CN105668642A - Preparation method of bismuth ferrite monocrystalline nanometer sheet - Google Patents

Preparation method of bismuth ferrite monocrystalline nanometer sheet Download PDF

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Publication number
CN105668642A
CN105668642A CN201610019232.0A CN201610019232A CN105668642A CN 105668642 A CN105668642 A CN 105668642A CN 201610019232 A CN201610019232 A CN 201610019232A CN 105668642 A CN105668642 A CN 105668642A
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bismuth
fluoride
molar concentration
preparation
reactor
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韩高荣
杨鑫
任召辉
周迪逵
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a preparation method of a bismuth ferrite BiFeO3 monocrystalline nanometer sheet. The preparation method comprises that ferric nitrate and bismuth amine citrate as raw materials, deionized water and an appropriate amount of potassium hydroxide or sodium hydroxide for crystallization promotion undergo a hydrothermal reaction at a temperature of 160-240 DEG C to produce the bismuth ferrite BiFeO3 monocrystalline nanometer sheet. The preparation method has simple processes, can be controlled easily, does not product pollution, has a low cost and can be industrialized easily. The bismuth ferrite monocrystalline nanometer sheet has stable crystallization quality and has wide and latent application prospects in high and new technology fields of energy transducers, sensors, memory devices and photocatalysis.

Description

A kind of preparation method of bismuth ferrite single crystal nanoplate
Technical field
The preparation method that the present invention relates to a kind of bismuth ferrite single crystal nanoplate, belongs to field of inorganic nonmetallic material.
Background technology
The performance of functional material is largely dependent upon their pattern, size and degree of crystallinity, and the utilization of material is had very big value by the control of microscopic appearance. The progress of science and technology and the miniaturization of electronic device, it is also proposed increasing requirement to the size of material. Therefore, the preparation controlling material morphology becomes the focus that material science is paid close attention to and studied in recent years.
Along with the development of information industry, in line with the pursuit to the more best performance such as high speed, Large Copacity, low-loss, the integrated of device and miniaturization are proposed increasingly higher requirement by people. Multi-ferroic material, as a kind of novel functional material, not only has non-single ferrum, and there is coupling synergism between different ferrum, thus have broad application prospects due to it. As the typical material bismuth ferrite (BiFeO in multi-iron material3) it is the only a few material more than room temperature with magnetoelectric effect, become the study hotspot of multifunctional material. Due to its energy gap very narrow (～2.1eV), illustrating that it has good photoresponse in visible-range, it is very huge in the using value of photocatalysis field.
The method preparing bismuth iron series compound at present mainly adopts high temperature solid-state method and sol-gal process, and it reacts poor controllability, and product purity is low. Owing to there is high-temperature burning process, particle agglomeration is very serious, and the size of granule and pattern are also difficult to control to. Hydro-thermal method is the material preparation method of a kind of uniform, controllable, has environmental protection, consume energy the advantage such as low, easy to control, is commonly used to prepare the product of various multicomponent system, also it is the conventional preparation method of a kind of nano material, and the method is simple to operate, low for equipment requirements, with low cost.
Summary of the invention
It is an object of the invention to provide a kind of technique and simply prepare bismuth ferrite BiFeO3The method of single crystal nanoplate.
The bismuth ferrite BiFeO of the present invention3The preparation method of single crystal nanoplate, comprises the following steps:
1) 3:1～1:1 metering in molar ratio weighs ferric nitrate and bismuth citrate amine, adds deionized water and is sufficiently stirred for, and forms the suspension containing bismuth citrate amine and ferric nitrate;
2) under stirring, to step 1) suspension containing bismuth citrate amine and ferric nitrate for preparing adds potassium hydroxide or sodium hydrate aqueous solution, obtain the suspension that the oxyhydroxide containing bismuth and ferrum precipitates;
3) suspension of the precipitation of the oxyhydroxide containing bismuth and ferrum obtained is transferred in reactor inner bag, regulate the reaction mass volume in reactor inner bag with deionized water and reach the 70%-90% of reactor inner bag volume, stir at least 10 minutes, in reaction mass, the molar concentration of ferric nitrate is 0.05mol/L, the molar concentration of bismuth citrate amine is 0.05mol/L～0.15mol/L, the molar concentration of potassium hydroxide or sodium hydroxide is 0.4～0.8mol/L, and the volume radix of molar concentration is the volume of material in all introducing reactor inner bags;
4) potassium fluoride KF, sodium fluoride NaF, calcium fluoride CaF are added2, ammonium fluoride NH4One or more in F, and making the added fluoride concentration to be: potassium fluoride molar concentration is 0.04～1.3mol/L, sodium fluoride molar concentration is 0.05～1.8mol/L, and calcium fluoride molar concentration is 0.3～1mol/L, and ammonium fluoride molar concentration is 0.1～0.3mol/L. Magnetic agitation suspension 1～48h.
5) by step 4) the reactor inner bag that is configured with reaction mass is placed in reactor, seal, at 160 DEG C-240 DEG C, insulation carries out hydrothermal treatment consists in 8-72 hour, then reactor is allowed to naturally cool to room temperature, by deionized water and dehydrated alcohol cyclic washing product, filter, dry, obtain bismuth ferrite BiFeO3Single crystal nanoplate.
In preparation process of the present invention, the reactor of use is polytetrafluoroethylliner liner, the reactor that rustless steel external member is airtight.
In process of the present invention, the purity of described bismuth citrate amine, ferric nitrate, potassium hydroxide, potassium fluoride, sodium fluoride, calcium fluoride, ammonium fluoride and dehydrated alcohol is all not less than chemical pure.
The bismuth ferrite BiFeO that the inventive method prepares3Single crystal nanoplate thickness is 50nm-1um, is sized to 5-20um.
The beneficial effects of the present invention is:
The present invention is when ferrum and bismuth molar concentration rate are 3:1～1:1, by regulating some hydro-thermal reaction parameters and fluorine-containing reagent is prepared for the monocrystalline BiFeO of a kind of oriented growth3Nanometer sheet. Present invention process process is simple, it is easy to controlling, pollution-free, cost is low, it is easy to produce. The monocrystalline BiFeO of synthesis3Nanometer sheet can be used to make transducer of good performance, sensor, memory, it is also possible to as the photocatalyst of degradation of contaminant under visible ray. It is all very good in feasibility and controllability that it realizes condition.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of bismuth ferrite single crystal nanoplate prepared by the present invention;
Fig. 2 is the stereoscan photograph of bismuth ferrite single crystal nanoplate prepared by the present invention.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Example 1
1) 1:1 metering in molar ratio weighs ferric nitrate and bismuth citrate amine, adds deionized water and is sufficiently stirred for, and forms the suspension containing bismuth citrate amine and ferric nitrate;
2) under stirring, to step 1) suspension containing bismuth citrate amine and ferric nitrate for preparing adds potassium hydroxide aqueous solution, obtain the suspension that the oxyhydroxide containing bismuth and ferrum precipitates;
3) suspension of the precipitation of the oxyhydroxide containing bismuth and ferrum obtained is transferred in reactor inner bag, the reaction mass volume regulated in reactor inner bag with deionized water reaches the 90% of reactor inner bag volume, stir 10 minutes, in reaction mass, the molar concentration of ferric nitrate and bismuth citrate amine is 0.05mol/L, the molar concentration of potassium hydroxide is 0.4mol/L, and the volume radix of molar concentration is the volume of material in all introducing reactor inner bags;
4) adding potassium fluoride KF, in reaction mass, potassium fluoride molar concentration is 0.6mol/L, magnetic agitation suspension 12h.
5) by step 4) the reactor inner bag that is configured with reaction mass is placed in reactor, seal, at 240 DEG C, insulation carries out hydrothermal treatment consists in 4 hours, then reactor is allowed to naturally cool to room temperature, by deionized water and dehydrated alcohol cyclic washing product, filter, dry, obtain bismuth ferrite BiFeO3Single crystal nanoplate.
Example 2
1) 2.5:1 metering in molar ratio weighs ferric nitrate and bismuth citrate amine, adds deionized water and is sufficiently stirred for, and forms the suspension containing bismuth citrate amine and ferric nitrate;
2) under stirring, to step 1) suspension containing bismuth citrate amine and ferric nitrate for preparing adds potassium hydroxide aqueous solution, obtain the suspension that the oxyhydroxide containing bismuth and ferrum precipitates;
3) suspension of the precipitation of the oxyhydroxide containing bismuth and ferrum obtained is transferred in reactor inner bag, the reaction mass volume regulated in reactor inner bag with deionized water reaches the 90% of reactor inner bag volume, stir 10 minutes, in reaction mass, the molar concentration of ferric nitrate is 0.125mol/L, the molar concentration of bismuth citrate amine is 0.05mol/L, and the molar concentration of potassium hydroxide is 0.6mol/L, and the volume radix of molar concentration is the volume of material in all introducing reactor inner bags;
4) adding sodium fluoride NaF, in reaction mass, sodium fluoride molar concentration is 0.125mol/L, magnetic agitation suspension 12h.
5) by step 4) the reactor inner bag that is configured with reaction mass is placed in reactor, seal, at 200 DEG C, insulation carries out hydrothermal treatment consists in 12 hours, then reactor is allowed to naturally cool to room temperature, by deionized water and dehydrated alcohol cyclic washing product, filtering, dry, obtaining thickness is 50-1um, is sized to the bismuth ferrite BiFeO of 5-20um3Single crystal nanoplate. Its XRD figure spectrum is shown in Fig. 1, and Fig. 2 is shown in by scanning electron microscope (SEM) photo. Monocrystalline BiFeO as seen from the figure3Nanometer sheet oriented growth.
Example 3
1) 1:1 metering in molar ratio weighs ferric nitrate and bismuth citrate amine, adds deionized water and is sufficiently stirred for, and forms the suspension containing bismuth citrate amine and ferric nitrate;
2) under stirring, to step 1) suspension containing bismuth citrate amine and ferric nitrate for preparing adds sodium hydrate aqueous solution, obtain the suspension that the oxyhydroxide containing bismuth and ferrum precipitates;
3) suspension of the precipitation of the oxyhydroxide containing bismuth and ferrum obtained is transferred in reactor inner bag, the reaction mass volume regulated in reactor inner bag with deionized water reaches the 90% of reactor inner bag volume, stir 10 minutes, in reaction mass, the molar concentration of ferric nitrate and bismuth citrate amine is 0.05mol/L, the molar concentration of sodium hydroxide is 0.8mol/L, and the volume radix of molar concentration is the volume of material in all introducing reactor inner bags;
4) ammonium fluoride NH is added4F and potassium fluoride KF, in reaction mass, amine fluoride molar concentration is 0.1mol/L, and potassium fluoride molar concentration is 0.04mol/L, magnetic agitation suspension 12h.
5) by step 4) the reactor inner bag that is configured with reaction mass is placed in reactor, seal, at 240 DEG C, insulation carries out hydrothermal treatment consists in 6 hours, then reactor is allowed to naturally cool to room temperature, by deionized water and dehydrated alcohol cyclic washing product, filter, dry, obtain bismuth ferrite BiFeO3Single crystal nanoplate.

Claims (4)

1. the preparation method of a bismuth ferrite single crystal nanoplate, it is characterised in that comprise the following steps:
1) 3:1～1:1 metering in molar ratio weighs ferric nitrate and bismuth citrate amine, adds deionized water, is sufficiently stirred for, and forms the suspension containing bismuth citrate amine and ferric nitrate;
2) under stirring, to step 1) suspension containing bismuth citrate amine and ferric nitrate for preparing adds potassium hydroxide or sodium hydrate aqueous solution, obtain the suspension that the oxyhydroxide containing bismuth and ferrum precipitates;
3) suspension of the precipitation of the oxyhydroxide containing bismuth and ferrum obtained is transferred in reactor inner bag, regulate the reaction mass volume in reactor inner bag with deionized water and reach the 70%-90% of reactor inner bag volume, stir at least 10 minutes, in reaction mass, the molar concentration of ferric nitrate is 0.05mol/L, the molar concentration of bismuth citrate amine is 0.05mol/L～0.15mol/L, the molar concentration of potassium hydroxide or sodium hydroxide is 0.4～0.8mol/L, and the volume radix of molar concentration is the volume of material in all introducing reactor inner bags;
4) one or more in potassium fluoride, sodium fluoride, calcium fluoride, ammonium fluoride are added, and making the added fluoride concentration to be: potassium fluoride molar concentration is 0.04～1.3mol/L, sodium fluoride molar concentration is 0.05～1.8mol/L, calcium fluoride molar concentration is 0.3～1mol/L, and ammonium fluoride molar concentration is 0.1～0.3mol/L; Magnetic agitation suspension 1～48h.
5) by step 4) the reactor inner bag that is configured with reaction mass is placed in reactor, seal, at 160 DEG C-240 DEG C, insulation carries out hydrothermal treatment consists in 8-72 hour, then reactor is allowed to naturally cool to room temperature, by deionized water and dehydrated alcohol cyclic washing product, filter, dry, obtain bismuth ferrite single crystal nanoplate.
2. the preparation method of bismuth ferrite single crystal nanoplate according to claim 1, is characterized in that reactor is polytetrafluoroethylliner liner, the reactor that rustless steel external member is airtight.
3. the preparation method of bismuth ferrite monocrystalline micron film according to claim 1, is characterized in that the purity of described bismuth citrate amine, ferric nitrate, potassium hydroxide, sodium hydroxide, potassium fluoride, sodium fluoride, calcium fluoride, ammonium fluoride and dehydrated alcohol is all not less than chemical pure.
4. the preparation method of bismuth ferrite single crystal nanoplate according to claim 1, is characterized in that obtained bismuth ferrite single crystal nanoplate thickness is 50nm-1um, is sized to 5-20um.
CN201610019232.0A 2016-01-12 2016-01-12 Preparation method of bismuth ferrite monocrystalline nanometer sheet Pending CN105668642A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626440A (en) * 2019-01-17 2019-04-16 天津城建大学 BiFeO is prepared based on hydro-thermal method3The method and BiFeO of nanometer sheet3Nanometer sheet
CN111229240A (en) * 2020-01-17 2020-06-05 力行氢能科技股份有限公司 Bismuth ferrite catalyst and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102877130A (en) * 2012-10-24 2013-01-16 浙江大学 Preparation method of bismuth ferrite BiFeO3 monocrystal micrometer sheet
CN103420427A (en) * 2012-05-23 2013-12-04 浙江大学 Preparation method for bismuth ferrite Bi2Fe4O9 monocrystal nanosheets
CN103641130A (en) * 2013-12-12 2014-03-19 山东大学 Method for preparing fluorinated boron nitride in fluorinating and stripping manners
CN103771506A (en) * 2013-12-24 2014-05-07 中国科学院合肥物质科学研究院 Micro/nano hierarchical titanium dioxide microspheres as well as preparation method and application thereof
CN105129861A (en) * 2015-08-27 2015-12-09 华南理工大学 Preparation method for bismuth ferrite BiFeO3 nanosheet
CN105347377A (en) * 2015-10-13 2016-02-24 刘冠华 Preparation method for high-purity flaky alumina

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420427A (en) * 2012-05-23 2013-12-04 浙江大学 Preparation method for bismuth ferrite Bi2Fe4O9 monocrystal nanosheets
CN102877130A (en) * 2012-10-24 2013-01-16 浙江大学 Preparation method of bismuth ferrite BiFeO3 monocrystal micrometer sheet
CN103641130A (en) * 2013-12-12 2014-03-19 山东大学 Method for preparing fluorinated boron nitride in fluorinating and stripping manners
CN103771506A (en) * 2013-12-24 2014-05-07 中国科学院合肥物质科学研究院 Micro/nano hierarchical titanium dioxide microspheres as well as preparation method and application thereof
CN105129861A (en) * 2015-08-27 2015-12-09 华南理工大学 Preparation method for bismuth ferrite BiFeO3 nanosheet
CN105347377A (en) * 2015-10-13 2016-02-24 刘冠华 Preparation method for high-purity flaky alumina

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626440A (en) * 2019-01-17 2019-04-16 天津城建大学 BiFeO is prepared based on hydro-thermal method3The method and BiFeO of nanometer sheet3Nanometer sheet
CN109626440B (en) * 2019-01-17 2021-06-25 天津城建大学 BiFeO preparation based on hydrothermal method3Method for nanosheet and BiFeO3Nano-sheet
CN111229240A (en) * 2020-01-17 2020-06-05 力行氢能科技股份有限公司 Bismuth ferrite catalyst and preparation method and application thereof
CN111229240B (en) * 2020-01-17 2021-05-04 力行氢能科技股份有限公司 Bismuth ferrite catalyst and preparation method and application thereof

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