CN103641149B - Method of synthesizing monodisperse hexagonal rare earth fluoride nanosheet by adopting rheological phase reaction method - Google Patents
Method of synthesizing monodisperse hexagonal rare earth fluoride nanosheet by adopting rheological phase reaction method Download PDFInfo
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- CN103641149B CN103641149B CN201310685015.1A CN201310685015A CN103641149B CN 103641149 B CN103641149 B CN 103641149B CN 201310685015 A CN201310685015 A CN 201310685015A CN 103641149 B CN103641149 B CN 103641149B
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Abstract
The invention discloses a method of synthesizing a monodisperse hexagonal rare earth fluoride nanosheet by adopting a rheological phase reaction method. The method is characterized by comprising the following steps: fully mixing and uniformly grinding a rare earth metal compound, a fluoride and a mixed solvent of an organic solvent and water to a rheological phase matter; and keeping the reaction time in a sealed reaction kettle at constant temperature to obtain the monodisperse hexagonal rare earth fluoride nanosheet. The rare earth fluoride nanosheet prepared by the invention is widely applied in aspects such as luminescent materials, magnetic materials, hydrogen storage materials, gas sensitive materials, lubricant additives, chemical sensors and electrode materials. The method disclosed by the invention is simple in process, free from organic wastewater discharge and environment-friendly, and satisfies the environmental requirements. The reaction is carried out in a sealed system to avoid dust generated by industrialized production. Meanwhile, the product has good uniformity, high purity and low cost, and is suitable for industrialized production on a large scale.
Description
Technical field
The invention belongs to nano material and field of nanometer technology, be specifically related to a kind of method adopting rheological phase reaction method to synthesize monodisperse hexagonal rare-earth fluoride nano sheet.
Background technology
Rare earth fluorine is a kind of excellent inorganic materials, has a wide range of applications in ion selective electrode, solid electrolyte sensor, optics etc.The rare earth fluorine of nanoscale has the much character being different from bulk material, and its application prospect is more wide.The existing multiple method preparing the rare earth fluorine of nanoscale at present, as liquid-phase precipitation method, hydrothermal method, emulsion method, microwave method etc.King such as to instruct at the mixing by rare earth ion and fluoride aqueous solution and alkali metal hydroxide, lipid acid and organic polar solvent in patent of invention [CN1749170A], adopts solvent structure rare earth metal fluoride nano particles.But the rare earth fluorine of these methods synthesis mostly is spherical or erose nanoparticle.The structure of nano material, pattern are the important factors affecting its performance, research synthesis has rule and the nano rare earth fluorochemical of novel pattern also causes the interest of investigator, [the Chem. Mater. such as Lemyre, 2005,17,3040] square and hexagonal nanometer LaF has been synthesized by reverse microemulsion process
3, Zhang Mao peaks etc. [Chinese Journal of Inorganic Chemistry, 2006,10,152] have synthesized LaF by the hot method of alcohol solvent
3nano wire.But these preparation methods often need a large amount of organic solvents or water medium, reaction process needs to stir energetically, adds facility investment, and long reaction time, and energy consumption is high, and preparation cost is high.The report adopting the inventive method synthesis monodisperse hexagonal rare-earth fluoride nano sheet is there is not yet at present in the article delivered and patent.
Summary of the invention
The object of the invention is the deficiency existed to overcome prior art, providing that a kind of technique is simple, the covert preparation method of stream of the synthesis monodisperse hexagonal rare-earth fluoride nano sheet of low cost.
For achieving the above object, the technical scheme that the present invention takes is: a kind of method adopting rheological phase reaction method to synthesize monodisperse hexagonal rare-earth fluoride nano sheet of the present invention, after the abundant mixed grinding of mixed solvent of rare earth compound, fluorochemical and organic solvent/water is evenly become to flow covert material, in the reactor of sealing, constant temperature keeps the reaction times, obtains monodisperse hexagonal rare-earth fluoride nano sheet.
Specifically preparation method of the present invention is: 1) first rare earth compound, fluorochemical are mixed by a certain percentage, and fully grinding evenly; 2) add the mixed solvent of organic solvent-water composition, fully grinding obtains flowing covert material uniformly; 3) by step 2) the covert material of the stream that obtains moves in autoclave, and constant temperature keeps certain hour, carries out rheological phase reaction, rear naturally cooling; 4) repeatedly wash through distilled water, ethanol, filter, vacuum 60 DEG C of dryings obtain described monodisperse rare-earth fluoride nanometer sheet.
Above-mentioned steps 1) in, the mol ratio of rare earth compound and fluorochemical is 1:2-6.
Above-mentioned steps 1) in, described rare earth metal is the rare earth compound of lanthanum, cerium, praseodymium or neodymium, rare earth compound or solubility.
Above-mentioned steps 1) in, described fluorochemical is Neutral ammonium fluoride, Sodium Fluoride or ammonium bifluoride.
Above-mentioned steps 2) in, described organic solvent has at least one to be selected from methyl alcohol, ethanol, Virahol, acetone or propyl carbinol, and the volume ratio of described organic solvent and water is 1-4:1.
Above-mentioned steps 2) in, the total mass ratio of the quality of the mixed solvent of organic solvent/water and rare earth compound and fluorochemical is 0.3-1.2:1.
Above-mentioned steps 3) in, described temperature of reaction is 60-180 DEG C, and the time is 10-48h.
The rare earth compound of above-mentioned solubility is nitrate or chlorate.
Furthermore, the covert preparation method of stream of monodisperse hexagonal rare-earth fluoride nano sheet of the present invention, synthesizes according to the following steps:
1) first rare earth compound, fluorochemical are mixed by a certain percentage, fully grinding evenly; 2) add the mixed solvent of organic solvent-water, fully grinding obtains flowing covert material uniformly; 3) by step 2) the covert material of the stream that obtains moves in autoclave, and constant temperature keeps certain hour, carries out rheological phase reaction, rear naturally cooling; 4) repeatedly wash through distilled water, ethanol, filter, vacuum 60 DEG C of dryings obtain described monodisperse rare-earth fluoride nano particles.
Described, rare earth compound is mol ratio 1:2-6 with the preferred proportion that mixes of fluorochemical.
The preferred lanthanum of described rare earth metal, cerium, praseodymium, neodymium, and the soluble salt of preferred these rare earth metals, as nitrate or chlorate etc., or carry out obtain solution with its oxide compound and nitric acid, hydrochloric acid etc.
Described fluorochemical preferred fluorinated ammonium, Sodium Fluoride or ammonium bifluoride.
Described organic solvent particular methanol, ethanol, Virahol, acetone, propyl carbinol, and be any one or a few mixing wherein, organic solvent is volume ratio 1-4:1 with the preferred proportion mixed of water.
The quality of the mixed solvent of described organic solvent/water and the total mass ratio of rare earth compound and fluorochemical are preferably 0.3-1.2:1.
Described temperature of reaction is preferably 60-180 DEG C, and the time is 10-48h.
The present invention adopts rheological phase reaction synthetic technology, at a lower temperature, synthesizes monodisperse hexagonal rare-earth fluoride nano sheet in sealing system.Rheological Phase Method is at room temperature mixed by a certain percentage by solid reaction raw material, after abundant grinding, adding appropriate solvent mixes homogeneous by system, be modulated into solia particle and liquid substance is evenly distributed, not stratified pasty state or sticky shape solid-liquid mixing system, namely flow covert system, under system being placed in suitable reaction conditions, can product be obtained.Under the state that stream is covert unique, many materials can show excess of export concentration phenomenon and new response characteristic, can obtain be different from traditional liquid phase, solid-phase synthesis there is novel pattern and the nano material of performance.Further, under the covert state of stream, solid mixture fully contacts with solvent, and form system that is not stratified, stream change, solia particle surface energy effectively utilizes, and makes reaction more abundant; Product purity and productive rate high, avoid the use of a large amount of solvent of liquid phase method, be convenient to batch production; The dust that building-up process produces is few, is conducive to environmental protection; Heat exchange is good, there will not be local superheating, and temperature of reaction is low and easily control, and is a kind of " energy-conservation, efficient, subtract dirt " green syt route.
The invention has the advantages that: be built into rheological phase reaction system with a small amount of water and organic solvent, avoid the generation of a large amount of dust in the use of a large amount of solvent in existing liquid phase reaction method and solid reaction process, the inventive method technological operation is simple, cost is low, safety, the synthesis of effective implemention monodisperse hexagonal rare-earth fluoride nano sheet, is applicable to industrialized mass production.
Accompanying drawing explanation
Fig. 1 is that the stream of the embodiment of the present invention 1 in a disguised form synthesizes monodisperse hexagonal LaF
3the X-ray diffractogram of nanometer sheet.
Fig. 2 is that the stream of the embodiment of the present invention 1 in a disguised form synthesizes monodisperse hexagonal LaF
3the transmission electron microscope picture of nanometer sheet.
Fig. 3 is that the stream of the embodiment of the present invention 1 in a disguised form synthesizes monodisperse hexagonal LaF
3the selected area electron diffraction figure of nanometer sheet.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Take 2.2g analytical pure lanthanum nitrate and 0.6g analytical pure Neutral ammonium fluoride powder in mortar, abundant grinding is homogeneous, ethanol-water mixed solvent (adopt dehydrated alcohol and water volume ratio be 1:1) the furnishing stream adding 2.8g is abnormal, after proceed in 20mL reactor, sealing, in 120 DEG C of insulation 10h, after naturally cooling, take out, through distilled water wash for several times, centrifugation, 60 DEG C, vacuum is dry obtains white powder product.Product is accredited as lanthanum trifluoride through X-ray powder diffraction as shown in Figure 1, products pure, does not have the diffraction peak of other impurity; As can be seen from the morphology analysis of Fig. 2 transmission electron microscope, pattern is hexagonal nano sheet structure, and dispersion is comparatively even, and particle average dimension is 10-15nm; Good polycrystalline diffraction ring can be seen from Fig. 3 selected area electron diffraction figure, show that product has good degree of crystallinity.
Embodiment 2:
Take 2.2g analytical pure cerous nitrate and 1g analytical pure sodium fluoride powder in mortar, abundant grinding is homogeneous, acetone-water mixed solvent (both volume ratios are 2:1) the furnishing stream adding 3g is abnormal, after proceed in 20mL reactor, sealing, in 100 DEG C of insulation 12h, after naturally cooling, take out, after distilled water wash is clean, centrifugation, 60 DEG C, vacuum is dry obtains black powder product.Product is accredited as cerous fluoride through X-ray powder diffraction; As can be seen from the morphology analysis of transmission electron microscope, pattern is monodisperse hexagonal flaky nanometer structure, and particle average dimension is 15-20nm.
Embodiment 3:
Take 1g analytical pure Praseodymium trioxide to add in 1mL concentrated nitric acid, be heated to dissolve completely, add 1g analytical pure ammonium bifluoride powder in mortar, abundant grinding is homogeneous, Methanol+Water (both volume ratios are 4:1) the furnishing stream adding 2g is abnormal, after proceed in 20mL reactor, sealing, in 150 DEG C of insulation 14h, after naturally cooling, take out, washing for several times, centrifugation, 60 DEG C, vacuum is dry obtains white powder product.Product is accredited as borontrifluoride praseodymium through X-ray powder diffraction; As can be seen from the morphology analysis of transmission electron microscope, pattern is monodisperse hexagonal flaky nanometer structure, and particle average dimension is 20-30nm.
Embodiment 4:
Take 2.5g analytical pure Neodymium trichloride and 1.2g analytical pure Neutral ammonium fluoride powder in mortar, abundant grinding is homogeneous, Isopropanol Water Solvent Mixtures (both volume ratios are 3:1) the furnishing stream adding 3g is abnormal, after proceed in 20mL reactor, sealing, in 100 DEG C of insulation 12h, after naturally cooling, take out, through distilled water wash for several times, centrifugation, 60 DEG C, vacuum is dry obtains sky-blue powdery product.Product is accredited as borontrifluoride neodymium through X-ray powder diffraction; As can be seen from the morphology analysis of transmission electron microscope, pattern is monodisperse hexagonal flaky nanometer structure, and particle average dimension is 20-30nm.
Claims (4)
1. the method adopting rheological phase reaction method to synthesize monodisperse hexagonal rare-earth fluoride nano sheet, after the abundant mixed grinding of mixed solvent of rare earth compound, fluorochemical and organic solvent/water is evenly become to flow covert material, in the reactor of sealing, constant temperature keeps the reaction times, obtains monodisperse hexagonal rare-earth fluoride nano sheet; Concrete steps are: 1) first rare earth compound, fluorochemical are mixed by a certain percentage, and fully grinding evenly; 2) add the mixed solvent of organic solvent-water composition, fully grinding obtains flowing covert material uniformly; 3) by step 2) the covert material of the stream that obtains moves in autoclave, and constant temperature keeps certain hour, carries out rheological phase reaction, rear naturally cooling; 4) repeatedly wash through distilled water, ethanol, filter, vacuum 60 DEG C of dryings obtain described monodisperse rare-earth fluoride nanometer sheet; In step 1) in, the mol ratio of rare earth compound and fluorochemical is 1:2-6; In step 2) in, described organic solvent has at least one to be selected from methyl alcohol, ethanol, Virahol, acetone or propyl carbinol, and the volume ratio of described organic solvent and water is 1-4:1; In step 2) in, the total mass ratio of the quality of the mixed solvent of organic solvent/water and rare earth compound and fluorochemical is 0.3-1.2:1; In step 3) in, described temperature of reaction is 60-180 DEG C, and the time is 10-48h.
2. method according to claim 1, is characterized in that: step 1) in, described rare earth metal is lanthanum, cerium, praseodymium or neodymium, and described rare earth compound is the rare earth compound of solubility.
3. method according to claim 1 and 2, is characterized in that: step 1) in, described fluorochemical is Neutral ammonium fluoride, Sodium Fluoride or ammonium bifluoride.
4. method according to claim 2, is characterized in that: the rare earth compound of described solubility is nitrate or chlorate.
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| CN108358233B (en) | 2018-02-09 | 2019-11-26 | 天津工业大学 | A kind of lanthanide series fluoride two dimension porous nano-sheet and its preparation method and application |
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| CN101962181A (en) * | 2010-11-17 | 2011-02-02 | 湖北省宏源药业有限公司 | Preparation of lithium hexafluorophosphate by rheological phase reaction method |
| CN102391870A (en) * | 2011-09-29 | 2012-03-28 | 宁波浩威尔新材料科技有限公司 | Preparation method of YAG (yttrium aluminum garnet): Ce rare earth fluorescent powder |
| CN102585824A (en) * | 2011-01-07 | 2012-07-18 | 中国科学院理化技术研究所 | Coprecipitation-rheological phase preparation method of rare earth-doped yttrium aluminum garnet fluorescent powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962181A (en) * | 2010-11-17 | 2011-02-02 | 湖北省宏源药业有限公司 | Preparation of lithium hexafluorophosphate by rheological phase reaction method |
| CN102585824A (en) * | 2011-01-07 | 2012-07-18 | 中国科学院理化技术研究所 | Coprecipitation-rheological phase preparation method of rare earth-doped yttrium aluminum garnet fluorescent powder |
| CN102391870A (en) * | 2011-09-29 | 2012-03-28 | 宁波浩威尔新材料科技有限公司 | Preparation method of YAG (yttrium aluminum garnet): Ce rare earth fluorescent powder |
Non-Patent Citations (3)
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| Design》.2009,第9卷(第4期), * |
| Ruifei Qin et al.."polyol-mediated synthesis of hexagonal LaF3 nanoplates using NaNO3 as a mineralizier".《Crystal Growth & * |
| 周享春等."用流变相-前驱体热分解法制备R2O3(R=La,Y,Gd)纳米粉体".《武汉大学学报(理学版)》.2004,第50卷(第6期), * |
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