CN105521772A - Magnetic core-shell-structured nano-material, preparation method therefor and application of magnetic core-shell-structured nano-material - Google Patents
Magnetic core-shell-structured nano-material, preparation method therefor and application of magnetic core-shell-structured nano-material Download PDFInfo
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- CN105521772A CN105521772A CN201610009331.0A CN201610009331A CN105521772A CN 105521772 A CN105521772 A CN 105521772A CN 201610009331 A CN201610009331 A CN 201610009331A CN 105521772 A CN105521772 A CN 105521772A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 121
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 101
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229960003638 dopamine Drugs 0.000 claims abstract description 47
- 150000002815 nickel Chemical class 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005530 etching Methods 0.000 claims abstract description 12
- 239000013522 chelant Substances 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 5
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims description 111
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000002077 nanosphere Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- -1 aromatic nitro compounds Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 31
- 239000002245 particle Substances 0.000 description 31
- 229910052759 nickel Inorganic materials 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OUIITAOCYATDMY-UHFFFAOYSA-N 4-amino-2-phenylphenol Chemical compound NC1=CC=C(O)C(C=2C=CC=CC=2)=C1 OUIITAOCYATDMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/755—Nickel
-
- B01J35/396—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention discloses a magnetic core-shell-structured nano-material, a preparation method therefor and application of the magnetic core-shell-structured nano-material. The magnetic core-shell-structured nano-material is prepared through coating silicon dioxide nanospheres by a chelate of dopamine and a nickel salt so as to obtain a Ni<2+>-PDA@SiO2 core-shell-structured nano-material, subjecting the Ni<2+>-PDA@SiO2 core-shell-structured nano-material to roasting or etching and then carrying out roasting. Shown by experiments, the magnetic core-shell-structured nano-material disclosed by the invention has the advantages of large specific surface area, good morphology, relatively high magnetic property, excellent adsorption and catalysis performance and the like, can serve as a protein adsorbent and a reduction reaction catalyst of aromatic nitro compounds and has relatively good use values and application prospects in the fields of environment, energy sources and the like.
Description
Technical field
The present invention relates to a kind of magnetic core-shell structure nano material and its preparation method and application, belongs to technical field of nano material.
Background technology
Along with the development of nanometer technology, nuclear-shell structured nano-composite material becomes the focus of the area research such as composite, nano material.The nano composite material (CSNC) of nucleocapsid structure generally by center core and be coated on outside shell and form, the kernel in CSNC and being interconnected by physics, chemical action between shell.The nucleocapsid structure of broad sense not only comprises the nano composite material with nucleocapsid structure be made up of different material, also comprises the nano composite material such as hollow microsphere, microcapsules.Because CSNC has the physics and chemistry characteristic of many uniquenesses, in fields such as super-hydrophobic surface coating, materialogy, chemistry, magnetics, electricity, optics, biomedicine, catalysis, all there is potential using value.
Research shows: SiO
2nanometer bead has the advantages such as specific area is large, size adjustable, nontoxicity, therefore, not only can as the carrier of functional material, also can as the preparation template of core-shell nano material; Dopamine and silica have good biocompatibility, and environmental friendliness is pollution-free, and make the carbon source obtained by it can have very large application prospect in ultracapacitor containing nitrogen element in dopamine.Existing research at present adopts dopamine to SiO
2nanometer bead carries out finishing, prepares core-shell structured nanomaterials, but at present also not by the chelate of nickel salt and dopamine and SiO
2nanometer bead combines and prepares the report of core-shell structured nanomaterials, more not the related application report of this core-shell structured nanomaterials.
In addition, in the past with SiO
2nanometer bead is template, and the method that the chelate of coated dopamine or transition metal salt and dopamine prepares core-shell structured nanomaterials is two steps and synthesizes, and is all first synthesize SiO
2nanometer bead, then needs the presoma SiO of preparation
2the centrifugation of nanometer bead also carries out several carrying out washing treatment with solvent, again to SiO after process terminates
2nanometer bead carries out the coated of the chelate of dopamine or dopamine and transition metal salt, the product that finally obtains needs centrifugation again and solvent wash, because separation each time all needs the washing of long period and solvent, so just cause the consumption of waste of time and solvent, and repeatedly wash the loss also causing sample.
Summary of the invention
For the problems referred to above that prior art exists, the object of this invention is to provide a kind of magnetic core-shell structure nano material and its preparation method and application, to expand kind and the application of core-shell structured nanomaterials.
For achieving the above object, the present invention adopts following technical scheme:
A kind of magnetic core-shell structure nano material carries out the coated Ni obtained by the chelate of dopamine and nickel salt to silica nanosphere
2+-PDASiO
2core-shell structured nanomaterials through roasting or after over etching again roasting obtain.
Prepare a method for magnetic core-shell structure nano material of the present invention, comprise the steps:
A) first adopt
legal system prepared silicon dioxide nanosphere, then directly to the mixed solution adding dopamine and nickel salt in the reaction solution preparing silica nanosphere, makes the core-shell structured nanomaterials of the chelate coated silica of obtained dopamine and nickel salt, that is: Ni
2+-PDASiO
2core-shell structured nanomaterials;
B) by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials carries out insulation roasting or carry out insulation roasting again after over etching, obtains described magnetic core-shell structure nano material.
Preferably, described step a) comprises following operation:
First in the mixed solution system of alcohol water and ammoniacal liquor, drip tetraethyl orthosilicate (i.e. TEOS), at room temperature stir 3 ~ 8 hours, make tetraethyl orthosilicate complete hydrolysis generate silica nanosphere; Then in the reaction solution of silica nanosphere, directly add the mixed solution of dopamine and nickel salt, at room temperature continue stirring 6 ~ 24 hours; Terminate reaction, centrifugation, the solid collected washed, dry, obtain Ni
2+-PDASiO
2core-shell structured nanomaterials.
As further preferred version, 1 milliliter of tetraethyl orthosilicate uses the mixed solution of 10 ~ 40 milliliters of alcohol water and ammoniacal liquor.
As further preferred version, described alcohol water is by volume for 1:1 ~ 20:1 (best with 2:1 ~ 15:1) is formed by alcoholic solvent (such as ethanol) and water.
As further preferred version, the mixed solution of described alcohol water and ammoniacal liquor is by volume for 8:1 ~ 40:1 (best with 10:1 ~ 35:1) is formed by alcohol water and ammoniacal liquor.
As further preferred version, the mol ratio of described dopamine and nickel salt is 2:1 ~ 2:10 (best with 2:1 ~ 2:8).
Preferably; step b) in insulation roasting be gas (such as nitrogen) protection under; first be warming up to 350 ~ 800 DEG C (with 450 ~ 550 DEG C of the bests) with the heating rate of 8 ~ 12 DEG C/min, then carry out insulation roasting 4 ~ 6 hours.
Preferably, step b) in etching adopt deionized water.
As further preferred version, described etching comprises following operation: first by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials dispersion in deionized water, ultrasonic evenly after be transferred in reactor, then 150 ~ 170 DEG C of insulations 12 ~ 24 hours.
Nickel salt described in the present invention is water soluble nickel salt, can selective chlorination nickel, nickel nitrate etc.
Magnetic core-shell structure nano material of the present invention can be used as protein adsorbent, especially can be used as BHb adsorbent.
Magnetic core-shell structure nano material of the present invention also can be used as the reduction catalyst of fragrant nitro compound, especially can be used as the reduction catalyst of nitrophenol (such as: p-nitrophenol).
The concentration of ammoniacal liquor described in the present invention is 32wt%.
Compared with prior art, the present invention has following conspicuousness beneficial effect:
1, first the present invention by making the chelate coated silica nanosphere of dopamine and nickel salt, obtained Ni
2+-PDASiO
2core-shell structured nanomaterials, then to Ni
2+-PDASiO
2core-shell structured nanomaterials carries out roasting, makes the nickel particle in reduction precipitation material, obtains the particle studded thorn-like magnetic core-shell structure nano material on surface of metallic nickel; When carrying out roasting again after over etching, hollow thorn-like magnetic core-shell structure nano material can be obtained; After tested: thorn-like magnetic core-shell structure nano material provided by the present invention has that specific area is large, appearance structure good, magnetic is comparatively strong, absorption and the advantage such as catalytic performance is excellent, especially can be used for the selective absorption of BHb and the reduction catalysts reaction of p-nitrophenol, and in the field such as environment, the energy, also there is good use value and application prospect;
2, the present invention adopts one-step method to obtain Ni
2+-PDASiO
2core-shell structured nanomaterials, process without the need to the silica nanosphere of generation is separated in advance in preparation, save the time and decreased the consumption of reagent greatly, synthetic method is simply effective, environmental friendliness, reagent is easy to get and consumes few, and output is high, and the product stable appearance of preparation, is applicable to large-scale production;
3, the present invention is by regulating the mol ratio of alcohol water when dopamine and nickel salt, regulates and controls the particle size of the magnetic core-shell structure nano material prepared, the nickel metallic particles amount of institute's load, the nickel grain diameter size of institute's load; In addition, to Ni
2+-PDASiO
2core-shell structured nanomaterials carries out roasting after carrying out deionized water etching again, can obtain hollow core-shell structured nanomaterials, and can have comparatively bigger serface by opposing solid core-shell structured nanomaterials, adsorbance is larger.
Accompanying drawing explanation
Fig. 1-1 adopts different alcohol water than the Ni prepared in embodiment 1
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials;
Fig. 1-2 is the scanning electron microscope (SEM) photograph adopting different alcohol water in embodiment 1 than the magnetic core-shell structure nano material prepared;
Fig. 2-1 is the Ni adopting the different mol ratio of dopamine and nickel salt to prepare in embodiment 2
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials;
Fig. 2-2 is the scanning electron microscope (SEM) photograph of the magnetic core-shell structure nano material adopting the different mol ratio of dopamine and nickel salt to prepare in embodiment 2;
Fig. 3-1 is the Ni prepared in embodiment 3
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials;
Fig. 3-2 is the scanning electron microscope (SEM) photograph of the magnetic core-shell structure nano material prepared in embodiment 3;
Fig. 4 a is that the XRD of the magnetic core-shell structure nano material adopting the different mol ratio of dopamine and nickel salt to prepare in embodiment 4 schemes; Fig. 4 b is the XRD figure of the magnetic core-shell structure nano material adopting different sintering temperature to prepare in embodiment 4;
Fig. 5 be in application examples 1 magnetic core-shell structure nano material to the catalytic effect figure of p-nitrophenol reduction reaction, wherein: Fig. 5 a embodies the conversion ratio impact that magnetic core-shell structure nano material reacts the reduction catalysts of p-nitrophenol; Fig. 5 b embodies the catalytic activity that magnetic core-shell structure nano material circulation uses; Fig. 5 c embodies the feasibility that magnetic core-shell structure nano material reacts for the reduction catalysts of p-nitrophenol;
Fig. 6 be in application examples 2 magnetic core-shell structure nano material to the adsorption isothermal curve figure of BHb;
Fig. 7 be in application examples 3 magnetic core-shell structure nano material to the design sketch of protein adsorption, wherein: Fig. 7 A, 7B, 7C embody the selective absorption effect of magnetic core-shell structure nano material to albumen; Fig. 7 D embodies the absorption property that magnetic core-shell structure nano material recycles BHb.
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.
Embodiment 1
A) by 30mL absolute ethyl alcohol, 3mL water (alcohol water is than being 10:1) and 1mL concentration are that the ammoniacal liquor of 32wt% joins in a clean beaker, stirring makes it to mix, then 1.2mLTEOS (ethyl orthosilicate) is under agitation dropwise added, at room temperature stir 6 hours, then mixed solution (the wherein dopamine 2 50mg of dopamine and Nickel dichloride hexahydrate (mol ratio is 2:4) is dripped, Nickel dichloride hexahydrate 775mg), at room temperature continue stirring 7 hours, then centrifugation (6000rpm, 3min), centrifuge washing 3 times are distinguished to the solid collected successively use water and ethanol, then dry, namely Ni is obtained
2+-PDASiO
2core-shell structured nanomaterials,
B) by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials 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, namely obtaining the magnetic core-shell structure nano material of nickel-loaded particle.
Under same experimental conditions, alcohol water is replaced with 2:1,6:1,15:1 than respectively, prepare corresponding Ni respectively
2+-PDASiO
2and magnetic core-shell structure nano material of the present invention.
Fig. 1-1 is the Ni prepared under different alcohol water ratio
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials under high low power lens; Fig. 1-2 is the scanning electron microscope (SEM) photograph of magnetic core-shell structure nano material under high low power lens prepared under different alcohol water ratio; In figure: a, b are 2:1 alcohol water ratio; C, d are 6:1 alcohol water ratio; E, f are 10:1 alcohol water ratio; G, h are 15:1 alcohol water ratio; From Fig. 1-1: adopt preparation method described in embodiment 1, the Ni that size is homogeneous, smooth surface, appearance structure are good can be obtained
2+-PDASiO
2core-shell structured nanomaterials; From Fig. 1-2: adopt preparation method described in embodiment 1, size is homogeneous, area load particle diameter is comparatively homogeneous metallic nickel particle can be obtained and nickel particle dispersion is good, the thorn-like magnetic core-shell structure nano material that overall appearance structure is good; Composition graphs 1-1 and 1-2 can also find: ditto put at other condition homogeneous phase, only changes alcohol water ratio, the Ni obtained
2+-PDASiO
2and the particle size of magnetic core-shell structure nano material can change thereupon, explanation can regulate and control Ni by regulating alcohol water ratio
2+-PDASiO
2and the particle size of magnetic core-shell structure nano material; Adopt above-mentioned different alcohol water than the magnetic core-shell structure nano material prepared, its silica nanosphere particle diameter is between 118 ~ 218nm, and its shell thickness is about 24nm, and nickel grain diameter is about 10nm.
Embodiment 2
A) by 30mL absolute ethyl alcohol, 5mL water (alcohol water is than being 6:1) and 1mL concentration are that the ammoniacal liquor of 32wt% joins in a clean beaker, stirring makes it to mix, then 1.2mLTEOS (ethyl orthosilicate) is under agitation dropwise added, at room temperature stir 4 hours, then mixed solution (the wherein dopamine 2 50mg of dopamine and Nickel dichloride hexahydrate (mol ratio is 2:4) is dripped, Nickel dichloride hexahydrate 775mg), at room temperature continue stirring 24 hours, then centrifugation (6000rpm, 3min), centrifuge washing 3 times are distinguished to the solid collected successively use water and ethanol, then dry, namely Ni is obtained
2+-PDASiO
2core-shell structured nanomaterials,
B) by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials 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, namely obtaining the magnetic core-shell structure nano material of nickel-loaded particle.
Under same experimental conditions, the mol ratio of dopamine and nickel salt is replaced with 2:1,2:6,2:8 respectively, prepare corresponding Ni respectively
2+-PDASiO
2and magnetic core-shell structure nano material of the present invention.
Fig. 2-1 is the Ni prepared under the mol ratio of different dopamine and nickel salt
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials under high low power lens, Fig. 2-2 is the magnetic core-shell structure nano material scanning electron microscope (SEM) photographs under high low power lens prepared under the mol ratio of different dopamine and nickel salt, in figure: a, b are 2:1 mol ratio, c, d are 2:4 mol ratio, e, f are 2:6 mol ratio, g, h are 2:8 mol ratio, from Fig. 2-1: adopt preparation method described in embodiment 2, the Ni that size is homogeneous, smooth surface, appearance structure are good can be obtained
2+-PDASiO
2core-shell structured nanomaterials, from Fig. 2-2: adopt preparation method described in embodiment 2, size is homogeneous, area load particle diameter is comparatively homogeneous metallic nickel particle can be obtained and the good magnetic core-shell structure nano material of good, the overall appearance structure of nickel particle dispersion, can also be found by Fig. 2-2: along with the change of the mol ratio of dopamine and nickel salt, the nickel grain amount of the surperficial institute load of the magnetic core-shell structure nano material obtained, nickel grain diameter size and nickel distribution of particles situation all also change to some extent, when wherein mol ratio is 2:1 and 2:4, nickel grain diameter is about 10nm, when mol ratio is 2:6, particle size range is 7 ~ 20nm, when mol ratio is 2:8, particle size range is 15 ~ 28nm, illustrate thus, can regulate and control by regulating the nickel particle situation of mol ratio to the surperficial institute load of magnetic core-shell structure nano material of dopamine and nickel salt.
Embodiment 3
A) by 25mL absolute ethyl alcohol, 15mL water (alcohol water is than being 25:15) and 3.75mL concentration are that the ammoniacal liquor of 32wt% joins in a clean beaker, stirring makes it to mix, then 3.4mLTEOS (ethyl orthosilicate) is under agitation dropwise added, at room temperature stir 8 hours, then mixed solution (the wherein dopamine 2 50mg of dopamine and Nickel dichloride hexahydrate (mol ratio is 2:6) is dripped, Nickel dichloride hexahydrate 1164mg), at room temperature continue stirring 7 hours, then centrifugation (6000rpm, 3min), centrifuge washing 3 times are distinguished to the solid collected successively use water and ethanol, then dry, namely Ni is obtained
2+-PDASiO
2core-shell structured nanomaterials,
B) by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials 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, namely obtaining the magnetic core-shell structure nano material of nickel-loaded particle.
Under identical experiment condition, the mol ratio of dopamine and nickel salt is replaced with 2:1,2:4,2:8 respectively, prepare corresponding Ni respectively
2+-PDASiO
2and magnetic core-shell structure nano material of the present invention.
Fig. 3-1 is the Ni prepared under the mol ratio of different dopamine and nickel salt
2+-PDASiO
2the scanning electron microscope (SEM) photograph of core-shell structured nanomaterials under high low power lens; Fig. 3-2 is the magnetic core-shell structure nano material scanning electron microscope (SEM) photographs under high low power lens prepared under the mol ratio of different dopamine and nickel salt; In figure: a, b are 2:1 mol ratio; C, d are 2:4 mol ratio; E, f are 2:6 mol ratio; G, h are 2:8 mol ratio; From Fig. 3-1: adopt preparation method described in embodiment 2, the Ni that size is homogeneous, smooth surface, appearance structure are good can be obtained
2+-PDASiO
2core-shell structured nanomaterials; From Fig. 2-2: adopt preparation method described in embodiment 2, size is homogeneous, area load particle diameter is comparatively homogeneous metallic nickel particle can be obtained and the good magnetic core-shell structure nano material of good, the overall appearance structure of nickel particle dispersion; Can find in conjunction with Fig. 1-2, Fig. 2-2 and Fig. 3-2: when the amount in alcohol water ratio, dopamine and the mol ratio of nickel salt, the amount of ammoniacal liquor and silicon source changes all to some extent, adopt the inventive method still can prepare excellent, the stable magnetic core-shell structure nano material of appearance structure, illustrate that preparation method of the present invention has universality, can be applicable; In addition, the particle diameter of the magnetic core-shell structure nano material adopting the present embodiment to prepare is 300 ~ 350nm, and shell thickness is about 10nm, and the particle diameter of nickel particle is about 10nm.
Embodiment 4
1, nickel content is on the impact of magnetic:
The Ni prepared when the mol ratio of dopamine and nickel salt is respectively 2:1,2:4,2:6,2:8 in Example 2
2+-PDASiO
2core-shell structured nanomaterials is incubated roasting 5 hours at 500 DEG C, the XRD collection of illustrative plates of prepared magnetic core-shell structure nano material as shown in fig. 4 a, in figure: a is dopamine Ni corresponding when being 2:6 with the mol ratio of nickel salt
2+-PDASiO
2core-shell structured nanomaterials, b, c, d, e are the mol ratio of dopamine and nickel salt respectively magnetic core-shell structure nano material prepared when being 2:1,2:4,2:6,2:8; From Fig. 4 a: along with the increase of nickel content and the increase of nickel grain diameter, the peak intensity of XRD collection of illustrative plates more by force and narrower, illustrates that the magnetic of magnetic core-shell structure nano material also increases thereupon.
2, sintering temperature is on the impact of magnetic:
Get the Ni prepared when the mol ratio of dopamine and nickel salt is 2:4 in three parts of a certain amount of embodiments 2
2+-PDASiO
2core-shell structured nanomaterials, roasting is incubated 5 hours at 350 DEG C, 500 DEG C, 800 DEG C, as shown in Figure 4 b, in figure, a, b, c represent sintering temperature is successively 350 DEG C, 500 DEG C, 800 DEG C to the XRD collection of illustrative plates of three parts of prepared magnetic core-shell structure nano materials; From Fig. 4 b: along with the rising of sintering temperature, the particle diameter of the nickel particle of three sample institutes load changes from small to big successively, illustrates that the magnetic of magnetic core-shell structure nano material also increases thereupon.
To sum up experiment is visible: nickel content and the magnetic of sintering temperature on magnetic core-shell structure nano material all can affect to some extent.In addition, about sintering temperature, although the magnetic that 800 DEG C of roastings obtain product is best, but nickel particle agglomeration can be made to be the excessive particle of particle diameter simultaneously, and then it is excessive to make nickel specific grain surface amass, degradation, therefore consider from nickel grain diameter size and magnetism of material, be about 500 DEG C the bests with sintering temperature; About nickel content, although within the specific limits along with the increase of nickel content can improve the magnetic of product, nickel content is more, roasting back loading metallic nickel grain amount is more, but easily can reunite for larger particles too much, make product specific area excessive, degradation.
Embodiment 5
Choose Ni prepared when alcohol water is 2:4 than the mol ratio for 6:1, dopamine and nickel salt in embodiment 1 or embodiment 2
2+-PDASiO
2core-shell structured nanomaterials is appropriate, make to be scattered in 30mL deionized water, ultrasonic evenly after be transferred in reactor, insulation etching 18h at 160 DEG C, then centrifugal treating, dry after 3 times are washed with water and ethanol successively to the solid collected, then be warming up to 500 DEG C under nitrogen protection, so that heating rate 10 DEG C is per minute, then be incubated roasting 5 hours, obtain thorn-like magnetic hollow core-shell structured nanomaterials; General knowledge from this area: hollow core-shell structure nano material will have comparatively bigger serface than solid core-shell structured nanomaterials, and adsorbance is large.
Application examples 1
Catalytic performance is examined or check:
1, getting the magnetic core-shell structure nano material that 1mL concentration is 1mg/4mL (compares for 6:1 at alcohol water in embodiment 1, the mol ratio of dopamine and nickel salt is product prepared under 2:4 condition) ethanolic solution be in the p-nitrophenol aqueous solution of 0.2mmol/L in 9mL concentration, then by 5mgNaBH
4add in p-nitrophenyl phenol solution fast, with UV UV spectrophotometer measuring p-nitrophenol concentration over time, testing result is shown in shown in Fig. 5 a.
2, catalysis terminate after by magnetic core-shell structure nano material centrifuge washing, then vacuum drying, is cycled to used in the reduction reaction of catalysis p-nitrophenol, to examine or check the activity that it recycles, refers to shown in Fig. 5 b.
3, the feasibility of catalytic reaction is verified: when adding 5mg sodium borohydride in the p-nitrophenyl phenol solution of 9mL, p-nitrophenyl phenol solution becomes glassy yellow from light yellow, the ultraviolet absorption peak of p-nitrophenol is that 317nm is advanced to 400nm place by wavelength immediately, 400nm place is the ultraviolet absorption peak of intermediate product, when solution becomes colorless, p-nitrophenyl phenol solution has been reduced to p-aminophenyl phenol solution, its ultraviolet absorption peak is at wavelength 295nm place, and the change of course of reaction medium ultraviolet absworption peak as shown in Figure 5 c.
Composition graphs 5a, Fig. 5 b and Fig. 5 c is visible: p-nitrophenol catalytic reduction can be effectively para-aminophenol by magnetic core-shell structure nano material of the present invention, and catalytic action is obvious, can the reduction reaction of in minutes quick catalysis p-nitrophenol, and after 5 times recycle, still there is obvious catalytic activity.
Application examples 2
Absorption property is examined or check:
The BHb solution of 0.025,0.05,0.1,0.2,0.3 and 0.4mg/mL is respectively with PBS (phosphate buffer be made up of sodium dihydrogen phosphate and the sodium hydrogen phosphate) compound concentration that pH is about 8.0, concentration is 20mmol/L, survey its ultraviolet absorption peak with ultraviolet specrophotometer, and make standard concentration curve figure;
Get the BHb solution 6mL of above-mentioned each concentration respectively, (compare for 6:1 at alcohol water in embodiment 1 respectively to wherein adding 0.5mg magnetic core-shell structure nano material, the mol ratio of dopamine and nickel salt is product prepared under 2:4 condition), vibrate on the oscillator again 5 ~ 6 hours after ultrasonic disperse is even, leave standstill a night, centrifugation, get supernatant, its ultraviolet absorption peak is surveyed with ultraviolet specrophotometer, by the BHb concentration after the known absorption of the calibration curve made before, can according to protein adsorption quantity formulae discovery to the adsorbance of BHb, finally make the adsorption isothermal curve of BHb, in detail as shown in Figure 6, as seen from Figure 6: magnetic core-shell structure nano material of the present invention has excellent isothermal adsorption effect to BHb, can be used as the adsorbent of BHb.
Application examples 3
Selective absorption performance check study:
1, BHb (BHb), BSA (bovine serum albumin) and the BHb/BSA solution of 0.4mg/mL is with PBS (phosphate buffer be made up of sodium dihydrogen phosphate and the sodium hydrogen phosphate) compound concentration that pH is about 8.0, concentration is 20mmol/L, by its UV absorption situation of UV spectrophotometer measuring, refer to shown in Fig. 7 A;
Get above-mentioned each solution 4mL respectively, (compare for 6:1 at alcohol water in embodiment 1 respectively to wherein adding 4mg magnetic core-shell structure nano material, the mol ratio of dopamine and nickel salt is product prepared under 2:4 condition), vibrate on the oscillator again 5 ~ 6 hours after ultrasonic disperse is even, leave standstill a night, centrifugation, gets supernatant, by its UV absorption situation of UV spectrophotometer measuring, refer to shown in Fig. 7 B;
After twice is washed to the PBS that is 20mmol/L of the precipitation concentration after centrifugation, add the methylimidazole solution (preparing with the PBS of 20mmol/L) that 4mL concentration is 0.2g/mL more wherein, implement wash-out, vibrate on the oscillator again 5 ~ 6 hours after ultrasonic disperse is even, leave standstill a night, centrifugation, gets supernatant, by its UV absorption situation of UV spectrophotometer measuring, refer to shown in Fig. 7 C.
2, recycle:
Getting 4mg magnetic core-shell structure nano material, to add 9mL concentration be adsorb in the BHb solution of 0.2mg/mL, examines or check the change of the adsorption rate recycled for 5 times, refer to shown in Fig. 7 D.
Composition graphs 7A, 7B and 7C are visible: magnetic core-shell structure nano material of the present invention is obviously better than the suction-operated to bovine serum albumin to the suction-operated of BHb, illustrate that magnetic core-shell structure nano material of the present invention has stronger selective absorption effect to albumen; From Fig. 7 D: magnetic core-shell structure nano material of the present invention, after recycling 5 times, does not substantially change the adsorption rate of BHb, illustrates to have excellent absorption property.
Finally need to herein means out: be only part preferred embodiment of the present invention above; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. a magnetic core-shell structure nano material, is characterized in that: be carry out the coated Ni obtained by the chelate of dopamine and nickel salt to silica nanosphere
2+-PDASiO
2core-shell structured nanomaterials through roasting or after over etching again roasting obtain.
2. prepare a method for magnetic core-shell structure nano material according to claim 1, it is characterized in that, comprise the steps:
A) first adopt
legal system prepared silicon dioxide nanosphere, then directly to the mixed solution adding dopamine and nickel salt in the reaction solution preparing silica nanosphere, makes the core-shell structured nanomaterials of the chelate coated silica of obtained dopamine and nickel salt, that is: Ni
2+-PDASiO
2core-shell structured nanomaterials;
B) by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials carries out insulation roasting or carry out insulation roasting again after over etching, obtains described magnetic core-shell structure nano material.
3. method as claimed in claim 2, it is characterized in that, described step a) comprises following operation:
First in the mixed solution system of alcohol water and ammoniacal liquor, drip tetraethyl orthosilicate, at room temperature stir 3 ~ 8 hours, make tetraethyl orthosilicate complete hydrolysis generate silica nanosphere; Then in the reaction solution of silica nanosphere, directly add the mixed solution of dopamine and nickel salt, at room temperature continue stirring 6 ~ 24 hours; Terminate reaction, centrifugation, the solid collected washed, dry, obtain Ni
2+-PDASiO
2core-shell structured nanomaterials.
4. method as claimed in claim 3, is characterized in that: described alcohol water is formed for 1:1 ~ 20:1 by volume by alcoholic solvent and water; The mixed solution of described alcohol water and ammoniacal liquor is formed for 8:1 ~ 40:1 by volume by alcohol water and ammoniacal liquor.
5. method as claimed in claim 3, is characterized in that: the mol ratio of described dopamine and nickel salt is 2:1 ~ 2:10.
6. method as claimed in claim 2, is characterized in that: step b) in insulation roasting be under gas shield, be first warming up to 350 ~ 800 DEG C with the heating rate of 8 ~ 12 DEG C/min, then carry out insulation roasting 4 ~ 6 hours.
7. method as claimed in claim 2, is characterized in that: step b) in etching adopt deionized water.
8. method as claimed in claim 7, it is characterized in that, described etching comprises following operation: first by obtained Ni
2+-PDASiO
2core-shell structured nanomaterials dispersion in deionized water, ultrasonic evenly after be transferred in reactor, then 150 ~ 170 DEG C of insulations 12 ~ 24 hours.
9. an application for magnetic core-shell structure nano material according to claim 1, is characterized in that: as protein adsorbent.
10. an application for magnetic core-shell structure nano material according to claim 1, is characterized in that: as the reduction catalyst of fragrant nitro compound.
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