CN103964485A - Method for preparing multi-element doped RE-M-O solid solution nanopowder - Google Patents
Method for preparing multi-element doped RE-M-O solid solution nanopowder Download PDFInfo
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- CN103964485A CN103964485A CN201410130421.6A CN201410130421A CN103964485A CN 103964485 A CN103964485 A CN 103964485A CN 201410130421 A CN201410130421 A CN 201410130421A CN 103964485 A CN103964485 A CN 103964485A
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Abstract
The invention relates to a method for preparing multi-element doped RE-M-O solid solution nanopowder. The method comprises the steps as follows: materials comprise components in percentage by mass as follows: 82%-92% of RE, 5%-10% of M and 5%-10% of graphite powder and are smelted by a 25-kg vacuum induction furnace; a graphite crucible is selected, and carbide alloy is obtained after the materials are molten and cast; and ferro cerium carbide alloy powder with the grain size smaller than 3 mm and deionized water are prepared in a mass ratio of (1:10)-(1: 100), mixing reaction is performed at the constant temperature of 10-100 DEG C for 18-72 hours, and the composite nanopowder with the specific surface area of 50-200 m<2>/g is obtained through washing and drying. With the adoption of the method, the multi-element doped RE-M-O solid solution nanopowder can be obtained, the operation is simple, the method is environment-friendly, and the industrial production is realized easily.
Description
Technical field
The present invention relates to a kind of with the RE-M-O(RE that carbide hydrolysis method is prepared polynary element doping be rare earth element; M comprises transition element, rare earth element) concrete grammar of Nano Solid Solution powder, metal nanometer material technical field.
Background technology
Rare earth element has unique optical, electrical and magnetic property, is described as the treasure-house of novel material.Nano material is because the features such as its unique interfacial effect, volume effect, quantum size effect and macro quanta tunnel effect become one of study hotspot in recent years.Nano Rare-earth Materials combines the premium properties of nano material and rare earth material, is the new function material of 1 ﹢ 1 >=2, is the focus of new functional materials of 21 century.
Changeable valence rare earth oxide compound has good catalytic performance.With CeO
2for example, based on the Ce of Ce element
3+/ Ce
4+variable valence characteristic, realizes the release of oxygen-store this working cycle, makes CeO
2become good catalyzer and support of the catalyst.People are to CeO
2doping vario-property study, research shows, metal ion replaces CeO
2in lattice, after part cerium ion, make CeO
2lattice distortion, produces defect thus, thereby has strengthened redox and low-temperature catalytic activity.
China is the first in the world Rare Earth Production big country, but not rare earth power, rare earth is with export of raw material Europe, the United States, Deng state for a long time, then exports back with several times to tens times high-tech product of added value, rare earth deep processing enormous profits are contributed to abroad, and environmental pollution are stayed domestic.Although people have carried out a large amount of research to nanocrystalline rare earth oxides, these methods have certain shortcoming, as sol-gel method long reaction time, hydrothermal method exist potential safety hazard and energy expenditure large.Due to reasons such as cost performances, generally all rest on laboratory stage, therefore seek a kind of low cost, method pollution-free and scale operation nanocrystalline rare earth oxides is investigator's striving direction always.
Summary of the invention
The RE-M-O(RE that the object of the invention is to provide a kind of polynary element doping is rare earth element; M comprises transition element, rare earth element) preparation method of Nano Solid Solution powder, this technique low temperature, green, be convenient to suitability for industrialized production.
For achieving the above object, the present invention adopts following technical scheme, point following processing step:
A) with 82 ~ 92% metal RE for mass percent
5 ~ 10% metal M
5 ~ 10% graphite
With 25 kg vacuum induction meltings, select plumbago crucible, after fusing, casting obtains brittle carbides alloy.RE is rare-earth elements La, Ce, and Pr, the one in Nd, M is rare-earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr or transition element Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Au, the one in Ag;
B) brittle carbides alloy is crushed to the powder that granularity is less than 3 mm, powdered alloy and deionized water 1:10 in mass ratio ~ 1:100 preparation, it is slowly poured in the beaker that fills deionized water, and be positioned on magnetic stirring apparatus and stir, regulate temperature to make it be stabilized in 10 ~ 100 DEG C, powdered alloy has just been poured in deionized water and water generation hydrolysis reaction, there are at once small bubbles to occur, and emit heat, outwell upper strata liquid through 18 ~ 72 hours stirring reactions, add again deionized water and stirring washing, several times so repeatedly, in the baking oven of 50 ~ 100 DEG C, drying and obtaining specific surface area is 50 ~ 200 m
2the rare earth doped oxide nonmetallic powder of M of/g.
C) nano powder after drying is obtained to the nanocrystalline rare earth oxides that M adulterates after 600 ~ 1000 DEG C/1 h thermal treatment.
This technological operation is simple, and temperature of reaction is low, and mechanical stirring can be carried out in open container, due to without the chemical reagent such as catalyzer, bronsted lowry acids and bases bronsted lowry, is a kind of genuine friendly process, is easy to realize suitability for industrialized production.
Brief description of the drawings
Fig. 1: embodiment 1Fe doped Ce O
2the transmission electron microscope photo of nano powder
Fig. 2: embodiment 1Fe doped Ce O
2the high-resolution-ration transmission electric-lens lattice image of nano powder
Fig. 3: embodiment 1Fe doped Ce O
2nano powder and pure CeO
2xRD figure spectrum
Fig. 4: embodiment 1Fe doped Ce O
2nano powder and pure CeO
2xRD figure spectrum after 600 DEG C/1 h thermal treatment
Fig. 5: embodiment 1Fe doped Ce O
2nano powder and pure CeO
2methyl hydride catalyzed activity curve figure after 600 DEG C/1 h thermal treatment.
Embodiment
Below by embodiment, the present invention is described in detail.
embodiment 1 (RE=Ce M=Fe)
With the metallic cerium of 25 kg vacuum induction meltings 85%, 7% metallic iron and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains cerium carbide iron alloy.Cerium carbide iron alloy is broken into granularity and is less than 1 mm powder, get 100 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 20 DEG C, get cerium carbide ferroalloy powder 5 g, it is slowly poured in deionized water, obtain yellow suspension through 24 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Fe doped Ce O
2nano powder, the specific surface area of this nano powder is 119 m
2/ g.By gained Fe doped Ce O
2nano powder is after 600 DEG C/1 h thermal treatment, and surveying its specific surface area is 59 m
2/ g.
Fig. 1 is embodiment 1Fe doped Ce O
2nano powder transmission electron microscope photo, is the coacervate of hundreds of nanometer, it be reunited by the large a few nanometer small-particles of surface free energy due to.Fig. 2 is its high-resolution-ration transmission electric-lens lattice image, and grain size is 5 ~ 7 nm.Fig. 3 is embodiment F e doped Ce O
2nano powder and pure CeO
2the X ray diffracting spectrum of nano powder, has all occurred that principal phase is fluorite structure CeO
2characteristic peak.Fig. 4 is Fe doped Ce O
2nano powder and pure CeO
2the X ray diffracting spectrum of nano powder after 600 DEG C/1 h thermal treatment, can find out that the diffraction peak halfwidth of Fe doped nano powder after 600 DEG C/1 h thermal treatment is than pure CeO
2wide, illustrate that iron ion replaces after part cerium ion, produce textural defect, Fe doping has improved CeO
2the thermostability of nano powder.Fig. 5 is Fe doped Ce O
2the methyl hydride catalyzed activity curve of nano powder sample after 600 DEG C/1 h thermal treatment, in relatively, CeO
2the methyl hydride catalyzed activity curve of nano powder is also listed in figure.As can be seen from the figure, Fe doped Ce O after 360 DEG C
2the rate of curve of nano powder is surged suddenly, shows that the catalytic activity of this nano powder increases sharply.Temperature of reaction when methane conversion is 10%, 50% and 90% is designated as respectively T
10and T
50and T
90, table 1 is Fe doped Ce O
2nano powder and pure CeO
2the comparison of the methyl hydride catalyzed performance of nano powder.As can be seen from the table, the Fe doped Ce O that prepared by present method
2the T of nano powder
90than pure CeO
2the methyl hydride catalyzed activity low 30 DEG C, obviously it has had.Fe doped Ce O prepared by this and present method
2nano powder has larger specific surface area relevant with homogeneity in the time of high temperature.
Table 1 Fe doped Ce O
2nano powder and pure CeO
2the methyl hydride catalyzed activity of nano powder
| T 10(℃) | T 50(℃) | T 90(℃) | |
| Fe doped Ce O 2 | 438 | 512 | 579 |
| Pure CeO 2 | 382 | 512 | 612 |
embodiment 2 (RE=Gd M=Co)
With the metal gadolinium of 25 kg vacuum induction meltings 89%, 3% cobalt metal and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains carbonization gadolinium cobalt-base alloy.Carbonization gadolinium cobalt-base alloy is broken into granularity and is less than 2 mm powder, get 100 ml deionized waters in the beaker of 300 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 20 DEG C, get carbonization gadolinium cobalt alloy powder 5 g, it is slowly poured in deionized water, obtain white suspension through 48 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Co doping Gd
2o
3nano powder, the specific surface area of this nano powder is 180 m
2/ g.
embodiment 3(RE=Ce M=Gd)
With the metallic cerium of 25 kg vacuum induction meltings 89%, 3% metal gadolinium and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains cerium carbide gadpolinium alloy.Cerium carbide gadpolinium alloy is broken into granularity and is less than 1 mm powder, get 100 ml deionized waters in the beaker of 500 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 25 DEG C, get cerium carbide gadpolinium alloy powder 5 g, it is slowly poured in deionized water, obtain yellow suspension through 72 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Gd doped Ce O
2nano powder, the specific surface area of this nano powder is 120 m
2/ g.
embodiment 4(RE=La M=Mn)
With the lanthanoid metal of 25 kg vacuum induction meltings 88%, 7% manganese metal and 5% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains lanthanum carbide manganese alloy.Lanthanum carbide manganese alloy is broken into granularity and is less than 2 mm powder, get 80 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 30 DEG C, get lanthanum carbide manganese alloy powder 5 g, it is slowly poured in deionized water, obtain white suspension through 60 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 70 DEG C of oven for drying obtain Mn doping La
2o
3nano powder, the specific surface area of this nano powder is 111 m
2/ g.
embodiment 5(RE=Pr M=Y)
With the metal praseodymium of 25 kg vacuum induction meltings 89%, 3% metallic yttrium and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains carbonization praseodymium yittrium alloy.Carbonization praseodymium yittrium alloy is broken into granularity and is less than 0.8 mm powder, get 100 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 20 DEG C, get carbonization praseodymium yittrium alloy powder 5 g, it is slowly poured in deionized water, obtain black suspension through 24 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Mn doping La
2o
3nano powder, the specific surface area of this nano powder is 96.7 m
2/ g.
embodiment 6(RE=Nd M=Cu)
With the neodymium metal of 25 kg vacuum induction meltings 85%, 7% metallic copper and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains neodymium carbide copper alloy.Neodymium carbide copper alloy is broken into granularity and is less than 1 mm powder, get 50 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 20 DEG C, get neodymium carbide copper alloy powder 5 g, it is slowly poured in deionized water, obtain light blue suspension through 72 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 60 DEG C of oven for drying obtain Cu doping Nd
2o
3nano powder, the specific surface area of this nano powder is 136 m
2/ g.
embodiment 7(RE=Pr M=Ti)
With the metal praseodymium of 25 kg vacuum induction meltings 89%, 3% metal titanium and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains carbonization praseodymium titanium alloy.Carbonization praseodymium titanium alloy is broken into granularity and is less than 2 mm powder, get 60 ml deionized waters in the beaker of 180 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 24 DEG C, get carbonization praseodymium titanium alloy powder 5 g, it is slowly poured in deionized water, obtain black suspension through 24 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 85 DEG C of oven for drying obtain Ti doping Pr
2o
3nano powder, the specific surface area of this nano powder is 113 m
2/ g.
embodiment 8(RE=Tb M=Mn)
With the terbium metal of 25 kg vacuum induction meltings 86%, 6% manganese metal and 8% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains terbium carbide manganese alloy.Terbium carbide manganese alloy is broken into granularity and is less than 3 mm powder, get 80 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 25 DEG C, get terbium carbide manganese alloy powder 8 g, it is slowly poured in deionized water, obtain white suspension through 30 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Mn doping Tb
2o
3nano powder, the specific surface area of this nano powder is 79 m
2/ g.
embodiment 9(RE=Er M=Mo)
With the metal erbium of 25 kg vacuum induction meltings 87%, 3% metal molybdenum and 10% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains carbonization erbium molybdenum alloy.Carbonization erbium molybdenum alloy is broken into granularity and is less than 1 mm powder, get 100 ml deionized waters in the beaker of 300 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 25 DEG C, get carbonization erbium molybdenum alloy powder 4 g, it is slowly poured in deionized water, obtain red suspension through 48 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Mo doping Er
2o
3nano powder, the specific surface area of this nano powder is 88 m
2/ g.
embodiment 10(RE=Dy M=Y)
With the metal dysprosium of 25 kg vacuum induction meltings 92%, 1% metallic yttrium and 7% graphite (mass percent), select plumbago crucible, and fully after fusing, casting obtains carbonization dysprosium yittrium alloy.Carbonization dysprosium yittrium alloy is broken into granularity and is less than 2 mm powder, get 100 ml deionized waters in the beaker of 200 ml, be placed on magnetic stirring apparatus, regulate temperature to make it be stabilized in 25 DEG C, get carbonization dysprosium yittrium alloy powder 5 g, it is slowly poured in deionized water, obtain white suspension through 18 h stirring reactions.Outwell upper strata liquid, then add deionized water and stirring washing, several times so repeatedly, in air, 80 DEG C of oven for drying obtain Y doping Dy
2o
3nano powder, the specific surface area of this nano powder is 92 m
2/ g.
Claims (1)
1. a preparation method for the RE-M-O sosoloid nanometer powder of polynary element doping, is characterized in that the method has following processing step:
A. by percentage to the quality, by 82 ~ 92% RE, 5 ~ 10% M and 5 ~ 10% Graphite Powder 99 vacuum induction melting, select plumbago crucible, and after fusing, casting obtains carbide alloy; RE is rare-earth elements La, Ce, and Pr, the one in Nd, M is rare-earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr or transition element Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Au, the one in Ag;
B. carbide alloy is broken into the powder that granularity is less than 3 mm, by this powder and deionized water 1:10 in mass ratio ~ 1:100 preparation, through 18 ~ 72 hours, after 10 ~ 100 DEG C of constant temperature stirring reactions, dries;
C. the nano powder after drying is obtained after 600 ~ 1000 DEG C/1 h thermal treatment to the nanocrystalline rare earth oxides of M doping.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105855536A (en) * | 2016-05-16 | 2016-08-17 | 上海大学 | Element-dropped Si-Cr-M solid solution powder and preparation method thereof |
| CN115805068A (en) * | 2022-11-09 | 2023-03-17 | 太原理工大学 | Multifunctional metal oxide catalyst KCeMn as well as preparation method and application thereof |
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|---|---|---|---|---|
| JPS60166222A (en) * | 1984-02-09 | 1985-08-29 | Mitsubishi Metal Corp | Preparation of fine powder of rare earth element oxide |
| CN102009994A (en) * | 2010-12-24 | 2011-04-13 | 上海大学 | Method for preparing CeO2 nano power by cerium carbide oxydrolysis method |
| CN102275972A (en) * | 2011-06-07 | 2011-12-14 | 上海大学 | Preparation method of Mn-doped CeO2 nano powder |
| CN103203230A (en) * | 2013-04-15 | 2013-07-17 | 上海大学 | Preparation method of lanthanum doped CeO2 nano powder |
-
2014
- 2014-04-02 CN CN201410130421.6A patent/CN103964485A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166222A (en) * | 1984-02-09 | 1985-08-29 | Mitsubishi Metal Corp | Preparation of fine powder of rare earth element oxide |
| CN102009994A (en) * | 2010-12-24 | 2011-04-13 | 上海大学 | Method for preparing CeO2 nano power by cerium carbide oxydrolysis method |
| CN102275972A (en) * | 2011-06-07 | 2011-12-14 | 上海大学 | Preparation method of Mn-doped CeO2 nano powder |
| CN103203230A (en) * | 2013-04-15 | 2013-07-17 | 上海大学 | Preparation method of lanthanum doped CeO2 nano powder |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105855536A (en) * | 2016-05-16 | 2016-08-17 | 上海大学 | Element-dropped Si-Cr-M solid solution powder and preparation method thereof |
| CN105855536B (en) * | 2016-05-16 | 2019-04-16 | 上海大学 | Si-Cr-M solid-solution powder of element doping and preparation method thereof |
| CN115805068A (en) * | 2022-11-09 | 2023-03-17 | 太原理工大学 | Multifunctional metal oxide catalyst KCeMn as well as preparation method and application thereof |
| CN115805068B (en) * | 2022-11-09 | 2023-11-24 | 太原理工大学 | Multifunctional metal oxide catalyst KCeMn and preparation method and application thereof |
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Application publication date: 20140806 |