CN108793231A - The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles - Google Patents
The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles Download PDFInfo
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- CN108793231A CN108793231A CN201810915718.1A CN201810915718A CN108793231A CN 108793231 A CN108793231 A CN 108793231A CN 201810915718 A CN201810915718 A CN 201810915718A CN 108793231 A CN108793231 A CN 108793231A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2004/01—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
- C01P2004/30—Particle morphology extending in three dimensions
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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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
Abstract
The present invention relates to technical field of nano material, especially a kind of method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles includes the following steps：(1) by divalent zinc ion salt, germanium oxide, KCl, LiCl, by the ratio between amount of substance 2: 1: 50x: 20x, 0.4<x<1.8 uniformly mixing；(2) obtained mixture is put into Muffle furnace, heating roasting, natural cooling；(3) it by the deionized water dipping desalination of the product after reaction, filters, obtains pale solid；(4) obtained pale solid is taken out to centrifuge tube, for several times with deionized water centrifuge washing, vacuum drying is fusiform germanic acid zinc nanoparticles to get product.The method of the present invention is environmental-friendly, and the time is short, and low energy consumption, and reaction step is few, and simple process, equipment is simple, and raw material is easy to get, excellent product performance, and controllability is strong.
Description
Technical field
The present invention relates to technical field of nano material, specific field is a kind of side of synthesis fusiform germanic acid zinc nanoparticles
Method.
Background technology
Germanic acid Zinc material energy gap be 4.4eV, be direct semiconductor, according to Mulliken electronegativity calculate valence band and
Conduction band potential is respectively 3.88eV and -0.62eV (relative to standard hydrogen electrode).Valence band is mainly by O 2p, Zn 3d and Ge4p rails
Road hydridization forms, and conduction band is mainly formed by Ge 4s, Ge 4p, Zn 4s and Zn 3d orbital hybridizations.Valence band track significantly weighs
It is folded so that the electronics in valence band has high migration, it is suppressed that light induced electron and hole it is compound, urged to improve zinc germanate
Change performance.It is dirty to be mainly used for decomposing water, processing all kinds of organic benzene, organics difficult to degrade difficult to degrade, fragrant diameter class as photochemical catalyst for zinc germanate
Object and all kinds of organic dyestuff and reduction carbon dioxide are contaminated, there is good decomposition water to prepare hydrogen and oxygen and reduction carbon dioxide
For catalytic performances such as methane, carbon monoxide.
Germanate nano material is in addition to having a good luminescent properties, outside excellent photochemical catalyst, can also be used as lithium from
The negative material of sub- battery.Germanium metal is due to higher theoretical specific capacity (1600mA.h.g-1), ideal lithium ion diffusion
Coefficient is considered as one of the ideal material for substituting conventional graphite.However its synthesis cost of germanium metal nano material is higher, prepares
Difficulty seriously hinders its practical process.Zinc germanate has 1443mA.h.g as semiconducting compound-1Theory it is embedding
The theoretical specific capacity of lithium capacity, zinc germanate is germanium 90.19%, but mass fraction of the germanium in zinc germanate is only 27.15%, can
To be effectively reduced material cost, possibility is provided for large-scale application in future.Zn elements have storage lithium activity, and cheap,
Higher specific capacity is also can guarantee while reducing material cost.Germanic acid zinc nano material is used for lithium ion battery negative material
Show highly stable cycle and high rate performance.
Develop it is a kind of it is environmental-friendly, dimensional controllability is good, pattern is uniform, good dispersion while being easy to largely synthesizes
Zn2GeO4Nano material is conducive to improve Zn2GeO4The photoelectric properties of nano material explore its answering in energy and environment
With.
Invention content
The purpose of the present invention is to provide a kind of methods that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles, existing to solve
There is Zn in technology2GeO4Synthesis technology is of high cost, performance is bad, and product size controllability obtained is bad, pattern is inhomogenous, divides
Dissipate the problems such as property is bad.
To achieve the above object, the present invention provides the following technical solutions：
A kind of method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles, includes the following steps：
(1) by divalent zinc ion salt, germanium oxide, KCl, LiCl, by the ratio between amount of substance 2: 1: 50x: 20x, 0.4<x<1.8
Uniformly mixing；
(2) obtained mixture is put into Muffle furnace, heating roasting, natural cooling；
(3) it by the deionized water dipping desalination of the product after reaction, filters, obtains pale solid；
(4) obtained pale solid is taken out to centrifuge tube, for several times with deionized water centrifuge washing, vacuum drying, i.e.,
It is fusiform germanic acid zinc nanoparticles to obtain product.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein the divalent zinc ion
Salt is the one or more of zinc nitrate, zinc oxide, zinc acetate, zinc oxalate or zinc carbonate.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein described in step (1)
Uniformly mixing is to be ground mixing in the agate mortar.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein in step (2), will
To mixture be collected in alumina crucible and place into Muffle furnace.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein in step (2), heating
Rate is 5 DEG C/min, is warming up to 540~880 DEG C.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein in step (2), roasting 3
~8 hours.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein described in step (4)
Vacuum drying temperature is 40 DEG C~80 DEG C.
The method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles of the present invention, wherein described in step (4)
The length of fusiform germanic acid zinc nanoparticles is 1~2 μm, a diameter of 300~800nm, is in fusiform.
Compared with prior art, the beneficial effects of the invention are as follows：The method of the present invention using divalent zinc ion salt, germanium oxide,
Uniformly mixing is distilled water retting desalination, is filtered, wash again through high-temperature roasting by the ratio between amount of certain substance by KCl, LiCl, dry
It is monodisperse fusiform germanic acid zinc nanoparticles to obtain product.Cheap, the simple for process synthetic method system of use cost of the present invention
The good Zn of standby chemical stability2GeO4Nano material has effectively expanded Zn2GeO4Application of micron.The method of the present invention ring
Border is friendly, and the time is short, and low energy consumption, and reaction step is few, and simple process, equipment is simple, and raw material is easy to get, excellent product performance, controllably
Property is strong, will possess vast market prospect in light, electricity, catalysis etc..
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of fusiform germanic acid zinc nano material prepared by the embodiment of the present invention 2；
Fig. 2 is the scanning electron microscope diagram of fusiform germanic acid zinc nanoparticles prepared by the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope diagram of fusiform germanic acid zinc nanoparticles prepared by the embodiment of the present invention 4；
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles, includes the following steps：
(1) by divalent zinc ion salt, germanium oxide, KCl, LiCl, by the ratio between amount of substance 2: 1: 50x: 20x, 0.4<x<
1.8, it is ground using agate mortar, uniformly mixes, obtain solid mixture；
(2) mixture obtained in step 1 is collected in alumina crucible and is placed into Muffle furnace, by 5 DEG C/min's
Rate is warming up to 540~880 DEG C, roasts 3~8 hours, natural cooling；
(3) the product deionized water dipping desalination after reacting step 2 filters, obtains pale solid；
(4) pale solid will be obtained in step 3 to take out to centrifuge tube, for several times with deionized water centrifuge washing, 40 DEG C~
It is dried in vacuo between 80 DEG C, it is 1~2 μm that length of the present invention, which is made, the fusiform particle of a diameter of 300~800nm.
If the reaction temperature in step 2 is less than 540 DEG C or the reaction time is less than 3h, solid mixture cannot be complete
Full response cannot generate pure phase compound, can not obtain fusiform germanic acid zinc nanoparticles；If the reaction temperature in step 2
Higher than 880 DEG C, then solid mixture can be converted to that particle is larger and non-uniform zinc germanate particle to degree.
Embodiment 2
By Zn (CH3COO)2, germanium oxide, KCl, LiCl ground by the ratio between amount of substance 2: 1: 50: 20 using agate mortar
Mill uniformly mixes, obtains solid mixture；Obtained mixture is collected in alumina crucible and is placed into Muffle furnace, by 5
DEG C/rate of min is warming up to 540 DEG C, it roasts 4 hours, natural cooling；By the deionized water dipping desalination of the product after reaction,
It filters, obtains pale solid；Pale solid will be obtained to take out to centrifuge tube, for several times with deionized water centrifuge washing, 60 DEG C
Between be dried in vacuo, be made canescence zinc germanate powder of the present invention.
XRD tests show that product is pure phase germanic acid zinc compound (Fig. 1), and scanning electron microscope detection shows (Fig. 2), closes
At the sample fusiform germanic acid zinc nanoparticles that are, good dispersion, length is 1~2 μm, a diameter of 300~600nm.With other
Preparation method is compared, and the method for the present invention is of low cost, and synthesis technology is simple, and pattern is uniform, good dispersion.
Embodiment 3
ZnO, germanium oxide, KCl, LiCl are ground by the ratio between amount of substance 2: 1: 50: 20 using agate mortar, it is uniformly mixed
It closes, obtains solid mixture；Obtained mixture is collected in alumina crucible and is placed into Muffle furnace, by 5 DEG C/min's
Rate is warming up to 680 DEG C, roasts 4 hours, natural cooling；By the deionized water dipping desalination of the product after reaction, filters, obtain
Pale solid；Pale solid will be obtained to take out to centrifuge tube, for several times with deionized water centrifuge washing, 60 DEG C of vacuum drying,
Canescence zinc germanate powder of the present invention is made.
Embodiment 4
By Zn (CH3COO)2, germanium oxide, KCl, LiCl ground by the ratio between amount of substance 2: 1: 25: 10 using agate mortar
Mill uniformly mixes, obtains solid mixture；Obtained mixture is collected in alumina crucible and is placed into Muffle furnace, by 5
DEG C/rate of min is warming up to 600 DEG C, it roasts 6 hours, natural cooling；By the deionized water dipping desalination of the product after reaction,
It filters, obtains pale solid；Pale solid will be obtained to take out to centrifuge tube, for several times with deionized water centrifuge washing, 60 DEG C
Canescence zinc germanate powder of the present invention is made in vacuum drying.Scanning electron microscope, which detects, to be shown (Fig. 3), the sample of synthesis
Fusiform germanic acid zinc nanoparticles, good dispersion, length are 1~2 μm, a diameter of 500~800nm.
Embodiment 5
By Zn (CH3COO)2, germanium oxide, KCl, LiCl ground by the ratio between amount of substance 2: 1: 75: 30 using agate mortar
Mill uniformly mixes, obtains solid mixture；Obtained mixture is collected in alumina crucible and is placed into Muffle furnace, by 5
DEG C/rate of min is warming up to 580 DEG C, it roasts 5 hours, natural cooling；By the deionized water dipping desalination of the product after reaction,
It filters, obtains pale solid；Pale solid will be obtained to take out to centrifuge tube, for several times with deionized water centrifuge washing, 60 DEG C
Canescence zinc germanate powder of the present invention is made in vacuum drying.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of method of molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles, which is characterized in that include the following steps：
(1) by divalent zinc ion salt, germanium oxide, KCl, LiCl, by the ratio between amount of substance 2: 1: 50x: 20x, 0.4<x<1.8 uniformly
Mixing；
(2) obtained mixture is put into Muffle furnace, heating roasting, natural cooling；
(3) it by the deionized water dipping desalination of the product after reaction, filters, obtains pale solid；
(4) obtained pale solid is taken out to centrifuge tube, for several times with deionized water centrifuge washing, is dried in vacuo to get production
Object is fusiform germanic acid zinc nanoparticles.
2. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：It is described
Divalent zinc ion salt is the one or more of zinc nitrate, zinc oxide, zinc acetate, zinc oxalate or zinc carbonate.
3. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(1) in, the uniform mixing is to be ground mixing in the agate mortar.
4. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(2) in, obtained mixture is collected in alumina crucible and is placed into Muffle furnace.
5. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(2) in, heating rate is 5 DEG C/min, is warming up to 540~880 DEG C.
6. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(2) it in, roasts 3~8 hours.
7. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(4) in, the vacuum drying temperature is 40 DEG C~80 DEG C.
8. the method for molten-salt growth method synthesis fusiform germanic acid zinc nanoparticles according to claim 1, it is characterised in that：Step
(4) in, the length of the fusiform germanic acid zinc nanoparticles is 1~2 μm, a diameter of 300~800nm, is in fusiform.
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| CN201810915718.1A CN108793231B (en) | 2018-08-13 | 2018-08-13 | Method for synthesizing spindle-shaped zinc germanate nanoparticles by molten salt method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502629A (en) * | 2018-12-04 | 2019-03-22 | 江苏理工学院 | Zinc oxide nano-sheet/nano particle preparation method |
| CN109607600A (en) * | 2018-12-04 | 2019-04-12 | 江苏理工学院 | Li2ZnGeO4The preparation method of nanometer rods |
| CN111196610A (en) * | 2020-01-21 | 2020-05-26 | 江苏理工学院 | Zn2GeO4Molten salt method for synthesizing nano rod |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962049A (en) * | 2012-11-26 | 2013-03-13 | 南京大学 | Method for preparing nanometer photocatalytic material via hydrothermal reaction |
| CN103073052A (en) * | 2012-12-19 | 2013-05-01 | 东华大学 | Preparation method of zinc germanate longitudinal twin crystal nano-wire |
| CN104261482A (en) * | 2012-11-29 | 2015-01-07 | 江苏理工学院 | Method for preparing ferrate nanosphere from molten salt |
| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
-
2018
- 2018-08-13 CN CN201810915718.1A patent/CN108793231B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962049A (en) * | 2012-11-26 | 2013-03-13 | 南京大学 | Method for preparing nanometer photocatalytic material via hydrothermal reaction |
| CN104261482A (en) * | 2012-11-29 | 2015-01-07 | 江苏理工学院 | Method for preparing ferrate nanosphere from molten salt |
| CN103073052A (en) * | 2012-12-19 | 2013-05-01 | 东华大学 | Preparation method of zinc germanate longitudinal twin crystal nano-wire |
| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
Non-Patent Citations (2)
| Title |
|---|
| CHENG-YAN XU等: "Synthesis of Single-Crystalline Niobate Nanorods via Ion-Exchange Based on Molten-Salt Reaction", 《J. AM. CHEM. SOC.》 * |
| REBECCA STEVENS等: "Heat capacities, third-law entropies and thermodynamic functions of the negative thermal expansion material Zn2GeO4 from T=(0 to 400) K", 《J. CHEM. THERMODYNAMICS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502629A (en) * | 2018-12-04 | 2019-03-22 | 江苏理工学院 | Zinc oxide nano-sheet/nano particle preparation method |
| CN109607600A (en) * | 2018-12-04 | 2019-04-12 | 江苏理工学院 | Li2ZnGeO4The preparation method of nanometer rods |
| CN111196610A (en) * | 2020-01-21 | 2020-05-26 | 江苏理工学院 | Zn2GeO4Molten salt method for synthesizing nano rod |
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