CN110223834A - The separable double-deck core-shell structure mesoporous organosilicon Fe of magnetism3O4- DYSNs-PMO nano material and preparation method - Google Patents
The separable double-deck core-shell structure mesoporous organosilicon Fe of magnetism3O4- DYSNs-PMO nano material and preparation method Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 60
- 239000010703 silicon Substances 0.000 claims abstract description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 27
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 27
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 27
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 21
- PONXTPCRRASWKW-KBPBESRZSA-N diphenylethylenediamine Chemical compound C1([C@H](N)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-KBPBESRZSA-N 0.000 claims abstract description 17
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 80
- 239000000463 material Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000035484 reaction time Effects 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010907 mechanical stirring Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 2
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 5
- 210000002969 egg yolk Anatomy 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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Abstract
The present invention relates to a kind of mesoporous organosilicon Fe of magnetic separable double-deck core-shell structure3O4- DYSNs-PMO nano material and preparation method the steps include: 1, synthesize Fe with ferric chloride hexahydrate3O4Magnetic nano-particle；2, the Fe synthesized by tetraethoxysilane in step 13O4Magnetic nano-particle surface forms silica dioxide coating, synthesizes Fe3O4@SiO2Nano particle；3, it is reacted with (1S, 2S) -1,2- diphenyl ethylene diamine with 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy silane (Ts silicon source) and generates Ts-DPEN function silicon source；4, the Fe synthesized with step 23O4@SiO2Nano particle is precursor, makees template with CTAB, is copolymerized to obtain Fe with (triethoxy silicon substrate) ethane of 1,2- bis- and step 3 gained Ts-DPEN function silicon source3O4- DYSNs-PMO nano particle.
Description
Technical field
The present invention relates to nano material preparation and catalyst preparation technologies, and in particular to a kind of separable bilayer of novel magnetic
The mesoporous organosilicon Fe of core-shell structure3O4- DYSNs-PMO nano material and preparation method thereof.
Background technique
In recent years, yolk shell structural nano composite material causes the interest of many researchers, and it is compound to become traditional nucleocapsid
The important extension of material.Yolk core-shell nanoparticles (YSNs) generally include a hollow porous shell and a functional nano
Core particle.Different core particles and sheathing material can produce the YSNs with different characteristics.The uniqueness having due to it
Structure and property, such as higher specific surface area, bigger interstitial space, lower density and in core and hollow shell
Adjustable function so that YSNs can be widely applied for many key areas, such as drug conveying, absorption, catalysis, it is biomedical and
The energy storage etc. of supercapacitor.Therefore, the preparation of yolk shell composite material, especially with removable magnetic core and functionality
The yolk shell mesoporous organosilicon nano material of regulatable shell composition, because they have unique magnetic response ability, low
Cytotoxicity and chemically regulatable surface etc., therefore more and more attention has been paid to.That is, the nano combined material of yolk shell structure
Material has become the research field of a rapid growth.
Summary of the invention
Technical problem to be solved by the present invention lies in provide one kind with Fe3O4For the novel magnetic bilayer nucleocapsid of core
Mesoporous organosilicon Fe3O4- DYSNs-PMO nano material.
Its technical problem to be solved can be implemented by the following technical programs.
A kind of mesoporous organosilicon Fe of the magnetic separable double-deck core-shell structure3O4- DYSNs-PMO nano material, using as follows
Step is prepared:
(1), Fe is synthesized with ferric chloride hexahydrate first3O4Magnetic nano-particle；
(2), then pass through tetraethoxysilane (TEOS) Fe synthesized by step (1)3O4Magnetic nano-particle surface shape
At silica dioxide coating, Fe is synthesized3O4@SiO2Nano particle；
(3), again with (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) and 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy
Silane (Ts silicon source) reaction generates Ts-DPEN function silicon source；
(4), the Fe then synthesized with step (2)3O4@SiO2Nano particle is precursor, under mechanical stirring, is made with CTAB
Template, and 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) and the obtained Ts-DPEN function silicon source of step (3), in height
It presses in hydrothermal reaction kettle, is copolymerized to obtain Fe using water and ethyl alcohol as solvent3O4- DYSNs-PMO nano particle.
As the further improvement of the technical program, step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is
180-240 DEG C, reaction time 10-14h.
As one of the preferred embodiment of the present invention, step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is
220 DEG C, reaction time 12h.
Also as the further improvement of the technical program, in step (2), tetraethoxysilane (TEOS) is in alkaline condition
Under, using second alcohol and water, isopropyl alcohol and water or first alcohol and water as solvent, it is further formed the silica dioxide coating；Wrap up dioxy
Reaction temperature is 25-35 DEG C, reaction time 6-12h, mixing speed 400-600r/min when SiClx；
As another preferred embodiment of the invention, the volume ratio of the ethyl alcohol and water is 4: 1；The reaction temperature is 30
DEG C, reaction time 10h.
Also as the further improvement of the technical program, in the preparation of Ts-DPEN function silicon source, solvent is step (3)
Methylene chloride is slowly added dropwise into (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) as Ts silicon source under the conditions of -5-0 DEG C
After 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy silane 0.5-1h, it is to slowly warm up to room temperature；The reaction time 3-5h.
Wherein, the dropwise addition preferably is carried out under the conditions of 0 DEG C.
Equally further improvement as the technical program, in step (4): with the Fe of step (2) synthesis3O4@SiO2Nanometer
Particle is precursor, and when using water and ethyl alcohol as solvent, the volume ratio of water and ethyl alcohol is 2: 1, and 0.1-0.3ml is added in every 33ml solution
Concentrated ammonia solution (ammonium hydroxide effect is to provide alkaline environment at this, and the additional amount of ammonium hydroxide can according to need adjustment), will be above-mentioned molten
Liquid ultrasound 10-30min, and 30min processing is stirred at 25-30 DEG C of temperature.
The amount for the concentrated ammonia solution being added is preferably 0.2ml/33ml solution.
Also as the further improvement of the technical program, step (4) is under mechanical stirring to the Fe for adding ammonium hydroxide3O4@SiO2
It is slowly added dropwise organic silicon source 1 in ethyl alcohol and water mixed solution, 2- bis- (triethoxy silicon substrate) ethane (BTEE) drips after 15-30min
Add the resulting Ts-DPEN function silicon source of step (3), mechanical stirring speed is 400-600r/min, and Ts-DPEN function silicon source is added dropwise
It finishes, continues stirring 2-4h and (be stirred to react the time preferably as 3h)；Wherein, BTEE skeleton silicon source and Ts-DPEN function silicon source
The molar fraction ratio for accounting for silicon source total amount respectively is 88-92% and 12-8%；
Also further, the heating reaction temperature of step (4) mesohigh hydrothermal reaction kettle is 100-110 DEG C；Reaction time is
22-28h；Vacuum after orange product obtained by reaction kettle is collected with magnetIt is dryDry, vacuum drying temperature is 40-60 DEG C, and the time is
8-12h；
Preferably, the reaction temperature is 100 DEG C, and the reaction time is for 24 hours.
Also further, in step (4), in step (4), the step of removing template CTAB is in the ethanol solution of ammonium nitrate
It completes, orange product obtained by reaction kettle is placed in the ethanol solution of ammonium nitrate, heating temperature is at 60-80 DEG C, return time
For 6-12h, separating obtained product is dried in vacuo 8-12h at 40-60 DEG C.
Another technical problem to be solved by this invention is, provides a kind of the mesoporous of the magnetic separable double-deck core-shell structure
Organosilicon Fe3O4The preparation method of-DYSNs-PMO nano material.
Its technical solution is as follows:
A kind of mesoporous organosilicon Fe of the magnetic separable double-deck core-shell structure3O4The preparation side of-DYSNs-PMO nano material
Method, using following steps:
(1), Fe is synthesized with ferric chloride hexahydrate first3O4Magnetic nano-particle；
(2), then pass through tetraethoxysilane (TEOS) Fe synthesized by step (1)3O4Magnetic nano-particle surface shape
At silica dioxide coating, Fe is synthesized3O4@SiO2Nano particle；
(3), again with (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) and 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy
Silane (Ts silicon source) reaction generates Ts-DPEN function silicon source；
(4), the Fe then synthesized with step (2)3O4@SiO2Nano particle is precursor, under mechanical stirring, is made with CTAB
Template, and 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) and the obtained Ts-DPEN function silicon source of step (3), in height
It presses in hydrothermal reaction kettle, is copolymerized to obtain Fe using water and ethyl alcohol as solvent3O4- DYSNs-PMO nano particle.
As the further improvement of this preparation method,
Step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 180-240 DEG C, reaction time 10-14h；
In step (2), tetraethoxysilane (TEOS) is under alkaline condition, with second alcohol and water, isopropyl alcohol and water or first
Alcohol and water is solvent, it is preferred to use volume ratio is ethyl alcohol: water=4: 1 is solvent, is further formed the silica dioxide coating；Packet
Reaction temperature is 25-35 DEG C, reaction time 6-12h, mixing speed 400-600r/min when wrapping up in silica；
For step (3) in the preparation of Ts-DPEN function silicon source, solvent is methylene chloride, under the conditions of -5-0 DEG C to (1S,
2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy as Ts silicon source is slowly added dropwise in 2S) -1,2- diphenyl ethylene diamine (DPEN)
After silane 0.5-1h, it is to slowly warm up to room temperature；The reaction time 3-5h；
In step (4): the Fe synthesized with step (2)3O4@SiO2Nano particle is precursor, when using water and ethyl alcohol as solvent,
The volume ratio of water and ethyl alcohol is 2: 1, concentrated ammonia solution is added, by above-mentioned solution ultrasound 10-30min, and at 25-30 DEG C of temperature
Lower stirring 30min processing；Wherein the additional proportion of concentrated ammonia solution is the ammonia that 0.1-0.3ml is added in every 33ml final solution
Water；
Step (4) is under mechanical stirring to the Fe for adding ammonium hydroxide3O4@SiO2It has been slowly added dropwise in ethyl alcohol and water mixed solution
Machine silicon source 1,2- bis- (triethoxy silicon substrate) ethane (BTEE), the resulting Ts-DPEN function silicon of a dropping step (3) after 15-30min
Source, mechanical stirring speed are 400-600r/min, and Ts-DPEN function silicon source is added dropwise, and continue to stir 2-4h, (preferable anti-
It is 3h between seasonable)；Wherein, it is 88- that BTEE skeleton silicon source and Ts-DPEN function silicon source account for the molar fraction ratio of silicon source total amount respectively
92% and 12-8%；
The heating reaction temperature of step (4) mesohigh hydrothermal reaction kettle is 100-110 DEG C；Reaction time is 22-28h；It will
Orange product obtained by reaction kettle is dried in vacuo after being collected with magnet, and vacuum drying temperature is 40-60 DEG C, time 8-12h；
In step (4), the step of removing template CTAB, is completed in the ethanol solution of ammonium nitrate, will be obtained by reaction kettle
Orange product is placed in the ethanol solution of ammonium nitrate, and heating temperature is at 60-80 DEG C, return time 6-12h, separating obtained production
Object is dried in vacuo 8-12h at 40-60 DEG C.
As the preferred implementing form of this preparation method,
Step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 220 DEG C, reaction time 12h；
In step (2), when the solvent uses second alcohol and water, the volume ratio of ethyl alcohol and water is 4: 1；The reaction temperature is
30 DEG C, reaction time 10h；
In step (3), the dropwise addition is carried out under the conditions of 0 DEG C；
In step (4), the amount for the concentrated ammonia solution being added is 0.2ml/33ml solution；
In step (4), the reaction temperature is 100 DEG C, and the reaction time is for 24 hours.
Preparation method and its nano material by adopting the above technical scheme technically pass through first synthetic precursor template
Fe3O4@SiO2Nano particle, Ts-DPEN function silicon source, then hydrolyze with BTEE skeleton silicon source, copolymerization obtains under alkaline condition
Catalyst carrier Fe3O4- DYSNs-PMO is realized.Further, the metals such as ruthenium, rhodium, iridium are grafted after this carrier can pass through to be formed
The mesoporous organic catalyst of double-layer hollow with magnetic core.
Fe prepared by it3O4- DYSNs-PMO nano material have following features or the utility model has the advantages that
(1), simpler than traditional magnetic material synthetic method, particle is more uniform；
(2), its separation, recycling can just be made with common magnet, it is convenient and efficient；
(3), different chiral catalysts can be made by loading different metals, be reacted for various catalysis.
(4), the knot of the nano material is adjusted by the amount of adjusting TEOS silicon source and different organic silicon sources and its usage amount
Structure parameter；
(5), because material surface contains a large amount of silicone hydroxyl, function dough can be further modified, and then be widely used in
The fields such as catalysis, sewage treatment.
Detailed description of the invention
Make one to a specific embodiment of the invention with reference to the accompanying drawing to be described in detail.
Fig. 1 is Fe of the present invention3O4The synthetic route chart of-DYSNs-PMO nano material；
Fig. 2 is Fe of the present invention3O4The TEM of magnetic nano-particle schemes, and wherein Fig. 2 a, Fig. 2 b are Fe3O4Transmission electron microscope picture
(transmission electron microscope picture respectively under different multiplying)；
Fig. 3 is Fe3O4@SiO2The TEM of magnetic nano-particle schemes, and wherein Fig. 3 a, Fig. 3 b are package SiO2Fe afterwards3O4It is magnetic
Nanoparticle transmission electron microscope picture (respectively Fe3O4@SiO2Transmission electron microscope picture under different multiplying)；
Fig. 4 is Fe3O4The TEM of-DYSNs-PMO magnetic nano-particle schemes, and wherein Fig. 4 a, Fig. 4 b are magnetic bi-layer nucleocapsid
Mesoporous organosilicon nano material Fe3O4Transmission electron microscope picture (the respectively Fe of-DYSNs-PMO3O4Under-DYSNs-PMO different multiplying
Transmission electron microscope picture)；
Specific embodiment
The present invention provides a kind of mesoporous organosilicon nano material Fe of the separable double-deck core-shell structure of novel magnetic3O4-
DYSNs-PMO and preparation method thereof.
As shown in Figure 1, firstly, with FeCl3·6H2The Fe of O Material synthesis magnetism3O4Particle；Then, TEOS silicon source is added dropwise,
Form SiO2The Fe of package3O4Nano particle；Organic silicon source is added dropwise again, generates Fe after removing template agent removing CTAB3O4-DYSNs-PMO。
It is with nanoscale Fe3O4Particle is as core, using inorganic silicon, organosilicon as the double-deck core-shell structure shell.This knot
The unique material of structure has magnetic responsiveness and mesoporous protective shell.The design feature and outer surface hydrophily and uniqueness of shell
Hydrophobic cavity be dispersed in these materials in water and organic-rich aqueous solution, magnetic core, which can provide, has unique separation energy
The material of power simultaneously recycles in which can be convenient.
And utilize Fe3O4Nanoparticle constructs Fe3O4- DYSNs-PMO nanostructure is a kind of effective method, is assigned
The certain intensity of magnetization of porous material, and form functional magnetic nano material.
By Ts-DPEN function silicon source 1, (triethoxy silicon substrate) ethane of 2- bis- (BTEE) is in one pot of hydro-thermal method by mould
A kind of mesoporous organosilicon Fe of separable double-deck core-shell structure of novel magnetic is made in plate agent cocondensation3O4- DYSNs-PMO nanometers of materials
Material.This kind of material outer layer has the nano pore of sequence, strong hydro-thermal and mechanical stability.
Related art scheme of the invention will be further illustrated by specific case study on implementation below.
Embodiment 1:Fe3O4The synthesis of magnetic nano-particle
Referring to above formula, by 1.3g Iron(III) chloride hexahydrate (FeCl3·6H2) and 0.52g trisodium citrate (C O6H5Na3O7·
2H2O it) is dissolved in 40ml ethylene glycol, magnetic agitation, obtains yellow solution, 2.4g sodium acetate is then added under stiring.By gained
Yellow mixture is transferred in the stainless steel autoclave of the polytetrafluoroethylene (PTFE) of a 60ml, is heated 12h at 220 DEG C, is cooled to
Room temperature.Black magnetic nanoparticle is collected with one block of magnet, is respectively washed three or four times with deionized water and ethyl alcohol, the vacuum at 60 DEG C
Dry 12h, obtains the Fe of 0.62g3O4Magnetic nanoparticle.
Embodiment 2:Fe3O4@SiO2The synthesis of magnetic nano-particle
With reference to above formula, the Fe of 0.2g is taken3O4Nano particle is dispersed in the mixture of 80ml ethyl alcohol and 20ml deionized water
In.It is ultrasonically treated 30min.Then, 2.0ml concentrated ammonia solution (28%) and 1.5ml tetraethoxysilane (TEOS) are sequentially added,
10h hydrolysis, polymerization, the Fe of generation are stirred at 30 DEG C3O4@SiO2Nano particle is collected with one block of magnet, and uses deionization respectively
Water and ethyl alcohol clean 3 times, are dried in vacuo at 55 DEG C, obtain 0.5g Fe3O4@SiO2Magnetic nanoparticle.
The preparation of embodiment 3:Ts-DPEN organic silicon source
With reference to above formula, by (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) of 86mg (0.40mmol) be dissolved in 10ml without
In water methylene chloride, 0.2ml anhydrous triethylamine is then added, is stirred under ice-water bath, then 0.15ml is slowly added dropwise
(0.31mmol) 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy silane (Ts silicon source) is dissolved in molten in 10ml anhydrous methylene chloride
Liquid after being added dropwise, is slowly increased to room temperature, continues after stirring 6h at room temperature, is spin-dried for being concentrated to get 0.15g Ts-DPEN function
Silicon source.
Embodiment 4: the mesoporous organosilicon Fe of magnetic bi-layer nucleocapsid3O4The preparation of-DYSNs-PMO
With reference to above formula, by 200mgFe3O4@SiO2Nano particle is dispersed in deionized water containing 44mL and 22ml ethyl alcohol is molten
In liquid, 0.24g CTAB and 2ml concentrated ammonia solution is added.With ultrasonication 30min, then stirring 30min makes it uniformly
1,2- bis- (triethoxy silicon substrate) ethane (BTEE) of 0.6ml is slowly added dropwise in the case of stirring in dispersion, after 15min by
Ts-DPEN function silicon source is added dropwise in drop, continues to stir 3h at room temperature.Next, obtained mixture is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene, 100 DEG C at a temperature of handle for 24 hours, after being cooled to room temperature, collected with magnet, then with ethyl alcohol and deionization
Water washing three times, obtain orange product.Then 10h is dried in vacuo at 60 DEG C.Finally use 0.2MNH4NO3Ethanol solution, by mould
Plate agent CTAB removes, and obtains 0.62gFe3O4-DYSNs-PMO。
The present invention first synthesizes Ts-DPEN function silicon source, then with 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) skeleton
Silicon source hydrolyzes copolymerization under alkaline condition and obtains catalyst carrier Fe3O4- DYSNs-PMO after forming destination carrier, can be grafted more
Kind metallic catalyst eventually forms the mesoporous organosilicon nanocatalyst of the double-deck core-shell structure with magnetic core.
Claims (16)
1. a kind of magnetic separable double-deck core-shell structure mesoporous organosilicon Fe3O4- DYSNs-PMO nano material, which is characterized in that
It is prepared using following steps:
(1), Fe is synthesized with ferric chloride hexahydrate first3O4Magnetic nano-particle；
(2), then pass through tetraethoxysilane (TEOS) Fe synthesized by step (1)3O4Magnetic nano-particle surface forms two
Silica coating synthesizes Fe3O4@SiO2Nano particle；
(3), again with (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) and 2- (4- chlorine sulfonyl-phenyl) ethyl as Ts silicon source
Trimethoxy silane reaction generates Ts-DPEN function silicon source；
(4), the Fe then synthesized with step (2)3O4@SiO2Nano particle is precursor, under mechanical stirring, makees template with CTAB
Agent, and 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) and the obtained Ts-DPEN function silicon source of step (3), in high pressure water
In thermal response kettle, Fe is copolymerized to obtain using water and ethyl alcohol as solvent3O4- DYSNs-PMO nano particle.
2. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 180-240 DEG C, and the reaction time is
10-14h。
3. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 23O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 220 DEG C, reaction time 12h.
4. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that it is characterized in that, tetraethoxysilane (TEOS) is that under alkaline condition, solvent is second in step (2)
Alcohol and water, isopropyl alcohol and water or first alcohol and water, are further formed the silica dioxide coating；Reaction temperature when wrapping up silica
Degree is 25-35 DEG C, reaction time 6-12h, mechanical stirring speed 400-600r/min.
5. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 43O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that when the solvent uses second alcohol and water, the volume ratio of ethyl alcohol and water is 4: 1；The reaction temperature is 30
DEG C, reaction time 10h.
6. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that for step (3) in the preparation of Ts-DPEN function silicon source, solvent is methylene chloride, under the conditions of -5-0 DEG C
2- (4- chlorine sulfonyl-phenyl) ethyl three as Ts silicon source is slowly added dropwise into (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN)
After methoxy silane 0.5-1h, it is to slowly warm up to room temperature；The reaction time 3-5h.
7. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that carry out the dropwise addition under the conditions of 0 DEG C.
8. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that in step (4): the Fe synthesized with step (2)3O4@SiO2Nano particle is precursor, is molten with water and ethyl alcohol
When agent, the volume ratio of water and ethyl alcohol is 2: 1, concentrated ammonia solution is added, by above-mentioned solution ultrasound 10-30min, and in temperature
30min processing is stirred at 25-30 DEG C；Wherein the additional proportion of concentrated ammonia solution is that 0.1- is added in every 33ml final solution
The ammonium hydroxide of 0.3ml.
9. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 83O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that the amount for the concentrated ammonia solution being added is the ammonium hydroxide that 0.2ml is added in every 33ml final solution.
10. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that step (4) is under mechanical stirring to the Fe for adding ammonium hydroxide3O4@SiO2In ethyl alcohol and water mixed solution slowly
Organic silicon source 1,2- bis- (triethoxy silicon substrate) ethane (BTEE), a dropping step (3) resulting Ts-DPEN after 15-30min is added dropwise
Function silicon source, mechanical stirring speed are 400-600r/min, and Ts-DPEN function silicon source is added dropwise, and continue to stir 2-4h；Its
In, BTEE skeleton silicon source and Ts-DPEN function silicon source account for the molar fraction ratio of silicon source total amount respectively as 88-92% and 12-8%.
11. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that the heating reaction temperature of step (4) mesohigh hydrothermal reaction kettle is 100-110 DEG C；Reaction time is 22-
28h；It is dried in vacuo after orange product obtained by reaction kettle is collected with magnet, vacuum drying temperature is 40-60 DEG C, time 8-
12h。
12. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 113O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that the reaction temperature is 100 DEG C, and the reaction time is for 24 hours.
13. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
Material, which is characterized in that in step (4), the step of removing template CTAB is completed in the ethanol solution of ammonium nitrate, will be reacted
Orange product obtained by kettle is placed in the ethanol solution of ammonium nitrate, and heating temperature is at 60-80 DEG C, and flow back 6-12h, separating obtained production
Object is dried in vacuo 8-12h at 40-60 DEG C.
14. a kind of magnetic separable double-deck core-shell structure mesoporous organosilicon Fe3O4The preparation method of-DYSNs-PMO nano material, it is special
Sign is, using following steps:
(1), Fe is synthesized with ferric chloride hexahydrate first3O4Magnetic nano-particle；
(2), then pass through tetraethoxysilane (TEOS) Fe synthesized by step (1)3O4Magnetic nano-particle surface forms two
Silica coating synthesizes Fe3O4@SiO2Nano particle；
(3), again with (1S, 2S) -1,2- diphenyl ethylene diamine (DPEN) and 2- (4- chlorine sulfonyl-phenyl) ethyl as Ts silicon source
Trimethoxy silane reaction generates Ts-DPEN function silicon source；
(4), the Fe then synthesized with step (2)3O4@SiO2Nano particle is precursor, under mechanical stirring, makees template with CTAB
Agent, and 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) and the obtained Ts-DPEN function silicon source of step (3), in high pressure water
In thermal response kettle, Fe is copolymerized to obtain using water and ethyl alcohol as solvent3O4- DYSNs-PMO nano particle.
15. the 4 magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 13O4- DYSNs-PMO nanometers of materials
The preparation method of material, which is characterized in that
Step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 180-240 DEG C, reaction time 10-14h；
In step (2), tetraethoxysilane (TEOS) be under alkaline condition, with second alcohol and water, isopropyl alcohol and water or methanol and
Water is solvent, is further formed the silica dioxide coating；Reaction temperature is 25-35 DEG C when wrapping up silica, the reaction time
For 6-12h, mixing speed 400-600r/min；
For step (3) in the preparation of Ts-DPEN function silicon source, solvent is methylene chloride, to (1S, 2S)-under the conditions of -5-0 DEG C
2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy silane as Ts silicon source is slowly added dropwise in 1,2- diphenyl ethylene diamine (DPEN)
After 0.5-1h, it is to slowly warm up to room temperature；The reaction time 3-5h；
In step (4): the Fe synthesized with step (2)3O4@SiO2Nano particle is precursor, when using water and ethyl alcohol as solvent, water and
The volume ratio of ethyl alcohol is 2: 1, adds concentrated ammonia solution, stirs by above-mentioned solution ultrasound 10-30min, and at 25-30 DEG C of temperature
Mix 30min processing；Wherein the additional proportion of concentrated ammonia solution is the ammonium hydroxide that 0.1-0.3ml is added in every 33ml final solution；
Step (4) is under mechanical stirring to the Fe for adding ammonium hydroxide3O4@SiO2Organosilicon is slowly added dropwise in ethyl alcohol and water mixed solution
Source 1,2- bis- (triethoxy silicon substrate) ethane (BTEE), the resulting Ts-DPEN function silicon source of a dropping step (3) after 15-30min,
Mechanical stirring speed is 400-600r/min, and Ts-DPEN function silicon source is added dropwise, and continues to stir 2-4h；Wherein, BTEE skeleton
The molar fraction ratio that silicon source and Ts-DPEN function silicon source account for silicon source total amount respectively is 88-92% and 12-8%；
The heating reaction temperature of step (4) mesohigh hydrothermal reaction kettle is 100-110 DEG C；Reaction time is 22-28h；It will reaction
Orange product obtained by kettle is dried in vacuo after being collected with magnet, and vacuum drying temperature is 40-60 DEG C, time 8-12h；
In step (4), the step of removing template CTAB, is completed in the ethanol solution of ammonium nitrate, will be orange obtained by reaction kettle
Product is placed in the ethanol solution of ammonium nitrate, and heating temperature is at 60-80 DEG C, return time 6-12h, separating obtained product,
8-12h is dried in vacuo at 40-60 DEG C.
16. the magnetic separable double-deck core-shell structure mesoporous organosilicon Fe according to claim 153O4- DYSNs-PMO nanometers of materials
The preparation method of material, which is characterized in that
Step (1) Fe3O4In the preparation of magnetic nano-particle, reaction temperature is 220 DEG C, reaction time 12h；
In step (2), when the solvent uses second alcohol and water, the volume ratio of ethyl alcohol and water is 4: 1；The reaction temperature is 30
DEG C, reaction time 10h；
In step (3), the dropwise addition is carried out under the conditions of 0 DEG C；
In step (4), the amount for the concentrated ammonia solution being added is the ammonium hydroxide that 0.2ml is added in every 33ml final solution；
In step (4), the reaction temperature is 100 DEG C, and the reaction time is for 24 hours.
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| CN114011240A (en) * | 2021-10-25 | 2022-02-08 | 西南交通大学 | Functional group Fe3O4/SiO2Preparation and forward osmosis application of core-shell composite magnetic nano material |
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