CN103964505A - Method for preparing nano structure of columbite-type metal niobate - Google Patents
Method for preparing nano structure of columbite-type metal niobate Download PDFInfo
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- CN103964505A CN103964505A CN201410178429.XA CN201410178429A CN103964505A CN 103964505 A CN103964505 A CN 103964505A CN 201410178429 A CN201410178429 A CN 201410178429A CN 103964505 A CN103964505 A CN 103964505A
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Abstract
The invention discloses a method for preparing nano structure of columbite-type metal niobate. The method is characterized by comprising the following steps: conducting reaction of niobium pentoxide and melted potassium hydroxide, performing recrystallization in a water solution to prepare a precursor of six potassium niobate, and performing hydrothermal reaction of six potassium niobate and soluble metal salt. The technical method disclosed by the invention has the following obvious advantages: 1, the adopted hydrothermal method is simple in technology, convenient to operate, low in manufacturing cost, and environment-friendly; 2, the synthesis technology can be carried out in a relatively low reaction temperature; 3, the whole reaction is carried out in a liquid phase, so that the precursor is fully and uniformly mixed; 4, the method has obvious applicability to the preparation of metal niobate series.
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
6the general chemical formula of type, wherein A is divalent alkaline-earth metal or transition metal.First, this class material has higher specific inductivity and lower dissipation loss under microwave frequency, therefore can have huge applications potentiality as dielectric resonator material in satellite communication field; Secondly the columbite niobate that, part comprises magnetic ion can show unique antiferromagnetic character; Finally, this series material also has the character such as good electricity, electrochemistry, optics and catalysis.
At present, preparing the topmost method of columbite niobate is solid-phase synthesis, utilizes Niobium Pentxoxide and metal simple-substance, oxide compound or carbonate for raw material, and at high temperature (>=1000 DEG C) are calcined and made.These class methods require heating for multiple times and grinding conventionally, 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 larger, 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 are mix and design for the homogeneous phase of precursor substantially, obtain final columbite niobate product, still need further high-temperature process.Therefore, explore a kind of simple, pervasive preparation method and 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 in niobate prior synthesizing method overcritical to hot conditions, the present invention proposes a kind of universality method of preparing columbite shaped metal niobate nanostructure under cold condition.The method is without complex apparatus, and processing condition are simple, easy handling control, and synthetic 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 to 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 gained material, filter and remove not molten thing, obtained soln using heating evaporation or subcooled method are carried out to recrystallization, after filtration, the mixing solutions washing with ethanol and water again, can obtain presoma after being dried.
2) hydro-thermal reaction.Take six niobium potassium hydrogen phthalate presomas prepared in soluble metallic salt and step 1) by stoichiometric ratio, 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 finishes.
3) carrying out washing treatment.By step 2) in hydro-thermal reaction product filter, water and ethanol is washing alternately, removes the complete ion of unreacted, makes columbite metal niobates product after dry.
Step 2 of the present invention) described in soluble metallic salt be the one in divalent alkaline-earth metal or the transition 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.
The prepared metal niobates of the present invention has typical orthogonal phase columbite structure, and the multilevel hierarchy that product is primitive by nano particle or with nano particle is formed.
Technological method involved in the present invention has following obvious advantage: 1. the present invention uses hydrothermal technique, and technique is simple, easy to operate, and production cost is low, and environmentally friendly; 2. this synthetic technology can be carried out under lower temperature of reaction; 3. whole reaction is to carry out in liquid phase, and the mixing of precursor is full and uniform; 4. the method has obvious universality to the preparation of metal niobates series.
Brief description of the drawings
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 spectrums of embodiment 2 samples after 800 DEG C of annealing.
Fig. 4 is the electron scanning micrographs of embodiment 2 samples after 800 DEG C of annealing.
Fig. 5 is the X-ray diffracting spectrums of embodiment 3 samples after 800 DEG C of annealing.
Fig. 6 is the electron scanning micrographs of embodiment 3 samples after 800 DEG C of annealing.
Fig. 7 is the X-ray diffracting spectrum of embodiment 4 samples.
Fig. 8 is the electron scanning micrograph of embodiment 4 samples.
Embodiment
In order to understand better the present invention, 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 to nickel crucible heating and melting, then slowly add 2g Niobium Pentxoxide, after reacting completely, be cooled to room temperature, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at 90 DEG C of gained settled solutions is obtained to needle-like crystal, and the mixing solutions with ethanol and water (volume ratio is 1:1) after filtering washs, and after being dried, obtains six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol Manganous chloride tetrahydrate, 0.2mmol six niobium potassium hydrogen phthalate presomas, are dissolved in respectively in 10mL distilled water.Under magnetic agitation, manganese chloride solution is added drop-wise in six niobic acid hydrogen potassium solutions gradually, form suspension.
3) gained suspension is shifted in hydrothermal reaction kettle, add 80% left and right of distilled water to cumulative volume, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, naturally cool to room temperature after reaction finishes.
4) hydro-thermal reaction product is carried out to suction filtration, water and ethanol is washing several alternately, and 50 DEG C are dried 6 hours, obtain niobic acid manganese powdered product.
Embodiment 2: niobic acid cobalt (CoNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in to nickel crucible heating and melting, then slowly add 2g Niobium Pentxoxide, after reacting completely, be cooled to room temperature, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at 90 DEG C of gained settled solutions is obtained to needle-like crystal, and the mixing solutions with ethanol and water (volume ratio is 1:1) after filtering washs, and after being dried, obtains six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol cobalt chloride, 0.2mmol six niobium potassium hydrogen phthalate presomas, are dissolved in respectively in 10mL distilled water.Under magnetic agitation, cobalt chloride solution is added drop-wise in six niobic acid hydrogen potassium solutions gradually, form suspension.
3) gained suspension is shifted in hydrothermal reaction kettle, add 80% left and right of distilled water to cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, naturally cool to room temperature after reaction finishes.
4) hydro-thermal reaction product is carried out to suction filtration, water and ethanol is washing several alternately, and 50 DEG C are dried 6 hours, obtain niobic acid cobalt dust product.
Embodiment 3: niobic acid nickel (NiNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in to nickel crucible heating and melting, then slowly add 2g Niobium Pentxoxide, after reacting completely, be cooled to room temperature, gained material is dissolved in 150mL distilled water, filter and remove not molten thing, heating evaporation at 90 DEG C of gained settled solutions is obtained to needle-like crystal, and the mixing solutions with ethanol and water (volume ratio is 1:1) after filtering washs, and after being dried, obtains six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol nickelous chloride, 0.2mmol six niobium potassium hydrogen phthalate presomas, are dissolved in respectively in 10mL distilled water.Under magnetic agitation, nickel chloride solution is added drop-wise in six niobic acid hydrogen potassium solutions gradually, form suspension.
3) gained suspension is shifted in hydrothermal reaction kettle, add 80% left and right of distilled water to cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, naturally cool to room temperature after reaction finishes.
4) hydro-thermal reaction product is carried out to suction filtration, water and ethanol is washing several alternately, and 50 DEG C are dried 6 hours, obtain niobic acid nickel by powder product.
Embodiment 4: calcium niobate (CaNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in to nickel crucible heating and melting, then slowly add 2g Niobium Pentxoxide, after reacting completely, be cooled to room temperature, 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 to 2 ~ 3 DEG C but obtains needle-like crystal, after filtering, with the mixing solutions washing of ethanol and water (volume ratio is 1:1), after being dried, obtains six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol calcium chloride, 0.2mmol six niobium potassium hydrogen phthalate presomas, are dissolved in respectively in 10mL distilled water.Under magnetic agitation, calcium chloride solution is added drop-wise in six niobic acid hydrogen potassium solutions gradually, form suspension.
3) gained suspension is shifted in hydrothermal reaction kettle, add 80% left and right of distilled water to cumulative volume, sealing, 160 DEG C of isothermal reactions 12 hours, naturally cool to room temperature after reaction finishes.
4) hydro-thermal reaction product is carried out to suction filtration, water and ethanol is washing several alternately, and 50 DEG C are dried 6 hours, obtain calcium niobate powdered product.
Embodiment 5: zinc niobate (ZnNb
2o
6) preparation.
1) 10g potassium hydroxide is placed in to nickel crucible heating and melting, then slowly add 2g Niobium Pentxoxide, after reacting completely, be cooled to room temperature, 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 to 2 ~ 3 DEG C but obtains needle-like crystal, after filtering, with the mixing solutions washing of ethanol and water (volume ratio is 1:1), after being dried, obtains six niobium potassium hydrogen phthalate presomas.
2) take 0.6mmol zinc acetate, 0.2mmol six niobium potassium hydrogen phthalate presomas, are dissolved in respectively in 10mL distilled water.Under magnetic agitation, acetic acid zinc solution is added drop-wise in six niobic acid hydrogen potassium solutions gradually, form suspension.
3) gained suspension is shifted in hydrothermal reaction kettle, add 80% left and right of distilled water to cumulative volume, sealing, 180 DEG C of isothermal reactions 12 hours, naturally cool to room temperature after reaction finishes.
4) hydro-thermal reaction product is carried out to suction filtration, water and ethanol is washing several alternately, and 50 DEG C are dried 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 to nickel crucible heating and melting, then add Niobium Pentxoxide, 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 gained material, filter and remove not molten thing, obtained soln using heating evaporation or subcooled method are carried out to recrystallization, and after filtration, the mixing solutions washing with ethanol and water again, can obtain presoma after being dried;
(2) take six niobium potassium hydrogen phthalate presomas prepared in soluble metallic salt and step (1) by stoichiometric ratio, 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 finishes;
(3) the hydro-thermal reaction product in step (2) is filtered, water and ethanol is washing alternately, removes the complete ion of unreacted, after being dried, makes columbite metal niobates product;
Soluble metallic salt described in step (2) is the one in divalent alkaline-earth metal or the transition metal of magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, zinc, cadmium, copper.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109273280A (en) * | 2018-08-06 | 2019-01-25 | 江苏大学 | A kind of flexible composite electrode material and its preparation method and application |
| CN113042033A (en) * | 2021-01-20 | 2021-06-29 | 西南交通大学 | Method for improving crystallization degree of columbite phase multi-element oxide material and material application |
| CN113401943A (en) * | 2021-06-16 | 2021-09-17 | 福州大学 | Transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound and preparation method 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 |
| CN114551892A (en) * | 2022-04-27 | 2022-05-27 | 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109273280A (en) * | 2018-08-06 | 2019-01-25 | 江苏大学 | A kind of flexible composite electrode material and its preparation method and application |
| 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 |
| CN113042033A (en) * | 2021-01-20 | 2021-06-29 | 西南交通大学 | Method for improving crystallization degree of columbite phase multi-element oxide material and material application |
| CN113401943A (en) * | 2021-06-16 | 2021-09-17 | 福州大学 | Transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound and preparation method thereof |
| 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 |
| CN114551892A (en) * | 2022-04-27 | 2022-05-27 | 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 |
| 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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