CN106861739A - A kind of hollow core-shell type magnetic mesoporous carbonitride and preparation method thereof - Google Patents
A kind of hollow core-shell type magnetic mesoporous carbonitride and preparation method thereof Download PDFInfo
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- CN106861739A CN106861739A CN201510920946.4A CN201510920946A CN106861739A CN 106861739 A CN106861739 A CN 106861739A CN 201510920946 A CN201510920946 A CN 201510920946A CN 106861739 A CN106861739 A CN 106861739A
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims description 27
- 229910052682 stishovite Inorganic materials 0.000 claims description 27
- 229910052905 tridymite Inorganic materials 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 14
- 238000002955 isolation Methods 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011257 shell material Substances 0.000 claims description 3
- 241001502050 Acis Species 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- -1 SBA-15 Chemical compound 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OAGSFHDUINSAMQ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium;hydrate Chemical compound O.[Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OAGSFHDUINSAMQ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- B01J35/613—10-100 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
- B01J35/615—100-500 m2/g
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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
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention provides a kind of hollow core-shell type magnetic mesoporous carbonitride and preparation method thereof.Template is done using the magnetic mesoporous silica spheres with double-deck core shell structure, it is placed in the aqueous solution of carbon nitrogen predecessor and is sufficiently impregnated, after vacuum drying, it is calcined in a nitrogen atmosphere, recycle sodium hydroxide solution to dissolve silica, obtain the magnetic mesoporous carbonitride with hollow core shell structure.The material is presented spherical morphology, 20~200m of specific surface area2/ g, with typical core shell structure, kernel is the magnetic iron oxide microballoon of 100~400nm of diameter, and outer shell is hollow mesoporous carbonitride, its mesoporous pore size 2~8nm, cavity diameter 140-600nm, thickness 20-100nm.The invention has the advantages that providing a kind of new multifunctional composite, there is good application prospect in fields such as catalysis, adsorbing separation, the depollutions of environment.
Description
Technical field
The invention belongs to field of new material preparation, and in particular to a kind of hollow core-shell type magnetic mesoporous
Carbonitride and preparation method thereof.
Background technology
Carbonitride (C3N4) it is by manually calculating and the new inorganic polymeric of the class that successfully synthesizes
Thing material.There is optical property, semiconductive, the bio-compatibility of uniqueness due to it, and
Hardness is high, good stability the features such as, the extensive concern of whole world researchers is received in recent years.
In five kinds of (α, β, cube, accurate cube, graphite) thing phases of carbonitride, graphite-phase nitridation
Carbon (g-C3N4) possess special physics and electronic band structure, in photocatalysis, solar-electricity
The fields such as pond, energy conversion, the depollution of environment show good application prospect.At present, synthesize
The method of graphite phase carbon nitride mainly have solid reaction process, solvent-thermal method, electrochemical deposition method with
And thermal polymerization.Wherein thermal polymerization is to form carbonitride by being calcined nitrogenous organic precursor,
Used because its is simple to operate extensively.But, the product of conventional thermal polymerization synthesis often compares table
Area is very low, seriously limits its practical application.Therefore, how to prepare with compared with high-ratio surface
Long-pending g-C3N4Material turns into the focus of current research.
Using mesoporous silicon oxide such as SBA-15, KIT-6 or micro porous molecular sieve such as ZSM-5,
MCM-22 is template, and the nitrogen with high specific surface area can be prepared by hard template method
Change carbon material (Adv.Mater., 2005,17,1648；J.Mater.Chem.,2012,22,9831；
Microporous Mesoporous Mater.,2008,108,340；Microporous
Mesoporous Mater.,2008,110,216).But prepared sample often particle compared with
Greatly, pattern is single.It is template that Wang Xin morning research teams use solid mesoporous silicon oxide bead,
Cyanamide mesoporous nitridation carbon hollow ball for precursor synthesis go out, not only with larger specific surface
Product, its unique hollow-core construction may assign material some special performance (Nat.
Commun.,2012,1139；Nanoscale,2015,7,465).But the component of material is single,
Its function is limited.Possess high-specific surface area, the multicomponent feature carbon nitride material of its unique structure
There is not been reported.
The content of the invention
It is an object of the invention to provide a kind of new hollow core-shell type magnetic mesoporous carbonitride and
Its preparation method.
A kind of hollow core-shell type magnetic mesoporous carbonitride, with core shell structure, kernel is diameter
The magnetic Fe of 100-400nm3O4Or γ-Fe2O3Microballoon, shell is thickness in 20-100nm
Empty mesoporous graphite phase carbon nitride, mesoporous is aperture 2-8nm, cavity diameter 140-600nm, than
Surface area 20-200m2/g。
A kind of preparation method of hollow core-shell type magnetic mesoporous carbonitride is divided into three steps, specially：
(1) by the Fe of 0.08-0.25g3O4It is scattered in 60-200ml absolute ethyl alcohols and 10-50ml
In deionized water, the concentrated ammonia liquor that 2-10ml mass concentrations are 28%, 0.5-5ml tetraethyls are added
Esters of silicon acis, stirs 6~24h at room temperature, and Magnetic Isolation goes out product, at 450-550 DEG C after drying
Roasting 3-6h, obtains the non-porous SiO of individual layer2The core-shell material of coated magnetic iron oxide；
(2) core-shell material that 0.2g steps (1) are obtained is scattered in 50-200ml deionizations
In water and 30-120ml absolute ethyl alcohols, the mesoporous directed agents of 0.2-0.6g are added, after stirring and dissolving,
Add the concentrated ammonia liquor regulation system that mass concentration is 2% watery hydrochloric acid or mass concentration is 28%
PH value is 5-11, adds 0.5-1.0ml silicon tetraethyl acid esters, and 6-48h is persistently stirred at 40 DEG C,
Magnetic Isolation goes out product, after drying, 3-6h is calcined at 450-550 DEG C, obtains double-deck nucleocapsid knot
The magnetic mesoporous SiO of structure2Ball；
(3) the magnetic mesoporous SiO for obtaining 0.2g steps (2)2It is dense that ball impregnated in 8-20ml
Spend in the carbon nitrogen predecessor aqueous solution for 0.04-0.4g/ml, after 60-70 DEG C of vacuum drying, in nitrogen
500-550 DEG C of roasting 2-4h under gas atmosphere, the products therefrom hydrogen-oxygen of mass concentration 15%-30%
Change sodium solution treatment 24-72h, dissolving removes SiO2, obtain hollow core-shell type magnetic mesoporous nitrogen
Change carbon.
Described described ferroso-ferric oxide is that, with ferric trichloride as raw material, ethylene glycol is reduction
Agent, sodium citrate is protective agent, is prepared by solvent-thermal method.
Described mesoporous directed agents are cetyl trimethylammonium bromide or triblock copolymer
P123。
Described carbon nitrogen predecessor is cyanamide, cdicynanmide or melamine.
The hollow core-shell type magnetic mesoporous carbonitride compound with regular structure that the present invention is provided, regular appearance,
Structure is adjustable, and feature is strong, and prepares simple.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of hollow core-shell type magnetic mesoporous carbonitride of the invention, right
Answer embodiment 2.
Specific embodiment
Bibliography prepares magnetic ferroferric oxide nanometer particle：
1.6g Iron(III) chloride hexahydrates are taken, the citric acid monohydrate sodium of 0.6g bis- is dissolved in 60ml second two
In alcohol, 3.6g sodium acetates are added, stir 0.5h, reactant is transferred to band polytetrafluoroethylene (PTFE)
In the stainless steel autoclave of liner, 10h is stood at 200 DEG C.Centrifugation goes out solid after cooling
Product, with respectively washing three times of ethanol and deionized water, vacuum freeze drying obtains particle diameter
The ferroferric oxide nano granules of 100-400nm.
Embodiment 1
Take the Fe of 0.2g3O4It is scattered in 100ml absolute ethyl alcohols and 20ml deionized waters, plus
Enter 3ml concentrated ammonia liquors, 1ml silicon tetraethyl acid esters, at room temperature mechanical agitation 18h, Magnetic Isolation
Go out product, 4h is calcined at 500 DEG C after drying, obtain the non-porous SiO of individual layer2Coated magnetic is aoxidized
Core-shell material (γ-the Fe of iron2O3@SiO2)；Take 0.2g γ-Fe2O3@SiO2It is scattered in 100ml
In deionized water and 60ml absolute ethyl alcohols, 0.2g cetyl trimethylammonium bromides are added, stirred
After mixing dissolving, 3ml concentrated ammonia liquors are added, add 1ml silicon tetraethyl acid esters, continued at 40 DEG C
Stirring 6-48h, Magnetic Isolation goes out product, after drying, 4h is calcined at 550 DEG C, obtains bilayer
The mesoporous SiO of core-shell structure magnetic2Ball (γ-Fe2O3@SiO2@mSiO2)；Take 0.2g
γ-Fe2O3@SiO2@mSiO2Impregnated in the cyanamide aqueous solution that 10ml concentration is 0.4g/ml
In, after 60 DEG C of vacuum drying, 550 DEG C are calcined 3h, products therefrom quality in a nitrogen atmosphere
The sodium hydroxide solution treatment 24h of concentration 20%, dissolving removes SiO2, obtain hollow core-shell type
Magnetic mesoporous carbonitride.
Embodiment 2
Take the Fe of 0.2g3O4It is scattered in 100ml absolute ethyl alcohols and 20ml deionized waters, plus
Enter 3ml concentrated ammonia liquors, 1ml silicon tetraethyl acid esters, at room temperature mechanical agitation 18h, Magnetic Isolation
Go out product, 4h is calcined at 500 DEG C after drying, obtain the non-porous SiO of individual layer2Coated magnetic is aoxidized
Core-shell material (γ-the Fe of iron2O3@SiO2)；Take 0.2g γ-Fe2O3@SiO2It is scattered in 100ml
In deionized water and 60ml absolute ethyl alcohols, 0.2g cetyl trimethylammonium bromides are added, stirred
After mixing dissolving, 3ml concentrated ammonia liquors are added, add 1ml silicon tetraethyl acid esters, continued at 40 DEG C
Stirring 6-48h, Magnetic Isolation goes out product, after drying, 4h is calcined at 550 DEG C, obtains bilayer
The mesoporous SiO of core-shell structure magnetic2Ball (γ-Fe2O3@SiO2@mSiO2)；Take 0.2g
γ-Fe2O3@SiO2@mSiO2Impregnated in the dicyan amine aqueous solution that 10ml concentration is 0.16g/ml
In, after 60 DEG C of vacuum drying, 550 DEG C are calcined 3h, products therefrom quality in a nitrogen atmosphere
The sodium hydroxide solution treatment 24h of concentration 20%, dissolving removes SiO2, obtain hollow core-shell type
Magnetic mesoporous carbonitride.
Embodiment 3
Take the Fe of 0.2g3O4It is scattered in 100ml absolute ethyl alcohols and 20ml deionized waters, plus
Enter 3ml concentrated ammonia liquors, 1ml silicon tetraethyl acid esters, at room temperature mechanical agitation 18h, Magnetic Isolation
Go out product, 4h is calcined at 500 DEG C after drying, obtain the non-porous SiO of individual layer2Coated magnetic is aoxidized
Core-shell material (γ-the Fe of iron2O3@SiO2)；Take 0.2g γ-Fe2O3@SiO2It is scattered in 100ml
In deionized water and 60ml absolute ethyl alcohols, 0.4g block copolymer P123, stirring and dissolving are added
Afterwards, 0.1ml watery hydrochloric acid (0.05M) is added, 1ml silicon tetraethyl acid esters is added, at 40 DEG C
48h is persistently stirred, Magnetic Isolation goes out product, after drying, 4h is calcined at 550 DEG C, obtain double
The mesoporous SiO of layer core-shell structure magnetic2Ball (γ-Fe2O3@SiO2@mSiO2)；Take 0.2g
γ-Fe2O3@SiO2@mSiO2Impregnated in the dicyan amine aqueous solution that 10ml concentration is 0.16g/ml
In, after 60 DEG C of vacuum drying, 550 DEG C are calcined 3h, products therefrom quality in a nitrogen atmosphere
The sodium hydroxide solution treatment 24h of concentration 20%, dissolving removes SiO2, obtain hollow core-shell type
Magnetic mesoporous carbonitride.
Embodiment 4
Take the Fe of 0.2g3O4It is scattered in 100ml absolute ethyl alcohols and 20ml deionized waters, plus
Enter 3ml concentrated ammonia liquors, 1ml silicon tetraethyl acid esters, at room temperature mechanical agitation 18h, Magnetic Isolation
Go out product, 4h is calcined at 500 DEG C after drying, obtain the non-porous SiO of individual layer2Coated magnetic is aoxidized
Core-shell material (γ-the Fe of iron2O3@SiO2)；Take 0.2g γ-Fe2O3@SiO2It is scattered in 100ml
In deionized water and 60ml absolute ethyl alcohols, 0.4g block copolymer P123, stirring and dissolving are added
Afterwards, 0.1ml watery hydrochloric acid (0.05M) is added, 1ml silicon tetraethyl acid esters is added, at 40 DEG C
48h is persistently stirred, Magnetic Isolation goes out product, after drying, 4h is calcined at 550 DEG C, obtain double
The mesoporous SiO of layer core-shell structure magnetic2Ball (γ-Fe2O3@SiO2@mSiO2)；Take 0.2g
γ-Fe2O3@SiO2@mSiO2Impregnated in the melamine that 10ml concentration is 0.04g/ml water-soluble
In liquid, after 60 DEG C of vacuum drying, 550 DEG C are calcined 3h, products therefrom matter in a nitrogen atmosphere
The sodium hydroxide solution treatment 24h of concentration 20% is measured, dissolving removes SiO2, obtain hollow nucleocapsid
The magnetic mesoporous carbonitride of formula.
Embodiment 5
Take the Fe of 0.2g3O4It is scattered in 200ml absolute ethyl alcohols and 40ml deionized waters, plus
Enter 3ml concentrated ammonia liquors, 2ml silicon tetraethyl acid esters, at room temperature mechanical agitation 18h, Magnetic Isolation
Go out product, 4h is calcined at 500 DEG C after drying, obtain the non-porous SiO of individual layer2Coated magnetic is aoxidized
Core-shell material (γ-the Fe of iron2O3@SiO2)；Take 0.2g γ-Fe2O3@SiO2It is scattered in 200ml
In deionized water and 120ml absolute ethyl alcohols, 0.4g block copolymer P123 are added, stirred molten
Xie Hou, adds 0.1ml watery hydrochloric acid (0.05M), 2ml silicon tetraethyl acid esters is added, 40
48h DEG C is persistently stirred, Magnetic Isolation goes out product, after drying, 4h are calcined at 550 DEG C, obtained
The double-deck magnetic mesoporous SiO of core shell structure2Ball (γ-Fe2O3@SiO2@mSiO2)；Take 0.2g
γ-Fe2O3@SiO2@mSiO2Impregnated in the dicyan amine aqueous solution that 10ml concentration is 0.16g/ml
In, after 60 DEG C of vacuum drying, 550 DEG C are calcined 3h, products therefrom quality in a nitrogen atmosphere
The sodium hydroxide solution treatment 24h of concentration 20%, dissolving removes SiO2, obtain hollow core-shell type
Magnetic mesoporous carbonitride.
Application examples 1
The methylene blue solution of 40ml 10ppm is added in 100ml beakers with 0.040g's
Magnetic carbonitride, mixes 30min in camera bellows, then opens and is configured with λ >=400nm
300W xenon lamps (light intensity 6.4mW) of optical filter is irradiated to reaction vessel, persistently stirs
After mixing a period of time, supernatant is taken, methylene blue is measured using ultraviolet-visible spectrophotometer
Concentration.Reaction result：After 2h, methylene blue degradation rate is 80%.
Application examples 2
The Orange II solution of 50ml 20ppm is added in 100ml beakers, is subsequently adding
0.04g magnetic carbonitrides, after mixing 30min at room temperature, add 0.0249g PMS,
Persistently after stirring 2h, supernatant is taken, Orange II are measured using ultraviolet-visible spectrophotometer
Concentration.Reaction result：After 2h, the degradation rate of orange II is 98%.
Claims (8)
1. a kind of hollow core-shell type magnetic mesoporous carbonitride, it is characterized in that：With core shell structure,
Kernel is the magnetic iron oxide microballoon of diameter 100-400nm, and shell is that thickness is 20-100nm
Hollow mesoporous graphite phase carbon nitride, mesoporous is aperture 2-8nm.
2. hollow core-shell type magnetic mesoporous carbonitride according to claim 1, its feature
It is：Described magnetic iron oxide microballoon is Fe3O4Or γ-Fe2O3。
3. hollow core-shell type magnetic mesoporous carbonitride according to claim 1, its feature
It is：The shell internal cavity diameter 140-600nm.
4. hollow core-shell type magnetic mesoporous carbonitride according to claim 1, its feature
It is：The hollow core-shell type magnetic mesoporous carbonitride specific surface area 20-200m2/g。
5. the system of any described hollow core-shell type magnetic mesoporous carbonitrides of a kind of claim 1-4
Preparation Method, it is characterized in that：
(1) by the Fe of 0.08-0.25g3O4It is scattered in 60-200ml absolute ethyl alcohols and 10-50ml
In deionized water, the concentrated ammonia liquor that 2-10ml mass concentrations are 28%, 0.5-5ml tetraethyls are added
Esters of silicon acis, stirs 6~24h at room temperature, and Magnetic Isolation goes out product, at 450-550 DEG C after drying
Roasting 3-6h, obtains the non-porous SiO of individual layer2The core-shell material of coated magnetic iron oxide；
(2) core-shell material that 0.2g steps (1) are obtained is scattered in 50-200ml deionizations
In water and 30-120ml absolute ethyl alcohols, the mesoporous directed agents of 0.2-0.6g are added, after stirring and dissolving,
Add the concentrated ammonia liquor regulation system that mass concentration is 2% watery hydrochloric acid or mass concentration is 28%
PH value is 5-11, adds 0.5-1.0ml silicon tetraethyl acid esters, and 6-48h is persistently stirred at 40 DEG C,
Magnetic Isolation goes out product, after drying, 3-6h is calcined at 450-550 DEG C, obtains double-deck nucleocapsid knot
The magnetic mesoporous SiO of structure2Ball；
(3) the magnetic mesoporous SiO for obtaining 0.2g steps (2)2It is dense that ball impregnated in 8-20ml
Spend in the carbon nitrogen predecessor aqueous solution for 0.04-0.4g/ml, after 60-70 DEG C of vacuum drying, in nitrogen
500-550 DEG C of roasting 2-4h under gas atmosphere, the products therefrom hydrogen-oxygen of mass concentration 15%-30%
Change sodium solution treatment 24-72h, dissolving removes SiO2, obtain hollow core-shell type magnetic mesoporous nitrogen
Change carbon.
6. preparation method according to claim 3, it is characterized in that：Four described oxidations three
Iron is that, with ferric trichloride as raw material, ethylene glycol is reducing agent, and sodium citrate is protective agent, is passed through
It is prepared by solvent-thermal method.
7. preparation method according to claim 3, it is characterized in that：Described mesoporous guiding
Agent is cetyl trimethylammonium bromide or triblock copolymer P123.
8. preparation method according to claim 3, it is characterized in that：Described carbon nitrogen forerunner
Thing is cyanamide, cdicynanmide or melamine.
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