CN101003388A - Method for preparing Nano cube of hematite - Google Patents
Method for preparing Nano cube of hematite Download PDFInfo
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- CN101003388A CN101003388A CN 200610156050 CN200610156050A CN101003388A CN 101003388 A CN101003388 A CN 101003388A CN 200610156050 CN200610156050 CN 200610156050 CN 200610156050 A CN200610156050 A CN 200610156050A CN 101003388 A CN101003388 A CN 101003388A
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Abstract
This invention discloses a method for preparing hematite nanocubes. The method comprises: (1) adding soluble inorganic ferric salt 0.8-2.4 mmol, potassium oleate or sodium oleate 2-4 mol times of ferric ions, ethanol 4-10 mL and oleic acid 1-5 mL into water 16 mL, stirring to uniformly demix, and placing in a sealed container; (2) standing at 160-220 deg.C for more than 8 h; (3) centrifuging to separate the solid precipitate, washing with ethanol, drying, and dispersing in alkane solvent; (4) centrifuging to separate the solid precipitate, adding ethanol into the obtained red alkane colloidal solution to precipitate aggregates of hematite nanocubes with average side length of 14-17 nm. The method has such advantages as easy operation, easy control, mild conditions and no pollution. The obtained hematite nanocubes have good monodispersity, uniform particle sizes, and regular and uniform morphology. The hematite nanocubes exhibit superparamagnetism at normal temperature, and can be used in magnetic storage and medical fields.
Description
Technical field:
The invention belongs to the nano material preparation technical field, be specifically related to the method for the synthetic rhombohedral iron ore nanocubes of hydrothermal method.
Background technology:
Britain's " materials chemistry magazine " (Journal of Materials Chemistry, 2002,12 volumes, the 1676-1683 page or leaf) dropping ethylene oxide and alcoholic acid mixture in the aqueous solution of iron trichloride have been reported, through pyroprocessing more than 300 ℃, prepare the rhombohedral iron ore nano particle by sol-gel method.The grain diameter that this method obtains smaller (20-60 nanometer), owing to lack tensio-active agent in the preparation system, the nucleation of crystal grain and growth can not reach balance, so the product size distribution that obtains is wide, particle agglomeration is serious and do not have how much regular patterns; Need pyroprocessing, preparation procedure more complicated, energy consumption height in the preparation process simultaneously.
Holland " colloid and surface " (Colloids and Surfaces A:Physicochemical and Engineering Aspects, 1996,109 volumes, 155-165 page or leaf) introduced and worn out in the presence of alkaline condition and dense dielectric medium that (β-FeOOH) fine particle suspension prepares dish shape rhombohedral iron ore particle to akaganeite.The particle monodispersity that obtains is good, how much patterns are regular, but the homogeneity of particle diameter big (3 μ m), pattern is not so good; Owing to the highly spissated akaganeite fine particle suspension of this method preparation earlier, be allowed to condition at 70 ℃ then and wore out whole process of preparation complexity, consuming time 8 days down.This magazine (1993,70 volumes, 167-169 page or leaf) also reported by sol-gel method and prepared accurate cubes and peanut shape rhombohedral iron ore particle, and the granule-morphology that obtains is regular, monodispersity good, but particle diameter big (1.65 μ m) and preparation process are consuming time.
U.S.'s " sharp interface science magazine of colloid " (Journal of Colloid and Interface Science, 1996,184 volumes, the 626-638 page or leaf) reported that the employing sol method prepares the reasonable regular oval rhombohedral iron ore particle of monodispersity, obtains the particle about particle diameter 0.5 μ m.But the same with other sol-gel method, the whole process of preparation of this method is consuming time, complicated.
Switzerland's " Material Physics and chemistry " (Materials Chemistry and Physics, 2005,89 volumes, the 321-325 page or leaf) reported in molysite and sodium bicarbonate system and be settled out the rhombohedral iron ore presoma, prepare the rhombohedral iron ore nano particle 500 ℃ of high-temperature calcinations then.This method relates to two processes, complex process, consuming time, and resulting rhombohedral iron ore nanoparticle agglomerates is serious simultaneously.
Germany " advanced function material " (Advanced Functional Materials, 2006,16 volumes, the 1805-1813 page or leaf) reported in oleic acid, ethanol and sodium hydroxide system and added ferric salt solution, hydrothermal treatment consists is synthesized the rhombohedral iron ore nanocubes then, obtained the reasonable rhombohedral iron ore nano particle of monodispersity, but the homogeneity of the shape of nanoparticle and particle diameter not fine.
Summary of the invention:
The present invention proposes a kind of method for preparing Nano cube of hematite, to overcome the shortcoming on the prior art.
Method for preparing Nano cube of hematite of the present invention, it is characterized in that: with used 16mL water is benchmark, add 0.8～2.4mmol soluble iron inorganic salt, 2～4 times to the potassium oleate or the sodium oleate of iron ion mole number, 4～10mL ethanol and 1～5mL oleic acid, being stirred to phase-splitting evenly is placed in the sealed vessel, leave standstill above 8 hours at 160～220 ℃ of constant temperature, centrifugation goes out solid sediment then, use washing with alcohol, after the drying, be scattered in the alkane solvent, after recentrifuge is isolated solid precipitation, in resulting red alkane colloidal solution, add ethanol, promptly be settled out rhombohedral iron ore nanocubes product.
Described alkane solvent comprises chloroform, hexanaphthene or hexane.
Described soluble iron inorganic salt comprise iron nitrate, iron(ic) chloride or iron protochloride.
The invention provides a kind of in the presence of the oleate tensio-active agent, single force method of disperseing the rhombohedral iron ore nanocubes that the preparation particle diameter is even, pattern is regular.Because the present invention has utilized oleic acid root and iron ion to form the degraded of complex compound under hydrothermal condition, preparation process is simple, quick, and reaction process is easy to control, and resulting product rhombohedral iron ore nano particle consistent appearance, particle diameter are even; Simultaneously because the oleate tensio-active agent that adopts has served as stablizer again, therefore good, shape of the nano particle monodispersity of gained and particle diameter evenly and particle diameter all be in the nanoscale scope, having overcome the hydrolysis of existing dependence iron inorganic salt, to obtain the product particle grain size excessive or size distribution is wide, shape is inhomogeneous and shortcoming such as reunion very easily.
The rhombohedral iron ore cubes that adopts the inventive method to prepare, its average length of side is 14～17nm, and shape is regular, shows as superparamagnetism at normal temperatures, demonstrate the feature uv-absorbing relevant at the 230nm place, can be used for fields such as magnetic storage and medical treatment with the cubes pattern.
Description of drawings:
Fig. 1 is transmission electron microscope (TEM) photo of embodiment 1 preparation product;
Fig. 2 is transmission electron microscope (TEM) photo of embodiment 1 product rhombohedral iron ore cubes self-assembled monolayer.
Fig. 3 is the susceptibility-temperature curve (M-K curve) of embodiment 1 product rhombohedral iron ore nanocubes.
Fig. 4 is the visible-UV spectrum absorption curve (UV-Vis curve) of embodiment 1 product rhombohedral iron ore nanocubes.
Fig. 5 is transmission electron microscope (TEM) photo of the low magnification of embodiment 2 products.
Fig. 6 is transmission electron microscope (TEM) photo of the low magnification of embodiment 3 products.
Embodiment:
Below in conjunction with embodiment the present invention is done specific description.
Embodiment 1:
Press the mol ratio 3: 1 of sodium oleate and iron ion number, successively 1.6g (5.1mmol) sodium oleate, 0.48g (1.7mmol) Iron(III) chloride hexahydrate, 1mL oleic acid and 10mL ethanol being joined the volume that the 16mL aqueous solution is housed is in the 30mL tetrafluoroethylene reactor, with 400rpm rotating speed magnetic agitation one hour, solution was divided into even two-phase: upper strata sorrel, lower floor are colourless; After this reactor sealing, place 180 ℃ baking oven constant temperature to leave standstill 8 hours.The resulting solution that obtains is cooled to room temperature, obtains the 0.12g solid after the centrifugation, with this solid with washing with alcohol after, be distributed in the 10mL hexanaphthene, after recentrifuge is isolated solid precipitation, in the red hexanaphthene colloidal solution that obtains, add 10mL ethanol, promptly be settled out solid product.
In building-up process, the even two-phase that the reaction soln that is made into is divided into after stirring after testing, the upper strata is russet to be the oleic acid solutions of iron oleate, lower floor be the alcoholic acid aqueous solution.Experiment shows: the decomposition temperature of iron oleate is 120 ℃, if temperature of reaction is between 120 ℃～160 ℃, then iron oleate decompose that the product that the back forms is poor for some degree of crystallinity, the nano particle that do not have regular shape and not changing with the reaction times; Have only temperature of reaction to reach more than 160 ℃ and under this temperature constant temperature time surpass 8 hours, iron oleate just can decompose and generates pattern and the uniform cubes of size.Constant temperature is in order to guarantee that thereby nanocrystalline the growth fully has more uniform pattern more than 8 hours, constant temperature be less than 8 hours resulting cubes degree of crystallinity and the pattern homogeneity relatively poor.Experiment between 160～220 ℃ shows that temperature is high more, and the homogeneity of cubical degree of crystallinity and pattern is just good more, but from save energy and protection experimental installation, consider that from quick and economic angle the temperature of reaction that present embodiment is selected is 180 ℃, constant temperature has been selected 8 hours; Constant temperature surpassed 8 hours and the longer reaction times does not influence basically to product.In addition, the resulting nanocrystalline oleic acid coating that has in the present embodiment is so can be dispersed in many alkane solvents.Situation too in the following examples 2,3.
Adopt JEOL-2010 transmission electron microscope (TEM), Philips X ' Pert PRO SUPER x-ray diffractometer (XRD), Tianjin, island UV-2550 ultra-violet absorption spectrum instrument, bruker EQUINOX55 vector22 infrared spectra absorption apparatus, Quantum Design MPMS XL superconducting quantum interference device (SQUID) magnetometer that gained solid product sample is characterized respectively.
The product that obtains in the present embodiment is 10-80 ℃ of XRD figure spectrum in the scope and coincideing that powdery diffractometry card (JCPDScard no.33-664) is reported at 2 θ angles, shows that product is the rhombohedral iron ore phase.
Fig. 1 and Fig. 2 have provided transmission electron microscope (TEM) photo of the evenly distributed and single nanocubes of the rhombohedral iron ore nanocubes individual layer for preparing in the present embodiment respectively.Can see that from this TEM photo the preparation-obtained product of present embodiment is the nanocubes aggregate of the average length of side 15 nanometer rhombohedral iron ore, its size distribution is even, shape is regular, monodispersity is very good.Illustrate the present invention overcome effectively the size distribution of the prepared rhombohedral iron ore nano particle of conventional art wide, do not have regular shape or shape is inhomogeneous, the shortcoming such as serious of reuniting.
Fig. 3 is the M-K curve of the rhombohedral iron ore nanocubes that obtains in the present embodiment.Under externally-applied magnetic field 100 oersteds, the locking temperature (T of rhombohedral iron ore nanocubes
B) be 80K, be superparamagnetism at normal temperatures.
Fig. 4 shows that for the UV-Vis spectrum of the rhombohedral iron ore nanocubes that obtains in the present embodiment product has at 230nm place and cube pattern characteristic of correspondence absorption peak.
Embodiment 2:
Press the mol ratio 2: 1 of potassium oleate and iron ion number, successively 1.5g (4.8mmol) potassium oleate, 0.48g (2.4mmol) four hydration ferrous chloride, 2mL oleic acid and 8mL ethanol being joined the volume that the 16mL aqueous solution is housed is in the 30mL tetrafluoroethylene reactor, with 500rpm rotating speed magnetic agitation two hours, solution was divided into upper strata sorrel, the colourless even two-phase of lower floor; Reactor sealing is placed on constant temperature left standstill 8 hours in 220 ℃ the baking oven; Resulting resulting solution is cooled to room temperature, obtains the 0.14g solid after the centrifugation, with this solid with washing with alcohol after, be distributed in the 20mL hexane, after recentrifuge is isolated solid precipitation, in the red hexane colloidal solution that obtains, add 20mL ethanol, promptly be settled out solid product.
Characterizing method is with embodiment 1.
Fig. 5 has provided the transmission electron microscope photo (TEM) of present embodiment product.The mole number that photo is presented at potassium oleate and iron ion is that the product that obtains is regular, the uniform rhombohedral iron ore nanocubes of particle diameter of the average length of side 17 nanometers, pattern under 2: 1 the condition.
Embodiment 3:
Press the mol ratio 4: 1 of sodium oleate and iron ion number, successively 0.97g (3.2mmol) sodium oleate, 0.32g (0.8mmol) nine nitric hydrate iron, 5mL oleic acid and 4mL alcoholic acid mixing solutions being joined the volume that the 16mL aqueous solution is housed is in the 30mL tetrafluoroethylene reactor, with 200rpm rotating speed magnetic agitation two hours, after being divided into even two-phase to solution, with the reactor sealing, place 180 ℃ baking oven constant temperature to leave standstill 8 hours.Resulting resulting solution is cooled to room temperature, obtains the 0.09g solid after the centrifugation, this solid is added washing with alcohol after, be distributed in the 2mL chloroform, after centrifugation goes out solid precipitation again, in the red chloroform colloidal solution that obtains, add 2mL ethanol, promptly be settled out solid product.Characterizing method is the same.
Fig. 6 has provided the transmission electron microscope photo (TEM) of present embodiment product.The mol ratio that photo is presented at sodium oleate and iron ion is that the product that obtains is regular, the uniform rhombohedral iron ore nanocubes of particle diameter of the average length of side 14 nanometers, pattern under 4: 1 the condition.
Claims (3)
1, a kind of method for preparing Nano cube of hematite, it is characterized in that: with used 16mL water is benchmark, add 0.8～2.4mmol soluble iron inorganic salt, 2～4 times to the potassium oleate or the sodium oleate of iron ion mole number, 4～10mL ethanol and 1～5mL oleic acid, being stirred to phase-splitting evenly is placed in the sealed vessel, leave standstill above 8 hours at 160～220 ℃ of constant temperature, centrifugation goes out solid sediment then, use washing with alcohol, after the drying, be scattered in the alkane solvent, after recentrifuge is isolated solid precipitation, in resulting red alkane colloidal solution, add ethanol, promptly be settled out rhombohedral iron ore nanocubes product.
2, method for preparing Nano cube of hematite according to claim 1 is characterised in that described alkane solvent comprises chloroform, hexanaphthene or hexane.
3, method for preparing Nano cube of hematite according to claim 1 is characterised in that described soluble iron inorganic salt comprise iron nitrate, iron(ic) chloride or iron protochloride.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115211A (en) * | 2011-01-04 | 2011-07-06 | 华南理工大学 | Nano iron trioxide water-soluble colloid and preparation method thereof |
| CN102180522A (en) * | 2011-03-28 | 2011-09-14 | 陕西宏炬电子科技有限公司 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
| CN102744419A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Morphology control method of magnetic nanometer particles |
| CN102744420A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method of magnetic nanometer particles with adjustable and controllable particle diameter |
| CN105905948A (en) * | 2016-02-19 | 2016-08-31 | 中国科学技术大学 | Preparation method of hematite submicron particles |
| CN108713000A (en) * | 2016-03-09 | 2018-10-26 | 朗盛德国有限责任公司 | The preparation of ferric oxide red colorant |
| CN112897592A (en) * | 2021-01-25 | 2021-06-04 | 中国科学院广州地球化学研究所 | Micro-nano iron oxide mineral color developing agent and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083476A (en) * | 1996-05-08 | 2000-07-04 | Mitsui Mining & Smelting Company, Ltd. | Black ultrafine magnetite particles and process for preparing the same |
| CN1168665C (en) * | 2002-12-24 | 2004-09-29 | 华中科技大学 | Prepn process of nanometer granular Fe3O4 |
| KR20060012346A (en) * | 2004-08-03 | 2006-02-08 | 강영수 | Preparation of monodispersed magnetic nanoparticles using m-oleate (m = fe, co) complex |
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2006
- 2006-12-30 CN CNB2006101560504A patent/CN100453469C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115211A (en) * | 2011-01-04 | 2011-07-06 | 华南理工大学 | Nano iron trioxide water-soluble colloid and preparation method thereof |
| CN102115211B (en) * | 2011-01-04 | 2012-12-05 | 华南理工大学 | Preparation method of nano iron trioxide water-soluble colloid |
| CN102180522B (en) * | 2011-03-28 | 2012-11-28 | 陕西宏炬电子科技有限公司 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
| CN102180522A (en) * | 2011-03-28 | 2011-09-14 | 陕西宏炬电子科技有限公司 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
| CN102744420B (en) * | 2012-06-20 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of magnetic nanometer particles with adjustable and controllable particle diameter |
| CN102744420A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method of magnetic nanometer particles with adjustable and controllable particle diameter |
| CN102744419A (en) * | 2012-06-20 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Morphology control method of magnetic nanometer particles |
| CN102744419B (en) * | 2012-06-20 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Morphology control method of magnetic nanometer particles |
| CN105905948A (en) * | 2016-02-19 | 2016-08-31 | 中国科学技术大学 | Preparation method of hematite submicron particles |
| CN105905948B (en) * | 2016-02-19 | 2017-07-25 | 中国科学技术大学 | A kind of preparation method of bloodstone submicron particles |
| CN108713000A (en) * | 2016-03-09 | 2018-10-26 | 朗盛德国有限责任公司 | The preparation of ferric oxide red colorant |
| CN108713000B (en) * | 2016-03-09 | 2020-10-27 | 朗盛德国有限责任公司 | Preparation of iron oxide red pigments |
| CN112897592A (en) * | 2021-01-25 | 2021-06-04 | 中国科学院广州地球化学研究所 | Micro-nano iron oxide mineral color developing agent and preparation method and application thereof |
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