CN105664936A - Method for preparing nano composite material having core-shell structure with dopamine as carbon source - Google Patents
Method for preparing nano composite material having core-shell structure with dopamine as carbon source Download PDFInfo
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229960003638 dopamine Drugs 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 239000011258 core-shell material Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002041 carbon nanotube Substances 0.000 claims description 29
- 239000002105 nanoparticle Substances 0.000 claims description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 229910000859 α-Fe Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 230000005291 magnetic effect Effects 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002042 Silver nanowire Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229960004756 ethanol Drugs 0.000 description 11
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 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 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920001690 polydopamine Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 after stirring Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a method for preparing a nano composite material having a core-shell structure with dopamine as a carbon source; the method comprises the steps: firstly, by a stober method, coating the surface of a nano material as an inner core with silicon dioxide, then carrying out in-situ polymerization to make the silicon dioxide surface coated with dopamine, and thus obtaining a composite nano material, namely a nano material @SiO2@Pdop as the inner core; then carrying out baking treatment in a nitrogen atmosphere; and finally, etching in an ammonia water solution. The method has the advantages of simple operation, short preparation cycle, less reagent consumption and the like, and is suitable for scale production; the prepared nano material having the core-shell structure has the advantages of good and regulatable morphology structure, and especially has remarkable adsorption and catalysis actions on organic dyes.
Description
Technical field
The present invention relates to the preparation of nuclear-shell structured nano-composite material, specifically, relate to a kind of method preparing nuclear-shell structured nano-composite material for carbon source with dopamine, belong to technical field of nanometer material preparation.
Background technology
Along with the development of nanotechnology, nuclear-shell structured nano-composite material has now become the focus of the area research such as composite, nano material. The general core by center of the nano composite material (CSNC) of nucleocapsid structure and be coated on the shell of outside and form, is connected with each other by physics, chemical action between kernel and the shell in CSNC. Due to its physics with many uniquenesses and chemical characteristic so that it all has using value potential very greatly in fields such as super-hydrophobic surface coating, materialogy, chemistry, magnetics, electricity, optics, biomedicine, catalysis.
Research shows: have good biocompatibility between dopamine and silicon dioxide, and dopamine make its obtained carbon source can have very big application prospect in ultracapacitor containing nitrogen element, therefore, existing employing dopamine is the report that carbon source prepares nuclear-shell structured nano-composite material at present, but current preparation method all has following defects that
1) needed presoma centrifugation before cladding dopamine and wash with solvent, then the cladding of dopamine can just be carried out, last product is still required for solvent wash, owing to separation each time is required for the long period and washs a lot of solvents of needs, so that causing consumption and the waste of time of a large amount of solvent, it is unfavorable for large-scale production;
2) carbonization calcination process needs classification to carry out: be first warmed up to 400 DEG C with the heating rate of 1 DEG C/min, insulation roasting 2 hours, then it is warmed up to 800 DEG C with the heating rate of 5 DEG C/min again, insulation roasting 3 hours, not only making manufacturing cycle long, preparation condition is harsh, and the sintering temperature of 800 DEG C, the inner core materials being coated with had selectivity, so that hindering range of application;
3) current etching operation is all react 24 hours in HF aqueous solution, owing to HF is a kind of severe corrosive extremely toxic substance, volatile, and human body and environmental hazard is big, is therefore also unfavorable for large-scale production.
Summary of the invention
For the problems referred to above that prior art exists, it is an object of the invention to provide a kind of simple to operate, applied widely, the method preparing nuclear-shell structured nano-composite material for carbon source with dopamine of scale can be realized.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method preparing nuclear-shell structured nano-composite material for carbon source with dopamine, comprises the steps:
A) first the nano material as kernel is dispersed in alcohol-water solution, passes throughMethod, at the Surface coating silicon dioxide of the nano material as kernel, is then directly added into dopamine in reaction system, makes dopamine be coated on silica surface by in-situ polymerization, prepares composite nano materials, is abbreviated as: as the nano material SiO of kernel2Pdop;
B) using prepared composite nano materials: as the nano material SiO of kernel2Pdop, carries out calcination process: be warming up to 450～550 DEG C with the heating rate of 8～12 DEG C/min under nitrogen atmosphere, is then incubated 4～6 hours, obtains the composite nano materials of carbonization, be abbreviated as: as the nano material SiO of kernel2Carbon;
C) using the composite nano materials of prepared carbonization: as the nano material SiO of kernel2Carbon is dispersed in ammonia spirit, carries out insulation etching 10～16 hours at 130～150 DEG C, obtains described core-shell structured nanomaterials, be abbreviated as: as the nano material voidCarbon of kernel.
The described nano material as kernel can be nano-particle, nano wire or nanotube etc., includes but not limited to: gold nano grain, nano silver wire, magnetic carbon nano-tube, α-iron sesquioxide nano-particle, ferroferric oxide nano granules etc.
Preferably, it is 2:1～1:25 as the nano material of kernel and the mass ratio of silicon dioxide, with 1:1～1:5 for the best.
Preferably, it is 1:5～5:1 as the nano material of kernel and the mass ratio of dopamine, with 1:4～3:1 for the best.
Preferably, described alcohol-water solution is to be formed for 1:1～20:1 (with 2:1～15:1 for the best) by volume by alcoholic solvent and water.
Preferably, the concentration of etching ammonia spirit used is 5～15wt%.
Compared with prior art, the present invention has following significance beneficial effect:
1, the present invention cladding dopamine before without presoma is centrifuged separate and washing, hence it is evident that shorten manufacturing cycle, saved energy consumption, improve productivity;
2, the carbonization calcination process of the present invention is without complicated staged care, only need to be warming up to 450～550 DEG C with the heating rate of 8～12 DEG C/min, then be incubated 4～6 hours, not only simple to operate, and avoid the damage to the inner core materials being coated with, applied widely;
3, the present invention adopts and performs etching in ammonia spirit, can not only stably obtain the pattern of good nucleocapsid structure, and be conducive to large-scale production;
4, especially, experiments show that: the core-shell structured nanomaterials prepared by the inventive method, there is appearance structure better, specific surface area is big, the advantages such as catalytic performance is excellent, have good absorption and catalytic action, have good use value and application prospect in fields such as environment organic dyestuff.
Accompanying drawing explanation
Fig. 1 is gold nano grain, AuSiO in embodiment 12The scanning electron microscope (SEM) photograph of Pdop, AuvoidCarbon, wherein: a, b are the gold nano grain under different times mirror; C, d are the AuSiO under different times mirror2Pdop; E, f are the AuvoidCarbon under different times mirror;
Fig. 2 is the AuSiO of embodiment 1 preparation2The transmission electron microscope picture of Pdop, AuvoidCarbon, wherein: A, B are the AuSiO under different times mirror2Pdop; C, D are the AuvoidCarbon under different times mirror;
Fig. 3 is α-Fe in embodiment 22O3Nano-particle, α-Fe2O3The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the α-Fe under different times mirror2O3Nano-particle; C, d are the α-Fe under different times mirror2O3VoidCarbon;
Fig. 4 is α-Fe in embodiment 22O3Nano-particle, α-Fe2O3The transmission electron microscope picture of voidCarbon, wherein: a, b are the α-Fe under different times mirror2O3Nano-particle; C, d are the α-Fe under different times mirror2O3VoidCarbon;
Fig. 5 is Fe in embodiment 33O4Nano-particle, Fe3O4The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the Fe under different times mirror3O4Nano-particle; C, d are the Fe under different times mirror3O4VoidCarbon;
Fig. 6 is Fe in embodiment 33O4Nano-particle, Fe3O4The transmission electron microscope picture of voidCarbon, wherein: a, b are the Fe under different times mirror3O4Nano-particle; C, d are the Fe under different times mirror3O4VoidCarbon;
Fig. 7 is CNTs/Fe in embodiment 43O4、CNTs/Fe3O4The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the CNTs/Fe under different times mirror3O4; C, d are the CNTs/Fe under different times mirror3O4VoidCarbon;
Fig. 8 is CNTs/Fe in embodiment 43O4、CNTs/Fe3O4The transmission electron microscope picture of voidCarbon, wherein: a, b are the CNTs/Fe under different times mirror3O4; C, d are the CNTs/Fe under different times mirror3O4VoidCarbon;
Fig. 9 is the scanning electron microscope (SEM) photograph of AgNWs, AgNWsvoidCarbon in embodiment 5, wherein: a, b are the AgNWs under different times mirror; C, d are the AgNWsvoidCarbon under different times mirror;
Figure 10 is the transmission electron microscope picture of AgNWs, AgNWsvoidCarbon in embodiment 5, wherein: a, b are the AgNWs under different times mirror; C, d are the AgNWsvoidCarbon under different times mirror;
Figure 11 embodies the AuvoidCarbon catalytic effect to methylene blue in application examples of the present invention.
Detailed description of the invention
Below in conjunction with embodiment and application examples, technical solution of the present invention is described in further detail and completely.
The nano material as kernel used in embodiment can be directly commercial, it is also possible to by existing method now-making-now-using.
Embodiment 1
A) adding 4.5mL concentration in 30mL deionized water is the aqueous solution of chloraurate of 5mg/mL, stirring is so as to after mix homogeneously, mixture is heated to boiling, is then quickly added into the trisodium citrate aqueous solution that 1mL concentration is 3.3wt%, back flow reaction 30min; Terminate reaction, naturally cool to room temperature, add 10mg polyvinylpyrrolidone, stir 24 hours under room temperature; Centrifugation, the solid of collection is gold nano grain;
B) gold nano grain obtained is dispersed in the deionized water of 4mL, adding 40mL dehydrated alcohol, after mix homogeneously, adding 1mL concentration is the ammonia of 32wt%, then 0.2mLTEOS (tetraethyl orthosilicate) it is slowly added dropwise, at room temperature stirring 12 hours; It is directly added into 200mg dopamine again, at room temperature continues stirring 24 hours; Centrifugation, washs respectively three times with water and ethanol successively the solid collected, then dries, and obtains the composite nano materials of poly-dopamine coated silica and gold nano grain, is abbreviated as: AuSiO2Pdop; By prepared AuSiO2Pdop is placed in tube furnace, under nitrogen protection, is warming up to 500 DEG C with the heating rate of 10 DEG C/min and is incubated roasting 5 hours at this temperature, obtaining AuSiO2Carbon; By prepared AuSiO2Carbon is dispersed in the mixed solution formed by the ammonia that 30mL water and 10mL concentration are 32wt%, and ultrasonic making is uniformly dispersed, it is then transferred in reactor, insulation etching 12h at 140 DEG C, etching terminates rear centrifugation, with water and ethanol, the solid collected is washed three times respectively successively, final drying, obtain described core-shell structured nanomaterials, be abbreviated as: AuvoidCarbon.
Fig. 1 is gold nano grain, AuSiO in the present embodiment2The scanning electron microscope (SEM) photograph of Pdop, AuvoidCarbon, wherein: a, b are the gold nano grain under different times mirror; C, d are the AuSiO under different times mirror2Pdop; E, f are the AuvoidCarbon under different times mirror; Fig. 2 is AuSiO prepared by the present embodiment2The transmission electron microscope picture of Pdop, AuvoidCarbon, wherein: A, B are the AuSiO under different times mirror2Pdop; C, D are the AuvoidCarbon under different times mirror; Visible in conjunction with Fig. 1 and Fig. 2: to adopt the AuvoidCarbon core-shell structured nanomaterials that the inventive method can prepare even particle size distribution.
Embodiment 2
A) 680mgFeCl is taken3.6H2O and 10mgNaH2PO4Be dissolved in the deionized water of 80mL, ultrasonic make mix homogeneously after be transferred in the reactor of 100mL, then insulation reaction 6 hours at 180 DEG C, centrifugation, the solid of collection is α-Fe2O3Nano-particle;
B) prepared α-Fe is taken2O3Nano-particle 50mg is dissolved in the mixed liquor formed by 40mL dehydrated alcohol and 4mL water and ammonia that 1mL concentration is 32wt%, is slowly added dropwise 0.2mLTEOS, at room temperature stirs 12 hours after mix homogeneously; It is directly added into 200mg dopamine again, at room temperature continues stirring 24 hours; Centrifugation, washs respectively three times with water and ethanol successively the solid collected, then dries, and obtains poly-dopamine coated silica and α-Fe2O3The composite nano materials of nano-particle, is abbreviated as: α-Fe2O3SiO2Pdop; By prepared α-Fe2O3SiO2Pdop is placed in tube furnace, under nitrogen protection, is warming up to 500 DEG C with the heating rate of 10 DEG C/min and is incubated roasting 5 hours at this temperature, obtaining α-Fe2O3SiO2Carbon; By prepared α-Fe2O3SiO2Carbon is dispersed in the mixed solution formed by the ammonia that 30mL water and 10mL concentration are 32wt%, and ultrasonic making is uniformly dispersed, it is then transferred in reactor, insulation etching 12h at 140 DEG C, etching terminates rear centrifugation, with water and ethanol, the solid collected is washed three times respectively successively, final drying, obtain described core-shell structured nanomaterials, be abbreviated as: α-Fe2O3voidCarbon。
Fig. 3 is α-Fe in the present embodiment2O3Nano-particle, α-Fe2O3The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the α-Fe under different times mirror2O3Nano-particle; C, d are the α-Fe under different times mirror2O3VoidCarbon; Fig. 4 is α-Fe in the present embodiment2O3Nano-particle, α-Fe2O3The transmission electron microscope picture of voidCarbon, wherein: a, b are the α-Fe under different times mirror2O3Nano-particle; C, d are the α-Fe under different times mirror2O3VoidCarbon; Visible in conjunction with Fig. 3 and Fig. 4: to adopt the α-Fe that the inventive method can prepare even particle size distribution2O3VoidCarbon core-shell structured nanomaterials.
Embodiment 3
A) by 1.08gFeCl3.6H2O and 4.0gNaOAc under agitation joins in the 80mL mixed liquor formed by ethylene glycol and diethylene glycol 1:1 by volume, ultrasonic make mix homogeneously after be transferred in reactor, maintenance 15 hours at 200 DEG C, Magnetic Isolation, the solid of collection is Fe3O4Nano-particle;
B) prepared Fe is taken3O4Nano-particle 50mg is dissolved in the mixed liquor formed by 40mL dehydrated alcohol and 4mL water and ammonia that 1mL concentration is 32wt%, is slowly added dropwise 0.2mLTEOS, at room temperature stirs 12 hours after mix homogeneously; It is directly added into 200mg dopamine again, at room temperature continues stirring 24 hours; Centrifugation, washs respectively three times with water and ethanol successively the solid collected, then dries, and obtains poly-dopamine coated silica and Fe3O4The composite nano materials of nano-particle, is abbreviated as: Fe3O4SiO2Pdop; By prepared Fe3O4SiO2Pdop is placed in tube furnace, under nitrogen protection, is warming up to 500 DEG C with the heating rate of 10 DEG C/min and is incubated roasting 5 hours at this temperature, obtaining Fe3O4SiO2Carbon; By prepared Fe3O4SiO2Carbon is dispersed in the mixed solution formed by the ammonia that 30mL water and 10mL concentration are 32wt%, and ultrasonic making is uniformly dispersed, it is then transferred in reactor, insulation etching 12h at 140 DEG C, etching terminates rear centrifugation, with water and ethanol, the solid collected is washed three times respectively successively, final drying, obtain described core-shell structured nanomaterials, be abbreviated as: Fe3O4voidCarbon。
Fig. 5 is Fe in the present embodiment3O4Nano-particle, Fe3O4The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the Fe under different times mirror3O4Nano-particle; C, d are the Fe under different times mirror3O4VoidCarbon; Fig. 6 is Fe in the present embodiment3O4Nano-particle, Fe3O4The transmission electron microscope picture of voidCarbon, wherein: a, b are the Fe under different times mirror3O4Nano-particle; C, d are the Fe under different times mirror3O4VoidCarbon; Visible in conjunction with Fig. 5 and Fig. 6: to adopt the Fe that the inventive method can prepare even particle size distribution3O4VoidCarbon core-shell structured nanomaterials.
Embodiment 4
A) the praseodynium ferrum (CAS#14024-18-1) of 80mg CNT (being abbreviated as CNTs) and 120mg is dissolved in the triethylene glycol of 30mL; ultrasonic so as to back flow reaction 30 minutes under nitrogen protection after being uniformly dispersed; reaction terminates; reaction solution is made to naturally cool to room temperature; Magnetic Isolation; the solid collected, with dry after washing with alcohol 3 times, namely obtain magnetic carbon nano-tube and (is abbreviated as CNTs/Fe3O4);
B) prepared CNTs/Fe is taken3O450mg is dissolved in the mixed liquor formed by 40mL dehydrated alcohol and 4mL water and ammonia that 1mL concentration is 32wt%, is slowly added dropwise 0.2mLTEOS, at room temperature stirs 12 hours after mix homogeneously; It is directly added into 200mg dopamine again, at room temperature continues stirring 24 hours; Centrifugation, washs respectively three times with water and ethanol successively the solid collected, then dries, and obtains poly-dopamine coated silica and CNTs/Fe3O4Composite nano materials, be abbreviated as: CNTs/Fe3O4SiO2Pdop; By prepared CNTs/Fe3O4SiO2Pdop is placed in tube furnace, under nitrogen protection, is warming up to 500 DEG C with the heating rate of 10 DEG C/min and is incubated roasting 5 hours at this temperature, obtaining CNTs/Fe3O4SiO2Carbon; By prepared CNTs/Fe3O4SiO2Carbon is dispersed in the mixed solution formed by the ammonia that 30mL water and 10mL concentration are 32wt%, and ultrasonic making is uniformly dispersed, it is then transferred in reactor, insulation etching 12h at 140 DEG C, etching terminates rear centrifugation, with water and ethanol, the solid collected is washed three times respectively successively, final drying, obtain described core-shell structured nanomaterials, be abbreviated as: CNTs/Fe3O4voidCarbon。
Fig. 7 is CNTs/Fe in the present embodiment3O4、CNTs/Fe3O4The scanning electron microscope (SEM) photograph of voidCarbon, wherein: a, b are the CNTs/Fe under different times mirror3O4; C, d are the CNTs/Fe under different times mirror3O4VoidCarbon; Fig. 8 is CNTs/Fe in the present embodiment3O4、CNTs/Fe3O4The transmission electron microscope picture of voidCarbon, wherein: a, b are the CNTs/Fe under different times mirror3O4; C, d are the CNTs/Fe under different times mirror3O4VoidCarbon; Visible in conjunction with Fig. 7 and Fig. 8: to adopt the CNTs/Fe that the inventive method can prepare even particle size distribution3O4VoidCarbon core-shell structured nanomaterials.
Embodiment 5
A) 2.73g polyvinylpyrrolidone (K30) is joined in 95mL glycerol, 90 DEG C of stirrings to being completely dissolved, then 50 DEG C are naturally cooled to, add 0.79g silver nitrate powder and 5mL contains 29.5mg sodium chloride and the glycerin solution of 0.25mL deionized water, 210 DEG C it are heated in 25min, then turn off heating, rapidly the celadon solution of gained is transferred in a large beaker volume ratio with 1:1 in this solution, adds deionized water, after stirring, mixed solution is stood one week (solution layering), after one week, upper solution is outwelled, ethanol is added in beaker, ultrasonic make nano silver wire (being abbreviated as AgNWs) dispersed in a solvent, centrifugal settling method is finally adopted to collect AgNWs, collected AgNWs is dispersed in 20mL dehydrated alcohol, prepared concentration is about the AgNWs alcoholic solution of 10mg/mL with standby,
B) take the AgNWs alcoholic solution of the above-mentioned preparation of 5mL, make to be dispersed in the mixed liquor formed by 35mL dehydrated alcohol and 4mL water and ammonia that 1mL concentration is 32wt%, be slowly added dropwise 0.2mLTEOS after mix homogeneously, at room temperature stir 12 hours; It is directly added into 200mg dopamine again, at room temperature continues stirring 24 hours; Centrifugation, washs respectively three times with water and ethanol successively the solid collected, then dries, and obtains the composite nano materials of poly-dopamine coated silica and AgNWs, is abbreviated as: AgNWsSiO2Pdop; By prepared AgNWsSiO2Pdop is placed in tube furnace, under nitrogen protection, is warming up to 500 DEG C with the heating rate of 10 DEG C/min and is incubated roasting 5 hours at this temperature, obtaining AgNWsSiO2Carbon; By prepared AgNWsSiO2Carbon is dispersed in the mixed solution formed by the ammonia that 30mL water and 10mL concentration are 32wt%, and ultrasonic making is uniformly dispersed, it is then transferred in reactor, insulation etching 12h at 140 DEG C, etching terminates rear centrifugation, with water and ethanol, the solid collected is washed three times respectively successively, final drying, obtain described core-shell structured nanomaterials, be abbreviated as: AgNWsvoidCarbon.
Fig. 9 is the scanning electron microscope (SEM) photograph of AgNWs, AgNWsvoidCarbon in the present embodiment, wherein: a, b are the AgNWs under different times mirror; C, d are the AgNWsvoidCarbon under different times mirror; Figure 10 is the transmission electron microscope picture of AgNWs, AgNWsvoidCarbon in the present embodiment, wherein: a, b are the AgNWs under different times mirror; C, d are the AgNWsvoidCarbon under different times mirror; Visible in conjunction with Fig. 9 and Figure 10: to adopt the AgNWsvoidCarbon core-shell structured nanomaterials that the inventive method can prepare even particle size distribution.
Application examples
1mL concentration, in the aqueous solution of methylene blue that 5mL concentration is 40mg/L, is then the NaBH of 0.4mol/L by the AuvoidCarbon nano material 1mg ultrasonic disperse of Example 1 preparation4Aqueous solution rapidly joins in methylene blue solution, by UV UV spectrophotometer measuring methylene blue concentration over time (UV-Vis absorbs spectrogram to be seen shown in Figure 11 a); AuvoidCarbon centrifuge washing final vacuum is dried after terminating by catalysis, is cycled to used in catalysis methylene blue, to detect its recycling activity, refers to shown in Figure 11 b.
From Figure 11 a: methylene blue exists obvious absworption peak at visible light wave range 664nm place, after adding AuvoidCarbon nano material, prolongation over time, absworption peak is reduced rapidly to basic disappearance, thus illustrates: methylene blue is had obvious catalytic effect by AuvoidCarbon nano material provided by the present invention.
Being recycled the catalysis activity of 5 times from Figure 11 b: AuvoidCarbon substantially not change, catalytic performance is excellent.
It addition, the present invention can regulate the thickness of carbon shell by the addition of dopamine; Can by change add ammonia vol, alcohol water ratio, TEOS amount regulate the pore size between the size of core-shell structured nanomaterials, kernel and shell, will not enumerate at this.
Finally need it is pointed out here that: be only the part preferred embodiment of the present invention above; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.
Claims (7)
1. the method preparing nuclear-shell structured nano-composite material for carbon source with dopamine, it is characterised in that comprise the steps:
A) first the nano material as kernel is dispersed in alcohol-water solution, passes throughMethod, at the Surface coating silicon dioxide of the nano material as kernel, is then directly added into dopamine in reaction system, makes dopamine be coated on silica surface by in-situ polymerization, prepares composite nano materials, is abbreviated as: as the nano material SiO of kernel2Pdop;
B) using prepared composite nano materials: as the nano material SiO of kernel2Pdop, carries out calcination process: be warming up to 450～550 DEG C with the heating rate of 8～12 DEG C/min under nitrogen atmosphere, is then incubated 4～6 hours, obtains the composite nano materials of carbonization, be abbreviated as: as the nano material SiO of kernel2Carbon;
C) using the composite nano materials of prepared carbonization: as the nano material SiO of kernel2Carbon is dispersed in ammonia spirit, carries out insulation etching 10～16 hours at 130～150 DEG C, obtains described core-shell structured nanomaterials, be abbreviated as: as the nano material voidCarbon of kernel.
2. the method for claim 1, it is characterised in that: the described nano material as kernel is nano-particle, nano wire or nanotube.
3. method as claimed in claim 2, it is characterised in that: the described nano material as kernel includes but not limited to gold nano grain, nano silver wire, magnetic carbon nano-tube, α-iron sesquioxide nano-particle, ferroferric oxide nano granules.
4. the method for claim 1, it is characterised in that: it is 2:1～1:25 as the nano material of kernel and the mass ratio of silicon dioxide.
5. the method for claim 1, it is characterised in that: it is 1:5～5:1 as the nano material of kernel and the mass ratio of dopamine.
6. the method for claim 1, it is characterised in that: described alcohol-water solution is to be formed for 1:1～20:1 by volume by alcoholic solvent and water.
7. the method for claim 1, it is characterised in that: the concentration of etching ammonia spirit used is 5～15wt%.
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