CN104445392A - Method for preparing BaZrO3:(Ce, Pr) nano powder by utilizing hydrothermal solvent process - Google Patents

Method for preparing BaZrO3:(Ce, Pr) nano powder by utilizing hydrothermal solvent process Download PDF

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Publication number
CN104445392A
CN104445392A CN201410607343.4A CN201410607343A CN104445392A CN 104445392 A CN104445392 A CN 104445392A CN 201410607343 A CN201410607343 A CN 201410607343A CN 104445392 A CN104445392 A CN 104445392A
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powder
metal salt
bazro
salt solution
nano
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CN104445392B (en
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马伟民
吴影
马雷
王花蕾
刘佳男
纪连永
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for preparing BaZrO3:(Ce, Pr) nano powder by utilizing a hydrothermal solvent process and relates to a method for preparing nano powder. The method disclosed by the invention comprises the following steps: weighing a certain amount of Ba(NO3)2, ZrOCl2.8H2O, Ce(NO3)3 and Pr(NO3)3 according to an accurate stoichiometric ratio, dissolving into an ethanol-water solution in which the ratio of ethanol to water is 1:1 to 4:1 so as to obtain a metal salt solution with concentration of 0.01-1mol/L; dropwise adding a mineralizer which is a KOH solution with concentration of 2mol/L to the metal salt solution and stirring for 1h; then, loading the metal salt solution into a reaction kettle, putting the reaction kettle into a microwave oven and reacting under proper conditions to obtain sediment; and aging, filtering the sediment, washing, grinding and sieving to obtain a sample. The BaZrO3:(Ce, Pr) powder prepared by the method disclosed by the invention is good in dispersity, uniform in particle size, simple in process, short in production cycle, low in cost and therefore suitable for batch production.

Description

A kind of hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder
Technical field
The present invention relates to a kind of method preparing nano-powder, particularly relate to a kind of hydro-thermal solvent method and prepare BaZrO 3: the method for (Ce, Pr) nano-powder.
Background technology
Scintillator is important optical function material, is mainly used in the field such as high energy physics and nuclear medicine, comprises inorganic scintillation crystal and Inorganic scintillation pottery.The metal compound material system of perovskite structure obtained the extensive concern of Chinese scholars in recent years, (Sr; Ba; Ca) HfO 3: Ce and (Sr:Ba; Ca) ZrO 3: Ce has different report as the document of scintillation material.Target is the problem solving ceramic scintillation materials synthesis and preparation technology, and one of study hotspot becoming field of new.Alkaline earth BaZrO 3as a kind of compound of perovskite structure, high (the 5.42g/ cm of density 3), ordination number is large, has excellent electricity and thermomechanical property, doping Pr 3+, Ce 3+baZrO 3material has higher receptivity to energetic ray or high energy particle, simultaneously Pr 3+, Ce 3+(4f 1) optics electronegativity is little, can realize the complete transition of 5d-4f, the feature request meeting scintillator decay of luminescence <100ns is the candidate material preparing scintillating ceramic.
Prepare BaZrO both at home and abroad at present 3and rare earth doped BaZrO 3preparation method comprise solid phase method, sol-gel method, coprecipitation method etc.In above-mentioned synthesis method, solid phase method technique is simple but sintering temperature is high and particle size skewness, purity are low.The powder granule of sol-gel method synthesis is large, reunion is serious.Hydrothermal method product good dispersity, purity are high, but high to equipment requirements, and cost is high, yields poorly, and is not suitable for suitability for industrialized production.Compared with aforesaid method, hydrothermal method is prepared powder and is had plurality of advantages, the reactive component mixing of hydrothermal method is molecule, atom level, reaction product reaches nano level, can realize ion doping evenly, doping scope is wide, product purity is high, uniform particle sizes, technique is simple, is the synthetic method that a kind of component with low cost, each accurately can control, be easy to realize industrialization.
Summary of the invention
A kind of hydro-thermal solvent method is the object of the present invention is to provide to prepare BaZrO 3: the method for (Ce, Pr) nano-powder, the method forms pure crystalline phase BaZrO 3: (Ce, Pr), crystallization temperature is low, without dephasign, better crystallinity degree, raw materials cost is low, preparation technology is simple, the cycle is short, is applicable to batch production.
The object of the invention is to be achieved through the following technical solutions:
A kind of hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder, described method comprises following preparation process:
1), the configuration of solution: take Ba (NO by accurate stoichiometric ratio 3) 2, ZrOCl 28H 2o, Ce (NO 3) 3, Pr (NO 3) 3and be dissolved in alcohol-water solution, be configured to metal salt solution; KOH is diluted for mineralizer;
2), the preparation of presoma: above-mentioned mineralizer is added drop-wise in the metal salt solution configured, after stirring, reactant is loaded in reactor, then reactor is put into microwave oven and react; The precursor precipitate obtained is through timeliness, and cleaning, suction filtration, dries and obtain powdered sample.
Described a kind of hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder, described Ce 3+doping content 0.2mol% ~ 1.0mol%, Ce 3+, Pr 3+mole doping content than being 1:0 ~ 1:7.
Described a kind of hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder, described alcohol-water is than being 1:1 ~ 4:1, and the starting point concentration of metal salt solution is 0.01 ~ 1mol/L.
Described a kind of hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder, the PH of the completely rear regulation system of described precipitation is 8 ~ 14, and temperature of reaction and time are respectively 120 ~ 240 DEG C and 12 ~ 24 h.
Advantage of the present invention and effect are:
1, the present invention can form pure crystalline phase BaZrO 3: (Ce, Pr), crystallization temperature is low, without dephasign, better crystallinity degree.
2, raw materials cost of the present invention is low, and preparation technology is simple, and the cycle is short, has broad application prospects, and is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is BaZrO 3the SEM pattern of powder.Can find out that powder dispersity is good, almost spherical;
Fig. 2 Ce 3+doping content on the impact of powder luminescent properties, work as Ce 3+when doping content is 0.4mol%, the luminescent properties of powder is the strongest;
Fig. 3 Ce 3+, Pr 3+the impact of doping volumetric molar concentration comparison powder luminescent properties, add Pr as seen 3+after, powder luminescent properties strengthens, best Ce 3+, Pr 3+doping molar concentration rate is 1:3.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described.
Embodiment 1:
Ba (NO 3) 2, ZrOCl 28H 2o mixes and is dissolved in (second alcohol and water ratio is 3:1) in alcohol-water solution, is made into 0.2 mol/L metal salt solution.Be the mineralizer of 3mol/L by KOH weaker concn.Then mineralizer is instilled in the metal salt solution prepared, until pH=14, and by magnetic stirrer, titration terminates to be loaded in reactor, then reactor is put into microwave oven, react under suitable condition (temperature, time, pH etc.).After reaction, through timeliness, the throw out distilled water of generation is cleaned three times, detects filtrate with Silver Nitrate, until exist without chlorion, then wash twice with dehydrated alcohol, being placed in temperature is 80 DEG C of dry 24h of loft drier, and grinding, obtains good dispersity, subglobose BaZrO 3powder.
Embodiment 2:
Ba (NO 3) 2, ZrOCl 28H 2ce (the NO of O and different amount 3) 3mix and be dissolved in (second alcohol and water ratio is 3:1) in alcohol-water solution, being made into 0.2 mol/L metal salt solution.Be the mineralizer of 3mol/L by KOH weaker concn.Then mineralizer is instilled in the metal salt solution prepared, until pH=14, and by magnetic stirrer, titration terminates to be loaded in reactor, then reactor is put into microwave oven, react under suitable condition (temperature, time, pH etc.).After reaction, through timeliness, the throw out distilled water of generation is cleaned three times, detect filtrate with Silver Nitrate, until exist without chlorion, then wash twice with dehydrated alcohol, being placed in temperature is 80 DEG C of dry 24h of loft drier, and grinding, obtains good dispersity, subglobose BaZrO 3: Ce powder.
Embodiment 3:
Ba (NO 3) 2, ZrOCl 28H 2pr (the NO of O and different amount 3) 3, Ce (NO 3) 3and be dissolved in (second alcohol and water ratio is 3:1) in alcohol-water solution, be made into 0.2 mol/L metal salt solution.Be the mineralizer of 3mol/L by KOH weaker concn.Then mineralizer is instilled in the metal salt solution prepared, until PH=14, and by magnetic stirrer, titration terminates to be loaded in reactor,, then reactor is put into microwave oven, reacts under suitable condition (temperature, time, pH etc.).After reaction, after timeliness, the throw out distilled water of acquisition cleans three times, detects filtrate with Silver Nitrate, until exist without chlorion, then wash twice with dehydrated alcohol, being placed in temperature is 80 DEG C of dry 24h of loft drier, and grinding, obtains good dispersity, subglobose BaZrO 3: (Ce, Pr) powder.

Claims (4)

1. a hydro-thermal solvent method prepares BaZrO 3: the method for (Ce, Pr) nano-powder, is characterized in that, described method comprises following preparation process:
1), the configuration of solution: take Ba (NO by accurate stoichiometric ratio 3) 2, ZrOCl 28H 2o, Ce (NO 3) 3, Pr (NO 3) 3and be dissolved in alcohol-water solution, be configured to metal salt solution; KOH is diluted for mineralizer;
2), the preparation of presoma: above-mentioned mineralizer is added drop-wise in the metal salt solution configured, after stirring, reactant is loaded in reactor, then reactor is put into microwave oven and react; The precursor precipitate obtained is through timeliness, and cleaning, suction filtration, dries and obtain powdered sample.
2. a kind of hydro-thermal solvent method according to claim 1 prepares BaZrO 3: the method for (Ce, Pr) nano-powder, is characterized in that, described Ce 3+doping content 0.2mol% ~ 1.0mol%, Ce 3+, Pr 3+mole doping content than being 1:0 ~ 1:7.
3. a kind of hydro-thermal solvent method according to claim 1 prepares BaZrO 3: the method for (Ce, Pr) nano-powder, is characterized in that, described alcohol-water is than being 1:1 ~ 4:1, and the starting point concentration of metal salt solution is 0.01 ~ 1mol/L.
4. a kind of hydro-thermal solvent method according to claim 1 prepares BaZrO 3: the method for (Ce, Pr) nano-powder, is characterized in that, the PH of the completely rear regulation system of described precipitation is 8 ~ 14, and temperature of reaction and time are respectively 120 ~ 240 DEG C and 12 ~ 24 h.
CN201410607343.4A 2014-11-03 2014-11-03 A kind of hydro-thermal solvent method prepares BaZrO3: the method for (Ce, Pr) nano-powder Expired - Fee Related CN104445392B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107583638A (en) * 2017-11-01 2018-01-16 辽宁大学 A kind of double frequency sound catalyst and its preparation method and application

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CN102491416A (en) * 2011-12-12 2012-06-13 沈阳化工大学 Method for preparing Eu2Zr207 nanometer powder
CN103357406A (en) * 2013-08-02 2013-10-23 福州大学 Rare earth element-doped perovskite-type Ru-loading ammonia-synthesis catalyst

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CN102131732A (en) * 2008-07-18 2011-07-20 日本化学工业株式会社 Modified perovskite type composite oxide, manufacturing method thereof, and composite dielectric material
CN102491416A (en) * 2011-12-12 2012-06-13 沈阳化工大学 Method for preparing Eu2Zr207 nanometer powder
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107583638A (en) * 2017-11-01 2018-01-16 辽宁大学 A kind of double frequency sound catalyst and its preparation method and application
CN107583638B (en) * 2017-11-01 2019-12-06 辽宁大学 double-frequency acoustic catalyst and preparation method and application thereof

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