CN108264087B - Single reagent self-reaction preparation of Nb with directional arrangement2O5Method for producing nano-rod - Google Patents
Single reagent self-reaction preparation of Nb with directional arrangement2O5Method for producing nano-rod Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 98
- 239000002073 nanorod Substances 0.000 title claims abstract description 75
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 39
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011591 potassium Substances 0.000 claims abstract description 37
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 37
- 238000007789 sealing Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052737 gold Inorganic materials 0.000 claims abstract description 28
- 239000010931 gold Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims description 51
- 238000005303 weighing Methods 0.000 claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- 238000003466 welding Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 57
- 238000004458 analytical method Methods 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- 238000007605 air drying Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- -1 hydrogen, fluoride ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910019648 Nb(OH)3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019660 Nb(OH)5 Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- 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
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for preparing Nb with directional arrangement by adopting single reagent self-reaction2O5A method of nanorods, comprising the steps of: (1) selecting potassium fluoroniobate powder, dissolving the potassium fluoroniobate powder in deionized water, placing the dilute potassium fluoroniobate solution in a pretreated noble gold tube, and sealing; (2) placing the noble metal tube in a hydrothermal reaction kettle, sealing, adjusting the temperature in the hydrothermal reaction kettle to 200-500 ℃, adjusting the pressure in the hydrothermal reaction kettle to 50-200 MPa by adopting inert gas or deionized water, carrying out hydrolysis reaction for 12-24 h, and cooling the reaction kettle to room temperature after the reaction is finished; (3) opening the hydrothermal reaction kettle, taking out the reacted noble metal tube and opening, recovering the residual solution, collecting the sample to obtain the directionally arranged Nb2O5And (4) nanorods. The method adopts a single reagent as a synthetic raw material, the raw material is simple and easy to obtain, the cost is low, the energy consumption is low, and the prepared Nb is2O5The nano-rod has perfect crystal form and obvious directionality.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing directionally arranged Nb by self-reaction of a single reagent2O5A method of nano-rod.
Background
Nb2O5As a typical n-type semiconductor material, the material has acid and alkali corrosion resistance, excellent optical properties and stable and excellent electrochemical properties, so that the material has wide application potential in the aspects of capacitors, optical guide materials, superconducting materials, photoelectrocatalysis, solar cells, biosensors, lithium ion batteries and the like, and particularly has wide application potential in electronic materials such as capacitors, lithium ion batteries and the likeThe material aspect has huge potential application.
As early as 1981, Reichman et al first introduced Nb2O5As the original electrode material of lithium battery, Koshiba et al studied Nb in 1994 under different configurations2O5But these studies all used Nb2O5And (3) microparticles. Up to 2008, it was first reported that Wei et al synthesized Nb by solvothermal method for up to 14 days using niobium powder and niobium source2O5The nanobelt has good effect as an electrode. One-dimensional Nb2O5Nanomaterials (nanorods, nanotubes, nanobelts, nanofibers) are beginning to be widely used in capacitor electrodes, lithium ion batteries, and the like.
At present about Nb2O5The reports of nanorod synthesis are relatively few, such as 2013, Huang Meng, etc. with NbCl5Is a single niobium source, and the one-dimensional Nb with uniform appearance and small size is prepared by a 72-hour one-step solvothermal method under the condition of no dispersant2O5Nanorod, 2015, Dingjuan, etc. with niobium pentachloride (NbCl)5) And Graphene Oxide (GO) as raw materials, and NbCl is synthesized by adopting an ultraviolet irradiation method5And (4) nanorods.
Various prior Nb2O5The synthesis method of the nano-rod is generally complicated and has the characteristics of high cost, high energy consumption and the like, and the synthesized Nb2O5The directionality of the nanorods is poor. This limits Nb to some extent2O5The application and popularization of the nano-rod in industrial production.
Disclosure of Invention
The invention aims to provide a method for preparing Nb with oriented arrangement by single-reagent self-reaction2O5The method of the nano rod adopts a single reagent as a synthetic raw material, the raw material is simple and easy to obtain, the cost is low, the energy consumption is low, and the prepared Nb is2O5The nano-rod has perfect crystal form and obvious directionality.
The above object of the present invention is achieved by the following technical solutions: single reagent self-reaction preparation of Nb with directional arrangement2O5Of nanorodsThe method comprises the following steps:
(1) selecting potassium fluoroniobate powder to be dissolved in water to obtain a dilute potassium fluoroniobate solution, placing the dilute potassium fluoroniobate solution in a pretreated noble metal tube, and then sealing the noble metal tube;
(2) placing the sealed noble metal tube in a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to be 200-500 ℃, adjusting the pressure in the hydrothermal reaction kettle to be 50-200 MPa by adopting inert gas or deionized water, carrying out hydrolysis reaction for 12-24 h, and cooling the hydrothermal reaction kettle to room temperature after the reaction is finished;
(3) opening the hydrothermal reaction kettle, taking out the reacted noble metal tube and opening, recovering the residual solution, collecting the sample, washing and drying the obtained sample to obtain the directionally arranged Nb2O5And (4) nanorods.
Preparation of Nb with oriented arrangement by single reagent self-reaction2O5The method of the nano-rod comprises the following steps:
the potassium fluoroniobate (K) described in the step (1)2NbF7) The concentration of the dilute solution is 0.005-0.02 mol/L, and the volume of the potassium fluoroniobate dilute solution accounts for 40-70% of the total volume of the noble metal tube.
Wherein the potassium fluoroniobate (K) described in the step (1)2NbF7) The powder is preferably an analytical purity reagent to avoid interference of impurities with the experiment.
The water in the step (1) is preferably deionized water or distilled water.
The pretreatment of the noble metal tube in the step (1) comprises the following steps: the method comprises the steps of selecting a noble metal pipe, and carrying out truncation, acid boiling, washing and quenching treatment, so that the experiment is ensured to be free from other impurities in the noble metal pipe, and the complete sealing property of the noble metal pipe is ensured.
The noble metal in the step (1) preferably refers to silver, gold, platinum, silver target, gold palladium or platinum palladium alloy.
When the noble metal tube is completely sealed in the step (1), the potassium fluoroniobate dilute solution is placed in the noble metal tube for sealing by welding, then the temperature is adjusted to be 100-120 ℃ for drying for more than 2h, more preferably 110 ℃ for drying for more than 2h, and the noble metal tube is weighed again to ensure that the mass error before and after the weighing is less than 0.001 g. Thereby ensuring the complete sealing and the experimental effectiveness.
The reaction time in the step (2) does not include the time taken for temperature rise and temperature fall, and is reaction time at a specified temperature and pressure.
And (3) the inert gas in the step (2) is argon or helium.
And (3) when the temperature is reduced in the step (2), using ice water to carry out rapid temperature reduction or constant-pressure temperature reduction on the reaction kettle.
And (4) cleaning, drying and weighing the noble metal tube after the reaction in the step (3) to ensure the effectiveness of the experiment.
The residual solution in the step (3) comprises potassium fluoroniobate, hydrofluoric acid and potassium fluoride, the step of recovering the residual solution comprises the step of doping niobium oxide powder into the residual solution, and the hydrofluoric acid and the potassium fluoride are continuously synthesized into the potassium fluoroniobate to be used as an initial reaction solution, so that hydrofluoric acid pollution can be eliminated to a certain extent.
When the sample is collected in the step (3), taking out the residual solution, washing the inner wall of the noble metal tube for 2-3 times by using deionized water and absolute ethyl alcohol respectively to ensure the cleanness of the sample, collecting the sample attached to the inner wall of the noble metal tube, and drying to obtain the directionally arranged Nb2O5And (4) nanorods. The drying can be air drying or drying dish storage.
The invention adopts single reagent self-reaction to prepare Nb with directional arrangement2O5The method of the nano-rod is characterized in that a single reagent of potassium fluoroniobate is utilized to generate Nb through self-hydrolysis reaction under specific temperature and pressure conditions2O5The nanorod uses a potassium fluoroniobate solution as a unique reagent, and the potassium fluoroniobate and water sequentially undergo the following hydrolysis reaction under the hydrothermal condition:
K2NbF7+H2O＝K2Nb(OH)F6+HF
K2Nb(OH)F6+H2O＝K2Nb(OH)2F5+HF
K2Nb(OH)2F5+H2O＝K2Nb(OH)3F4+HF
K2Nb(OH)3F4+H2O＝K2Nb(OH)4F3+HF
K2Nb(OH)4F3+H2O＝Nb(OH)5+2KF+HF
2Nb(OH)5＝Nb2O5↓+5H2O
nb is generated by the hydrolysis of potassium fluoroniobate2O5And potassium, hydrogen, fluoride ions, the product fluoride ions reducing Nb2O5(001) Surface energy of the planes, promoting growth of the (001) plane, and finally enabling synthesis of directionally aligned Nb2O5The nano-rod avoids the additional addition of hydrofluoric acid and other reagents in the traditional process.
Compared with the prior art, the invention has the following advantages:
(1) the method synthesizes the directionally arranged Nb by the self-reaction of a single reagent2O5The nano-rod avoids the proportioning weighing and the sequential process steps of various precursors and morphology control agents in the traditional process, so that the method has the advantages of simple process, easy operation and control and relatively low cost;
(2) the method adopts potassium fluoroniobate solution as a single reagent, and generates the directionally arranged Nb through the self hydrolysis reaction of the potassium fluoroniobate under the hydrothermal condition2O5The nanorod, hydrogen ions and fluorine ions generated simultaneously replace hydrofluoric acid added in the traditional process, so that the single reagent is self-reacted to generate directionally arranged Nb2O5A nanorod;
(3) the method of the invention adopts the high-purity noble metal tube as the outer sleeve, which can ensure that the reactant does not react with other substances, the sealing performance and the effectiveness of the reaction process, the cost is low, and the energy consumption is low;
(4) the method synthesizes the directionally arranged Nb by the incomplete hydrolysis reaction of potassium fluoroniobate2O5Nanorods, the recovered solution mainly containing potassium fluoroniobate, hydrofluoric acid and potassium fluoride, the recovered solution being subjected to a treatment such as doping niobium oxide powder thereto,hydrofluoric acid and potassium fluoride can be continuously synthesized into potassium fluoroniobate, and the obtained recovered solution can be continuously used for the initial raw materials of the invention, so that on one hand, the cost can be effectively recovered and reduced, on the other hand, the pollution of hydrofluoric acid can be eliminated, the process safety is maintained, and the environmental protection is emphasized;
(5) nb prepared by the method of the invention2O5The length of the nano rod is hundreds of nanometers to tens of micrometers, the diameter is tens of nanometers to tens of nanometers, even hundreds of nanometers, compared with the existing synthesis method, the Nb obtained by the method2O5The nano-rod has better directionality and more complete crystal form, thereby having great potential application value in the aspects of electronic materials such as capacitors, lithium ion batteries and the like.
Drawings
FIG. 1 is a diagram of the directionally aligned Nb prepared in examples 1-6 of this invention2O5Laser Raman spectrum of the nano rod;
FIG. 2 shows an oriented Nb prepared in example 1 of the present invention2O5Scanning electron microscope photographs of the nanorods;
FIG. 3 shows an oriented Nb prepared in example 2 of the present invention2O5Scanning electron microscope photographs of the nanorods;
FIG. 4 shows an oriented Nb prepared in example 3 of the present invention2O5Scanning electron microscope photographs of the nanorods;
FIG. 5 shows an oriented Nb prepared in example 4 of the present invention2O5Scanning electron microscope photographs of the nanorods;
FIG. 6 shows a single Nb prepared in example 5 of the present invention2O5Scanning electron microscope photographs of the nanorods;
FIG. 7 shows an oriented Nb prepared in example 6 of the present invention2O5Scanning electron micrograph of nanorod, (a) is oriented Nb2O5Photo of nano-rod, (b) is Nb capable of forming radial2O5And (5) photo of the nano rod.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings, but the scope of the present invention as claimed is not limited to the examples, as the reaction apparatus and the reaction temperature, the reaction time and the volume of the reaction liquid.
Example 1
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano rod comprises the following steps:
(1) cutting a high-purity gold tube with the diameter of 3-5 mm into 4cm, placing the tube in a beaker loaded with 0.01mol/L dilute nitric acid solution, and placing the beaker on a heating plate at 80 ℃ for cooking for two hours; then, the gold tube is subjected to early-stage treatment such as washing by deionized water, drying, welding and sealing in advance at one end and the like, so that no impurities or cracks are generated in the gold tube;
(2) 0.76g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7Commercially available product, the same applies hereinafter) was dissolved in 250mL of deionized water and sufficiently dissolved to obtain a concentration of 0.01mol/L K2NbF7Solution, namely filling about 0.2mL of prepared reaction solution into a gold tube, controlling the filling degree to be about 40-70%, performing welding sealing, performing weighing recording after welding sealing, then putting the gold tube filled with a solution sample into a drying box at 110 ℃ for more than 2 hours, and then weighing again, wherein the mass error before and after weighing is ensured to be less than 0.001g, which indicates that the gold tube is complete in sealing property;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a nickel-based alloy hydrothermal reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle through a gas booster pump to reach the pressure of 50MPa as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 200 ℃;
(4) after the temperature is increased to 200 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 12 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (4), taking out the gold tube in the reaction kettle, cleaning, drying and weighing, ensuring the sealing performance and effectiveness of the reaction process, and confirming no errorAnd then breaking the gold tube, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively to ensure that the Nb attached to the inner wall of the gold tube2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(a) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorod, FIG. 2 SEM photo shows synthesized Nb2O5The nano rod is of an oriented structure, the surface (001) opposite to the lens is a rod-shaped crystal form is complete;
(7) the residual solution is mainly potassium fluoroniobate, hydrofluoric acid and potassium fluoride, and the solution is processed, for example, niobium powder is doped into the solution, and the hydrofluoric acid and the potassium fluoride can be continuously synthesized into the potassium fluoroniobate and can be used as the initial reaction solution.
Example 2
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano rod comprises the following steps:
(1) the pretreatment of the platinum tube was the same as in example 1;
(2) 0.38g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7) The powder is dissolved in 250mL of deionized water and fully dissolved to obtain 0.005mol/L K2NbF7Solution, namely filling about 0.2mL of prepared reaction solution into a platinum tube, controlling the filling degree to be about 40-70%, performing welding sealing, performing weighing recording after welding sealing, then putting the platinum tube filled with a solution sample into a drying box at 110 ℃ for more than 2h, and then weighing again to ensure that the mass error before and after weighing is less than 0.001g, which indicates that the gold tube is complete in sealing property;
(3) putting a platinum pipe which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting deionized water into the kettle through a liquid booster pump to reach the pressure of 60MPa as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 300 ℃;
(4) after the temperature is increased to 300 ℃, opening the stop valve in the step (3), continuously adding deionized water to the pressure of 200MPa, keeping the temperature and pressure stable, reacting for 12 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) to rapidly cool or cool at constant pressure to normal temperature;
(5) opening the reaction kettle in the step (4), taking out, cleaning, drying and weighing the platinum pipe in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the platinum pipe after confirming that no errors exist, recovering residual solution of the platinum pipe, washing the inner wall of the platinum pipe with deionized water and alcohol for 2-3 times respectively, and enabling Nb attached to the inner wall of the platinum pipe to be attached to the inner wall of the platinum pipe2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(b) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorod, FIG. 3 SEM photo shows synthesized Nb2O5The nano-rod has an oriented structure, complete crystal form and part of Nb2O5The sample is in a short rod shape;
(7) the residual solution was recovered as in example 1.
Example 3
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano rod comprises the following steps:
(1) the pretreatment of the Au-Pd tube is the same as that of example 1;
(2) 0.76g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7) The powder is dissolved in 250mL of deionized water and fully dissolved to obtain 0.01mol/L K2NbF7Solution, about 0.2mL of prepared reaction solution is filled into a gold-palladium tube, the filling degree is controlled to be about 40% -70%, the gold-palladium tube is sealed by welding, weighing recording is carried out after the sealing, then the gold-palladium tube filled with the solution sample is placed into a drying box at 110 ℃ for more than 2h, weighing is carried out again after the weighing, the mass error before and after the weighing is ensured to be less than 0.001g, and the sealing performance of the gold-palladium tube is proved to be completeGood;
(3) putting a gold-palladium pipe which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle through an air duct to reach the pressure of 60MPa as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 400 ℃;
(4) after the temperature is increased to 400 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (4), taking out, cleaning, drying and weighing the gold-palladium tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold-palladium tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively, and enabling Nb attached to the inner wall of the gold-palladium tube2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(c) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorod, FIG. 4 SEM image shows synthesized Nb2O5The nano-rod has obvious oriented structure and complete crystal form;
(7) the residual solution was recovered as in example 1.
Example 4
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano rod comprises the following steps:
(1) the pretreatment of the Ag-Pd tube was the same as in example 1;
(2) 0.76g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7) The powder is dissolved in 250mL of deionized water and fully dissolved to obtain 0.01mol/L K2NbF7Solution, reaction of preparationFilling about 0.2mL of the solution into a silver-palladium tube, controlling the filling degree to be about 40% -70%, performing welding sealing, performing weighing record after welding sealing, then putting the silver-palladium tube filled with the solution sample into a drying box at 110 ℃ for more than 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the silver-palladium tube is complete in sealing property;
(3) putting a silver-palladium pipe which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting deionized water into the kettle through a liquid booster pump to reach the pressure of 50MPa as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 500 ℃;
(4) after the temperature is increased to 500 ℃, opening the stop valve in the step (3), continuously adding deionized water to the pressure of 200MPa, keeping the temperature and pressure stable, reacting for 12 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) to rapidly cool or cool at constant pressure to normal temperature;
(5) opening the reaction kettle in the step (4), taking out the silver palladium tube in the reaction kettle, cleaning, drying and weighing to ensure the sealing property and effectiveness of the reaction process, breaking the silver palladium tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively to ensure that the Nb attached to the inner wall of the silver palladium tube2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(d) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorod, FIG. 5 SEM image shows synthesized Nb2O5The nano-rod has an oriented structure and complete crystal form;
(7) the residual solution was recovered as in example 1.
Example 5
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano-rod comprises the following stepsThe method comprises the following steps:
(1) the pretreatment of the silver tube was the same as in example 1;
(2) 0.76g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7) The powder is dissolved in 250mL of deionized water and fully dissolved to obtain 0.01mol/L K2NbF7Solution, namely filling about 0.2mL of prepared reaction solution into a silver tube, controlling the filling degree to be about 40-70%, performing welding sealing, performing weighing recording after welding sealing, then putting the silver tube filled with the solution sample into a drying box at 110 ℃ for more than 2h, and then weighing again, wherein the mass error before and after weighing is ensured to be less than 0.001g, which indicates that the silver tube is intact in sealing property;
(3) putting a silver pipe which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, injecting deionized water as a medium, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 60MPa through a vent pipeline, taking the argon as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 200 ℃;
(4) after the temperature is increased to 200 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 23 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (4), taking out, cleaning, drying and weighing the silver tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the silver tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively, and enabling Nb attached to the inner wall of the silver tube2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(e) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorod, FIG. 6 SEM photo shows synthesized Nb2O5Nano meterA rod with a complete crystal form and a length of 150-250 nm;
(7) the residual solution was recovered as in example 1.
Example 6
The present embodiment provides a directional arrangement Nb2O5The preparation method of the nano rod comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 1.52g of potassium fluoroniobate (K) of analytical purity are introduced2NbF7) The powder is dissolved in 250mL of deionized water and fully dissolved to obtain 0.02mol/L K2NbF7Solution, namely filling about 0.2mL of prepared reaction solution into a gold tube, controlling the filling degree to be about 40-70%, performing welding sealing, performing weighing recording after welding sealing, then putting the gold tube filled with a solution sample into a drying box at 110 ℃ for more than 2 hours, and then weighing again, wherein the mass error before and after weighing is ensured to be less than 0.001g, which indicates that the gold tube is complete in sealing property;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle through an air duct to reach the pressure of 60MPa as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 200 ℃;
(4) after the temperature is increased to 200 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 12 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (4), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively, and enabling Nb attached to the inner wall of the gold tube to be attached to the inner wall of the gold tube2O5Cleaning the sample, and air-drying the precipitate sample with natural wind or oven-drying to obtain directionally arranged Nb2O5A nanorod;
(6) nb to be obtained2O5The sample is subjected to Raman analysis and morphology analysis, and FIG. 1(f) shows that the obtained nanorod is Nb by laser Raman analysis2O5Nanorods, FIG. 7, Panel (a), scanning Electron micrograph showing synthesized oriented Nb2O5Nanorods, complete crystal form, FIG. (b) shows partially synthesized Nb2O5The nano rod can also be in a radial shape, and the crystal form is complete;
(7) the residual solution was recovered as in example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (7)
1. Method for preparing directionally arranged Nb by adopting single reagent self-reaction2O5The method of the nano rod is characterized by comprising the following steps:
(1) selecting potassium fluoroniobate powder to be dissolved in water to obtain a dilute potassium fluoroniobate solution, placing the dilute potassium fluoroniobate solution in a pretreated noble metal tube, and then sealing the noble metal tube;
(2) placing the sealed noble metal tube in a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to be 300-500 ℃, adjusting the pressure in the hydrothermal reaction kettle to be 50-200 MPa by adopting inert gas or deionized water, carrying out hydrolysis reaction for 12-24 h, and cooling the hydrothermal reaction kettle to room temperature after the reaction is finished;
(3) opening the hydrothermal reaction kettle, taking out the reacted noble metal tube and opening, recovering the residual solution, collecting the sample, washing and drying the obtained sample to obtain the directionally arranged Nb2O5A nanorod;
the concentration of the dilute potassium fluoroniobate solution in the step (1) is 0.005-0.01 mol/L, and the volume of the dilute potassium fluoroniobate solution accounts for 40-70% of the total volume of the noble metal tube.
2. The method of claim 1 for preparing Nb with directional ordering using single reagent self-reaction2O5The method for preparing the nano-rod is characterized in that the pretreatment of the noble metal tube in the step (1) comprises the following steps: selecting a noble metal tube, and carrying out truncation, acid boiling, washing and drying treatment, wherein the noble metal comprises gold, silver, platinum, gold palladium, silver palladium or platinum palladium alloy.
3. The method of claim 1 for preparing Nb with directional ordering using single reagent self-reaction2O5The method of the nano rod is characterized in that: when the noble metal tube is sealed in the step (1), the potassium fluoroniobate dilute solution is placed in the noble metal tube for sealing by welding, then the temperature is adjusted to be 100-120 ℃, the noble metal tube is dried for more than 2 hours, and the noble metal tube is weighed again, so that the mass error before and after the weighing is ensured to be less than 0.001 g.
4. The method of claim 1 for preparing Nb with directional ordering using single reagent self-reaction2O5The method of the nano rod is characterized in that: and (3) the inert gas in the step (2) is argon or helium.
5. The method of claim 1 for preparing Nb with directional ordering using single reagent self-reaction2O5The method of the nano rod is characterized in that: and (3) when the temperature is reduced in the step (2), using ice water to carry out rapid temperature reduction or constant-pressure temperature reduction on the reaction kettle.
6. The method of claim 1 for preparing Nb with directional ordering using single reagent self-reaction2O5The method of the nano rod is characterized in that: and (3) recovering the residual solution, namely doping niobium oxide powder into the residual solution, and continuously synthesizing the hydrofluoric acid and the potassium fluoride into potassium fluoroniobate to be used as an initial reaction solution.
7. The adoption sheet of claim 1Preparation of Nb with directional arrangement by self-reaction of reagent2O5The method of the nano rod is characterized in that: when the sample is collected in the step (3), taking out the residual solution, washing the inner wall of the noble metal tube for 2-3 times by using deionized water and absolute ethyl alcohol respectively, collecting the sample attached to the inner wall of the noble metal tube, and drying to obtain the directionally arranged Nb2O5And (4) nanorods.
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| CN110217818A (en) * | 2019-06-13 | 2019-09-10 | 中国科学院广州地球化学研究所 | Uniform particle size zirconium dioxide nanosphere and its film and preparation method |
| CN110203968B (en) * | 2019-06-13 | 2020-08-11 | 中国科学院广州地球化学研究所 | High (001) sheet-shaped zirconium oxide and preparation method thereof |
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| CN110217835B (en) * | 2019-07-09 | 2020-08-07 | 中国科学院广州地球化学研究所 | PtO (PtO)2Preparation method of tapered nano-particle material |
| CN113620357B (en) * | 2021-08-04 | 2022-05-27 | 中国科学院广州地球化学研究所 | OsO (OsO)2Preparation method of spherical nano-particle material |
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