CN106000441A - Cyclodextrin-based aza-ordered mesoporous carbon preparation method and application - Google Patents
Cyclodextrin-based aza-ordered mesoporous carbon preparation method and application Download PDFInfo
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- CN106000441A CN106000441A CN201610409864.8A CN201610409864A CN106000441A CN 106000441 A CN106000441 A CN 106000441A CN 201610409864 A CN201610409864 A CN 201610409864A CN 106000441 A CN106000441 A CN 106000441A
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- cyclodextrin
- ethylbenzene
- black solid
- benzylalcohol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 32
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 96
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 93
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 16
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 229910052799 carbon Inorganic materials 0.000 claims description 81
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229960004217 benzyl alcohol Drugs 0.000 claims description 30
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 29
- 239000003575 carbonaceous material Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 14
- 235000011149 sulphuric acid Nutrition 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical group NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002024 ethyl acetate extract Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000013335 mesoporous material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000001116 FEMA 4028 Substances 0.000 abstract 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract 2
- 229960004853 betadex Drugs 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000004321 preservation Methods 0.000 abstract 2
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 abstract 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 51
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 14
- 239000004927 clay Substances 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- -1 cyanogen Amine Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 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
- B01J27/24—Nitrogen 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
- B01J35/617—500-1000 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
- B01J35/61—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
A cyclodextrin-based aza-ordered mesoporous carbon preparation method comprises the following steps that 1, beta-cyclodextrin and a nitrogen source are added into a sulfuric acid solution, and stirred under room temperature; 2, a template agent is added and stirred to be uniform, and two-time heating and heat preservation are performed to obtain a black solid a; 3, beta-cyclodextrin and a nitrogen source are added into a sulfuric acid solution and stirred to be uniform, then, the black solid a is added, the heating and heat preservation process is repeatedly executed, and a black solid b is obtained; 4, the black solid b is roasted in the nitrogen atmosphere, then, a HF acid or NaOH water solution is used for removing the template agent, filtering is performed, a filter cake is dried, and nitrogen-doped ordered mesoporous carbon is obtained. The method has the advantages that the raw materials are cheap and easy to obtain, the specific area of the obtained nitrogen-doped ordered mesoporous material is large, the morphology is in order, the aperture is large, the nitrogen-doped ordered mesoporous carbon can be used as a non-metal catalyst for selective oxidation of ethylbenzene and benzyl alcohol, the ethylbenzene conversion rate can reach 98.7%, and the benzyl alcohol can also reach 88.9%.
Description
Technical field
The present invention relates to azepine ordered mesoporous material prepare, a kind of azepine based on cyclodextrin is order mesoporous
The preparation method and application of carbon.
Technical background
Ordered mesopore carbon because have big specific surface area, controlled pore size and good electric conductivity,
Hydrothermal stability and resistance to acids and bases, the always emphasis of people's research and development.Its energy storage, adsorbing separation,
The application in the fields such as catalysis and electrochemistry emerges in an endless stream especially, sees: Zhang P.-F.；Yuan J.-Y.；Fellinger
T.-P.；Antonietti M.；LiH.-R.；Wang Y.；Angew.Chem.Int.Ed.,2013,52,6028-6032.
Qu Y.-H.；Zhang Z.-A.；Zhang X.-H.；Ren G.-D.；Lai Y.-Q.；Liu Y.-X.；Li J.；Carbon,
2015,84,399-408.Alsbaiee A.；Smith B.-J.；Xiao L.-L.；Ling Y.-H.；Helbling D.-E.；
Dichtel W.-R.；Nature,2016,529,190-194.Xia K.-S.；Gao Q.-M.；Wu C.-D.；Song
S.-Q.；Ruan M.-L.；Carbon,2007,45,1989-1996.In research, it has been found that mixing of hetero atom nitrogen
The miscellaneous hydrophilic that can improve material with carbon element, the most also gives the beyond thought attribute of some of.Li Yueming etc. are by nitrogen
The ordered mesopore carbon of doping is as anode material for sodium-ion battery, and they find that the doping of nitrogen can substantially carry
The energy storage of high battery and charging and discharging capabilities, see: LiY.-M.；Wang Z.-G.；LiL.-L.；Peng S.-J.；
Zhang L.；Srinivasan M.；Ramakrishna S.；Carbon,2016,99,556-563；Zhao Dongyuan pair cyanogen
Amine is nitrogen source, is that carbon source is prepared for N doping ordered mesopore carbon with phenolic resin, and this material has good energy storage
Ability, can serve as ultracapacitor, sees: Shi Q.；Zhang R.-Y.；Lv Y.-Y.；Deng Y.-H.；
Elzatahrya A.-A.；Zhao D.-Y.；Carbon,2015,84,335-346；Additionally, Ma Jiantai etc. are by palladium nanometer
Particle load is on N doping ordered mesopore carbon, and they find the dispersion doped with beneficially palladium ion of nitrogen, and then
Improve its catalysis activity, it is possible to be effectively catalyzed the hydrogenation-dechlorination reaction of chlorophenol, see: Zhang W.；Wang
F.-S.；LiX.-L.；Liu Y.-S.；Ma J.-T.；Rsc Adv.,2016,6,27313-27319；Wang Yong etc. are prepared for
The nitrogen-doped carbon material of load ferric oxide is for the cell reaction of water, and they find the phase of avtive spot and carrier
Interaction is the key factor that material has high electrolysis ability, sees: Su D.-F.；Wang J.；Jin H.-Y.；
Gong Y.-T.；LiM.-M.；Pang Z.-F.；J.Mater.Chem.A,2015,3,11756-11761.At present,
Nitrogen-doped carbon material is used for correlated response as carrier the most of common occurrence, and as a kind of non-metal catalyst
Directly very the fewest several of the report of catalytic chemistry reaction.Therefore, structure can directly be catalyzed the nitrogen of organic reaction
Doping ordered mesoporous carbon material still has the biggest challenge.
For the selective oxidation of ethylbenzene, it is immobilized to silicon dioxide and three that ferrocene is passed through covalent bond by Fierro etc.
The surface of aluminum oxide hybridization material, it is raw that this catalyst can effectively be catalyzed ethylbenzene under tert-butyl alcohol hydrogen peroxide effect
Become 1-Phenylethanone., see: Habibi D.；Faraji A.-R.；Arshadi M.；Fierro J.-L.-G.；J.Mol.Catal.
A-Chem.,2013,372,90-99；Yasutaka et al. uses HP and cobaltous acetate also
Achieve the selective oxidation of ethylbenzene, see: Yoshiki N.；Satoshi S.；Yasutaka I.；J.Org.Chem.,
2002,67,5663-5668.And for the oxidation reaction of benzylalcohol, Tatsuya et al. is prepared for load gold nano bunch
Polymeric material, can effectively be catalyzed benzylalcohol oxidation generate benzoic acid, see: Hironori T,；Hidehiro
S.；Yuichi N.；Tatsuya T.；J.Am.Chem.Soc.,2005,127,9374-9375；Additionally, palladium support type
Catalyst and gold-palladium bimetallic catalyst also can be catalyzed benzylalcohol oxidation and generate benzoic acid, sees: SavaraA.；
Chan-Thaw C.-E.；Rossetti I.；Villa A.；Prati L.；ChemCatChem,2015,6,3464-3473.
HouW.-B.；Dehm N.-A.；Scott R.-W.-J.；J.Catal.,2008,253,22-27.As can be seen here, ethylbenzene
There is metal to participate in the selective oxidation of benzylalcohol more, and be directly realized by ethylbenzene and benzylalcohol with the orderly material with carbon element of N doping
Selective oxidation there is the strongest novelty undoubtedly.The selective oxidation of ethylbenzene and benzylalcohol is as follows:
Summary of the invention
It is an object of the invention to for above-mentioned technical Analysis and existing problems, it is provided that a kind of raw material is easy to get, specific surface
Long-pending big, pore-size distribution rationally and can be used for the preparation of N doping ordered mesopore carbon of ethylbenzene and benzylalcohol selective oxidation
Method, this preparation method cheaper starting materials is easy to get, big (> 900 of the azepine ordered mesoporous carbon material specific surface area prepared
m2/ g), pattern is regular, the relatively big (> 3nm in aperture), pore passage structure is adjustable and can be as a kind of without metal
Catalyst is used for ethylbenzene and the selective oxidation of benzylalcohol.
Technical scheme:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) beta-schardinger dextrin-and nitrogen source 2-10:1 in mass ratio are separately added into the sulphuric acid that concentration is 2.7wt% molten
In liquid, it is stirred at room temperature, obtains mixed liquor；
2) adding mass percent in above-mentioned mixed liquor in terms of cyclodextrin and nitrogen source gross mass is the template of 80%
Agent, after stirring, is warming up to 80-110 DEG C, keeps 5-10h, then heats to 140-180 DEG C, keeps
5-10h, obtains black solid a；
3) beta-schardinger dextrin-and nitrogen source 2-10:1 in mass ratio are separately added into the sulphuric acid that concentration is 1.8wt% molten
In liquid, after stirring, add above-mentioned black solid a, and repeat above-mentioned intensification, insulating process, obtain black
Color solid b；
4) by above-mentioned black solid b roasting in nitrogen atmosphere, roasting process for rise to 600 DEG C with 1 DEG C/min,
Keep 3h, then rise to 900 DEG C with 5 DEG C/min, keep 2h, then with HF acid or the 1-5mol/L of 5wt%
NaOH aqueous solution remove template, after filtration, by filter cake in 50-100 DEG C be dried, obtaining N doping has
Sequence mesoporous carbon.
Described nitrogen source is Guanidine Sulfamate 99, tripolycyanamide or dicyandiamide.
Described template is SBA or MCM series silicon materials.
The application of a kind of azepine ordered mesopore carbon based on cyclodextrin prepared, uses as a kind of non-metal catalyst
In ethylbenzene and the selective oxidation of benzylalcohol, method is:
1), after oxidant and ethylbenzene 1-5:1 in molar ratio being mixed, it is separately added in water or organic solvent, water
Or the volume ratio of organic solvent and ethylbenzene is 32.8:1, it is subsequently adding the material with carbon element of ethylbenzene 5-20wt%, carbon material
The 5-20wt% that addition is ethylbenzene of material, 60-100 DEG C of reaction 24h, filter, and filtrate carries by ethyl acetate
Taking, extracting solution gas chromatogram is analyzed；
2), after oxidant and benzylalcohol 1-5:1 in molar ratio being mixed, it is separately added in water or organic solvent, water
Or volume ratio 105.3:1 of organic solvent and benzylalcohol, it is subsequently adding the material with carbon element of benzylalcohol 5-25wt%, 100-150
DEG C reaction 24h, filter, filtrate with ethyl acetate extract, extracting solution gas chromatogram is analyzed；
Described oxidant is tert-butyl hydroperoxide or hydrogen peroxide；Organic solvent be methanol, ethanol, isopropanol or
N-propane.
The invention have the advantage that
This preparation method cheaper starting materials is easy to get, the big (> 900m of the azepine ordered mesoporous material specific surface area prepared2/ g),
Pattern is regular, the relatively big (> 3nm in aperture), pore passage structure is adjustable and can use as a kind of non-metal catalyst
In ethylbenzene and the selective oxidation of benzylalcohol, the conversion ratio of ethylbenzene can reach 98.7%, and the selectivity of 1-Phenylethanone. is
88.7%, benzylalcohol conversion ratio can also reach 88.9%, and benzoic selectivity is 84.5%.
Accompanying drawing explanation
Fig. 1 is ordered mesopore carbon (a) and the TEM figure of N doping ordered mesopore carbon (b) of embodiment 1 preparation.
Fig. 2 is ordered mesopore carbon and the XRD of N doping ordered mesopore carbon of embodiment 1 preparation.
Fig. 3 is ordered mesopore carbon and the BET figure of N doping ordered mesopore carbon of embodiment 1 preparation.
Fig. 4 is ordered mesopore carbon and the graph of pore diameter distribution of N doping ordered mesopore carbon of embodiment 1 preparation.
Specific embodiments
Below in conjunction with specific embodiment, the invention will be further described, and following example are illustrative, and
It not determinate, it is impossible to limit protection scope of the present invention with this.
Embodiment 1:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) sulphuric acid that 1.14g beta-schardinger dextrin-and 0.57g tripolycyanamide are separately added into 5mL 2.7wt% is molten
In liquid, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-11, after stirring, be warming up to 110 DEG C, keep 5
H, then heats to 180 DEG C, keeps 5h to obtain black solid a；
3) sulphuric acid that 0.73g beta-schardinger dextrin-and 0.37g Guanidine Sulfamate 99 are separately added into 5mL 1.8wt% is molten
In liquid, after stirring, add above-mentioned black solid a, be warming up to 110 DEG C, keep 5h, then heat up
To 180 DEG C, 5h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution of 10mL 5mol/L, backflow 2h removes template, filters, and filter cake is dried in 50 DEG C
24h can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) 0.28g 30wt% hydrogen peroxide (2.5mmol) and 0.0531g ethylbenzene (0.5mmol) are added respectively
Enter in 2mL ethanol, add 10.6mg ordered mesoporous carbon material, react 24h in 100 DEG C, turning of ethylbenzene
Rate is 86.5%, and the selectivity of 1-Phenylethanone. is 75.2%.
2) 0.10g 30wt% hydrogen peroxide (0.9mmol) and 0.02g benzylalcohol (0.18mmol) are added respectively
Enter in 2mL ethanol, add 5mg ordered mesoporous carbon material, 150 DEG C of reaction 24h, the conversion ratio of benzylalcohol
Being 75.7%, benzoic selectivity is 70.2%.
Fig. 1 is ordered mesopore carbon (a) and the TEM figure of N doping ordered mesopore carbon (b) of preparation.Figure shows:
Both materials broadly fall into orderly mesoporous material.
Fig. 2 is ordered mesopore carbon and the XRD of N doping ordered mesopore carbon of preparation.Figure shows: both
Material all has diffraction maximum in (100) face, has orderly pore passage structure.
Fig. 3 is ordered mesopore carbon and the BET figure of N doping ordered mesopore carbon of preparation.Figure shows: these are two years old
The BET curve planting material all has back stagnant ring, belongs to mesoporous material
Fig. 4 is ordered mesopore carbon and the graph of pore diameter distribution of N doping ordered mesopore carbon of preparation.Figure shows: this
The average pore size of bi-material all about 3.5, belongs to mesoporous material.
Embodiment 2:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.14g beta-schardinger dextrin-and 0.11g Guanidine Sulfamate 99 are separately added into the sulphuric acid of 5mL 2.7wt%
In solution, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) sulphuric acid that 0.73g beta-schardinger dextrin-and 0.07g Guanidine Sulfamate 99 are separately added into 5mL 1.8wt% is molten
In liquid, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat up
To 160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried in 60 DEG C
12h can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, react 24h in 80 DEG C, ethylbenzene
Conversion ratio is 98.7%, and the selectivity of 1-Phenylethanone. is 88.7%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, turning of benzylalcohol
Rate is 88.9%, and benzoic selectivity is 84.5%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 3:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.14g beta-schardinger dextrin-and 0.11g dicyandiamide are separately added into the sulfuric acid solution of 5mL 2.7wt%
In, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g MCM-48, after stirring, be warming up to 80 DEG C, keep
10h, then heats to 140 DEG C, keeps 10h to obtain black solid a；
3) 0.73g beta-schardinger dextrin-and 0.07g dicyandiamide are separately added in the sulfuric acid solution of 5mL 1.8wt%,
After stirring, add above-mentioned black solid a, be warming up to 80 DEG C, keep 10h, then heat to 140 DEG C,
10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The HF aqueous solution backflow 2h of 10mL 5wt% removes template, filters, and filter cake can in 100 DEG C of dry 6h
Obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.064g 70wt% tert-butyl alcohol hydrogen peroxide (0.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL methanol, adds 2.65mg ordered mesoporous carbon material, react 24h, second in 60 DEG C
The conversion ratio of benzene is 61.3%, and the selectivity of 1-Phenylethanone. is 79.2%.
2) by 0.023g 70wt% tert-butyl alcohol hydrogen peroxide (0.18mmol) and 0.02g benzylalcohol (0.18mmol)
Being separately added in 2mL methanol, add 1mg ordered mesoporous carbon material, 100 DEG C are reacted 24h, benzylalcohol
Conversion ratio is 56.2%, and benzoic selectivity is 61.7%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 4:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) sulphuric acid that 0.89g beta-schardinger dextrin-and 0.36g tripolycyanamide are separately added into 5mL 2.7wt% is molten
In liquid, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g MCM-41, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) 0.57g beta-schardinger dextrin-and 0.23g tripolycyanamide are separately added into the sulfuric acid solution of 5mL 1.8wt%
In, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat to
160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 3mol/L removes template, filters, and filter cake is dried 12 in 60 DEG C
H can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
Being separately added in 2mL isopropanol, add 5mg ordered mesoporous carbon material, 80 DEG C are reacted 24h, ethylbenzene
Conversion ratio is 95.2%, and the selectivity of 1-Phenylethanone. is 85.8%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL isopropanol, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, benzylalcohol
Conversion ratio be 79.2%, benzoic selectivity is 81.7%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 5:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.04g beta-schardinger dextrin-and 0.21g tripolycyanamide are separately added into the sulfuric acid solution of 5mL 2.7wt%
In, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep 10
H, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) 0.67g beta-schardinger dextrin-and 0.13g tripolycyanamide are separately added into the sulfuric acid solution of 5mL 1.8wt%
In, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat to
160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried in 60 DEG C
12h can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
Being separately added in 2mL n-propane, add 5mg ordered mesoporous carbon material, 80 DEG C are reacted 24h, ethylbenzene
Conversion ratio is 87.4%, and the selectivity of 1-Phenylethanone. is 67.9%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL n-propane, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, benzylalcohol
Conversion ratio be 65.2%, benzoic selectivity is 71.5%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 6:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) sulphuric acid that 1.14g beta-schardinger dextrin-and 0.11g tripolycyanamide are separately added into 5mL 2.7wt% is molten
In liquid, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) 0.73g beta-schardinger dextrin-and 0.07g tripolycyanamide are separately added into the sulfuric acid solution of 5mL 1.8wt%
In, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat to
160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried 12 in 60 DEG C
H can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 80 DEG C of reaction 24h, the conversion of ethylbenzene
Rate is 85.8%, and the selectivity of 1-Phenylethanone. is 66.3%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, turning of benzylalcohol
Rate is 79.5%, and benzoic selectivity is 79.9%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 7:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.14g beta-schardinger dextrin-and 0.11g dicyandiamide are separately added into the sulfuric acid solution of 5mL 2.7wt%
In, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) 0.73g beta-schardinger dextrin-and 0.07g dicyandiamide are separately added in the sulfuric acid solution of 5mL 1.8wt%,
After stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat to 160 DEG C,
10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried in 60 DEG C
12h can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 80 DEG C of reaction 24h, the conversion of ethylbenzene
Rate is 89.1%, and the selectivity of 1-Phenylethanone. is 59.1%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, turning of benzylalcohol
Rate is 69.3%, and benzoic selectivity is 63.3%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Embodiment 8:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.09g beta-schardinger dextrin-and 0.16g Guanidine Sulfamate 99 are separately added into the sulphuric acid of 5mL 2.7wt%
In solution, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) sulphuric acid that 0.70g beta-schardinger dextrin-and 0.1g Guanidine Sulfamate 99 are separately added into 5mL 1.8wt% is molten
In liquid, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat up
To 160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried 12 in 60 DEG C
H can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 80 DEG C of reaction 24h, the conversion of ethylbenzene
Rate is 98.0%, and the selectivity of 1-Phenylethanone. is 70.0%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, turning of benzylalcohol
Rate is 81.9%, and benzoic selectivity is 68.7%.
Embodiment 9:
A kind of preparation method of azepine ordered mesopore carbon based on cyclodextrin, step is as follows:
1) 1.04g beta-schardinger dextrin-and 0.21g Guanidine Sulfamate 99 are separately added into the sulphuric acid of 5mL 2.7wt%
In solution, it is stirred at room temperature, obtains mixed liquor；
2) in above-mentioned mixed liquor, add 1g SBA-15, after stirring, be warming up to 100 DEG C, keep
10h, then heats to 160 DEG C, keeps 10h to obtain black solid a；
3) sulphuric acid that 0.67g beta-schardinger dextrin-and 0.13g Guanidine Sulfamate 99 are separately added into 5mL 1.8wt% is molten
In liquid, after stirring, add above-mentioned black solid a, be warming up to 100 DEG C, keep 10h, then heat up
To 160 DEG C, 10h is kept to obtain black solid b；
4) above-mentioned black solid b is placed in the tube furnace of nitrogen protection and rises to 600 DEG C with 1 DEG C/min, protect
After holding 3h, rise to 900 DEG C with 5 DEG C/min, keep 2h, be cooled to room temperature, then clay into power, add
The NaOH aqueous solution backflow 2h of 10mL 1mol/L removes template, filters, and filter cake is dried 12 in 60 DEG C
H can obtain N doping ordered mesopore carbon.
The azepine ordered mesopore carbon based on cyclodextrin of preparation is for ethylbenzene and the selective oxidation of benzylalcohol, and method is:
1) by 0.193g 70wt% tert-butyl alcohol hydrogen peroxide (1.5mmol) and 0.0531g ethylbenzene (0.5mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 80 DEG C of reaction 24h, the conversion of ethylbenzene
Rate is 96.0%, and the selectivity of 1-Phenylethanone. is 68.3%.
2) by 0.085g 70wt% tert-butyl alcohol hydrogen peroxide (0.66mmol) and 0.02g benzylalcohol (0.18mmol)
It is separately added in 2mL water, adds 5mg ordered mesoporous carbon material, 120 DEG C of reaction 24h, turning of benzylalcohol
Rate is 84.2%, and benzoic selectivity is 71.3%.
The ordered mesopore carbon of preparation and the testing result of N doping ordered mesopore carbon are similar with embodiment 1.
Claims (4)
1. the preparation method of an azepine ordered mesopore carbon based on cyclodextrin, it is characterised in that step is as follows:
1) beta-schardinger dextrin-and nitrogen source 2-10:1 in mass ratio are separately added into the sulphuric acid that concentration is 2.7wt% molten
In liquid, it is stirred at room temperature, obtains mixed liquor；
2) adding mass percent in above-mentioned mixed liquor in terms of cyclodextrin and nitrogen source gross mass is the template of 80%
Agent, after stirring, is warming up to 80-110 DEG C, keeps 5-10h, then heats to 140-180 DEG C, keeps
5-10h, obtains black solid a；
3) beta-schardinger dextrin-and nitrogen source 2-10:1 in mass ratio are separately added into the sulphuric acid that concentration is 1.8wt% molten
In liquid, after stirring, add above-mentioned black solid a, and repeat above-mentioned intensification, insulating process, obtain black
Color solid b；
4) by above-mentioned black solid b roasting in nitrogen atmosphere, roasting process for rise to 600 DEG C with 1 DEG C/min,
Keep 3h, then rise to 900 DEG C with 5 DEG C/min, keep 2h, then with HF acid or the 1-5mol/L of 5wt%
NaOH aqueous solution remove template, after filtration, by filter cake in 50-100 DEG C be dried, obtaining N doping has
Sequence mesoporous carbon.
The most according to claim 1, the preparation method of azepine ordered mesopore carbon based on cyclodextrin, its feature exists
In: described nitrogen source is Guanidine Sulfamate 99, tripolycyanamide or dicyandiamide.
The most according to claim 1, the preparation method of azepine ordered mesopore carbon based on cyclodextrin, its feature exists
In: described template is SBA or MCM series silicon materials.
4. the application of the azepine ordered mesopore carbon based on cyclodextrin of claim 1 preparation, it is characterised in that
As a kind of non-metal catalyst for ethylbenzene and the selective oxidation of benzylalcohol, method is:
1), after oxidant and ethylbenzene 1-5:1 in molar ratio being mixed, it is separately added in water or organic solvent, water
Or the volume ratio of organic solvent and ethylbenzene is 32.8:1, it is subsequently adding the material with carbon element of ethylbenzene 5-20wt%, carbon material
The 5-20wt% that addition is ethylbenzene of material, 60-100 DEG C of reaction 24h, filter, and filtrate carries by ethyl acetate
Taking, extracting solution gas chromatogram is analyzed；
2), after oxidant and benzylalcohol 1-5:1 in molar ratio being mixed, it is separately added in water or organic solvent, water
Or volume ratio 105.3:1 of organic solvent and benzylalcohol, it is subsequently adding the material with carbon element of benzylalcohol 5-25wt%, 100-150
DEG C reaction 24h, filter, filtrate with ethyl acetate extract, extracting solution gas chromatogram is analyzed；
Described oxidant is tert-butyl hydroperoxide or hydrogen peroxide；Organic solvent be methanol, ethanol, isopropanol or
N-propane.
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