CN102515241B - Method for preparing CeO2 nanoparticles from W/O type microemulsion - Google Patents
Method for preparing CeO2 nanoparticles from W/O type microemulsion Download PDFInfo
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- CN102515241B CN102515241B CN201110434845.8A CN201110434845A CN102515241B CN 102515241 B CN102515241 B CN 102515241B CN 201110434845 A CN201110434845 A CN 201110434845A CN 102515241 B CN102515241 B CN 102515241B
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- emulsifying agent
- sodium hydroxide
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Abstract
The invention which relates to a method for preparing CeO2 nanoparticles from a W/O type microemulsion belongs to the nanomaterial preparation field. The method comprises the following steps: 1, determining a microemulsion region which comprises a surfactant 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (hereinafter referred to as P507), an oil phase sulfonated kerosene, an organic solvent n-heptane and a water phase sodium hydroxide solution, wherein an emulsifier comprises the surfactant P507 and the organic solvent n-heptane, and the range of the mass ratio of the emulsifier to the sulfonated kerosene to NaOH in the sodium hydroxide solution is 9.85-93.08:2.39-88.67:1.48-10.85; 2, adding a Ce salt solution to the microemulsion region under stirring to obtain a loaded organic phase; 3, adding a precipitant oxalic acid solution to the loaded organic phase to obtain a predecessor; and 4, roasting the predecessor at 250-750DEG C for 1.5-6.5h to obtain the spherical CeO2 nanoparticles with the powder morphology of 10-20nm. The CeO2 nanoparticles prepared in the invention have the advantages of no obvious particle agglomeration and uniform particle size distribution.
Description
One, technical field
The invention belongs to the preparation field of nano material, especially with microemulsion, prepare nano Ce O
2the method of particle.
Two, background technology
There is abundant rare earth resources in China, accounts for the world's the more than 80% of proven reserve, and wherein the content of cerium is the richest.Rare earth oxide CeO
2be the light rare earths product of outbalance, be widely used in luminescent material, catalyzer, electronic ceramics, UV light absorber, precise polishing materials etc.Again because it has superior oxygen function and the quick oxygen of the high temperature room diffusibility stored, therefore become the catalytic cleaning of car tail gas material, Solid Oxide Fuel Cell (SOFC) anode material, the electrochemical reaction that have an application prospect and promote material etc.
Prepare at present CeO
2the method of particle is numerous, but the reunion of ubiquity products therefrom is serious, disperses the problems such as inhomogeneous, and the existence of these problems has limited CeO
2the application and development of particle.Relevant research shows, microemulsion can be set up the media environment that a kind of oil/water coexists, and overcomes above preparation defect.
Microemulsion is a kind of system being comprised of oil, water, tensio-active agent (generally also containing cosurfactant), can by the material solubilising of wide range of types one mutually in, be the fine solvent of nonpolar organic matter and inorganic salt.Emulsion method can wrap up layer of surface active agent molecule at particle surface, and prepared particle surface is modified, and makes to be difficult between particle coalescent, and the particle size that finally reaches preparation is controlled, and particle diameter is little, narrow particle size distribution, the objects such as good dispersity.Reverse microemulsion process is to take water-fast organic solvent as dispersion medium, take the aqueous solution as disperse phase, under the mating reaction of tensio-active agent and the microemulsion obtaining, wherein water core (" pond " is otherwise known as) size is generally in nano-scale range, separated each other, thereby reverse microemulsion method becomes a focus of people's research in recent years.
Three, summary of the invention
The object of the present invention is to provide and a kind ofly with microemulsion, prepare nano Ce O
2the method of particle, and prepare without obvious particle agglomeration, the uniform nano Ce O of size distribution
2particle.
Provided by the present invention this with microemulsion fabrication CeO
2the method of particle, is characterized in that not containing cosurfactant in system, only tensio-active agent, oil phase and water, consists of.
A kind of w/o type microemulsion is prepared nano Ce O
2the method of particle, is characterized in that step is as follows:
Determining of micro-emulsion region: by tensio-active agent di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, hereinafter to be referred as P507, oil phase sulfonated kerosene, organic solvent normal heptane and water sodium hydroxide solution form; Emulsifying agent is comprised of tensio-active agent P507 and organic solvent normal heptane; Emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 9.85～93.08: 2.39～88.67: 1.48～10.85;
The cerium solution that is 0.1～1.2mol/L by concentration under stirring action joins in micro-emulsion region, wherein cerium ion in cerium solution: P507 mol ratio is 1: 3, obtains load organic phases; The precipitation agent oxalic acid solution of 40～120g/L is joined in load organic phases, and consumption of oxalic acid is that 4.5～6.75 times of P507 amount of substance obtain precursor; By precursor, at 250 ℃～750 ℃, 1.5～6.5h adds thermal bake-out and obtains yellow nano Ce O
2particle, its median size is 10～20nm.
Further, emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 75.47～87.5: 5.1～18.87: 5.66～10.85.
Further, emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 80.1: 9.05: 10.85.
P507: C in best emulsifying agent
7h
16mass ratio be 90: 10.
Above-mentioned this w/o type microemulsion is prepared nano Ce O
2the method of particle:
1. choose tensio-active agent, water-fast organic solvent (oil phase) and water.
(1) tensio-active agent
Tensio-active agent is divided into ionic and non-ionic type, has and can make the surface tension of solution obviously reduce, and makes the solubleness of insoluble substance the effect such as obviously increase, and generally has polyalcohols, ester class, ethers, amides etc.The present invention, according to the surfactivity of rare-earth extractant, selects acid Phosphorus organic extractant di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (being called for short P507) as tensio-active agent.
(2) water-fast organic solvent (oil phase)
Water-fast organic solvent (oil phase) is one or more the mixed solvent in water-fast various aliphatic hydrocarbon or aromatic hydrocarbon, and the present invention selects sulfonated kerosene as organic solvent (oil phase).The composition of kerosene separation and Extraction from oil, is mainly the organism that carbon hydrogen element forms, and is the mixture of multiple hydro carbons.Sulfonated kerosene washs common kerosene exactly with the vitriol oil, to remove the alkane of unsaturated link(age) wherein.
The present invention is also included in system and adds the saturated alkanes of organic solvent, and it is C6～C10 that institute adds saturated alkanes, and the present invention adds normal heptane (C
7h
16) as example.
(3) alkaline solution (water)
Alkaline solution makes its saponification as the mixed solution of water titration tensio-active agent and oil phase (comprising normal heptane), and alkaline solution can be to contain OH
-strong base solution, can be also ammonia soln, can be even organic bases triethanolamine solution.Consider that ammoniacal liquor is difficult for permanent placement and volatile, the feature of trolamine cost costliness, preferably strong base solution.The present invention uses sodium hydroxide solution as example.
2. by tensio-active agent P507 and organic solvent normal heptane C
7h
16be mixed into emulsifying agent, emulsifying agent and oil phase sulfonated kerosene are mixed with different mass ratioes, with the above-mentioned mixed solution of strong base solution NaOH titration, visual observations mixed solution becomes clear by mixing, until obtain limpid uniform solution, determine to be now formation microemulsion, according to the pure and impure variation of system, measure the territory, micro-liquid zone of water/oil (W/O).Its chemical reaction can be expressed as:
Saponification process: P507 (note is HA)+NaOH----P507-Na[Na (HA)]+H
2o...... (1)
3. constantly under stirring action, cerium solution being joined in micro-emulsion region, obtain load organic phases;
Loading process: 3Na (HA)+Ce
3+----Ce (HA)
3+ 3NaCl...... (2)
4. precipitation agent oxalic acid solution is joined in load organic phases, obtain white precipitate organic phase (precursor).
Precipitation process: 2Ce (HA)
3+ 3H
2c
2o
4----... Ce
2(C
2o
4)
3↓+6HA...... (3)
5. precursor separation, washing, dry post-heating roasting are obtained to yellow nano Ce O
2particle.
Thermal degradation process: Ce
2(C
2o
4)
3+ 2O
2----2CeO
2+ 6CO
2↑ ... (4)
The present invention prepare without obvious particle agglomeration, the uniform nano Ce O of size distribution
2particle, median size is 10～20nm.
Four. accompanying drawing explanation:
Fig. 1: P507-kerosene/normal heptane/NaOH-H that preparation method of the present invention obtains
2the micro emulsion liquid zone of O system.As seen from Figure 1: by NaOH solution saponification P507-sulfonated kerosene/n-heptane system, can obtain the micro emulsion liquid zone of certain area coverage, the base area that its regional extent surrounds for each data point, now emulsifying agent is comprised of P507 and normal heptane.When the mass ratio of emulsifying agent and oil phase (sulfonated kerosene) changes, in system, the amount of solubilising alkali lye also constantly changes, and the solubilizing amount of alkali lye is larger, illustrates that the w/o type emulsion district forming is more stable.When the mass ratio of emulsifying agent and sulfonated kerosene is 75.47～87.5: in the time of between 5.1～18.87, this microemulsion system all has larger solubilizing amount to alkali lye, and at 80.1: 9.05 o'clock, reach maximum, now interfacial film has higher stability, can think that this forms the w/o type microemulsion system forming the most stable, visible in figure, formed micro-emulsion region scope is comparatively broad.
In addition, adding of normal heptane, can reach microemulsion state within the specific limits in advance, also can expand saponification interval simultaneously.Thereby judge, in the mensuration process of micro emulsion liquid zone, normal heptane (C
7h
16) a role part exists for external phase, a part ofly forms interfacial film together with P507, alkali lye is dispersed in interfacial film.
Fig. 2: the SEM figure of the precursor precipitation that preparation method of the present invention obtains.From the image of the scanning electronic microscope of Fig. 2, can find out: presoma precipitated product is near-spherical, and particle is comparatively even, its median size is 110～130nm left and right;
Fig. 3: the XRD figure of the precursor precipitation that preparation method of the present invention obtains.The X ray collection of illustrative plates of Fig. 3 can know, gained white precursor powder is not Sedemesis Ce
2(C
2o
4)
3precipitation, its thing not yet finds in JCPDS powder crystal diffraction card, shows that precursor is the new thing phase with good crystallinity.
Fig. 4: the nano Ce O that preparation method of the present invention obtains
2the TEM figure of particle.From the image of the transmission electron microscope of Fig. 4, can find out: it is spherical particle that precursor is deposited in resulting yellow powder pattern 250 ℃～750 ℃ roasting 1.5～6.5h, there is no obvious agglomeration, granular size, distribute all comparatively evenly, median size is 10～20nm left and right.
Fig. 5: the nano Ce O that preparation method of the present invention obtains
2the XRD figure of particle.The X ray collection of illustrative plates of Fig. 5 can be known, products therefrom and face-centered cubic CeO
2standard diffraction data coincide, the degree of crystallization of gained powder is strengthened greatly, thereby identifies the CeO that product is fluorite structure
2and crystal formation is better.
Five. embodiment
1. tensio-active agent P507 and organic solvent normal heptane are mixed into emulsifying agent, wherein the mass ratio of P507 and normal heptane is 95: 5,90: 10,88: 12,85: 15,80: 20,70: 30,60: 40,50: 50,40: 60,30: 70,20: 80,10: 90, the emulsifying agent saponification of the NaOH solution of then using same concentration to different mass ratio, until visual observations obtains limpid uniform solution.
2. according to specific embodiment, obtain: when normal heptane mass ratio is 10%, the solubilizing effect of micro emulsion liquid zone is the most obvious, so P507 and C in emulsifying agent
7h
16mass ratio be defined as 90: 10.
The embodiment of emulsifying agent process for preparation sees the following form:
3. by emulsifying agent (P507: C
7h
16mass ratio be 90: 10) mix with sulfonated kerosene, the mass ratio of emulsifying agent and sulfonated kerosene is set as 9.75: 0.25 respectively, 9.5: 0.5, 9: 1, 8.5: 1.5, 8: 2, 7: 3, 6: 4, 5: 5, 4: 6, 3: 7, 2: 8, 1: 9, then with the NaOH solution titration of 2～10mol/L, make its saponification, visual observations mixed solution becomes faint yellow turbid liquid from white emulsion, until whole solution clarification is homogeneous phase (saponification deg>=80%), now form water-in-oil-type (W/O) reverse microemulsion, according to the pure and impure variation of system, measure the territory, micro-liquid zone of water/oil (W/O).Now system comprises four kinds of materials, tensio-active agent P507, and oil phase sulfonated kerosene, normal heptane and water strong base solution, be defined as emulsifying agent to be comprised of P507 and normal heptane, and system can be converted into quaternary system ternary system drawing diagram.
4. according to specific embodiment, obtain emulsifying agent: sulfonated kerosene: NaOH (take solid content) three's mass ratio range is 9.85～93.08: 2.39～88.67: 1.48～10.85, wherein optimization range is 75.47～87.5: 5.1～18.87: 5.66～10.85, optimum optimization value is 80.1: 9.05: 10.85, the micro-emulsion region now forming is the broadest, and the most wide in range to the concentration requirement of cerium solution and precipitation agent oxalic acid solution.
5. the cerium solution that is 0.1～1.2mol/L by concentration under continuous stirring action joins in micro-emulsion region by the required mole number of chemical reaction, wherein cerium ion in cerium solution: P507 mol ratio is 1: 3, obtains load organic phases.
6. the precipitation agent oxalic acid solution of 40～120g/L is joined in load organic phases, consumption of oxalic acid is 1～1.5 times of calculated value, be that consumption of oxalic acid is 4.5～6.75 times of P507 amount of substance, react completely guaranteeing, obtain white precipitate organic phase (precursor).
Precursor is centrifugal, separated, suction filtration, washing, dry after at 250 ℃～750 ℃, 1.5～6.5h adds thermal bake-out and obtains yellow nano Ce O
2particle, its median size is 10～20nm left and right.
The embodiment of micro-emulsion region process for preparation sees the following form:
| Embodiment | Emulsifying agent/g | Sulfonated kerosene/g | NaOH/g |
| 100 | 0 | 0 | |
| Embodiment 1 | 93.08 | 2.39 | 4.53 |
| Embodiment 2 | 87.5 | 5.1 | 7.4 |
| Embodiment 3 | 80.1 | 9.05 | 10.85 |
| Embodiment 4 | 77.6 | 14 | 8.4 |
| Embodiment 5 | 75.47 | 18.87 | 5.66 |
| Embodiment 6 | 66.83 | 28.64 | 4.53 |
| Embodiment 7 | 57.69 | 38.46 | 3.85 |
| Embodiment 8 | 49.02 | 49.03 | 1.95 |
| Embodiment 9 | 39.23 | 58.85 | 1.92 |
| Embodiment 10 | 29.46 | 68.73 | 1.81 |
| Embodiment 11 | 19.66 | 78.62 | 1.72 |
| Embodiment 12 | 9.85 | 88.67 | 1.48 |
| 0 | 100 | 0 |
Nano Ce O
2preparation method's specific embodiment of particle sees the following form:
Claims (4)
1. a w/o type microemulsion is prepared nano Ce O
2the method of particle, is characterized in that step is as follows:
Determining of micro-emulsion region: by tensio-active agent 2-ethylhexyl phosphonic acids single 2-ethyl base ester, hereinafter to be referred as P507, oil phase sulfonated kerosene, organic solvent normal heptane and water sodium hydroxide solution form; Emulsifying agent is comprised of tensio-active agent P507 and organic solvent normal heptane; With the NaOH solution titration of 2～10mol/L, make its saponification, visual observations mixed solution becomes faint yellow turbid liquid from white emulsion, until the clarification of whole solution is homogeneous phase, saponification deg >=80%; Emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 9.85～93.08:2.39～88.67:1.48～10.85;
The cerium solution that is 0.1～1.2mol/L by concentration under stirring action joins in micro-emulsion region, wherein cerium ion in cerium solution: P507 mol ratio is 1:3, obtains load organic phases; The precipitation agent oxalic acid solution of 40～120g/L is joined in load organic phases, and consumption of oxalic acid is that 4.5～6.75 times of P507 amount of substance obtain precursor; By precursor, at 250 ℃～750 ℃, 1.5～6.5h adds thermal bake-out and obtains yellow nano Ce O
2particle, its median size is 10～20nm.
2. a kind of w/o type microemulsion according to claim 1 is prepared nano Ce O
2the method of particle, is characterized in that: emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 75.47～87.5:5.1～18.87:5.66～10.85.
3. a kind of w/o type microemulsion according to claim 1 is prepared nano Ce O
2the method of particle, is characterized in that: emulsifying agent: sulfonated kerosene: the NaOH three's mass ratio range in sodium hydroxide solution is 80.1:9.05:10.85.
4. a kind of w/o type microemulsion according to claim 1 is prepared nano Ce O
2the method of particle, is characterized in that: P507:C in emulsifying agent
7h
16mass ratio be 90:10.
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| CN108813616A (en) * | 2018-07-05 | 2018-11-16 | 河北东之星生物科技股份有限公司 | A method of preparing lutein water-soluble microemulsion |
| CN109022837B (en) * | 2018-08-31 | 2020-12-25 | 内蒙古科技大学 | Method for preparing rod-like rare earth oxalate powder based on reverse microemulsion method |
| CN112370423B (en) * | 2020-11-04 | 2021-08-03 | 哈尔滨工业大学（深圳） | L-carnitine-based emulsion, preparation method and medicine |
| CN112939048A (en) * | 2021-04-21 | 2021-06-11 | 贺州学院 | Method for preparing superfine calcium carbonate by adopting P507 reverse microemulsion method |
Citations (1)
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|---|---|---|---|---|
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
Non-Patent Citations (4)
| Title |
|---|
| A novel method for the synthesis of perovskite-type mixed metal oxides by the inverse microemulsion technique;L. M. Gan et al.;《JOURNAL OF MATERIALS SCIENCE》;19960215;第31卷;全文 * |
| L. M. Gan et al..A novel method for the synthesis of perovskite-type mixed metal oxides by the inverse microemulsion technique.《JOURNAL OF MATERIALS SCIENCE》.1996,第31卷1071-1079. |
| 用草酸从P507载带物中反萃沉淀稀土的研究;鲍卫民;《稀有金属》;19960531;第20卷(第3期);第207页至第208页试验部分 * |
| 鲍卫民.用草酸从P507载带物中反萃沉淀稀土的研究.《稀有金属》.1996,第20卷(第3期),第207页至第208页试验部分. |
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