CN1326776C - Method for synthesizing one dimension nano material of lanthanum oxide through emulsion liquid membrane - Google Patents
Method for synthesizing one dimension nano material of lanthanum oxide through emulsion liquid membrane Download PDFInfo
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- CN1326776C CN1326776C CNB2004100174828A CN200410017482A CN1326776C CN 1326776 C CN1326776 C CN 1326776C CN B2004100174828 A CNB2004100174828 A CN B2004100174828A CN 200410017482 A CN200410017482 A CN 200410017482A CN 1326776 C CN1326776 C CN 1326776C
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Abstract
The present invention relates to a method for synthesizing one-dimensional nanometer lanthana materials by emulsion films. The method comprises the following steps: step 1, mixing 80 portions of kerosene, 10 portions of surface active agents and 10 portions of carriers according to the volume ratio to obtain oil film phases, adding 0.1 mol/L sodium oxalate solution as inner water phases according to the same volume, stirring the oil film phases and the solution at high speed to obtain W/O type emulsion, step 2, mixing 0.1 mol/L lanthanum chloride solution as outer water phases and the emulsion according to the volume ratio of 2 to 1, slightly stirring the mixtures, standing the mixtures for delamination, demulsifying the emulsion at the upper layer by organic solvents to obtain centrifugal precipitates as precursors, namely one-dimensional nanometer lanthanum oxalate, circularly returning the separated oil film phase solution to step 1, and recrystallizing the waste liquor of the inner water phases and the outer water phases to obtain byproduct sodium chloride, step 3, respectively washing the precursors, namely the one-dimensional nanometer lanthanum oxalate, with etanol and water for three to five times, and then burning and decomposing the one-dimensional nanometer lanthanum oxalate at a temperature of 650 DEG C to 800 DEG C for 3 to 8 hours to obtain products, namely one-dimensional lanthana nanometer materials. The present invention has the advantages of simple operation, controllable parameters, low cost, high yield and good product quality, is favorable for environmental protection, and the method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of one dimension lanthanum trioxide nano material.
Background technology
Nano material is meant that by diameter be the powder body material that the particle of 1-100 nanometer (part per billion meter) is formed.Because therefore small size, weird atom structure and huge specific surface area that nano material had have excellent light, electricity, magnetic, catalysis and mechanical property, become the research focus of current material science.What monodimension nanometer material was meant nanoparticle is shaped as the silk thread shape, also can be called nano thread, nano wire or nanometer rod.Science is verified, and the performance index of monodimension nanometer material are higher than common nanoparticle, but the synthetic difficulty has also substantially exceeded common nanoparticle, and therefore, with respect to common nanoparticle, monodimension nanometer material synthetic is still challenging problem.
Lanthanum trioxide is a kind of as rare earth material, is important commercial catalysts and solid electrolyte, can be applicable to methane oxidization catalyzing, wax hydrofining, oxynitride reduction, burning reaction and transmitter, electrical condenser, cathode material etc.Present common nano lanthanum oxide material is synthesized, and is proved to be and has the technical feature that surmounts common lanthanum trioxide powder.Existing nano lanthanum oxide material synthesis method roughly be divided into following several: (1) sluggish precipitation.This method is comparatively simple, can directly be precipitated by zwitterion, also can add a small amount of additive, but comparatively coarse to the control of production process, uneven, the bad dispersibility of product size.(2) microemulsion method.This method is to utilize the nano level space of microemulsion inside that reaction compartment is controlled, and the synthetic product size is comparatively even, good dispersity, but need use large amount of organic, so cost is higher, is not suitable for industrial application.(3) ball milling solid state reaction method.This method need be used ball mill, is fit to industrial mass manufacture, and the product size is uneven, the shortcoming of bad dispersibility but exist equally.In addition, above method all can only be synthesized common nano lanthanum oxide particle, and the synthetic of one dimension lanthanum trioxide nano material do not appear in the newspapers so far.
Summary of the invention
It is simple, pollution-free, low-cost and be fit to the method for fairly large industrial brand-new use emulsion liquid membrane synthesizing one-dimensional lanthanum trioxide nano material to the objective of the invention is to disclose a kind of technology.
In order to achieve the above object, we are by finding synthesizing common lanthanum trioxide nanoparticle Study on Technology at present, the 1-dimention nano lanthanum trioxide is because the difference of structural shape and common nano lanthanum oxide, thereby had the light more more excellent than common nano lanthanum oxide, electricity and catalytic performance.Through in theory repeatedly demonstration relatively, and after the thousands of times experiment, the emulsion liquid membrane method of finally having determined to contain carrier can obtain the technology of 1-dimention nano lanthanum trioxide.The three-phase system that the emulsion liquid membrane that is widely used in the industrial separation process of the invention sixties in last century is made up of water, oil, carrier and tensio-active agent, common appellation are that ecto-entad is followed successively by outer water, oil film phase and interior water.The solute of outer water can constantly migrate to interior water by carrier, therefore, has the bionic function of simulation microbial film mass transfer.Because carrier can be controlled the rate of migration of solute, the surfactant molecule on interior aqueous space and the oil film phase interface can play template action, therefore, and the degree of supersaturation and the crystalline direction of growth of aqueous solutes in relatively easily controlling.Select for use lanthanum chloride solution as outer water for this reason, sodium oxalate solution is as interior water, under the help of carrier, the solute lanthanum ion begins to move into interior water by outer water, under the degree of supersaturation condition at interior water and oil film phase interface place, the lanthanum ion that outer water enters will form lanthanum trioxide precursor lanthanum oxalate with the oxalate denominationby of interior water nanocrystalline, then, because the booster action of surfactant molecule long-chain, lanthanum oxalate is nanocrystalline can to grow up to the one dimension silk along this molecule long-chain direction, line, last because the restriction of interior aqueous space is grown formation 1-dimention nano lanthanum oxalate.After breakdown of emulsion and washing, precursor 1-dimention nano lanthanum oxalate after 650-800 ℃ of calcination decomposed, is promptly got product one dimension lanthanum trioxide nano material.
Concrete technology is as follows:
The first step is that organic solvent kerosene, tensio-active agent span 80 and the carrier tributyl phosphate volume ratio by 80: 10: 10 is mixed, obtain the oil film phase, and then add water sodium oxalate solution in the equal-volume 0.1mol/L in proportion, press speed at 3000-6000 rev/min, high-speed stirring 10 minutes obtains w/o type milk sap.
It is outer water that second step was got the 0.1mol/L lanthanum chloride solution, and the milk sap that outer water and last step are made mixes with 2: 1 volume ratio, by speed 200-400 rev/min, and gentle agitation 10 minutes, reaction is finished.Standing demix then, lower floor is outer water waste liquid, gets upper strata milk sap, with organic solvent ethanol it is carried out breakdown of emulsion, obtains interior water after getting breakdown of emulsion, all the other are isolated oil film phase solution.Oil film phase solution can return the first step once more by working cycle and carry out new synthesizing.The interior water of breakdown of emulsion carries out centrifugal precursor 1-dimention nano lanthanum oxalate solution and the interior water waste liquid of getting by 1000-2000 rev/min.The outer water waste liquid of interior water waste liquid and standing demix all contains inorganic salt sodium-chlor, and both are separated the purification recrystallization, obtains byproduct industrial raw material sodium-chlor.
The 3rd step washed precursor 1-dimention nano lanthanum oxalate 3-5 time respectively with organic solvent ethanol and water respectively, placed High Temperature Furnaces Heating Apparatus to decompose 3-8 hour with 650-800 ℃ of calcination then, obtained product one dimension lanthanum trioxide nano material.
The present invention has the following advantages:
1. the organic raw material of the present invention's use all can be recycled, and inorganic byproduct is essential industry inorganic salt sodium-chlor, can fully utilize, and can not pollute environment.Therefore, method of the present invention is with low cost, and productive rate is higher, helps protecting environment, is suitable for fairly large industrial production and Sustainable development requirement.
2. the present invention is an intelligent bionic method, can control the appearance structure of the one dimension lanthanum trioxide nano material of generation by changing various proportionings and processing condition, make it have superior physics and chemistry and photoelectricity and catalytic performance, and purity height, better crystallinity degree, be uniformly dispersed, simple to operate, controllable parameters.
3. not only can obtain one dimension lanthanum trioxide nano material with method of the present invention, and can be widely used in synthetic other 1-dimention nano rare earth oxides, as cerium, praseodymium, neodymium, terbium etc.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1:
See also accompanying drawing 1.The first step mixes kerosene, tensio-active agent span 80 and the carrier tributyl phosphate volume ratio by 80: 10: 10, makes oil film phase solution.Get 0.1mol/L sodium oxalate solution again as interior water, with isopyknic oil film mutually solution mix in the newborn device in system, and by speed at 3000-6000 rev/min, violent stirring 10 minutes obtains w/o type milk sap.
Second step was got the 0.1mol/L lanthanum chloride solution as outer water, outer water is mixed in reactor with 2: 1 volume ratio with above-mentioned milk sap, and by speed 200-400 rev/min, gentle agitation 10 minutes, reaction is finished, make emulsion liquid membrane and be placed on another container, standing demix, lower floor is outer water waste liquid, get the milk sap on upper strata earlier, with technical grade ethanol milk sap is carried out breakdown of emulsion: press milk sap: ethanol=20: 1 volume ratio adds, and gets the oil film that obtains behind the breakdown of emulsion and reclaims mutually and return the first step and utilize once more; The interior water that obtains adds in the sedimentator, by speed 1000-2000 rev/min centrifugation, obtains precursor and is precipitated as 1-dimention nano lanthanum oxalate and interior water waste liquid.Carry out recrystallization after the centrifugal interior water waste liquid that obtains of outer water waste liquid that static layering is obtained and breakdown of emulsion mixes, obtain byproduct sodium-chlor.
The 3rd step was precipitated the 1-dimention nano lanthanum oxalate with precursor and washs 3-5 time respectively with industrial alcohol and water, carried out the high temperature sintering decomposition with 650 ℃-800 ℃ again in High Temperature Furnaces Heating Apparatus, promptly got one dimension lanthanum trioxide nano material after 3-8 hour.By electron microscope, X-ray diffraction and spectrography it is gone looks, structure and performance characterization, the result show this product be diameter less than 50 nanometers, length is the hexagonal structure one dimension lanthanum trioxide monocrystal nano rod of 500 nanometers.
Claims (1)
1. method with emulsion liquid membrane synthesizing one-dimensional lanthanum trioxide nano material, it is characterized in that: the first step is that organic solvent kerosene, tensio-active agent span 80 and the carrier tributyl phosphate volume ratio by 80: 10: 10 is mixed, obtain the oil film phase, and then water sodium oxalate solution in the adding equal-volume 0.1mol/L, press speed at 3000-6000 rev/min, high-speed stirring 10 minutes obtains w/o type milk sap;
It is outer water that second step was got the 0.1mol/L lanthanum chloride solution, the milk sap that outer water and last step are made mixes with 2: 1 volume ratio, by speed 200-400 rev/min, gentle agitation 10 minutes, reaction is finished, standing demix then, lower floor is outer water waste liquid, gets upper strata milk sap, with technical grade ethanol milk sap is carried out breakdown of emulsion, the amount that adds is a milk sap: ethanol=20: 1 volume ratios, and get the oil film that obtains behind the breakdown of emulsion and reclaim mutually and return the first step and utilize once more; The interior water that obtains adds in the sedimentator, by speed 1000-2000 rev/min centrifugation, obtains precursor 1-dimention nano lanthanum oxalate precipitation and interior water waste liquid; Outer water waste liquid and interior water waste liquid contain inorganic salt sodium-chlor, separate purification, obtain byproduct sodium-chlor;
The 3rd step washed precursor 1-dimention nano lanthanum oxalate 3-5 time respectively with technical grade organic solvent ethanol and water respectively, placed High Temperature Furnaces Heating Apparatus to decompose 3-8 hour with 650-800 ℃ of calcination then, obtained product one dimension lanthanum trioxide nano material.
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| CN101850245B (en) * | 2010-06-01 | 2012-10-17 | 福建师范大学 | Preparation method of La2O3 nanofiber catalyst |
| CN101892386B (en) * | 2010-06-10 | 2012-05-30 | 南京中锗科技股份有限公司 | Demulsifying and detoxifying method of gallium extracting system |
| CN114933325A (en) * | 2022-05-31 | 2022-08-23 | 南开大学 | Method for preparing nano copper oxide by using waste mobile phone circuit board containing copper element as raw material |
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| CN1403375A (en) * | 2002-10-11 | 2003-03-19 | 清华大学 | Synthesis process of nanostring and nanopowder of RE hydroxide or oxide |
| WO2003053851A2 (en) * | 2001-07-20 | 2003-07-03 | President And Fellows Of Harvard College | Transition metal oxide nanowires |
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| WO2003053851A2 (en) * | 2001-07-20 | 2003-07-03 | President And Fellows Of Harvard College | Transition metal oxide nanowires |
| CN1403375A (en) * | 2002-10-11 | 2003-03-19 | 清华大学 | Synthesis process of nanostring and nanopowder of RE hydroxide or oxide |
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