CN105129862B - A kind of preparation method of rice-granule nano magnetic iron oxide and application - Google Patents
A kind of preparation method of rice-granule nano magnetic iron oxide and application Download PDFInfo
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- CN105129862B CN105129862B CN201510480659.6A CN201510480659A CN105129862B CN 105129862 B CN105129862 B CN 105129862B CN 201510480659 A CN201510480659 A CN 201510480659A CN 105129862 B CN105129862 B CN 105129862B
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Abstract
The invention discloses a kind of preparation method of rice-granule nano magnetic iron oxide, comprise the following steps：Molysite and anion surfactant are dissolved in deionized water respectively, stirring obtains clear solution, then by two kinds of solution hybrid reactions, magnetic agitation；Above-mentioned reaction solution is centrifuged, supernatant is removed, washing, dries, obtain rice-shaped hydroxyl ferriferous oxide；Rice-shaped hydroxyl ferriferous oxide is heat-treated in the certain atmosphere of certain temperature, that is, obtains rice-granule nano magnetic iron oxide.The preparation method of rice-granule nano magnetic iron oxide of the present invention obtains the rice-shaped FeOOH with homogeneous structural by magnetic agitation, and being made by different heat treatment has perfect rice-granule nano magnetic iron oxide；The inventive method simple possible, production cost is low, and Modulatory character is strong, can control the draw ratio of rice-shaped ferriferous oxide, products therefrom narrowly distributing, yield is high, purity is high, saturation magnetization is high.
Description
Technical field
The invention belongs to ferriferous oxide preparation field, is related to a kind of preparation method of ferriferous oxide, specifically a kind of grain of rice
The preparation method of shape nanometer magnetic iron oxide and application.
Background technology
Ferriferous oxide mainly includes Fe203And Fe304, the ferriferous oxide nano composite materials of various patterns because with
Unique physicochemical properties such as small-size effect, skin effect, cooperative effect, and the characteristics of easy functionalization, have fine
Application prospect, caused extensively in catalytic field, biomedical sector and cosmetic field, military field, new energy etc.
General concern.
It is well known that the property of ferriferous oxide determines its application.And the property of particle depends primarily on its size, shape
The structure and pattern of looks and structure, wherein particle are two the most key influence factors, therefore, the structure of nano material
With pattern control research as one of the forward position of present material scientific research and focus.And synthesizing, there is anisotropic magnetic to receive
Meter Jing, not only facilitate and understand nanocrystalline growth course, also help acquisition due to unique caused by pattern anisotropy
Magnetic property.Under usual conditions, with the change of the draw ratio of one-dimensional particle, the coercivity of particle can also change, therefore control
Magnetic material of the system synthesis with different draw ratios, helps to widen the application of ferriferous oxide.Up to the present, Ren Menyi
Monodispersed there is the anisotropic ferriferous oxide nano material of pattern, such as ball through having been prepared using various physico-chemical processes
The nanostructureds such as shape, octahedron, nano wire, nano chain, nanobelt, nanotube, nano-cone array, nano-hollow ball and nano flower
[1-6]（Bibliography：[1] Wu W, Xiao XH, Zhang SF, Li H, Zhou XD, Jiang CZ. One-pot
reaction and subsequent annealing to synthesis hollow spherical magnetite and
maghemite nanocages. Nanoscale Res. Lett., 2009, 4: 926. [2] Pitzschel K,
Moreno JMM, Escrig J, Albrecht O, Nielsch K, Bachmann J. Controlled
introduction of diameter modulations in arrayed magnetic iron oxide
nanotubes. ACS Nano, 2009, 3: 3463. [3] Fan HM, You GJ, Li Y, Zheng Z, Tan
HR, Shen ZX, Tang SH, Feng YP. Shape-controlled synthesis of single-
crystalline Fe2O3 hollow nanocrystals and their tunable optical properties.
J. Phys. Chem. C., 2009, 113: 9928. [4] Omi S, Kanetaka A, Shimamori Y,
Supsakulchai A, Nagai M, Ma GH. Magnetite (Fe3O4) microcapsules prepared
using a glass membrane and solvent removal. J. Microencapsule., 2001, 18:
749. [5] Mandal S, Muller AHE. Facile route to the synthesis of porous alpha-
Fe2O3 nanorods. Mater. Chem. Phys., 2008, 111: 438. [6] Wu W, Xiao XH, Zhang
SF, Fan LX, Peng TC, Ren F, Jiang CZ. Facile fabrication of ultrafine hollow
silica and magnetic hollow silica nanoparticles by a dual-templating
approach. Nanoscale Res. Lett., 2010, 5: 116.）.And for constructing compared with big L/D ratio ferriferous oxide,
Especially have monodispersity, well-crystallized rice-shaped iron oxide nanoparticle in terms of report it is relatively fewer.
The content of the invention
It is an object of the invention to provide a kind of preparation method of rice-granule nano magnetic iron oxide, this method raw material valency
Lattice are cheap, operating procedure is simple, the rice-shaped magnetic iron oxide stabilization of gained, have preferable magnetic, recoverable, may be used also
For use as preferable surface reinforced Raman active base material model.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of rice-granule nano magnetic iron oxide, it is characterised in that comprise the following steps：
（1）Molysite and anion surfactant are dissolved in deionized water respectively, stirring obtains clear solution, then by two
Kind solution hybrid reaction, magnetic agitation；
（2）By step（1）Obtained reaction solution centrifuges, and removes supernatant, washing, dries, obtain rice-shaped hydroxyl
Ferriferous oxide；
（3）By step（2）Obtained rice-shaped hydroxyl ferriferous oxide is heat-treated in the certain atmosphere of certain temperature, i.e.,
Obtain rice-granule nano magnetic iron oxide.
As further preferred, step of the present invention（1）Middle molysite be anhydrous ferric trichloride, Iron(III) chloride hexahydrate,
One kind in ferric sulfate, ferric nitrate.
As further preferred, step of the present invention（1）Middle anion surfactant is cetyl trimethyl bromine
Change one kind in ammonium, hexadecyltrimethylammonium chloride, DTAB, neopelex.
As further preferred, step of the present invention（1）The mol ratio of middle anion surfactant and molysite be 0 ~
2。
As further preferred, step of the present invention（1）The middle hybrid reaction time is 40-100 DEG C, reaction time 2-
12h。
As further preferred, step of the present invention（3）The temperature of middle heat treatment is 200-450 DEG C, heat treatment time
For 1-4h, the atmosphere of heat treatment is vacuum or hydrogen.
As further preferred, step of the present invention（2）Middle washing step is：First with deionized water by product cleaning 3
It is secondary, then washed, centrifuged with absolute ethyl alcohol；The drying is 50 DEG C and is dried overnight.
Invention additionally discloses application of the rice-granule nano magnetic iron oxide in surface reinforced Raman active base material.
The present invention can adjust rice-shaped hydroxyl by controlling dosage and the species of anion surfactant and molysite
The draw ratio of base iron oxide is 8:1~3:Change between 1.
Beneficial effects of the present invention：The preparation method of rice-granule nano magnetic iron oxide of the present invention is obtained by magnetic agitation
There must be the rice-shaped FeOOH of homogeneous structural, being made by different heat treatment has perfect rice-granule nano Armco magnetic iron
Oxide；The inventive method simple possible, production cost is low, and Modulatory character is strong, can control the draw ratio of rice-shaped ferriferous oxide,
Products therefrom narrowly distributing, yield is high, purity is high, saturation magnetization is high, thus in magnetic recording material, catalyst, biomedicine
The fields such as field, Magnetic resonance imaging, environment measuring embody important application prospect.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of rice-shaped sample prepared by the embodiment of the present invention 1（SEM）：A is rice-shaped
The stereoscan photograph of FeOOH, b are the stereoscan photographs of rice-shaped ferriferous oxide.
Fig. 2 is the X-ray diffractogram of rice-shaped FeOOH prepared by the embodiment of the present invention 1.
Fig. 3 is the Fe that the embodiment of the present invention 3 is prepared3O4The X-ray diffractogram of nano-particle.
Fig. 4 is that Fe is prepared in the embodiment of the present invention 33O4The hysteresis curve figure of nano-particle.
Fig. 5 is the rice-shaped Fe of the present invention3O4The SERS figure of@Au composite nanostructures.
Embodiment
For the ease of it will be appreciated by those skilled in the art that the present invention is further illustrated below in conjunction with the accompanying drawings.
Embodiment 1
FeOOH is prepared using Hydrolyze method.
By anhydrous FeCl3It is dissolved in respectively with hexadecyltrimethylammonium chloride in 30 mL deoxidation ionized waters, stirring obtains
Bright solution, obtains FeCl3Concentration be 0.1 mol/L, the concentration of hexadecyltrimethylammonium chloride is 0.05 mol/L.Then
Two kinds of solution are mixed, in 40 DEG C of magnetic agitation 12h, reaction is finished, and gained reaction solution is centrifuged, removes supernatant, then
Spend the cleaning of oxonium ion water three times, then washed, centrifuged with absolute ethyl alcohol, 50 DEG C are dried overnight, and finally obtain the length of rice-shaped
Footpath ratio is 4:1 yellow FeOOH.
By above-mentioned gained FeOOH in 200 DEG C of vacuum calcination 4h, obtain red rice-shaped draw ratio as 4:1
Fe2O3Nano-particle.
Fig. 1 is the stereoscan photograph of rice-shaped sample prepared by the embodiment of the present invention 1：A is rice-shaped FeOOH
Stereoscan photograph, b is the stereoscan photograph of rice-shaped ferriferous oxide.Contrasted from two pictures as can be seen that being heat-treated
Front and rear, the pattern of sample is rice-shaped, the nm of rice-shaped Fe2O3 length about 300, diameter about 75nm, size uniformity, is showed
Good dispersiveness.Fig. 2 is the X-ray diffractogram of rice-shaped FeOOH prepared by the embodiment of the present invention 1, with β-FeOOH
Standard card 34-1266 correspond to consistent, without other miscellaneous peaks, the sample for illustrating to obtain is the β-FeOOH of pure phase, and crystal formation knot
Structure is fine.
Embodiment 2
FeOOH is prepared using Hydrolyze method.
By Fe2(SO4)3It is dissolved in respectively with neopelex in 30 mL deoxidation ionized waters, stirring obtains transparent molten
Liquid, obtain Fe2(SO4)3Concentration be 0.2 mol/L, the concentration of neopelex is 0.15 mol/L.Then by two
Kind solution mixing, the magnetic agitation 4h under the conditions of 80 DEG C.Reaction is finished, and gained reaction solution is centrifuged, removes supernatant, then
Oxonium ion water is spent product cleaning three times, then washed, centrifuged with absolute ethyl alcohol, 50 DEG C are dried overnight, and finally obtain the grain of rice
The draw ratio of shape is 8:1 yellow FeOOH.
By above-mentioned gained FeOOH in 300 DEG C of vacuum calcination 3h, obtain red rice-shaped draw ratio as 8:1
Fe2O3Nano-particle.
Embodiment 3
FeOOH is prepared using Hydrolyze method.
By FeCl3·6H2O and DTAB are dissolved in 30 mL deoxidation ionized waters respectively, and stirring obtains
Bright solution, obtains FeCl3·6H2O concentration is 0.1 mol/L, and the concentration of DTAB is 0.2 mol/L.
Then two kinds of solution are mixed, the magnetic agitation 10h under the conditions of 50 DEG C.Reaction is finished, and gained reaction solution is centrifuged, removed
Supernatant, then spend oxonium ion water product cleaning three times, then washed, centrifuged with absolute ethyl alcohol, 50 DEG C are dried overnight, finally
The draw ratio for obtaining yellow rice-shaped is 6:1 FeOOH.
By above-mentioned gained FeOOH in 400 DEG C of hydrogen calcination 2h, obtain black rice-shaped draw ratio as 6:1
Fe3O4Nano-particle.
Fig. 3 is the Fe that the embodiment of the present invention 3 is prepared3O4The X-ray diffractogram of nano-particle, with Fe3O4Standard card
Piece 01-1111 corresponds to consistent, and without other miscellaneous peaks, the sample for illustrating to be thermally treated resulting in is the Fe of pure phase3O4, and crystalline structure is very
It is good.
Fig. 4 is that Fe is prepared in the embodiment of the present invention 33O4The hysteresis curve figure of nano-particle, rice-shaped Fe3O4Show
The magnetic property of superparamagnetism, and magnetic saturation intensity is about 87 emu/g, has higher magnetic responsiveness.
Embodiment 4
FeOOH is prepared using Hydrolyze method.
By Fe (NO3)3It is dissolved in respectively with cetyl trimethylammonium bromide in 30 mL deoxidation ionized waters, stirring obtains transparent
Solution, obtain Fe (NO3)3Concentration be 0.1 mol/L, the concentration of cetyl trimethylammonium bromide is 0 mol/L.Then will
Two kinds of solution mixing, the magnetic agitation 6h under the conditions of 100 DEG C.Reaction is finished, and gained reaction solution is centrifuged, removes supernatant
Liquid, then spend oxonium ion water product cleaning three times, then washed, centrifuged with absolute ethyl alcohol, 50 DEG C are dried overnight, and finally obtain
The draw ratio of yellow rice-shaped is 3:1 FeOOH.
By above-mentioned gained FeOOH in 450 DEG C of hydrogen calcination 1h, obtain black rice-shaped draw ratio as 3:1
Fe3O4Nano-particle.
Embodiment 5
With the gained rice-shaped Fe of embodiment 33O4Nano-particle, grafting Au particles, tests its surface reinforced Raman active.
Take the gained rice-shaped Fe of 10 mg embodiments 33O4Nano-particle, first carry out official with 3- aminopropyls trimethoxy siloxane
Energyization, then it is mixed with 20 mL Au nano-particles, after abundant assembling, product magnet collect and be dissolved in 1 mL go from
In sub- water, 10 mL deionized waters, the sodium citrate solutions of 2 mL 1% and the M hydroxylamine hydrochlorides of 1 mL 0.1 are subsequently added into.Then, 1
mL 1% HAuCl4It is added dropwise under vibration in above-mentioned solution, until the end of reduction process, product is collected simultaneously with magnet
Cleaning, rice-shaped Fe is made3O4@Au composite nanoparticles.
With the Fe obtained under the conditions of this3O4@Au composite nanoparticles are as surface-enhanced Raman spectrum active substrate, difference
The p-Mercaptoaniline of 20 μ L various concentrations is added dropwise（PATP）, after drying, its Raman signal is surveyed, obtains SERS
Figure, as shown in Figure 5.With rice-shaped Fe3O4For@Au composite nanoparticles as substrate, PATP is the Raman spectrogram of probe molecule,
It is 1 × 10 in PATP concentration-7During M, still there is very strong SERS signal, disclosure satisfy that national standard to contaminant trace species
Testing requirements, PATP signal is detailed in spectrogram, and resolution ratio is very high.The rice-shaped Fe that the present invention obtains3O4@Au composite nano-granules
Son be used as SERS substrates, and signal is uniform, favorable repeatability, detection sensitivity height, available for environmental contaminants and biomolecule
Detection.
Above content is only to structure example of the present invention and explanation, affiliated those skilled in the art couple
Described specific embodiment is made various modifications or supplement or substituted using similar mode, without departing from invention
Structure surmounts scope defined in the claims, all should belong to protection scope of the present invention.
Claims (4)
1. a kind of preparation method of rice-granule nano magnetic iron oxide, it is characterised in that comprise the following steps：
（1）Molysite and anion surfactant are dissolved in deionized water respectively, stirring obtains clear solution, then molten by two kinds
Liquid hybrid reaction, magnetic agitation；The step（1）Middle anion surfactant is cetyl trimethylammonium bromide, 16
One kind in alkyl trimethyl ammonium chloride, DTAB, neopelex；The anionic surface
The mol ratio of activating agent and molysite is 0 ~ 2；The hybrid reaction time is 40-100 DEG C, reaction time 2-12h；
（2）By step（1）Obtained reaction solution centrifuges, and removes supernatant, washing, dries, obtain rice-shaped iron carbonyl oxygen
Compound；
（3）By step（2）Obtained rice-shaped hydroxyl ferriferous oxide is heat-treated in the certain atmosphere of certain temperature, that is, is obtained
Rice-granule nano magnetic iron oxide；The temperature of the heat treatment is 200-450 DEG C, heat treatment time 1-4h, heat treatment
Atmosphere is vacuum or hydrogen.
2. the preparation method of rice-granule nano magnetic iron oxide according to claim 1, it is characterised in that the step
（1）Middle molysite is one kind in anhydrous ferric trichloride, Iron(III) chloride hexahydrate, ferric sulfate, ferric nitrate.
3. the preparation method of rice-granule nano magnetic iron oxide according to claim 1, it is characterised in that the step
（2）Middle washing step is：First with deionized water then product cleaning 3 times is washed with absolute ethyl alcohol, centrifuged；The drying is
50 DEG C are dried overnight.
4. the rice-granule nano magnetic iron oxide as made from any one of the claim 1-3 preparation methods is drawn in surface enhanced
Application in graceful active base material.
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| CN112320852A (en) * | 2020-11-23 | 2021-02-05 | 湖北大学 | Preparation method of spindle-shaped nano iron oxyhydroxide |
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