion liquid containing organic carbon, phosphorus source；
(3) by the porous flake hexagon magnesia that 0.5g step (1) obtains be added to that step (2) obtains containing organic
Carbon, phosphorus source dispersion liquid in, with revolving speed magnetic agitation 2 hours of 700r/min, a mixed liquor is obtained, then by the mixed liquor
It is 12 hours dry in 80 DEG C, obtain precursor mixture；
(4) precursor mixture is placed in quartz boat, and with 10 DEG C/min in tube furnace under protection of argon gas
Rate be warming up to 600 DEG C calcine 3 hours, after dropping to room temperature, obtain the mixture of template Yu p-doped porous graphene；
(5) by the mixture of the template and p-doped porous graphene be placed in dilute hydrochloric acid solution (according to 37% concentrated hydrochloric acid:
Water=10:1 volume ratio prepare) in reflux boil and kept for 1 hour, obtain black powder after filtering, washed later with ethyl alcohol
It washs, it is 5 hours dry then at 60 DEG C, obtain the p-doped porous graphene.
The thickness of p-doped porous graphene manufactured in the present embodiment is about 4nm, and two-dimensional slice diameter size is about 300nm, phosphorous
Amount is 1.6at%, specific surface area 1687m2/ g, average pore size 3.4nm.
The template prepared using p-doped porous graphene manufactured in the present embodiment and the present embodiment step (1)-(4) with
The mixture of p-doped porous graphene respectively as catalyst benzylamine oxidation reaction method the following steps are included:
(1) a certain amount of catalyst is placed in microscale reactor；
(2) then, a certain amount of benzylamine is added in the reactor, and is inserted into oxygen bag in the reactor
(1atm)；
(3) make the reactor be warming up to 90 DEG C to react 12 hours, obtain N- benzylidenebutyramide；
Wherein, the dosage of the p-doped porous graphene is the 10% of benzylamine quality, the template and p-doped porous stone
The dosage of p-doped porous graphene is the 10% of benzylamine quality in the mixture of black alkene.
It analyzes to obtain using thin-layered chromatography and there was only product point using two kinds of catalyst respectively, produced using filtration method
Object is simultaneously concentrated, and the yield for using two kinds of catalyst manufactured in the present embodiment to be catalyzed benzylamine oxidation reaction respectively is calculated and is
94%.
It proves after tested, using after 9 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Embodiment 3
A kind of p-doped porous graphene is present embodiments provided, through the following steps that be prepared, such as Fig. 1 institute
Show:
(1) magnesium oxide powder is flowed back in water and boils and is kept for 10 hours, it is small in 80 DEG C of dryings 10 after cooling, suction filtration
When, then be placed in Muffle furnace and be warming up to 300 DEG C in air atmosphere with the rate of 10 DEG C/min and roast 2 hours, it obtains porous
Sheet hexagon magnesia, specific surface area 190m2/ g, two-dimensional slice diameter size is about 200nm；
(2) 2g triphenyl phosphorus is added in 30mL ethyl alcohol, ultrasonic disperse 0.5 hour, and the power of ultrasound is
80kHz obtains the dispersion liquid containing organic carbon, phosphorus source；
(3) by the porous flake hexagon magnesia that 0.5g step (1) obtains be added to that step (2) obtains containing organic
Carbon, phosphorus source dispersion liquid in, with revolving speed magnetic agitation 3 hours of 500r/min, a mixed liquor is obtained, then by the mixed liquor
It is 10 hours dry in 90 DEG C, obtain precursor mixture；
(4) precursor mixture is placed in quartz boat, and with 10 DEG C/min in tube furnace under protection of argon gas
Rate be warming up to 500 DEG C calcine 3 hours, after dropping to room temperature, obtain the mixture of template Yu p-doped porous graphene；
(5) by the mixture of the template and p-doped porous graphene be placed in dilute hydrochloric acid solution (according to 37% concentrated hydrochloric acid:
Water=10:1 volume ratio prepare) in reflux boil and kept for 1 hour, obtain black powder after filtering, washed later with ethyl alcohol
It washs, it is 5 hours dry then at 60 DEG C, obtain the p-doped porous graphene.
The thickness of p-doped porous graphene manufactured in the present embodiment is about 4nm, and two-dimensional slice diameter size is about 200nm, phosphorous
Amount is 1.9at%, specific surface area 1325m2/ g, average pore size 3.9nm.
The template prepared using p-doped porous graphene manufactured in the present embodiment and the present embodiment step (1)-(4) with
The mixture of p-doped porous graphene respectively as catalyst benzylamine oxidation reaction method the following steps are included:
(1) a certain amount of catalyst is placed in microscale reactor；
(2) then, a certain amount of benzylamine is added in the reactor, and is inserted into oxygen bag in the reactor
(1atm)；
(3) make the reactor be warming up to 90 DEG C to react 12 hours, obtain N- benzylidenebutyramide；
Wherein, the dosage of the p-doped porous graphene is the 10% of benzylamine quality, the template and p-doped porous stone
The dosage of p-doped porous graphene is the 10% of benzylamine quality in the mixture of black alkene.
It analyzes to obtain using thin-layered chromatography and there was only product point using two kinds of catalyst respectively, produced using filtration method
Object is simultaneously concentrated, and the yield for using two kinds of catalyst manufactured in the present embodiment to be catalyzed benzylamine oxidation reaction respectively is calculated and is
97%.
It proves after tested, using after 7 times, catalytic activity nothing is substantially reduced two kinds of catalyst circulations.
Claims (16)
1. it is a kind of using the mixture of p-doped porous graphene or template and p-doped porous graphene as catalyst benzyl
The method of amine oxidation reaction, method includes the following steps:
Using the mixture of the p-doped porous graphene or the template and p-doped porous graphene as catalyst, with benzylamine
It is reacted under the action of oxidant, obtains N- benzylidenebutyramide；
Wherein, the mixture of the p-doped porous graphene and the template and p-doped porous graphene is according to following step
Suddenly it prepares:
(1) template is uniformly mixed with the dispersion liquid of the phosphorus source containing organic carbon, obtains a mixed liquor, then removes the mixed liquor
In solvent, obtain precursor mixture；
(2) precursor mixture is calcined 2~5 hours at 200~700 DEG C, obtains the template and p-doped porous stone
The mixture of black alkene；
(3) template in the mixture of the template and p-doped porous graphene is removed by the way of pickling, obtains institute
The p-doped porous graphene stated.
2. according to the method described in claim 1, wherein, the template includes porous flake hexagon magnesia.
3. according to the method described in claim 2, 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.
4. according to the method described in claim 3, 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.
5. according to the method described in claim 1, wherein, the organic carbon phosphorus source includes 2- dicyclohexyl phosphorus -2', 4', 6'- tri-
The combination of one or more of the bis- diphenylphosphine -9,9- xanthphos of isopropyl biphenyl, 4,5- and triphenylphosphine.
6. according to the method described in claim 1, wherein, the mass ratio of the template and organic carbon phosphorus source that are used in step (1)
For 10:1~1:10.
7. according to the method described in claim 1, wherein, the dispersion liquid of the phosphorus source containing organic carbon is by by organic carbon phosphorus source
It is added in solvent, and through obtained from ultrasonic disperse.
8. according to the method described in claim 1, wherein, ultrasonic power is 50~100kHz, the time of ultrasonic disperse processing
It is 10~30 minutes, the solvent in the dispersion liquid of the phosphorus source containing organic carbon includes ethyl alcohol and/or acetone.
9. according to the method described in claim 1, wherein, the dispersion liquid of the template in step (1) and the phosphorus source containing organic carbon
Mixing carries out under magnetic stirring, and the revolving speed of magnetic agitation is 300~800r/min, and mixing time is 2~5 small
When.
10. according to the method described in claim 1, wherein, the calcining in step (2) carries out under inert gas protection.
11. according to the method described in claim 10, wherein, the inert gas includes argon gas.
12. according to the method described in claim 1, wherein, in step (2), 200 are warming up to the rate of 5-15 DEG C/min~
700℃。
13. according to the method described in claim 1, wherein, the pickling in step (3) is specifically includes the following steps: by the mould
The mixture and acid-mixed of plate agent and p-doped porous graphene are boiled and are kept for 1~2 hour after closing.
14. according to the method for claim 13, wherein used acid includes hydrochloric acid solution.
15. according to the method described in claim 1, wherein, the p-doped porous graphene with a thickness of 1~5nm, two-dimensional slice diameter
Having a size of 200~400nm, phosphorus content is 1~2at%, and specific surface area is 1000~1800m2/ g, aperture are 3~5nm.
16. according to the method described in claim 1, wherein, the dosage of the p-doped porous graphene be benzylamine quality 8~
12%, in the mixture of the template and p-doped porous graphene the dosage of p-doped porous graphene be benzylamine quality 8~
12%；
The oxidant includes oxygen and/or hydrogen peroxide；
Reaction temperature is 80~100 DEG C, and the reaction time is 10~12 hours.
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| EP3085665A1 (en) * | 2014-01-17 | 2016-10-26 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Large-scale preparation method for graphene quantum dots |
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| CN104192819A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Clubbed phosphor-doped mesoporous carbon as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Phosphorus-Doped Ordered Mesoporous Carbons with Different Lengths as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media";Dae-Soo Yang，et al.;《J. Am. Chem. Soc.》;20120911;第134卷(第39期);第16127-16130页，Supporting Information S1-S11 |
| "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419-424页，Supporting Information S1-S9 |
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