CN103964505B - A kind of preparation method of columbite shaped metal niobate nanostructure - Google Patents
A kind of preparation method of columbite shaped metal niobate nanostructure Download PDFInfo
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- CN103964505B CN103964505B CN201410178429.XA CN201410178429A CN103964505B CN 103964505 B CN103964505 B CN 103964505B CN 201410178429 A CN201410178429 A CN 201410178429A CN 103964505 B CN103964505 B CN 103964505B
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Abstract
A kind of preparation method of columbite shaped metal niobate nanostructure, after it is characterized in that first utilizing Niobium Pentxoxide and molten potassium hydroxide reaction, recrystallization prepares six niobium potassium hydrogen phthalate forerunners in aqueous, re-use six niobium potassium hydrogen phthalates and soluble metallic salt carries out hydro-thermal reaction, form metal niobates finally by carrying out washing treatment.Technological method involved in the present invention has following obvious advantage: 1. the present invention uses hydrothermal technique, and technique is simple, and easy to operate, production cost is low, and environmentally friendly; 2. this synthetic technology can be carried out under lower temperature of reaction; 3. whole reaction carries out in the liquid phase, and the mixing of precursor is full and uniform; 4. the preparation of the method to metal niobates series has obvious universality.
Description
Technical field
The invention belongs to inorganic material chemistry field, relate to a kind of preparation method of columbite niobate.
Background technology
Columbite structural metal niobate ceramics material generally can be expressed as ANb
2o
6type general. formula, wherein A is divalent alkaline-earth metal or transition metal.First, this kind of material has higher specific inductivity and lower dissipation loss at microwave frequencies, therefore can have huge applications potentiality in satellite communication field as dielectric resonator material; Secondly, the columbite niobate that part comprises magnetic ion can show unique antiferromagnetic character; Finally, this series material also has the character such as excellent electricity, electrochemistry, optics and catalysis.
At present, preparing the topmost method of columbite niobate is solid-phase synthesis, and namely utilize Niobium Pentxoxide and metal simple-substance, oxide compound or carbonate to be raw material, at high temperature (>=1000 DEG C) carry out calcining and obtaining.These class methods require heating for multiple times and grinding usually, and need atmosphere protection, and gained sample generally has larger size, and do not have well-regulated form.Therefore, the method complex process equipment, energy consumption is comparatively large, and production cost is high.In recent years, other chemical preparation process are also constantly applied to the preparation of columbite niobate, as: mechanochemical reaction, sol-gel method, coprecipitation method etc., but these methods be substantially for precursor homogeneous phase mixing and design, obtain final columbite niobate product, still need further high-temperature process.Therefore, explore a kind of simple, pervasive preparation method to synthesize columbite type niobate series compound, especially prepare its nanostructure, there is larger challenge and important Research Significance all the time.
Summary of the invention
In order to overcome making excessive demands to hot conditions in niobate prior synthesizing method, the present invention proposes a kind of universality method preparing columbite shaped metal niobate nanostructure under cryogenic.The method is without the need to complex apparatus, and processing condition are simple, and easy handling controls, and synthesis cost is low.
The present invention is achieved by the following technical solutions.
1) preparation of six niobium potassium hydrogen phthalate presomas.Potassium hydroxide (KOH) is placed in nickel crucible heating and melting, then adds Niobium Pentxoxide (Nb
2o
5), the mass ratio of potassium hydroxide and Niobium Pentxoxide is 3 ~ 7:1, after question response is complete, naturally cool to room temperature, soluble in water for gained material, filter and remove not molten thing, obtained soln using heating evaporation or subcooled method are carried out recrystallization, wash with the mixing solutions of ethanol and water again after filtration, after drying, can presoma be obtained.
2) hydro-thermal reaction.Stoichiometrically take six niobium potassium hydrogen phthalate presomas prepared in soluble metallic salt and step 1), water-soluble respectively, then two kinds of aqueous solution are under agitation mixed, be then transferred in hydrothermal reaction kettle, 150 ~ 200 DEG C of constant temperature sealed reactions, are cooled to room temperature after reaction terminates.
3) carrying out washing treatment.By step 2) in hydro-thermal reaction product filter, with the alternately washing of water and ethanol, remove the ion that unreacted is complete, obtained columbite metal niobates product after dry.
Step 2 of the present invention) described in soluble metallic salt be one in the divalent alkaline-earth metal of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), cadmium (Cd), copper (Cu) etc. or transition metal.
Metal niobates prepared by the present invention has typical orthorhombic phase columbite structure, and product is made up of nano particle or the multilevel hierarchy with nano particle by primitive.
Technological method involved in the present invention has following obvious advantage: 1. the present invention uses hydrothermal technique, and technique is simple, and easy to operate, production cost is low, and environmentally friendly; 2. this synthetic technology can be carried out under lower temperature of reaction; 3. whole reaction carries out in the liquid phase, and the mixing of precursor is full and uniform; 4. the preparation of the method to metal niobates series has obvious universality.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of embodiment 1 sample.
Fig. 2 is the electron scanning micrograph of embodiment 1 sample.
Fig. 3 is the X-ray diffracting spectrum of embodiment 2 sample after 800 DEG C of annealing.
Fig. 4 is the electron scanning micrograph of embodiment 2 sample after 800 DEG C of annealing.
Fig. 5 is the X-ray diffracting spectrum of embodiment 3 sample after 800 DEG C of annealing.
Fig. 6 is the electron scanning micrograph of embodiment 3 sample after 800 DEG C of annealing.
Fig. 7 is the X-ray diffracting spectrum of embodiment 4 sample.
Fig. 8 is the electron scanning micrograph of embodiment 4 sample.
Embodiment
In order to understand the present invention better, below in conjunction with specific embodiment, the present invention will be further described, but protection content of the present invention is not limited to the following example.
Embodiment 1: niobic acid manganese (MnNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in nickel crucible heating and melting, then 2g Niobium Pentxoxide is slowly added, room temperature is cooled to after reacting completely, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at gained settled solution 90 DEG C is obtained needle-like crystal, washs with the mixing solutions of ethanol and water (volume ratio is 1:1) after filtering, after drying, obtain six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol Manganous chloride tetrahydrate, 0.2mmol six niobium potassium hydrogen phthalate presoma, is dissolved in 10mL distilled water respectively.Under magnetic stirring, manganese chloride solution is added drop-wise to gradually in six niobic acid hydrogen potassium solutions, forms suspension.
3) by gained suspension transfer hydrothermal reaction kettle, add distilled water to about 80% of cumulative volume, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cool to room temperature.
4) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain niobic acid manganese powdered product.
Embodiment 2: niobic acid cobalt (CoNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in nickel crucible heating and melting, then 2g Niobium Pentxoxide is slowly added, room temperature is cooled to after reacting completely, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at gained settled solution 90 DEG C is obtained needle-like crystal, washs with the mixing solutions of ethanol and water (volume ratio is 1:1) after filtering, after drying, obtain six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol cobalt chloride, 0.2mmol six niobium potassium hydrogen phthalate presoma, is dissolved in 10mL distilled water respectively.Under magnetic stirring, cobalt chloride solution is added drop-wise to gradually in six niobic acid hydrogen potassium solutions, forms suspension.
3) by gained suspension transfer hydrothermal reaction kettle, add distilled water to about 80% of cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, after reaction terminates, naturally cool to room temperature.
4) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain niobic acid cobalt dust product.
Embodiment 3: niobic acid nickel (NiNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in nickel crucible heating and melting, then 2g Niobium Pentxoxide is slowly added, room temperature is cooled to after reacting completely, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at gained settled solution 90 DEG C is obtained needle-like crystal, washs with the mixing solutions of ethanol and water (volume ratio is 1:1) after filtering, after drying, obtain six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol nickelous chloride, 0.2mmol six niobium potassium hydrogen phthalate presoma, is dissolved in 10mL distilled water respectively.Under magnetic stirring, nickel chloride solution is added drop-wise to gradually in six niobic acid hydrogen potassium solutions, forms suspension.
3) by gained suspension transfer hydrothermal reaction kettle, add distilled water to about 80% of cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, after reaction terminates, naturally cool to room temperature.
4) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain niobic acid nickel by powder product.
Embodiment 4: calcium niobate (CaNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in nickel crucible heating and melting, then 2g Niobium Pentxoxide is slowly added, room temperature is cooled to after reacting completely, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, the refrigerator and cooled that gained settled solution is placed in 2 ~ 3 DEG C is but obtained needle-like crystal, washs with the mixing solutions of ethanol and water (volume ratio is 1:1) after filtering, after drying, obtain six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol calcium chloride, 0.2mmol six niobium potassium hydrogen phthalate presoma, is dissolved in 10mL distilled water respectively.Under magnetic stirring, calcium chloride solution is added drop-wise to gradually in six niobic acid hydrogen potassium solutions, forms suspension.
3) by gained suspension transfer hydrothermal reaction kettle, add distilled water to about 80% of cumulative volume, sealing, 160 DEG C of isothermal reactions 12 hours, after reaction terminates, naturally cool to room temperature.
4) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain calcium niobate powdered product.
Embodiment 5: zinc niobate (ZnNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in nickel crucible heating and melting, then 2g Niobium Pentxoxide is slowly added, room temperature is cooled to after reacting completely, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, the refrigerator and cooled that gained settled solution is placed in 2 ~ 3 DEG C is but obtained needle-like crystal, washs with the mixing solutions of ethanol and water (volume ratio is 1:1) after filtering, after drying, obtain six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol zinc acetate, 0.2mmol six niobium potassium hydrogen phthalate presoma, is dissolved in 10mL distilled water respectively.Under magnetic stirring, acetic acid zinc solution is added drop-wise to gradually in six niobic acid hydrogen potassium solutions, forms suspension.
3) by gained suspension transfer hydrothermal reaction kettle, add distilled water to about 80% of cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, after reaction terminates, naturally cool to room temperature.
4) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain zinc niobate powdered product.
Claims (1)
1. a preparation method for columbite shaped metal niobate nanostructure, is characterized in that according to the following steps:
(1) potassium hydroxide is placed in nickel crucible heating and melting, then Niobium Pentxoxide is added, the mass ratio of potassium hydroxide and Niobium Pentxoxide is 3 ~ 7:1, after question response is complete, naturally cool to room temperature, soluble in water for gained material, filter and remove not molten thing, obtained soln using heating evaporation or subcooled method are carried out recrystallization, washs with the mixing solutions of ethanol and water again after filtration, after drying, can presoma be obtained;
(2) six niobium potassium hydrogen phthalate presomas prepared in soluble metallic salt and step (1) are stoichiometrically taken, water-soluble respectively, then two kinds of aqueous solution are under agitation mixed, be then transferred in hydrothermal reaction kettle, 150 ~ 200 DEG C of constant temperature sealed reactions, are cooled to room temperature after reaction terminates;
(3) the hydro-thermal reaction product in step (2) is filtered, with water and ethanol alternately washing, remove the ion that unreacted is complete, obtained columbite metal niobates product after dry;
Soluble metallic salt described in step (2) is the one in the divalent metal salt of magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, zinc, cadmium, copper.
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| CN105712403A (en) * | 2016-04-15 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for nanometer niobium pentoxide powder for lithium ion battery cathode material |
| CN106395903A (en) * | 2016-08-31 | 2017-02-15 | 周口师范学院 | Method for synthesis of hexaniobate and alkali metal salt using household microwave oven |
| CN109273280B (en) * | 2018-08-06 | 2020-02-21 | 江苏大学 | Flexible composite electrode material and preparation method and application thereof |
| CN113582715A (en) * | 2020-12-30 | 2021-11-02 | 苏州金宏气体股份有限公司 | Nickel doped KNbO3Piezoelectric ceramic, preparation method thereof and high-purity hydrogen production |
| CN113042033B (en) * | 2021-01-20 | 2022-07-22 | 西南交通大学 | Method for improving crystallization degree of columbite phase multi-element oxide material and material application |
| CN113401943B (en) * | 2021-06-16 | 2022-05-10 | 福州大学 | Transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound and preparation method thereof |
| CN114551892B (en) * | 2022-04-27 | 2022-08-02 | 浙江清华柔性电子技术研究院 | Cobalt niobate oxide-loaded graphene composite material and preparation method and application thereof |
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| CN102260501A (en) * | 2011-05-17 | 2011-11-30 | 内蒙古大学 | Method for preparing red nano-fluorescent material |
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| JPH0477318A (en) * | 1990-07-16 | 1992-03-11 | Chichibu Cement Co Ltd | Production of perovskite type pb(mg1/3nb2/3)o3 |
| JP3845720B2 (en) * | 2001-10-22 | 2006-11-15 | 独立行政法人産業技術総合研究所 | Potassium niobate photocatalyst and method for producing the same |
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| CN101921111A (en) * | 2010-07-12 | 2010-12-22 | 陕西科技大学 | Method for preparing MnNb2O6 microwave medium ceramic powder by utilizing hydrothermal method |
| CN102260501A (en) * | 2011-05-17 | 2011-11-30 | 内蒙古大学 | Method for preparing red nano-fluorescent material |
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