CN101538061B - Method for preparing nano cerium dioxide - Google Patents
Method for preparing nano cerium dioxide Download PDFInfo
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- CN101538061B CN101538061B CN2009100836012A CN200910083601A CN101538061B CN 101538061 B CN101538061 B CN 101538061B CN 2009100836012 A CN2009100836012 A CN 2009100836012A CN 200910083601 A CN200910083601 A CN 200910083601A CN 101538061 B CN101538061 B CN 101538061B
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Abstract
The invention discloses a method for preparing nano cerium dioxide. Organic solvent, surfactant and cosurfactant are added into solution of cerous nitrate as a raw material and ammonium oxalate as a precipitator respectively to generate precipitate under hydrothermal condition after mixing, and the precipitate is calcined to form the nano cerium dioxide. In the method, the solvent, the surfactant and the cosurfactant are added into the reaction solution, and an organic phase and a water phase which are not mutually soluble form a water-in-oil micro pool under the combined action of the surfactant and the cosurfactant to build a micro reactor so that reactants dissolved in the water phase are reacted in a nano-scale space under the hydrothermal condition to generate the precipitate so as to obtain the nano cerium dioxide. The diameter of the cerium dioxide is 20 to 120 nanometers, and the length of the cerium dioxide is 300 nanometers to 1 mu m.
Description
Technical field
The present invention relates to the preparation method of cerium oxide, be specifically related to a kind of preparation method of nano ceric oxide.
Background technology
The application of cerium oxide is very extensive, as three-way catalyst, can handle vehicle exhausts with precious metal actings in conjunction such as palladium, gold, and as the transmitter of oxygen in the vehicle exhaust, also by industry as polishing powder, fluorescent material, electron ceramic material and UV-light sorbent material.
Nano-cerium oxide is at the extensive concern that has caused material circle aspect optics, electricity, magnetics and the catalysis with its thundering characteristic, and the nano ceric oxide that variety of methods is prepared different-shape, different purposes is one of current research focus.
Patent CN101264922 utilizes cerous nitrate to be placed in the organic/inorganic solvent that tensio-active agent and precipitation agent exist, heating reflux method, obtain the product calcining after, finally make CeO
2Rhombus nano-sheet micro crystal material.But its preparation section is loaded down with trivial details, manufacturing cost is high, severe reaction conditions.
Document Riccardi C.S., Lima R.C.Santos M.L, Bueno P.R., Varela J.A., Longo E.SolidState Ionics, 2009,180 (2): among the 288-291, be to utilize microwave under hydrothermal condition, to prepare the cerium dioxide and the presoma thereof of hexagonal flake.
Patent CN1840480 utilizes the urea soln that has hydrothermal treatment consists solubility cerium salt under the situation at water, organic solvent or mixed solvent, obtains pattern materials such as bigger serface cerium oxide nano particle, nanometer rod.Yet, the distribution of the nanometer rod that it prepares wide (diameter is the 20-100 nanometer, and length is 100 nanometers-3 micron), homogeneity is poor.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano ceric oxide.Adopt the product homogeneity of this method preparation good, preparation cycle is short, and preparation is simple.
The present invention is raw material with the cerous nitrate, is precipitation agent with the ammonium oxalate, adds organic solvent, tensio-active agent and cosurfactant respectively in its solution, mixes the back and generate precipitation under hydrothermal condition, prepares nano ceric oxide after calcining.
Concrete preparation process is as follows:
A. the solubility cerous salt is dissolved in the deionized water, compound concentration is 0.05-0.3molL
-1Cerium solution; With cerium solution and solvent hexanaphthene is 1 by volume: the mixed of 25-30 is mixed with mixing solutions, add again the mass percent 8-20% account for above-mentioned mixing solutions tensio-active agent, account for the cosurfactant of the mass percent 5-10% of above-mentioned mixing solutions, be made into body lotion I;
B. ammonium oxalate is dissolved in the deionized water, being made into concentration is 0.1-0.5molL
-1Solution; With ammonium oxalate solution and solvent hexanaphthene is 1 by volume: the mixed of 25-30 is mixed with mixing solutions, add again the mass percent 8-20% account for above-mentioned mixing solutions tensio-active agent, account for the cosurfactant of the mass percent 5-10% of above-mentioned mixing solutions, wiring solution-forming II
Described tensio-active agent is any one or two kinds in Triton-100 (be called for short Tx-100), sodium lauryl sulphate (SDS), cetyl trimethylammonium bromide (CTAB), the succinate sodium sulfonate (AOT); Be preferably in Triton-100, sodium lauryl sulphate, the cetyl trimethylammonium bromide any one.
Described cosurfactant is a n-hexyl alcohol.
C. 1: 1 mixed with solution I and solution II according to volume ratio, put into 30-40 ℃ water bath with thermostatic control, continuously stirring 5-10 minute, it is moved in the autoclave, reaction is 6-12 hour under 140-180 ℃ of temperature, be cooled to room temperature, obtain precipitation, separate, washing, drying in 400-550 ℃ of roasting 3-5 hour, obtains nano ceric oxide; This CeO
2Size be: diameter 20-120nm, long 300nm-1 μ m.
The present invention adds solvent, tensio-active agent and cosurfactant in solution I and solution II, utilize immiscible organic phase and water under the acting in conjunction of tensio-active agent and cosurfactant, form water in oil small pond, build microreactor, make the reactant reaction under hydrothermal condition, in the nano level space be dissolved in aqueous phase generate precipitation, thereby obtain the nano level cerium dioxide.
Wherein under the hydrothermal condition, it is bigger that the pressure of generation is compared water in closed reaction kettle for the organic solvent hexanaphthene, helps the formation of nanoparticle; Tensio-active agent has been given full play to the effect of dispersion agent, has hindered the reunion of nano material.
The characterization result of product is seen Fig. 1-5,
Fig. 1 is embodiment 1 sample X-ray diffraction (XRD) figure, is seen that by measurement result the sample characteristic diffraction peak that the present invention makes is CeO
2Nanocrystalline.
Fig. 2 is embodiment 1 sample scanning electron microscope (SEM) figure, and the pattern of nano ceric oxide is diameter 80-100nm as seen from Figure 2, and length is 300-500nm.
Fig. 3 is embodiment 2 sample scanning electron microscope (SEM), and the pattern of nano ceric oxide is diameter 50-100nm as seen from Figure 3, long 800nm-1 μ m.
Fig. 4 is embodiment 3 sample scanning electron microscope (SEM), and the pattern of nano ceric oxide is diameter 20-120nm as seen from Figure 4, long 300-800nm.
Fig. 5 is the selected area electron diffraction figure of embodiment 1 sample, is a plurality of concentric(al) circless as seen from Figure 5, and interpret sample is CeO
2Nanocrystalline.
The invention has the beneficial effects as follows: the present invention adds solvent, tensio-active agent and cosurfactant in reaction soln, make the reactant reaction under hydrothermal condition, in the nano level space be dissolved in aqueous phase generate precipitation, thereby obtain the nano level cerium dioxide.Preparation is simple for this, and preparation cycle is short, and the nano ceric oxide homogeneity that makes is good.
Description of drawings
In order further to understand the present invention, elaborate with embodiment below, and drawn accompanying drawing and described the present invention and obtain CeO
2The sign of the feature of nanometer rod, wherein:
Fig. 1 is CeO
2The X-ray powder diffraction figure of embodiment 1 nanometer rod sample;
Fig. 2 is CeO
2Scanning electron microscope (SEM) photo of embodiment 1 nanometer rod sample;
Fig. 3 is CeO
2Scanning electron microscope (SEM) photo of embodiment 2 nanometer rod samples;
Fig. 4 is CeO
2Scanning electron microscope (SEM) photo of embodiment 3 nanometer rod samples;
Fig. 5 is CeO
2The selected area electron diffraction photo of embodiment 1 nanometer rod sample.
Embodiment
Embodiment 1:
A. prepare 0.2molL with cerous nitrate
-1Cerous nitrate aqueous solution 1ml adds 4ml tensio-active agent Triton-100,2ml cosurfactant n-hexyl alcohol solution and 30ml hexanaphthene successively, stirs;
B. be mixed with 0.3molL with ammonium oxalate
-1Ammonium oxalate aqueous solution 1ml adds 4ml tensio-active agent Triton-100,2ml cosurfactant n-hexyl alcohol solution and 30ml hexanaphthene successively, stirs;
C. above two kinds of solution are mixed, stirred 10 minutes, transfer in the autoclave.At 160 ℃ of reaction 6h, naturally cooling.Through ethanol, deionized water wash, drying is calcined 3h down at 500 ℃ and is obtained product.
Product is accredited as cerium oxide through X-ray powder diffraction (Fig. 1), observes the product pattern by SEM Electronic Speculum figure (Fig. 2), and its sectional dimension is 80-100nm, and length is the nanometer rod of 300-500nm.
Embodiment 2:
Change the tensio-active agent among steps A and the B among the embodiment 1 into sodium lauryl sulphate, add-on is 1.9g, and all the other are with embodiment 1.The product stereoscan photograph that obtains is seen Fig. 3, and its sectional dimension is 50-100nm, long 800nm-1 μ m.
Embodiment 3:
Change the tensio-active agent among steps A and the B among the embodiment 1 into cetyl trimethylammonium bromide, add-on is 2.5g, and all the other are with embodiment 1.The product stereoscan photograph that obtains is seen Fig. 4, and its sectional dimension is 20-120nm, long 300-800nm.
Embodiment 4:
Change the reaction conditions in autoclave among the embodiment 1 step C into 140 ℃ of reactions 6 hours, all the other conditions are with embodiment 1.The product that obtains from stereoscan photograph as seen, its sectional dimension is 80-100nm, long 800nm-1 μ m.
Embodiment 5:
Change the reaction conditions in autoclave among the embodiment 1 step C into 160 ℃ of reactions 12 hours, all the other conditions are with embodiment 1.The product that obtains from stereoscan photograph as seen, its sectional dimension is 50-100nm, long 300-500nm.
Embodiment 6:
Change the cerous nitrate compound concentration in the steps A among the embodiment 1 into 0.05molL
-1, the reaction conditions in autoclave among the step C changes 150 ℃ of reactions 6 hours into, and all the other conditions are with embodiment 1.The product that obtains from stereoscan photograph as seen, its sectional dimension is 80-100nm, long 300-500nm.
Claims (2)
1. the preparation method of a nano ceric oxide, concrete preparation process is as follows:
A. the solubility cerous salt is dissolved in the deionized water, compound concentration is 0.05-0.3molL
-1Cerium solution; With cerium solution and solvent hexanaphthene is 1 by volume: the mixed of 25-30 is mixed with mixing solutions, adding accounts for the tensio-active agent of the mass percent 8-20% of above-mentioned mixing solutions again, also adding accounts for the cosurfactant of the mass percent 5-10% of above-mentioned mixing solutions, wiring solution-forming I;
B. ammonium oxalate is dissolved in the deionized water, being made into concentration is 0.1-0.5molL
-1Solution; With ammonium oxalate solution and solvent hexanaphthene is 1 by volume: the mixed of 25-30 is mixed with mixing solutions, add again the mass percent 8-20% account for above-mentioned mixing solutions tensio-active agent, account for the cosurfactant of the mass percent 5-10% of above-mentioned mixing solutions, wiring solution-forming II;
Described tensio-active agent is any one or two kinds in Triton-100, sodium lauryl sulphate, cetyl trimethylammonium bromide, the succinate sodium sulfonate; Described cosurfactant is a n-hexyl alcohol;
C. 1: 1 mixed with solution I and solution II according to volume ratio, put into 30-40 ℃ water bath with thermostatic control, continuously stirring 5-10 minute, it is moved in the autoclave, reaction is 6-12 hour under 140-180 ℃ of temperature, be cooled to room temperature, obtain precipitation, separate, washing, drying in 400-550 ℃ of roasting 3-5 hour, obtains nano ceric oxide; This CeO
2Size be: diameter 20-120nm, long 300nm-1 μ m.
2. the preparation method of nano ceric oxide according to claim 1 is characterized in that, described tensio-active agent is any one in Triton-100, sodium lauryl sulphate, the cetyl trimethylammonium bromide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101824745B (en) * | 2010-04-12 | 2013-07-17 | 江苏工业学院 | Method for preparing anti-UV fabric by in-situ method |
| CN102515567A (en) * | 2011-12-14 | 2012-06-27 | 渤海大学 | Method for preparing nano CeO2 film having UV shielding property |
| CN103225202A (en) * | 2013-05-07 | 2013-07-31 | 浙江理工大学 | Preparation method of anti-ultraviolet fabric by ammonia steam method |
| CN103274442B (en) * | 2013-05-24 | 2015-04-08 | 成都理工大学 | Hydrothermal synthesis technology of mesoporous CeO2 by adopting CeO2 hydrosol |
| CN103387257B (en) * | 2013-07-19 | 2015-04-22 | 东华大学 | Method for preparing nano cerium dioxide material by utilizing tween-80 as surfactant |
| CN103708528A (en) * | 2014-01-03 | 2014-04-09 | 东华大学 | Preparation method of nano cerium dioxide with controllable size |
| CN103754922B (en) * | 2014-01-03 | 2015-08-12 | 东华大学 | A kind of take CTAB as the method that oil solubility nanometer cerium dioxide fluorescent material prepared by tensio-active agent |
| CN116251562A (en) * | 2023-02-10 | 2023-06-13 | 广州市汉宵科研技术有限公司 | Nanoscale cerium oxide particle material and preparation method thereof |
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