CN101648726B - Hydrothermal synthesis method of LuO(OH) nanorods and Lu2O3 nanorods luminescent powder - Google Patents
Hydrothermal synthesis method of LuO(OH) nanorods and Lu2O3 nanorods luminescent powder Download PDFInfo
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- CN101648726B CN101648726B CN2009100538795A CN200910053879A CN101648726B CN 101648726 B CN101648726 B CN 101648726B CN 2009100538795 A CN2009100538795 A CN 2009100538795A CN 200910053879 A CN200910053879 A CN 200910053879A CN 101648726 B CN101648726 B CN 101648726B
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- luo
- deionized water
- lutecium
- europium
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Abstract
The present invention discloses a hydrothermal synthesis method of LuO (OH) nanorods and Lu2O3 nanorods luminescent powder and relates to the rare earth nanometer material preparation and the microstructural regulation and control thereof. The method comprises the following steps: adopting commercial rare earth oxides (lutecium oxide and europium oxide) as raw materials, firstly dissolving the raw materials in concentrated nitric acid to prepared certain concentration lutecium nitrate doped with europium nitrate, then reacting with sodium hydroxide to prepare precipitate, then performing hydrothermal reaction in a sealed reaction tank at 160-200 DEG C to synthesize LuO(OH) nanorods; calcining LuO(OH) nanorods at 600-1000 DEG C for 1-3h and obtaining the corresponding Lu2O3 nanorods. The method process is simple and easily controllable and the feature of the product can be controlled within a certain concentration range of NaOH by adjusting the concentration of mineralizer NaOH in the hydrothermal process.
Description
Technical field
The present invention relates to a kind of LuO (OH) nanometer rod and Lu with bar-shaped pattern
2O
3The synthetic method of nanorods luminescent powder belongs to the rare earth luminescent material preparing technical field.
Background technology
Because rare earth compound is at the excellent properties of aspects such as luminescent device, catalysis, medicine, biology, people have carried out a large amount of research to the synthetic of rare earth compound material with performance.In recent years, synthesizing the very big interest that has caused material supplier author on the nano rare earth compound with certain length-to-diameter ratio.The method that present people are adopted mainly comprises following several big class: one, and hydrothermal method.Reported series of rare earth compound L n (OH) as Li Yadong seminar of Tsing-Hua University
3, Ln
2O
3(Ln=Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm) synthetic (the Xun Wang and Yadong Li.Rare-Earth-Compound Nanowires of nanometer rod and nano wire, Nanotubes, and Fullerene-Like Nanoparticles:Synthesis, Characterization, and Properties.Chem.Eur.J.2003,9,5627 ± 5635.).Two, template.People such as Jilin Zhang utilize aluminum oxide to be template, have made the Y of diameter about 50nm
2O
3: Eu
3+Nano-wire array.Three, microwave irradiation.People such as Asit B.Panda utilize microwave irradiation to synthesize M
2O
3(M=Pr, Nd, Sm, Eu, Gd, Tb, Dy) nanometer rod and square nano-plates.But the synthetic of lutetium based compound low-dimension nano material seldom there is report with performance study.And lutecium oxide (Lu
2O
3) owing to have high density (9.42g/cm
3), strong to the stopping power of all kinds of rays (X ray, gamma-rays), band gap wide (6.5eV) between valence band and conduction band, and in air characteristic such as highly stable, make lutetium base oxide luminescent material have great using value, as mix europium (Eu
3+) the lutecium oxide material be exactly a kind of novel scintillation material, have the application prospect of extremely wide model in fields such as medical imaging, X-ray detections.If can control the pattern of lutetium base oxide, make its have the 1-dimention nano functional materials characteristic, will greatly widen the application prospect of lutetium base oxide luminescent material.
The traditional method of preparation lutetium base oxide luminescent powder is a combustion method, uses urea to act as a fuel, and has prepared Lu as E.Zych etc. with combustion method
2O
3Base luminescent powder, and the Pechini method that in July, 1967, the U.S. reported.Recently reported new synthetic method, utilized this method to synthesize Lu as organic and inorganic microemulsion method Eugeniusz Zych etc.
2O
3: the Eu nano particle has also been studied its optical property.More than these method synthetic powders be irregular spheroidal particle mostly, be difficult to gained particulate length-to-diameter ratio is regulated and control.The people such as Liu Qian of Shanghai silicate institute have reported that to utilize hydrothermal method to synthesize different-shape (bar-shaped, laminar, the square brick shape) lutecium oxide luminescent powder, " Jiacheng Wang, Qian Liu; Qingfeng Liu.Controlled synthesisof europium-doped lutetium compounds:nanoflakes; nanoquadrels, and nanorods.J.Mater.Chem., 2005; 15,4141-4146. ".They utilize and regulate Lu in the initial action system
3+Concentration is controlled the pattern of product, the lutecium oxide powder that finally obtains on luminescent properties with the not too big difference of common powder body material.The present invention utilizes when regulating hydrothermal treatment consists the concentration of mineralizer NaOH in the thermal and hydric environment to control the pattern of hydrothermal product LuO (OH), by further calcining, the lutecium oxide nanometer rod that makes is compared with common lutecium oxide luminescent powder, has shown evident difference on luminous intensity and luminescence feature peak position.Have not yet to see this LuO (OH) and Lu about having bar-shaped pattern
2O
3The preparation method's of luminescent powder report.
Summary of the invention
The purpose of this invention is to provide a kind of Hydrothermal Preparation LuO (OH) nanometer rod and Lu of utilizing
2O
3The novel method of nanorods luminescent powder.This method makes bar-shaped LuO (OH) by hydrothermal method, by further calcining, keeps at pattern making Lu under the prerequisite of nanometer rod
2O
3Nano-luminescent powder body.The characteristics of this method be utilize in the water-heat process the pattern of mineralizer concentration control hydrothermal product, by calcination processing, obtain bar-shaped oxide compound.Experimental installation requires low, and technology is simple, can realize the atom level uniform mixing of activation ion and matrix oxide compound.
The technical solution used in the present invention is:
(1). with the rare earth nitrate is that raw material passes through precipitation, hydrothermal preparation LuO (OH) nanometer rod;
(2). adopt and (one) same technology, at first prepare LuO (OH) nanometer rod, under 600～1000 ℃ of temperature condition, calcined 1～3 hour then, prepare bar-shaped Lu
2O
3Luminescent powder.
The method of a kind of synthetic LuO provided by the invention (OH) nanometer rod, this method is carried out as follows:
(1) lutecium oxide and europium sesquioxide are dissolved with concentrated nitric acid respectively, be diluted to 0.5～1.0mol/L, get an amount of europium nitrate solution and join in the lutecium nitrate solution, the adulterated lutecium nitrate mixing solutions of preparation mol ratio 3%～6% europium nitrate with deionized water;
(2) under the magnetic agitation condition, above-mentioned mixing solutions is dropwise joined in the sodium hydroxide solution of 40ml the content of sodium hydroxide in the control solution, lutetium ion and sodium ion mol ratio Lu when making reaction
3+: Na
+=1: 4～1: 6, generate white depositions;
(3) with above-mentioned white depositions deionized water repetitive scrubbing, join the water heating kettle inner bag, and be 70%, add sodium hydrate solid then, make naoh concentration at 1.0～3.0mol/L with deionized water control filling ratio;
(4) the water heating kettle inner bag is put into closed reactor and carry out hydrothermal treatment consists, be incubated 24 hours down in 160～200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, reaction product is used the deionized water repetitive scrubbing with the B suction filtration, 80 ℃ of oven dry down, prepares LuO (OH) nanometer rod.
A kind of synthetic Lu provided by the invention
2O
3The method of nanorods luminescent powder, this method is carried out as follows:
(1) lutecium oxide and europium sesquioxide are dissolved with concentrated nitric acid respectively, be diluted to 0.5～1.0mol/L, get an amount of europium nitrate solution and join in the lutecium nitrate solution, the adulterated lutecium nitrate mixing solutions of preparation mol ratio 3%～6% europium nitrate with deionized water;
(2) under the magnetic agitation condition, above-mentioned mixing solutions is dropwise joined in the sodium hydroxide solution of 40ml the content of sodium hydroxide in the control solution, lutetium ion and sodium ion mol ratio Lu when making reaction
3+: Na
+=1: 4～1: 6, generate white depositions;
(3) with above-mentioned white depositions deionized water repetitive scrubbing, join the water heating kettle inner bag, and be 70%, add sodium hydrate solid then, make naoh concentration at 1.0～3.0mol/L with deionized water control filling ratio;
(4) the water heating kettle inner bag is put into closed reactor and carry out hydrothermal treatment consists, be incubated 24 hours down in 160～200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, reaction product is used the deionized water repetitive scrubbing with the B suction filtration, 80 ℃ of oven dry down, prepares LuO (OH) nanometer rod.
(6) LuO (OH) nanometer rod with above-mentioned acquisition is a presoma, calcines 1～3 hour down at 600～1000 ℃, makes corresponding Lu
2O
3The nanometer rod powder.
The present invention prepares bar-shaped LuO (OH) nano-powder by hydrothermal method, is presoma with bar-shaped LuO (OH) nano material that makes then, by calcining, keeps at pattern making the lutecium oxide nanorods luminescent powder under the prerequisite of nanometer rod.By in the water-heat process the pattern of mineralizer concentration control product, experimental installation requires low, technology is simple, and can realize the atom level uniform mixing of activation ion and matrix oxide compound.On luminescent properties, Lu
2O
3Nanometer rod is mixed europium lutecium oxide powder with routine and is compared, and shows different characteristics.The strongest excitation peak of powder is become by the 248nm of conventional powder and is 533nm, correspondingly can obtain the strongest emission peak under 533nm excites.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of LuO (OH).
Represent LuO (OH) phase of monocline.Hydrothermal condition: naoh concentration 0.1-5.0mol/L, 180 ℃ of temperature, 24 hours treatment times.
Fig. 2 is the TEM shape appearance figure of LuO (OH).
A, naoh concentration 0.1mol/L, 180 ℃ of temperature in 24 hours treatment times, obtain irregular pattern;
B, naoh concentration 1.0mol/L, 180 ℃ of temperature in 24 hours treatment times, obtain nano wire;
C, naoh concentration 3.0mol/L, 180 ℃ of temperature in 24 hours treatment times, obtain nanometer rod;
D, naoh concentration 5.0mol/L, 180 ℃ of temperature in 24 hours treatment times, obtain the nanometer square plate.
Fig. 3 is the X-ray powder diffraction figure of lutecium oxide nanometer rod.
Calcination condition: 600 ℃, 700 ℃, 800 ℃, 920 ℃ each 2 hours.
Fig. 4 is the TEM shape appearance figure of lutecium oxide nanometer rod.
A, 600 ℃, 2 hours; B, 700 ℃, 2 hours; C, 800 ℃, 2 hours; D, 920 ℃, 2 hours.Wherein the ring shape has appearred in 800 ℃ and 920 ℃ of incinerating powders.
Fig. 5 is the excitation spectrum (a) and emmission spectrum figure (b) of lutecium oxide nanometer rod, and the emmission spectrum highest peak is corresponding to 611nm.
Embodiment
The rare-earth oxidation raw material that relates among the present invention is Lu
2O
3, Eu
2O
3, Lu wherein
2O
3Be as body material, Eu
2O
3As dopant material.
Reaction process of the present invention is as follows:
The preparation of embodiment 1:LuO (OH) nanometer rod
(1), commercial oxidation lutetium powder and europium sesquioxide powder are dissolved with concentrated nitric acid, be diluted to Lu (NO respectively with deionized water then
3)
3Concentration is 0.927mol/L, Eu (NO
3)
3Concentration is 0.916mol/L.Measure the Eu (NO of 2.0ml
3)
3Solution joins 30.2mlLu (NO
3)
3In the solution, make mol ratio Eu/Lu=6.0% in the mixing solutions.
(2), under the magnetic stirring apparatus intense agitation, with the mixing solutions for preparing slowly be added drop-wise to 40ml contain NaOH 7.0g alkali lye in, white precipitate forms rapidly, continue to stir 30min, and solution is fully reacted.
(3), white depositions is filtered with cloth formula funnel, use the deionized water repetitive scrubbing, the foreign ion on the disgorging is poured in the inner bag that volume is 100ml, add deionized water, keep filling ratio 70%, add an amount of NaOH then, the glass stick stirring and dissolving, make that NaOH concentration is followed successively by 0.1mol/L, 1.0mol/L, 3.0mol/L, 5.0mol/L in the inner bag, in closed reactor under 180 ℃ of temperature condition hydrothermal treatment consists 24 hours.
(4), reaction finishes, and reactor is naturally cooled to room temperature, then reaction product is filtered with cloth formula funnel, use the deionized water thorough washing, remove the remaining impurities ion, the product that obtains is dried under 80 ℃ of conditions in baking oven, and finally obtaining product is white powder.
(5), carry out various signs.
Product is accredited as monocline phase LuO (OH) through X-ray powder diffraction.Hydrothermal condition be naoh concentration at 3.0mol/L, 180 ℃ of temperature, under 24 hours treatment times situation, TEM Electron microscope showed morphology microstructure is a nanometer rod: diameter 10～20nm, more than the length 100nm.
Embodiment 2:Lu
2O
3The preparation of nanorods luminescent powder
(1), commercial oxidation lutetium powder and europium sesquioxide powder are dissolved with concentrated nitric acid, be diluted to Lu (NO respectively with deionized water then
3)
3Concentration is 0.927mol/L, Eu (NO
3)
3Concentration is 0.916mol/L.Measure the Eu (NO of 2.0ml
3)
3Solution joins 30.2mlLu (NO
3)
3In the solution, make mol ratio Eu/Lu=6.0% in the mixing solutions.
(2), under the magnetic stirring apparatus intense agitation, with the mixing solutions for preparing slowly be added drop-wise to 40ml contain NaOH 7.0g alkali lye in, white precipitate forms rapidly, continue to stir 30min, and solution is fully reacted.
(3), white depositions is filtered with cloth formula funnel, use the deionized water repetitive scrubbing, the foreign ion on the disgorging is poured in the inner bag that volume is 100ml, add deionized water, keep filling ratio 70%, add an amount of NaOH then, the glass stick stirring and dissolving, make that NaOH concentration is followed successively by 0.1mol/L, 1.0mol/L, 3.0mol/L, 5.0mol/L in the inner bag, in closed reactor under 180 ℃ of temperature condition hydrothermal treatment consists 24 hours.
(4), reaction finishes, and reactor is naturally cooled to room temperature.Then reaction product is filtered with cloth formula funnel, use the deionized water thorough washing, remove the remaining impurities ion, the product that obtains is dried under 80 ℃ of conditions in baking oven, and finally obtaining product is white powder.
(5), the above-mentioned white powder that obtains is placed retort furnace, under 600 ℃, 700 ℃, 800 ℃, 920 ℃ temperature condition, calcined 2 hours respectively, lower the temperature with stove.
(6), the gained powder is carried out various signs.
Product is accredited as the Lu of cube phase through X-ray powder diffraction
2O
3,
With LuO (OH) nanometer rod is presoma incinerating sample, under 2 hours situation of 600 ℃ of calcinings, on pattern, compares with the irregular spheroidal particle lutecium oxide of routine, and it is nanometer rod that the TEM Electronic Speculum detects pattern: diameter 15-40nm; On luminescent properties, Lu
2O
3Nanometer rod is mixed europium lutecium oxide powder with routine and is compared, and the strongest excitation peak of powder is become by the 248nm of conventional powder and is 533nm, correspondingly can obtain the strongest emission peak 611nm under 533nm excites, and emission peak approaches the peak value of CCDs response curve.
Claims (2)
1. the hydrothermal synthesis method of a LuO (OH) nanometer rod is characterized in that this method carries out as follows:
(1) lutecium oxide and europium sesquioxide are dissolved with concentrated nitric acid respectively, be diluted to 0.5～1.0mol/L, get an amount of europium nitrate solution and join in the lutecium nitrate solution, the adulterated lutecium nitrate mixing solutions of preparation mol ratio 3%～6% europium nitrate with deionized water;
(2) under the magnetic agitation condition, above-mentioned mixing solutions is dropwise joined in the sodium hydroxide solution of 40ml the content of sodium hydroxide in the control solution, lutetium ion and sodium ion mol ratio Lu when making reaction
3+: Na
+=1: 4～1: 6, generate white depositions;
(3) with above-mentioned white depositions deionized water repetitive scrubbing, join the water heating kettle inner bag, and be 70%, add sodium hydrate solid then, make naoh concentration at 1.0～3.0mol/L with deionized water control filling ratio;
(4) the water heating kettle inner bag is put into closed reactor and carry out hydrothermal treatment consists, be incubated 24 hours down in 160～200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, reaction product is used the deionized water repetitive scrubbing with the B suction filtration, 80 ℃ of oven dry down, prepares LuO (OH) nanometer rod.
2. Lu
2O
3The hydrothermal synthesis method of nanorods luminescent powder is characterized in that this method carries out as follows:
(1) lutecium oxide and europium sesquioxide are dissolved with concentrated nitric acid respectively, be diluted to 0.5～1.0mol/L, get an amount of europium nitrate solution and join in the lutecium nitrate solution, the adulterated lutecium nitrate mixing solutions of preparation mol ratio 3%～6% europium nitrate with deionized water;
(2) under the magnetic agitation condition, above-mentioned mixing solutions is dropwise joined in the sodium hydroxide solution of 40ml the content of sodium hydroxide in the control solution, lutetium ion and sodium ion mol ratio Lu when making reaction
3+: Na
+=1: 4～1: 6, generate white depositions;
(3) with above-mentioned white depositions deionized water repetitive scrubbing, join the water heating kettle inner bag, and be 70%, add sodium hydrate solid then, make naoh concentration at 1.0～3.0mol/L with deionized water control filling ratio;
(4) the water heating kettle inner bag is put into closed reactor and carry out hydrothermal treatment consists, be incubated 24 hours down in 160～200 ℃ of temperature condition;
(5) water heating kettle is naturally cooled to room temperature, reaction product is used the deionized water repetitive scrubbing with the B suction filtration, 80 ℃ of oven dry down, prepares LuO (OH) nanometer rod;
(6) be presoma with above-mentioned LuO (OH) nanometer rod, under 600～1000 ℃ of temperature condition, calcined 1～3 hour, make corresponding Lu
2O
3Nanorods luminescent powder.
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| CN101787279A (en) * | 2010-03-04 | 2010-07-28 | 上海大学 | Solvent thermal synthesis method of Lu2O3 nanorod luminescent powder |
| CN102464348A (en) * | 2010-11-18 | 2012-05-23 | 中国科学院福建物质结构研究所 | Hydrothermal preparation method of lutetium oxide nanometer powder |
| CN104498036B (en) * | 2015-01-20 | 2016-04-06 | 山东大学 | A kind of one-dimensional rod-like rare-earth-dopping yttrium aluminum garnet luminescent material and its preparation method and application |
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Non-Patent Citations (4)
| Title |
|---|
| Jiacheng Wang et al..Controlled synthesis of europium-doped lutetium compounds: nanoflakes,nanoquadrels,and nanorods.《Journal of Materials Chemistry》.2005,第15卷4141–4146. * |
| Jiacheng Wang et al..Synthesis and luminescence properties of Eu or Tb doped Lu2O3 square nanosheets.《Optical Materials》.2006,第29卷593-597. * |
| Y. Shi et al..Processing and scintillation properties of Eu3+ doped Lu2O3 transparent ceramics.《Optical Materials》.2008,第31卷729–733. * |
| 施鹰等.稀土离子掺杂氧化镥透明陶瓷材料.《硅酸盐学报》.2008,第36卷(第6期),805-810. * |
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